FORM 2
THE PATENTS ACT 1970
(39 of 1970)
&
The Patents Rules  2003
COMPLETE SPECIFICATION
(See section 10 and rule 13)

1. METHOD FOR PRODUCING LIQUEFIED MATERIAL FROM GLYCERIN-BASED SOLID MATERIAL

2.

1. (A) ONEWORLD CORPORATION
(B) Japan
(C) 102  Neo-Osakajokoen No.2  1-2  Shiginonishi 2-chome  Joto-ku 
Osaka-shi  Osaka 5360014 Japan
2. (A) ITO Tomoaki
(B) Japan
(C) 4-2-3-104  Shiginonishi  Joto-ku  Osaka-shi  Osaka 5360014 Japan

The following specification particularly describes the invention and the manner in which it is to be performed.

DESCRIPTION
METHOD FOR PRODUCING LIQUEFIED MATERIAL FROM GLYCERIN-BASED SOLID MATERIAL
TECHNICAL FIELD
[0001]
The present invention relates to a method for liquefying a glycerin-based solid material and producing a liquefied material.
BACKGROUND ART
[0002]
Biodiesel fuel (BDF) is obtained for use from an esterification reaction in which an alcohol and sodium hydroxide are added to Jatropha oil  sunflower oil  rapeseed oil  olive oil  or another plant oil. Glycerin is also generated in the meanwhile  as a byproduct (secondary product) together with the biodiesel fuel (see Patent Document 1). Since the glycerin byproduct remaining after the BDF has been separated from the product has BDF  ethanol  sodium hydroxide  and other substances mixed therewith; and is a solid at normal temperatures  it gets discarded as a waste product  there being no applications therefor.
Prior Art Documents
Patent Documents
[0003]
Patent Document 1: Japanese Laid-open Patent Publication 2006-348191
DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[004]
However  because of the fact that the glycerin byproduct has been discarded as a waste product  it is impossible to fully meet the societal requirements of environmental conservation and the efficient use of resources.
[0005]
The present invention has been contrived in view of the technical background above  it being an objective thereof to provide a method for producing a liquefied material from a glycerin-based solid material  whereby it is possible to efficiently liquefy a glycerin-based solid material to produce a liquefied material that can be used as  for example  a fuel or the like.
MEANS FOR SOLVING THE PROBLEMS
[0006]
To achieve the aforesaid objective  the present invention provides the following means.
[0007]
According to a first aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0008]
According to a second aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0009]
According to a third aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the first or second aspect  wherein when the components are mixed  a mixture formed by mixing the oil and the acid is mixed with the glycerin-based solid material.
[0010]
According to a fourth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the first to third aspects  characterized in that when the components are to be mixed  mixing is performed such that the glycerin-based solid material content relative to the total volume of glycerin-based solid material and oil is 50 vol% to 90 vol%  and 2 to 10 parts by volume of the acid is mixed per 100 parts by volume of the total of the glycerin-based solid material and oil.
[0011]
According to a fifth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing a glycerin-based solid material containing glycerin with an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0012]
According to a sixth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the first to fifth aspects  wherein an inorganic acid is used as the acid.
[0013]
According to a seventh aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the sixth aspect  wherein the inorganic acid is hydrochloric acid.
[0014]
According to an eighth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
an oxidant;
and at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0015]
According to a ninth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
an oxidant;
and at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0016]
According to a tenth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the eighth or ninth aspect  wherein when the components are to be mixed  the glycerin-based solid material and the oxidant are mixed first  and the oil is mixed in thereafter.
[0017]
According to an eleventh aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the eighth to tenth aspects  characterized in that when the components are to be mixed  0.1 to 40 parts by volume of the oil and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 35 mass%  are mixed per 100 parts by volume of the glycerin-based solid material.
[0018]
According to a twelfth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing a glycerin-based solid material containing glycerin with an oxidant; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0019]
According to a thirteenth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the eighth to twelfth aspects  wherein hydrogen peroxide is used as the oxidant.
[0020]
According to a fourteenth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
an oxidant;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0021]
According to a fifteenth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
an oxidant;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0022]
According to a sixteenth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the fourteenth or fifteenth aspect  wherein when the components are to be mixed  the glycerin-based solid material and the oxidant are mixed first  whereupon the oil is then mixed in  after which the acid is mixed in.
[0023]
According to a seventeenth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the fourteenth to sixteenth aspects  characterized in that when the components are to be mixed  0.1 to 40 parts by volume of the oil  0.1 to 10 parts by volume of the acid  and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 5 mass%  per 100 parts by volume of the glycerin-based solid material.
[0024]
According to an eighteenth aspect  the present invention provides a method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin  an oxidant  and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0025]
According to a nineteenth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the fourteenth to eighteenth aspects  wherein hydrogen peroxide is used as the oxidant.
[0026]
According to a twentieth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the fourteenth to nineteenth aspects  wherein acetic acid is used as the acid.
[0027]
According to a twenty-first aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the fourteenth to twentieth aspects  wherein the acid is mixed in such that the pH of the liquefied material is 4 to 11.
[0028]
According to a twenty-second aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the first to twenty-first aspects  wherein petroleum is used as the oil.
[0029]
According to a twenty-third aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the twenty-second aspect  wherein the petroleum is one  two  or more types of petroleum selected from the group consisting of paraffin  light oil  and heavy oil.
[0030]
According to a twenty-fourth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to the twenty-second aspect  wherein the petroleum is paraffin.
[0031]
According to a twenty-fifth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the first to twenty-fourth aspects  characterized in that the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is subsequently filtered  whereby a filtrate is obtained; and the filtrate is subsequently distilled at a distillation temperature of 150 to 230°C.
[0032]
According to a twenty-sixth aspect  the present invention provides the method for producing a liquefied material from a glycerin-based solid material according to any of the first to twenty-fourth aspects  characterized in that the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is subsequently filtered  whereby a filtrate is obtained  the filtrate is cooled to a temperature of 5°C or lower; a supernatant is obtained from the cooled liquid; and the supernatant is subsequently distilled at a distillation temperature of 150°C to 230°C.
[0033]
According to a twenty-seventh aspect  the present invention provides a method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0034]
According to a twenty-eighth aspect  the present invention provides a method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0035]
According to a twenty-ninth aspect  the present invention provides a method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid and an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0036]
According to a thirtieth aspect  the present invention provides a liquefied material for fuel produced by the production method according to any of the first to twenty-ninth aspects.
ADVANTAGEOUS EFFECTS OF THE INVENTION
[0037]
In the first aspect  a glycerin-based solid material containing glycerin (inclusive of a solid material consisting only of glycerin); at least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0038]
In the second aspect  a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil; at least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful. Also  since the raw glycerin-based solid material  which is formed as a byproduct when a biodiesel fuel is produced from a plant oil  is being used effectively  the effective use of resources can be promoted.
[0039]
In the third aspect  since the mixing involves mixing the glycerin-based solid material with a mixture formed by pre-mixing the oil and the acid  efficient liquefaction is possible.
[0040]
In the fourth aspect  the act of mixing involves mixing such that the glycerin-based solid material content reaches 50 vol% to 90 vol% relative to the total volume of glycerin-based solid material and oil  and also involves mixing 2 to 10 parts by volume of acid per 100 parts by volume of the total of the glycerin-based solid material and oil; therefore  adequate liquefaction is possible even while a high proportion of glycerin is being used.
[0041]
In the fifth aspect  a glycerin-based solid material containing glycerin is mixed with an acid  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0042]
In the sixth aspect  since an inorganic acid is used as the acid  it is possible to promote the liquefaction.
[0043]
In the seventh aspect  since hydrochloric acid is used as the acid  it is possible to further promote the liquefaction.
[0044]
In the eighth aspect  a glycerin-based solid material containing glycerin (inclusive of a solid material consisting only of glycerin); an oxidant; and at least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the oxidant is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0045]
In the ninth aspect  a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil; an oxidant; and at least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the oxidant is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful. Also  since the raw glycerin-based solid material  which is formed as a byproduct when a biodiesel fuel is produced from a plant oil  is being used effectively  the effective use of resources can be promoted.
[0046]
In the tenth aspect  since the mixing involves first mixing the glycerin-based solid material and the oxidant  and later mixing the oil  efficient liquefaction is possible.
[0047]
In the eleventh aspect  since the mixing involves mixing 0.1 to 40 parts by volume of the oil and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 35 mass%  per 100 parts by volume of the glycerin-based solid material  adequate liquefaction is possible even while a high proportion of glycerin is being used.
[0048]
