DESC:FIELD
The present disclosure relates to detergents and surfactants. Particularly, the present disclosure relates to a process for the preparation of linear alkylbenzenes from renewable sources.
DEFINITIONS
As used in the present disclosure, the following terms are generally intended to have the meaning as set forth below, except to the extent that the context in which they are used, indicate otherwise.
Renewable feedstock- A renewable feedstock refers to a raw material used in a chemical process, either for manufacturing another product or in energy production, and is a resource that can replenish itself through natural processes.
WHSV (Weight hourly space velocity) - WHSV is defined as the ratio of mass of the feed per hour to the mass of the catalyst.
Hydrodeoxygenation (HDO) - Hydrodeoxygenation is a hydrogenolysis reaction in which the removal of the oxygen atom from the reactant occurs in the presence of hydrogen (H2). The reaction typically employs an HDO catalyst.
Dehydration - Dehydration reaction is a chemical reaction that involves the loss of water from the reacting molecule or ion.
Hydrotreatment - Hydrotreatment is a catalytic conversion process in petroleum refining, for removing impurities such as nitrogen and sulphur compounds from hydrocarbon streams by using high volume of hydrogen gas.
Dehydrogenation - Dehydrogenation refers to the process of removing hydrogen from an organic compound to create a new chemical, typically converting saturated compounds into unsaturated compounds.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
n-Paraffins are raw materials for the production of cleaning compositions. These n-paraffins are usually obtained from hydrocarbons, wherein the sources of hydrocarbons is mineral source such as petroleum. Linear paraffins are one of the raw materials that can be used in the production of linear alkylbenzenes, however, the cleaning composition requires specific lengths of the alkyl component for superior linear alkylbenzenes and biodegradability properties.
Commercially, n-paraffins are produced from the raw material, kerosene, which is a petroleum product. However, the petroleum product is a non-renewable resource. The growing environmental concerns over fossil fuel (non-renewable resources) and further a social pressure to utilize renewable resources for consumer product, has significantly increased the demand for using a renewable feedstock for producing surfactants for detergent and cleaning compositions.
The specifications of the cleaning composition include a mixture of even and odd numbered n-paraffins, where the even and odd numbered n-paraffins fall within desired concentration ranges. The existing processes for converting fatty acids and triglycerides in natural oils to n-paraffins (by hydrodeoxygenation, decarboxylation, or decarbonylation) tend to produce n-paraffins that do not have the desired concentration of n-paraffins both with an even number of carbon atoms and an odd number of carbon atoms to satisfy linear alkylbenzenes producers desired concentration ranges.
There is, therefore, felt a need to provide a process for the preparation linear alkylbenzenes that mitigates the drawbacks mentioned herein above or at least provides a useful alternative.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows:
It is an object of the present disclosure to ameliorate one or more problems of the background or to at least provide a useful alternative.
An object of the present disclosure is to provide a process for the preparation of linear alkylbenzenes from renewable sources.
Another object of the present disclosure is to provide a simple, economical and an environment friendly process for the preparation of linear alkylbenzenes.
Still another object of the present disclosure is to provide a process for the preparation of linear alkylbenzenes which is used in the preparation of biodegradable laundry cleaning compositions and detergents.
Yet another object of the present disclosure is to provide a process for the preparation of linear alkylbenzenes which reduces the fossil fuel carbon footprint.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
The present disclosure relates to a process for the preparation of linear alkylbenzene.
The process comprises the following steps:
(a) subjecting a renewable feedstock in a reactor to a controlled hydrodeoxygenation and a partial dehydration in the presence of a first catalyst system in a hydrogen rich environment at a first predetermined temperature, at a first predetermined pressure and at a first predetermined weight hourly space velocity (WHSV) to obtain a first mixture of paraffins and olefins;
(b) optionally, separately, hydrotreating a petroleum feedstock in the presence of a second catalyst system in a hydrogen rich environment at a second predetermined temperature, at a second predetermined pressure and at a second predetermined weight hourly space velocity (WHSV) followed by dehydrogenating in the presence of a third catalyst under hydrogen environment at a third predetermined temperature, at a third predetermined pressure and at a third predetermined weight hourly space velocity (WHSV) to obtain a second mixture of paraffins and olefins;
(c) optionally, mixing the first mixture and the second mixture to obtain a third mixture comprising paraffins and olefins;
(d) reacting the olefins selected from the first mixture and the third mixture with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined weight hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins; and
(e) separating the product mixture to obtain linear alkylbenzenes.
The renewable feedstock is at least one selected from the group consisting of crude coconut oil, palm kernel oil, and babassu oil.
The first catalyst system and the second catalyst system are independently selected from the group consisting of Ni-Mo supported highly porous ?-Al2O3 catalyst, and Co-Mo supported highly porous ?-Al2O3 catalyst.
The third catalyst system is selected from Pt/Al2O3 and Ni/Al2O3.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 275 °C to 325 °C.
In an embodiment of the present disclosure, the first predetermined pressure is in the range of 30 bar to 60 bar.
In an embodiment of the present disclosure, the first predetermined WHSV is in the range of 0.7 h-1 to 2 h-1.
In an embodiment of the present disclosure, the petroleum feedstock is kerosene.
In an embodiment of the present disclosure, petroleum feedstock is a pre-fractionated kerosene containing C10 to C13 hydrocarbons.
In an embodiment of the present disclosure, the second predetermined temperature is in the range of 275 °C to 325 °C.
In an embodiment of the present disclosure, the second predetermined pressure is in the range of 30 bar to 70 bar.
In an embodiment of the present disclosure, the second predetermined WHSV is in the range of 0.7 h-1 to 2 h-1.
In an embodiment of the present disclosure, the third predetermined temperature is in the range of 400 °C to 500 °C.
In an embodiment of the present disclosure, the third predetermined pressure is in the range of 1 bar to 5 bar.
In an embodiment of the present disclosure, the third predetermined WHSV is in the range of 1 h-1 to 2.5 h-1.
In an embodiment of the present disclosure, the fourth predetermined temperature is in the range of 100 °C to 150 °C.
In an embodiment of the present disclosure, the fourth predetermined pressure is in the range of 5 bar to 15 bar.
In an embodiment of the present disclosure, the fourth predetermined WHSV is in the range of 1 h-1 to 2 h-1.
In an embodiment of the present disclosure, a ratio of the renewable feedstock to the hydrogen is in the range of 1:800 Sm3/Nm3 to 1:2000 Sm3/Nm3
In an embodiment of the present disclosure, the first mixture is subjected to fractionation to obtain olefins having a carbon chain length of C10 to C13 hydrocarbons.
In an embodiment of the present disclosure, a predetermined amount of the first mixture is in the range of 5 wt% to 30 wt% with respect to the total amount of the third mixture.
In an embodiment of the present disclosure, the alkylation is carried out in the presence of an alkylation catalyst.
In an embodiment of the present disclosure, the process is a continuous process.
In an embodiment of the present disclosure, the paraffins from the product mixture are separated by fractionation and recycled back to a dehydrogenation reactor.
In an embodiment of the present disclosure, the linear alkyl benzene prepared by the process of the present disclosure is characterized by:
• average molecular weight in the range of 235 gm/mol to 244 gm/mol; and
• carbon distribution of C12 LAB with respect to total LAB in the range of 35 wt % to 85 wt%.
DETAILED DESCRIPTION
The present disclosure relates to detergents and surfactants. Particularly, the present disclosure relates to a process for the preparation of linear alkylbenzenes from renewable sources.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
The specifications of the cleaning composition include a mixture of even and odd numbered n-paraffins, where the even and odd numbered n-paraffins fall within desired concentration ranges. The existing processes for converting fatty acids and triglycerides in natural oils to n-paraffins (by hydrodeoxygenation, decarboxylation, or decarbonylation) tend to produce n-paraffins that do not have the desired concentration of n-paraffins both with an even number of carbon atoms and an odd number of carbon atoms to satisfy linear alkylbenzenes producers desired concentration ranges.
The present disclosure relates to detergents and surfactants. Particularly, the present disclosure relates to a process for the preparation of linear alkylbenzenes from renewable sources.
In accordance with the present disclosure, the process for the preparation of linear alkylbenzenes comprises the following steps:
(a) subjecting a renewable feedstock in a reactor to a controlled hydrodeoxygenation and a partial dehydration in the presence of a first catalyst system in a hydrogen rich environment at a first predetermined temperature, at a first predetermined pressure and at a first predetermined weight hourly space velocity (WHSV) to obtain a first mixture of paraffins and olefins;
(b) optionally, separately, hydrotreating a petroleum feedstock in the presence of a second catalyst system in a hydrogen rich environment at a second predetermined temperature, at a second predetermined pressure and at a second predetermined weight hourly space velocity (WHSV) followed by dehydrogenating in the presence of a third catalyst under hydrogen environment at a third predetermined temperature, at a third predetermined pressure and at a third predetermined weight hourly space velocity (WHSV) to obtain a second mixture of paraffins and olefins;
(c) optionally, mixing the first mixture and the second mixture to obtain a third mixture comprising paraffins and olefins;
(d) reacting the olefins selected from the first mixture and the third mixture with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined weight hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins; and
(e) separating the product mixture to obtain linear alkylbenzenes.