In the twelfth aspect  a glycerin-based solid material containing glycerin is mixed with an oxidant  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the oxidant is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0049]
In the thirteenth aspect  since hydrogen peroxide is used as the oxidant  the liquefied material can be obtained at a high yield. That is  a high-calorie liquefied material can be obtained.
[0050]
In the fourteenth aspect  a glycerin-based solid material containing glycerin (inclusive of a solid material consisting only of glycerin); an oxidant; at least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid and the oxidant are mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0051]
In the fifteenth aspect  a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil; an oxidant; at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid and the oxidant are mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful. Also  since the raw glycerin-based solid material  which is formed as a byproduct when a biodiesel fuel is produced from a plant oil  is being used effectively  the effective use of resources can be promoted.
[0052]
In the sixteenth aspect  since the mixing involves first mixing the glycerin-based solid material and the oxidant  and later further mixing the oil and thereafter mixing the acid  efficient liquefaction is possible.
[0053]
In the seventeenth aspect  since the mixing involves mixing 0.1 to 40 parts by volume of the oil  0.1 to 10 parts by volume of the acid  and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 5 mass%  per 100 parts by volume of the glycerin-based solid material  adequate liquefaction is possible even while a high proportion of glycerin is being used.
[0054]
In the eighteenth aspect  a glycerin-based solid material containing glycerin  an oxidant  and an acid are mixed  and it is therefore possible to liquefy the solid material  i.e.  obtain a liquefied material. Further  the acid and the oxidant are mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0055]
In the nineteenth aspect  since hydrogen peroxide is used as the oxidant  the liquefied material can be obtained at a high yield. That is  a high-calorie liquefied material can be obtained.
[0056]
In the twentieth aspect  since acetic acid is used as the acid  kinematic viscosity can be lowered  which is an advantage.
[0057]
In the twenty-first aspect  since the acid is mixed in such that the pH of the liquefied material is 4 to 11  the resulting liquefied material has greater long-term stability and maintains a liquid state.
[0058]
In the twenty-second aspect  since petroleum is used as the oil  the combustion performance of the liquefied material can be further enhanced  because petroleum is favorably combustible.
[0059]
In the twenty-third aspect  since the petroleum used is one  two  or more types of petroleum selected from the group consisting of kerosene  light oil  and heavy oil  all of which are further favorably combustible  the combustion performance of the liquefied material can be even further enhanced.
[0060]
In the twenty-fourth aspect  since the petroleum used is kerosene  the combustion performance of the liquefied material can be even further enhanced  and also the amount of residue in the liquefied material can be further lowered  which is an advantage.
[0061]
In the twenty-fifth aspect  coloring components and other substances in the liquefied material can be eliminated  and a substantially colorless or colorless transparent liquefied material can be produced since the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is filtered to obtain a filtrate  and the filtrate is subsequently distilled at a distillation temperature of 150 to 230°C.
[0062]
In the twenty-sixth aspect  coloring components and other substances in the liquefied material can be adequately eliminated  and also a substantially colorless or colorless transparent liquefied material can be produced since the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is filtered to obtain a filtrate  the filtrate is subsequently cooled to a temperature of 5°C or lower  the supernatant is obtained from the cooled liquid  and the supernatant is subsequently distilled at a distillation temperature of 150 to 230°C.
[0063]
In the twenty-seventh aspect  a liquid glycerin-based substance containing glycerin is mixed with an acid  making it possible to produce a liquefied material having a lower solidifying point than the solidifying point of the liquid glycerin-based substance. For example  a liquefied material having a solidifying point of -30°C can be produced from a liquid glycerin-based substance having a solidifying point of -5°C. Further  the acid is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0064]
In the twenty-eighth aspect  a liquid glycerin-based substance containing glycerin is mixed with an oxidant  making it possible produce a liquefied material having a lower solidifying point than the solidifying point of the liquid glycerin-based substance. For example  a liquefied material having a solidifying point of -30°C can be produced from a liquid glycerin-based substance having a solidifying point of -5°C. Further  the oxidant is mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0065]
In the twenty-ninth aspect  a liquid glycerin-based substance containing glycerin  an acid  and an oxidant are mixed; and it is therefore possible produce a liquefied material having a lower solidifying point than the solidifying point of the liquid glycerin-based substance. For example  a liquefied material having a solidifying point of -30°C can be produced from a liquid glycerin-based substance having a solidifying point of -5°C. Further  the acid and the oxidant are mixed in such that the pH of the liquefied material is 3 to 12; therefore  the liquefied material will not re-solidify even as time passes  and the liquefied material has long-term stability and maintains a liquid state. The resulting liquefied material has excellent combustion performance and can be used as  for example  a fuel  and is therefore extremely useful.
[0066]
The thirtieth aspect provides a liquefied material for fuel having excellent combustion performance.
Best Mode for Carrying Out the Invention
[0067]
The method for producing a liquefied material from a glycerin-based solid material according to the first group of aspects is characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin; at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid  the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0068]
The method for producing a liquefied material from a glycerin-based solid material according to the second group of aspects is characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin; an oxidant; and at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil  the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0069]
The method for producing a liquefied material from a glycerin-based solid material according to the third group of aspects is characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin; an oxidant; at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; and an acid  the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0070]
(Description relating to the first  second  and third groups of aspects)
In the first  second  and third groups of aspects  examples of the glycerin-based solid material include a solid material (inclusive of a viscous jelly-like material) consisting only of glycerin or a glycerin-based solid material (inclusive of a viscous jelly-like material) containing glycerin and also containing components other than the glycerin (for example  sodium hydroxide or the like).
[0071]
Conventionally  a glycerin-based solid material formed as a byproduct (secondary product) when a biodiesel fuel is produced from a plant oil (Jatropha oil  sunflower oil  rapeseed oil  olive oil  and the like) is a solid and is therefore discarded as a waste product  there being no application therefor. However  since it can be efficaciously used when used as the glycerin-based solid material (when it is to be liquefied)  resources can be efficaciously used.
[0072]
Glycerin (alone) exhibits a viscous  jelly-like condition at normal temperatures but will not quite reach a solidified state; however  the glycerin-containing material formed as a byproduct when a biodiesel fuel is produced from the plant oil does reach a solidified state. The production of a biodiesel fuel from a plant oil involves  for example  adding methanol or another alcohol and sodium hydroxide (a catalyst) to a plant oil  and performing esterification  whereby a biodiesel fuel (BDF) is produced. Since  however  residual free fatty acids and sodium hydroxide are believed to be present in the glycerin byproduct remaining after the biodiesel fuel is separated from the product containing the biodiesel fuel  the effect thereof is presumed to contribute to the formation of the solid material. Nevertheless  the reason for the formation of the solid material is unclear at present.
[0073]
At least one type of oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil is used as the aforesaid oil. Examples of mineral oils include  but are not particularly limited to  petroleum and the like. Examples of animal oils include  but are not particularly limited to  cow oil  pig oil  bird oil  and the like. Examples of plant oils include  but are not particularly limited to  Jatropha oil  sunflower oil  rapeseed oil  olive oil  palm oil  and the like.
[0074]
Preferably  petroleum is used as the oil. The combustion performance of the liquefied material can be further enhanced  because petroleum is favorably combustible.
[0075]
Examples of petroleum (including crude oil) include  but are not particularly limited to  paraffin  light oil  heavy oil  gasoline  BDF (biodiesel fuel)  kerosene (jet fuel  rocket fuel  and the like) and the like. Preferably  one or more types of petroleum selected from the group consisting of paraffin  light oil  and heavy oil are used. The combustion performance of the liquefied material can be further enhanced  because these [forms of petroleum] are favorably combustible. Among these  the use of paraffin is most preferred; in such a case  the combustion performance of the liquefied material can be further enhanced and the residue in the liquefied material can also be further reduced. After paraffin  light oil is the next most preferable; in the case of light oil  the residue can be reduced to a certain degree as well.
[0076]
The oil is added in the sense of being a solvent for the liquefaction reaction  but is also inherently highly combustible  and therefore is advantageous in not impairing the combustion performance of the resulting liquefied material.
[0077]
The following methods of production may be employed as modifications of the first  second  and third groups of aspects described above.
[0078]
The first method is characterized in that a liquefied material is produced by heating a glycerin-based solid material containing glycerin into a liquefied material and thereafter mixing the liquefied material with an acid  the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0079]
The second method is characterized in that a liquefied material is produced by heating a glycerin-based solid material containing glycerin into a liquefied material and thereafter mixing the liquefied material with an oxidant  the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0080]
The third method is characterized in that a liquefied material is produced by heating a glycerin-based solid material containing glycerin into a liquefied material and thereafter mixing the liquefied material with an oxidant and an acid  the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0081]
(Description relating to the first group of aspects)
Illustrative examples of acids include  but are not particularly limited to  hydrochloric acid  sulfuric acid  and other inorganic acids. Preferably  an inorganic acid is used; in such a case  the liquefaction can be accelerated. Hydrochloric acid is a particularly suitable inorganic acid.
[0082]
The act of mixing in the acid involves setting  for example  the amount of acid mixed or the concentration of the acid used (e.g.  dilute acid or concentrated acid) such that that liquefied material reaches a pH of 3 to 12. When the pH is greater than 12 and a highly alkaline state is in effect  the liquefied material will re-solidify as time passes. Problems are also presented when the conditions are more acidic than indicated by a pH of 3  in that the tanks and other containers used for the mixing will more readily corrode. Preferably  the amount of acid mixed in or the concentration of acid used or the like is set such that the pH of the liquefied material is 4 to 11; a pH of 6 to 8 is particularly suitable.
[0083]
The act of mixing preferably involves mixing such that the glycerin-based solid material content reaches 50 vol% to 90 vol% relative to the total volume of glycerin-based solid material and oil (in other words  such that the oil content reaches 10 vol% to 50 vol%)  and also mixing 2 to 10 parts by volume of the acid per 100 parts by volume of the total volume of glycerin-based solid material and oil. In a case where hydrochloric acid is used as the acid  the parts by volume of hydrochloric acid mixed in are equivalent to 2 to 10 parts by volume in terms of hydrochloric acid concentrated to 35 mass%; in a case where sulfuric acid is used as the acid  the parts by volume of sulfuric acid mixed in are equivalent to 2 to 10 parts by volume in terms of hydrochloric acid concentrated to 90 mass%. Preferably  the glycerin-based solid material content is 60 vol% to 85 vol% relative to the total volume of the glycerin-based solid material and oil. Further preferably  3 to 8 parts by volume of the acid is mixed in per 100 parts by volume of the total volume of the glycerin-based solid material and oil.
[0084]
The act of mixing also preferably involves mixing the glycerin-based solid material with a mixture formed by pre-mixing the oil and acid. In such a case  efficient liquefaction is possible.
[0085]
The mixed solution formed by mixing the glycerin-based solid material  the oil  and the acid may be maintained at normal temperature and liquefied  or may alternatively be heated and liquefied. The mixed solution is preferably liquefied under stirring.
[0086]
(Description relating to the second group of aspects)
Examples of oxidants include  but are not particularly limited to  hydrogen peroxide  ozone  and the like. Preferably  hydrogen peroxide is used as the oxidant. In a case where hydrogen peroxide is used as the oxidant  the liquefied material can be obtained a high yield  i.e.  a high-calorie liquefied material can be obtained.
[0087]
The act of mixing in the oxidant involves setting  for example  the amount of oxidant mixed in or the concentration of the oxidant solution or the like such that the pH of the liquefied material is 3 to 12. When the pH is greater than 12 and is strongly alkaline  the liquefied material  having become liquefied  will re-solidify as time passes. Being more acidic than a pH of 3 is also problematic in being prone to corroding the tank and other containers used for the mixing. Preferably  the amount of oxidant mixed in or the concentration of the oxidant solution or the like is set such that the pH of the liquefied material is 4 to 11; a pH of 6 to 8 is particularly suitable.
[0088]
Preferably  the act of mixing involves mixing in 0.1 to 40 parts by volume of the oil  and a number of parts by volume of the oxidant equivalent to 0.1 to 20 parts by volume in terms of an oxidant solution concentrated to 35 mass%  per 100 parts by volume of the glycerin-based solid material. In such a case  adequate liquefaction is possible even while a high proportion of glycerin is being used.
[0089]
Further  preferably  the act of mixing involves first mixing the glycerin-based solid material with the oxidant  and thereafter further mixing in the oil. In such a case  efficient liquefaction is possible.
[0090]
The mixed solution formed by mixing the glycerin-based solid material  the oxidant  and the oil may be maintained at normal temperature and liquefied  or may alternatively be heated and liquefied. The mixed solution is preferably liquefied under stirring.
[0091]
(Description relating to the third group of aspects)
Examples of oxidants include  but are not particularly limited to  hydrogen peroxide  ozone  and the like. Preferably  hydrogen peroxide is used as the oxidant. In a case where hydrogen peroxide is used as the oxidant  the liquefied material can be obtained a high yield  i.e.  a high-calorie liquefied material can be obtained.
[0092]
Illustrative examples of the acid include  but are not particularly limited to  acetic acid  formic acid  and other organic acids  or hydrochloric acid  sulfuric acid  and other inorganic acids. Preferably  acetic acid  formic acid  or another organic acid is used; such a case is advantageous in being able to lower the kinematic viscosity. Acetic acid is a particularly suitable organic acid.
[0093]
The act of mixing in the acid involves setting  for example  the amount of acid mixed or the concentration of the acid used or the like such that that liquefied material reaches a pH of 3 to 12. When the pH is greater than 12 and is strongly alkaline  the liquefied material  having become liquefied  will re-solidify as time passes. Being more acidic than a pH of 3 is also problematic in being prone to corroding the tank and other containers used for the mixing. Preferably  the amount of acid mixed in or the concentration of the acid used or the like is set such that the pH of the liquefied material is 4 to 11; a pH of 6 to 8 is particularly suitable.
[0094]
Preferably  the act of mixing involves mixing in 0.1 to 40 parts by volume of the oil  0.1 to 10 parts by volume of the acid  and a number of parts by volume of the oxidant equivalent to 0.1 to 20 parts by volume in terms of an oxidant solution having a concentration of 5 mass%  per 100 parts by volume of the glycerin-based solid material. In such a case  adequate liquefaction is possible even while a high proportion of glycerin is being used.
[0095]
Further  preferably  the act of mixing involves first mixing the glycerin-based solid material with the oxidant  and thereafter further mixing in the oil  and subsequently mixing in the acid. In such a case  efficient liquefaction is possible.
[0096]
The mixed solution formed by mixing the glycerin-based solid material  the oxidant  the oil  and the acid may be maintained at normal temperature and liquefied  or may alternatively be heated and liquefied. The mixed solution is preferably liquefied under stirring.
[0097]
(Description relating to the first  second  and third groups of aspects)
The liquefied material obtained in the manner described above  on combustion  yields a high temperature with less fuel  and thus has excellent combustion performance. Therefore  the material can be appropriately used as  for example  a liquid fuel. The liquefied material can also be used in fuel as a mixed solution formed by mixing with petroleum (paraffin  light oil  heavy oil  and so forth) or another oil. The liquefied material can be used without modification as a liquid fuel  but may also be used as a liquid fuel once the solid components have been removed by filtration and moisture has been isolated and removed by centrifugation.
[0098]
The liquefied material  when combusted  gives off less NOX (nitrogen oxide)  CO (carbon monoxide)  CO2 (carbon dioxide)  SO2 (sulfur dioxide) and other emissions; and can therefore contribute to protecting the environment.
[0099]
Preferably  the liquefied material obtained in the manner described above additionally undergoes the following post-treatment. Namely  the liquefied material obtained as described above is cooled to a temperature of 30°C or lower  after which a filtrate is obtained by filtering the precipitate; subsequently  the filtrate is distilled at a distillation temperature of 150°C to 230°C  whereby a distilled liquefied material is obtained. The coloring components and other substances in the resulting distilled liquefied material can be removed to produce a substantially colorless or colorless transparent liquefied material. The distilled liquefied material is suitable for use as  for example  a liquid fuel.
[0100]
Alternatively  it is particularly preferable to perform the following post-treatment. Namely  particularly preferably  the liquefied material obtained in the manner described above is cooled to a temperature of 30°C or lower; a filtrate is thereafter obtained by filtering out the precipitate  the filtrate being subsequently cooled to a temperature of 5°C or lower (it is suitable to cool the filtrate to -5°C or lower  and more suitably to -25°C to -10°C); and the supernatant is obtained from the cooled solution  the supernatant subsequently being distilled at a distillation temperature of 150°C to 230°C  whereby a distilled liquefied material is obtained. The coloring components and other substances in the distilled liquefied material thus obtained can be adequately removed to produce a substantially colorless or colorless transparent liquefied material. The distilled liquefied material is suitable for use as  for example  a liquid fuel.
[0101]
The precipitate can be filtered using  for example  a filter  a centrifuge  or the like. The distillation temperature is further preferably set to 160°C to 200°C. When the distillation temperature is greater than 230°C  some of the coloring components will more readily distilled out  which is undesirable.
[0102]
The methods of production described above can also be applied to a liquid glycerin-based substance containing glycerin. In such a case  it is possible to produce a liquefied material having a lower solidifying point than the solidifying point of the liquid glycerin-based substance.
[0103]
Namely  a first method for producing a liquefied material of the present invention is characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0104]
A second method for producing a liquefied material of the present invention is characterized in that a liquid glycerin-based substance containing glycerin is mixed with an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
[0105]
A third method for producing a liquefied material of the present invention is characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid and an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
[0106]
The first to third methods of production described above (see Claims 27 to 29) serve to establish production methods according to the steps after the reaction steps in the first to third groups of aspects (i.e.  the production methods for after the glycerin-based solid material has been made into a liquid glycerin-based substance by heating).
[0107]
Namely  liquid glycerin-based substances containing glycerin which can be used are in a liquid state a normal temperature (25°C)  or are a glycerin-based solid material containing glycerin in a solid state at normal temperature (25°C) which can be made into a liquid by being heated (a suitable heating temperature is 40°C to 80°C; a particularly suitable heating temperature is 40°C to 60°C).
WORKING EXAMPLES
[0108]
The following is a description of specific working examples of the present invention  but the present invention is not particularly limited to these working examples.
[0109]