The process is described in detail.
A renewable feedstock is subjected to controlled hydrodeoxygenation followed by a partial dehydration in the presence of a first catalyst system in a hydrogen rich environment at a first predetermined temperature, at a first predetermined pressure and at a first predetermined weight hourly space velocity (WHSV) to obtain a first mixture of n-paraffins and linear alpha olefins.
In an embodiment of the present disclosure, the renewable feedstock is at least one selected from crude coconut oil, palm kernel oil, and babassu oil. In an exemplary embodiment of the present disclosure, the renewable feedstock is crude coconut oil. In another exemplary embodiment of the present disclosure, the renewable feedstock is palm kernel oil. The vegetable oils typically comprise triglycerides, free fatty acids, or a combination of triglycerides and free fatty acids.
In an embodiment of the present disclosure, vegetable oil feed is delivered to a deoxygenation unit which also receives a hydrogen feed. The triglycerides and fatty acids present in the vegetable oil feed undergo controlled hydrodeoxygenation and partial dehydration by using a catalyst system under hydrogen environment to obtain a first mixture of paraffins and olefins. Structurally, triglycerides are formed by three, typically different, fatty acid molecules that are bonded together with a glycerol bridge. The glycerol molecule includes three hydroxyl groups (HO-) and each fatty acid molecule has a carboxyl group (COOH). In triglycerides, the hydroxyl groups of the glycerol join the carboxyl groups of the fatty acids to form ester bonds. Therefore, during controlled hydrodeoxygenation and a partial dehydration, the fatty acids are freed from the triglyceride structure and are converted into normal paraffins and olefin mixture. The glycerol is converted into propane, and the oxygen in the hydroxyl and carboxyl groups is converted into water.
In an embodiment of the present disclosure, the ratio of the renewable feedstock to the hydrogen is in the range of 1:800 Sm3/Nm3 to 1:2000 Sm3/Nm3. In an exemplary embodiment of the present disclosure, the ratio of the renewable feedstock to the hydrogen is 1:1200 Sm3/Nm3.
In accordance with the present disclosure, the renewable feedstock is in a liquid form and the volume of the liquid can be measured in m3 i.e., Normal unit form i.e. Nm3. Further, the hydrogen is in a gaseous form and the volume of the gas can also be measured in m3 i.e. Standard unit form i.e. Sm3. Therefore, the unit of ratio of the renewable feedstock to the hydrogen is provided as Sm3/Nm3 (unit).
The hydrodeoxygenation process preserves the carbon atoms present in the fatty acid or triglyceride, while the three carbon atoms from the triglyceride backbone are removed. The process involves hydrogenation followed by dehydration reaction. These two reactions occur simultaneously in fixed bed reactor system over catalyst system to produce normal paraffin and olefin mixture. In an embodiment, the mixture of n-paraffin’s and olefins is subjected to fractionation to obtain olefins of C10-C13 having the desired chain length, these selected olefins are reacted with benzene which undergo alkylation reaction to produce green linear alkylbenzenes (LABs).
In an embodiment of the present disclosure, the first catalyst system is selected from the group consisting of Ni-Mo supported highly porous ?-Al2O3 catalyst, and Co–Mo supported highly porous ?-Al2O3 catalyst. In an exemplary embodiment of the present disclosure, the catalyst system is Co–Mo supported highly porous ?-Al2O3 catalyst.
In an embodiment of the present disclosure, the controlled hydrodeoxygenation of the renewable feedstock depends on the properties of the catalyst system and the operating conditions.
The preferred catalyst system used in this embodiment has dual active sites a) metallic sites and b) mild acidic sites. The metallic sites help in controlled hydrogenolysis, hydrogenation and deoxygenation steps whereas mild acidic site help in dehydration steps under hydrogen environment at preferred operating conditions.