An esterification reaction was carried out by mixing 75 parts by mass of a plant oil obtained from Jatropha  20 parts by mass of methanol  and 5 parts by mass of sodium hydroxide  the mixture then being held for eight hours at normal temperature under stirring  thus obtaining a product that contained a biodiesel fuel (fatty acid methyl esters and the like). The product had a biodiesel fuel content of about 75 mass%  and a glycerin-based solid material byproduct (solid material containing glycerin) content of about 25 mass%. The biodiesel fuel was separated from the product by a precipitation separation method.
[0110]
Next  the glycerin-based solid material remaining from the separation (pH of about 14) was liquefied. Namely  first  50 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 300 mL of paraffin to obtain a mixture  and the mixture was mixed into 700 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 7.
[0111]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  50 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 200 mL of light oil to obtain a mixture  and the mixture was mixed into 800 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 7.
[0112]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  50 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 200 mL of heavy oil to obtain a mixture  and the mixture was mixed into 800 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 7.
[0113]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  20 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 300 mL of paraffin to obtain a mixture  and the mixture was mixed into 700 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 10.
[0114]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  80 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 300 mL of paraffin to obtain a mixture  and the mixture was mixed into 700 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 5.
[0115]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  10 mL of concentrated sulfuric acid (sulfuric acid concentrated to 90 mass%) was pre-mixed into 300 mL of paraffin to obtain a mixture  and the mixture was mixed into 700 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 8.
[0116]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. First  5 mL of concentrated hydrochloric acid (hydrochloric acid concentrated to 35 mass%) was pre-mixed into 300 mL of paraffin to obtain a mixture  and the mixture was mixed into 700 mL of the glycerin-based solid material  which was then stirred for 30 minutes at normal temperature  whereby a liquefied material was obtained. The resulting liquefied material had a pH of 13.
[0117]

The liquefied material obtained in Working Example 1 (pH 7; a brown  transparent liquid) was further subjected to the following post-treatment. Namely  the liquefied material obtained in Working Example 1 (a brown  transparent liquid) was cooled to 20°C and kept at 20°C for 1 440 minutes  after which a filtrate was obtained by the physical filtration of the precipitate present in the 20°C liquefied material  using a filter. The filtrate was distilled at a distillation temperature of 200°C  whereby a colorless  transparent distillate (distilled liquefied material) was obtained.

[0118]
[Table 1]
Mixture composition (parts by volume) Resulting liquefied material Evaluated stability of liquid state of the liquefied materials
(7 day period)
Glycerin-based solid material Oil Concentrated Hydrochloric acid Concentrated Sulfuric Acid
pH Residue content Color/transparency
Working Example 1 70 Paraffin  30 5 - 7 ? Brown  transparent Liquid state maintained
Working Example 2 80 Light oil  20 5 - 7 ? Brown  transparent Liquid state maintained
Working Example 3 80 Heavy oil  30 5 - 7 ? Brown  non-transparent Liquid state maintained
Working Example 4 70 Paraffin  30 2 - 10 ? Brown  transparent Liquid state maintained
Working Example 5 70 Paraffin  30 8 - 5 ? Brown  transparent Liquid state maintained
Working Example 6 70 Paraffin  30 - 1 8 ? Brown  transparent Liquid state maintained
Comparative Example 1 70 Paraffin  30 0.5 - 13 ? Brown  transparent Re-solidified
Working Example 8 70 Paraffin  30 5 - 7 ? Colorless  transparent Liquid state maintained

[0119]

The glycerin-based solid material obtained in Working Example 1 (pH of about 14; solidifying point at 25°C) was liquefied by the following procedure. A mixture formed by mixing 30 mL of hydrogen peroxide (water having 5 mass% hydrogen peroxide) into 700 mL of the glycerin-based solid material was stirred for 20 minutes at 60°C  after which 300 mL of paraffin was further added. After 10 minutes of stirring at 60°C  10 mL of acetic acid (purity: 99 mass%) was further added  followed by 10 minutes of stirring at 60°C  whereby a liquefied material (pH of 7; brown  transparent liquid) was obtained.
[0120]
Next  the liquefied material (a brown  transparent liquid) was cooled to 20°C and kept at 20°C for 30 minutes  after which a filtrate was obtained by the physical filtration of the precipitate present in the 20°C liquefied material  using a filter. The filtrate was cooled to a temperature of -10°C and kept at -10°C for 180 minutes  after which the supernatant was obtained from the cooled solution  the supernatant subsequently being distilled at a distillation temperature of 200°C  whereby a colorless transparent distillate (the distilled liquefied material) was obtained. The solidifying point of the resulting distilled liquefied material was less than -30°C (the material did not solidify at -30°C or more).
[0121]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that 300 mL of heavy oil was used instead of the 300 mL of paraffin.
[0122]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that 300 mL of light oil was used instead of the 300 mL of paraffin.
[0123]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that the amount of hydrogen peroxide (water having 5 mass% hydrogen peroxide) used was set to 10 mL.
[0124]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that the amount of hydrogen peroxide (water having 5 mass% hydrogen peroxide) used was set to 80 mL.
[0125]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that the amount of acetic acid used was set to 5 mL.
[0126]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 9  except in that the amount of acetic acid used was set to 40 mL.
[0127]

The glycerin-based solid material obtained in Working Example 1 (having a pH of about 14) was liquefied by the following procedure. A mixture formed by mixing 30 mL of hydrogen peroxide (water having 35 mass% hydrogen peroxide) into 700 mL of the glycerin-based solid material was stirred for 10 minutes at 60°C  after which 300 mL of paraffin was further added  followed by 10 minutes of stirring at 60°C  whereby a liquefied material (pH of 7; brown  transparent liquid) was obtained.
[0128]
Next  the liquefied material (a brown  transparent liquid) was cooled to 20°C and kept at 20°C for 60 minutes  after which a filtrate was obtained by the physical filtration of the precipitate present in the 20°C liquefied material  using a filter; subsequently  the filtrate was cooled to a temperature of -10°C and kept at -10°C for 1 440 minutes  after which the supernatant was obtained from the cooled solution  the supernatant subsequently being distilled at a distillation temperature of 200°C  whereby a colorless transparent distillate (the distilled liquefied material) was obtained.
[0129]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 16  except in that 300 mL of heavy oil was used instead of the 300 mL of paraffin.
[0130]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 16  except in that 300 mL of light oil was used instead of the 300 mL of paraffin.
[0131]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 16  except in that the amount of hydrogen peroxide (water having 35 mass% hydrogen peroxide) used was set to 10 mL.
[0132]

A colorless  transparent distillate (distilled liquefied material) was obtained in a manner similar with respect to Working Example 16  except in that the amount of hydrogen peroxide (water having 35 mass% hydrogen peroxide) used was set to 70 mL.
[0133]

The glycerin-based solid material obtained in Working Example 1 (pH of about 14; solidifying point at 25°C) was liquefied by the following procedure. A mixture formed by heating 700 mL of the glycerin-based solid material to 60°C to make a liquid material and thereafter mixing 10 mL of hydrogen peroxide (5 mass% of aqueous hydrogen peroxide) into the liquid material was stirred for 20 minutes at 60°C  after which 20 mL of acetic acid (purity: 99 mass%) was further added  followed by 10 minutes of stirring at 60°C  whereby a liquefied material (pH of 5; brown  transparent liquid) was obtained.
[0134]
Next  the liquefied material (a brown  transparent liquid) was cooled to 20°C and kept at 20°C for 30 minutes  after which a filtrate was obtained by the physical filtration of the precipitate present in the 20°C liquefied material  using a filter; subsequently  the filtrate was cooled to a temperature of -10°C and kept at -10°C for 180 minutes  after which the supernatant was obtained from the cooled solution  the supernatant subsequently being distilled at a distillation temperature of 200°C  whereby a colorless transparent distillate (the distilled liquefied material) was obtained. The solidifying point of the resulting distilled liquefied material was less than -30°C (the material did not solidify at -30°C or more).
[0135]

A mixture formed by mixing 10 mL of hydrogen peroxide (water having 5 mass% hydrogen peroxide) into 700 mL of a liquid glycerin-based substance (having a solidifying point of -5°C) was stirred for 20 minutes at 60°C  after which 300 mL of paraffin was added  and stirring was performed for 10 minutes at 60°C. 20 mL of acetic acid (purity: 99 mass%) was further added  followed by 10 minutes of stirring at 60°C  whereby a liquefied material (pH of 5; brown  transparent liquid) was obtained.
[0136]
Next  the liquefied material (a brown  transparent liquid) was cooled to 20°C and kept at 20°C for 30 minutes  after which a filtrate was obtained by the physical filtration of the precipitate present in the 20°C liquefied material  using a filter. The filtrate was cooled to a temperature of -10°C and kept at -10°C for 180 minutes  after which the supernatant was obtained from the cooled solution  the supernatant subsequently being distilled at a distillation temperature of 200°C  whereby a colorless transparent distillate (the distilled liquefied material) was obtained. The solidifying point of the resulting distilled liquefied material was less than -30°C (the material did not solidify at -30°C or more).

[0137]
[Table 2]
Mixture composition (parts by volume) Resulting liquefied materials Evaluated stability of liquid state of the liquefied materials
(7 day period)
Glycerin-based solid material Hydrogen peroxide Oil Acetic acid
pH Residue content Color/transparency
Working Example
9 70 3 Paraffin  30 1 5 ? Colorless  transparent Liquid state maintained
Working Example 10 70 3 Heavy oil  30 1 5 ? Colorless  transparent Liquid state maintained
Working Example 11 70 3 Light oil  30 1 5 ? Colorless  transparent Liquid state maintained
Working Example 12 70 1 Paraffin  30 1 7 ? Colorless  transparent Liquid state maintained
Working Example 13 70 8 Paraffin  30 1 7 ? Colorless  transparent Liquid state maintained
Working Example 14 70 3 Paraffin  30 0.5 8 ? Colorless  transparent Liquid state maintained
Working Example 15 70 3 Paraffin  30 4 5 ? Colorless  transparent Liquid state maintained
Working Example 16 70 3 Paraffin  30 - 7 ? Colorless  transparent Liquid state maintained
Working Example 17 70 3 Heavy oil  30 - 7 ? Colorless  transparent Liquid state maintained
Working Example 18 70 3 Light oil  30 - 7 ? Colorless  transparent Liquid state maintained
Working Example 19 70 1 Paraffin  30 - 7 ? Colorless  transparent Liquid state maintained
Working Example 20 70 7 Paraffin  30 - 6 ? Colorless  transparent Liquid state maintained
Working Example 21 70 1 - 2 5 ? Colorless  transparent Liquid state maintained
Working Example 22 70 liquid material 1 Paraffin  30 2 5 ? Colorless  transparent Liquid state maintained

[0138]
The following testing methods were used to evaluate the stability of the liquid state of each of the liquefied materials obtained as described above  as well as the approximate residue content of the liquefied materials and the color and transparency of the liquefied materials.
[0139]

1 000 mL of the resulting liquefied materials was allowed to stand for seven days under conditions of about 25°C  after which the liquid state thereof was visually observed. Tables 1 and 2 show the observation results.
[0140]

The resulting liquefied materials were visually observed and the approximate content of residue in the liquefied materials was evaluated on the basis of the following criteria. Tables 1 and 2 show the evaluation results.
(Criteria)
? ... Very little residue content in the liquefied material
? ... Some residue content in the liquefied material
? ... High residue content in the liquefied material
× ... Very high residue content in the liquefied material
[0141]

The resulting liquefied materials were visually observed to evaluate the color of the liquefied materials  and to evaluate the transparency of the liquefied materials on the basis of the following criteria. Tables 1 and 2 show the evaluation results.
(Criteria)
{Transparent} ... The liquefied material has excellent transparency.
{Semitransparent} ... The liquefied material  though transparent  is not highly transparent.
{Not transparent} ... The liquefied material is not transparent.
[0142]
As is apparent from Table 1  the liquefied materials of Working Examples 1 to 6 and 8 to 21  which were obtained by the method of production of the present invention  had long-term stability and maintained a liquid state. By contrast  Comparative Example 1  which re-solidified as time passed  was not readily used as  for example  a fuel  and was not commercially viable.
[0143]
Next  the combustion performance of the liquefied material obtained in Working Example 1 was evaluated. The liquefied material obtained in Working Example 1 was placed in a boiler and the combustion performance was evaluated. As a reference example  combustion performance was similarly evaluated with regard to A-heavy oil. Combustion performance was similarly evaluated with regard to a mixed solution (Working Example 7) formed by mixing 50 parts by volume of A-heavy oil in 50 parts by volume of the liquefied material of Working Example 1. Table 3 shows the results of the evaluations.
[0144]
As is apparent from Table 3  the liquefied material of Working Example 1 obtained by the method of production of the present invention results in a higher temperature with less fuel used than the A-heavy oil of the reference example  and has excellent combustion performance. Further  the liquefied material of Working Example 1  when combusted  gives off less NOX (nitrogen oxide)  CO (carbon monoxide)  CO2 (carbon dioxide)  SO2 (sulfur dioxide) and other emissions than the A-heavy oil of the reference example  and can therefore contribute to protecting the environment.
[0145]
The mixture of Working Example 7 also results in a higher temperature with less fuel used compared to the A-heavy oil of the reference example  and has excellent combustion performance. Further  the mixture solution of Working Example 7  when combusted  gives off less NOX (nitrogen oxide)  CO (carbon monoxide)  CO2 (carbon dioxide)  SO2 (sulfur dioxide) and other emissions than the A-heavy oil of the reference example  and can therefore contribute to protecting the environment.
[0146]
[Table 3]
Reference Example Working Example 1 Working Example 7
Sample (vol%) Liquefied material of Working Example 1 - 100 50
A-heavy oil 100 - 50
Combustion performance items Amount of fuel (L/hr) 7 6.7 6.7
Flue outlet temperature (°C) 824 854 874
NOx (ppm) 36 26 24
CO (ppm) 7.6 4.0 3.8
CO2 (%) 6.2 4.5 4.2
O2 (%) 13.6 14.8 15.2
SO2 (ppm) 4.0 0 0
Primary air amount (m3/hr) 27 27 27
Secondary air amount (m3/hr) 68 68 68

[0147]
Table 4 shows the results from the analysis of the liquefied material obtained in Working Example 1. Table 5 shows the results from the analysis of the liquefied material obtained in Working Example 4. Table 6 shows the results from the analysis of the liquefied material obtained in Working Example 5. Table 7 shows the results from the analysis of the liquefied material (distilled liquefied material) obtained in Working Example 9. Table 8 shows the results from the analysis of the liquefied material (distilled liquefied material) obtained in Working Example 10. Table 9 shows the results from the analysis of the liquefied material (distilled liquefied material) obtained in Working Example 16.
[0148]
The liquefied material obtained in Working Example 21 had a gross calorific value of about 23 500 J/g.
[0149]
[Table 4]
Item Liquefied material of Working Example 1 Testing method
Reaction*1) Not measurable JIS K2252
Ignition point (°C)*2) 30.0 (reference value) JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 6.91 JIS K2283
Pour point (°C) -20.0 JIS K2269
Residual carbon (mass%) 2.00 JIS K2270
Moisture (vol%) 2.2 JIS K2275
Ash (mass%) 1.05 JIS K2272
Sulfur (mass%) 0.01 JIS K2541-3
Gross calorific value (J/g) 40100 JIS K2279
*1) … The aqueous layer portion in the reaction test exhibited a dark brown color and was marked as “Not measurable”
*2) Deviates from the range “Liquid flammable at greater than 40°C” used in the JIS K2265 and so was marked as “Reference Value”
[0150]
[Table 5]
Item Liquefied material of Working Example 4 Testing method
Reaction*1) Not measurable JIS K2252
Ignition point (°C)*2) 30.0 (reference value) JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 6.91 JIS K2283
Pour point (°C) -20.0 JIS K2269
Residual carbon (mass%) 2.00 JIS K2270
Moisture (vol%) 2.2 JIS K2275
Ash (mass%) 1.05 JIS K2272
Sulfur (mass%) 0.01 JIS K2541-3
Gross calorific value (J/g) 40100 JIS K2279
*1) … The aqueous layer portion in the reaction test exhibited a dark brown color and was marked as “Not measurable”
*2) Deviates from the range “Liquid flammable at greater than 40°C” used in the JIS K2265 and so was marked as “Reference Value”
[0151]
[Table 6]
Item Liquefied material of Working Example 5 Testing method
Reaction*1) Not measurable JIS K2252
Ignition point (°C)*2) 30.0 (reference value) JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 4.62 JIS K2283
Pour point (°C) -25.0 JIS K2269
Residual carbon (mass%) 0.79 JIS K2270
Moisture (vol%) 2.0 JIS K2275
Ash (mass%) 0.50 JIS K2272
Sulfur (mass%) 0.02 JIS K2541-3
Gross calorific value (J/g) 41230 JIS K2279
*1) … The aqueous layer portion in the reaction test exhibited a dark brown color and was marked as “Not measurable”
*2) Deviates from the range “Liquid flammable at greater than 40°C” used in the JIS K2265 and so was marked as “Reference Value”
[0152]
[Table 7]
Item Liquefied material of Working Example 9 Testing method
Reaction Acidic JIS K2252
Ignition point (°C)*2) 36.0 (reference value) JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 0.987 JIS K2283
Pour point (°C) -30.0 JIS K2269
Residual carbon (mass%) 0.01 JIS K2270
Moisture (vol%) 0.02 JIS K2275
Ash (mass%) less than 0.001 JIS K2272
Sulfur (mass%) 0.0012 JIS K2541-3
Gross calorific value (J/g) 45500 JIS K2279
*2) Deviates from the range “Liquid flammable at greater than 40°C” used in the JIS K2265 and so was marked as “Reference Value”
[0153]
[Table 8]
Item Liquefied material of Working Example 10 Testing method
Reaction Acidic JIS K2252
Ignition point (°C)*2) 36.0 (reference value) JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 1.623 JIS K2283
Pour point (°C) -25.0 JIS K2269
Residual carbon (mass%) 0.03 JIS K2270
Moisture (vol%) 0.03 JIS K2275
Ash (mass%) 0.001 JIS K2272
Sulfur (mass%) 0.042 JIS K2541-3
Gross calorific value (J/g) 44850 JIS K2279
*2) Deviates from the range “Liquid flammable at greater than 40°C” used in the JIS K2265 and so was marked as “Reference Value”
[0154]
[Table 9]

Item Liquefied material of Working Example 16 Testing method
Reaction Alkaline JIS K2252
Ignition point (°C) 61.0 JIS K2265-3
Kinematic viscosity (50°C) (mm2/s) 1.825 JIS K2283
Pour point (°C) -17.5 JIS K2269
Residual carbon (mass%) 0.10 JIS K2270
Moisture (vol%) 0.05 JIS K2275
Ash (mass%) 0.024 JIS K2272
Sulfur (mass%) 0.01 JIS K2541-3
Gross calorific value (J/g) 43610 JIS K2279
[0155]
The present application claims the priority of Japanese Patent Application No. 2009-199944  filed on August 31  2009  the matter disclosed therein constituting a part of the present application verbatim.
Industrial Applicability
[0156]
The liquefied material produced by the method of production of the present invention has excellent combustion performance and is therefore suitable for use as  for example  a liquid fuel  but is not particularly limited to such applications.
We claim:-
1. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
2. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
3. The method for producing a liquefied material from a glycerin-based solid material according to Claim 1 or 2  wherein when the components are mixed  a mixture formed by mixing the oil and the acid is mixed with the glycerin-based solid material.
4. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 1 to 3  characterized in that when the components are to be mixed  mixing is performed such that the glycerin-based solid material content relative to the total volume of glycerin-based solid material and oil is 50 vol% to 90 vol%  and 2 to 10 parts by volume of the acid is mixed per 100 parts by volume of the total of the glycerin-based solid material and oil.
5. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing a glycerin-based solid material containing glycerin with an acid; and the acid is mixed in such that the pH of the liquefied material is 3 to 12.
6. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 1 to 5  wherein an inorganic acid is used as the acid.
7. The method for producing a liquefied material from a glycerin-based solid material according to Claim 6  wherein the inorganic acid is hydrochloric acid.
8. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
an oxidant;
and at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
9. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
an oxidant;
and at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
10. The method for producing a liquefied material from a glycerin-based solid material according to Claim 8 or 9  wherein when the components are to be mixed  the glycerin-based solid material and the oxidant are mixed first  and the oil is mixed in thereafter.
11. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 8 to 10  characterized in that when the components are to be mixed  0.1 to 40 parts by volume of the oil and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 35 mass%  are mixed per 100 parts by volume of the glycerin-based solid material.
12. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing a glycerin-based solid material containing glycerin with an oxidant; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
13. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 8 to 12  wherein hydrogen peroxide is used as the oxidant.
14. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin;
an oxidant;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
15. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material formed as a byproduct when a biodiesel fuel is produced from a plant oil;
an oxidant;
at least one oil selected from the group consisting of a mineral oil  an animal oil  and a plant oil;
and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
16. The method for producing a liquefied material from a glycerin-based solid material according to Claim 14 or 15  wherein when the components are to be mixed  the glycerin-based solid material and the oxidant are mixed first  whereupon the oil is then mixed in  after which the acid is mixed in.
17. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 14 to 16  characterized in that when the components are to be mixed  0.1 to 40 parts by volume of the oil  0.1 to 10 parts by volume of the acid  and 0.1 to 20 parts by volume of the oxidant  in terms of an oxidant solution having a concentration of 5 mass%  per 100 parts by volume of the glycerin-based solid material.
18. A method for producing a liquefied material from a glycerin-based solid material  characterized in that a liquefied material is produced by mixing: a glycerin-based solid material containing glycerin  an oxidant  and an acid; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
19. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 14 to 18  wherein hydrogen peroxide is used as the oxidant.
20. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 14 to 19  wherein acetic acid is used as the acid.
21. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 14 to 20  wherein the acid is mixed in such that the pH of the liquefied material is 4 to 11.
22. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 1 to 21  wherein petroleum is used as the oil.
23. The method for producing a liquefied material from a glycerin-based solid material according to Claim 22  wherein the petroleum is one  two or more types of petroleum selected from the group consisting of paraffin  light oil  and heavy oil.
24. The method for producing a liquefied material from a glycerin-based solid material according to Claim 22  wherein the petroleum is paraffin.
25. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 1 to 24  characterized in that the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is subsequently filtered  whereby a filtrate is obtained; and the filtrate is subsequently distilled at a distillation temperature of 150 to 230°C.
26. The method for producing a liquefied material from a glycerin-based solid material according to any of Claims 1 to 24  characterized in that the liquefied material obtained by the mixing is cooled to a temperature of 30°C or lower  a precipitate is subsequently filtered  whereby a filtrate is obtained  the filtrate is cooled to a temperature of 5°C or lower; a supernatant is obtained from the cooled liquid; and the supernatant is subsequently distilled at a distillation temperature of 150 to 230°C.
27. A method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
28. A method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the oxidant being mixed in such that the pH of the liquefied material is 3 to 12.
29. A method for producing a liquefied material  characterized in that a liquid glycerin-based substance containing glycerin is mixed with an acid and an oxidant  thereby producing a liquefied material having a solidifying point that is lower than the solidifying point of the liquid glycerin-based substance; the acid being mixed in such that the pH of the liquefied material is 3 to 12.
30. A liquefied material for fuel produced by the production method according to any of Claims 1 to 29.
Dated this 17th day of March 2012