The partial dehydration of the renewable feedstock depends on the temperature and pressure of the reaction system.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 275 °C to 325 °C. In an exemplary embodiment of the present disclosure, the first predetermined temperature is 300 °C.
In an embodiment of the present disclosure, the first predetermined pressure is in the range of 30 bar to 60 bar. In an exemplary embodiment of the present disclosure, the first predetermined pressure is 40 bar. In another exemplary embodiment of the present disclosure, the first predetermined pressure is 30 bar.
In an embodiment of the present disclosure, the first predetermined weight hourly space velocity/ liquid hourly space velocity (WHSV/LHSV) is in the range of 0.7 h-1 to 2 h-1. In an exemplary embodiment of the present disclosure, the first predetermined WHSV/LHSV is 1.25 h-1. In an exemplary embodiment of the present disclosure, the first predetermined WHSV/LHSV is 2 h-1.
Controlled hydrodeoxygenation majorly involve a) controlled hydrogenolysis, b) hydrogenation and c) deoxygenation steps. Vegetable oil undergoes controlled hydrodeoxygenation and partial dehydration reactions simultaneously under hydrogen environment at preferred operating conditions to produce mixture of linear alpha olefin, n-paraffin and water as major liquid product and propane as major gas product. Whereas uncontrolled hydrodeoxygenation involve complete hydrogenolysis, complete hydrogenation, complete dehydration, decarboxylation, decarbonylation reactions simultaneously under hydrogen environment at preferred operating conditions to produce only n-paraffin and water as major liquids product and propane, carbon dioxide, carbon monoxide, ethane as gas product.
Conventional process follows complete deoxygenation of vegetable oil to produce only n-paraffin hydrocarbon (C10 to C22) which undergoes fractionation unit to get C10 to C13 n-paraffin which subsequently enter dehydrogenation and mild hydrogenation unit to produce linear alpha olefin and n-paraffin mixture. The maximum conversion of n-paraffin into olefin for dehydrogenation and mild hydrogenation unit is 10 wt% to 13 wt%. The minimum olefin content in the mixture (olefin and n-paraffin) should be above 10 wt% to enter alkylation section where olefin reacts with benzene to produce green LAB.
Controlled deoxygenation and partial hydrogenation of crude coconut oil/palm kernel oil is carried out in first unit operation under hydrogen environment by using specific catalyst to produce linear alpha olefin and n-paraffin hydrocarbon mixture (C10 to C18). This mixture undergoes fractionation unit to get C10 to C13 linear alpha olefin and n-paraffin mixture. The linear alpha olefin content in the hydrocarbon mixture (olefin and n-paraffin) is achieved up to 36 wt% by the process of the present disclosure, which further undergoes alkylation section where olefin reacts with benzene to produce green LAB. Since only three-unit operations are required to produce green LAB from vegetable oil hence the process of the present disclosure has lower operating cost as compared to conventional process.
Further, optionally, separately, a petroleum feedstock is hydrotreated in the presence of a second catalyst system in a hydrogen rich environment at a second predetermined temperature, at a second predetermined pressure and at a second predetermined weight hourly space velocity (WHSV) followed by dehydrogenating in the presence of a third catalyst under hydrogen environment at a third predetermined temperature, at a third predetermined pressure and at a third predetermined weight hourly space velocity (WHSV) to obtain a second mixture of paraffins and olefins.
In an embodiment of the present disclosure, the petroleum feedstock is kerosene. In a preferred embodiment of the present disclosure, the feedstock i.e. kerosene is free of any sulfiding agent.
In an embodiment of the present disclosure, petroleum feedstock is a pre-fractionated kerosene containing C10 to C13 hydrocarbons.
In an embodiment of the present disclosure, the second catalyst system is selected from the group consisting of Ni-Mo supported highly porous ?-Al2O3 catalyst, and Co–Mo supported highly porous ?-Al2O3 catalyst. In an exemplary embodiment of the present disclosure, the catalyst system is Co–Mo supported highly porous ?-Al2O3 catalyst.
In an embodiment of the present disclosure, the third catalyst system is selected from Pt/Al2O3 and Ni/Al2O3. In an exemplary embodiment of the present disclosure, the third catalyst system is Pt/Al2O3.
In an embodiment of the present disclosure, the second predetermined temperature is in the range of 275 °C to 325 °C. In an exemplary embodiment of the present disclosure, the second predetermined temperature is 300 °C.
In an embodiment of the present disclosure, the second predetermined pressure is in the range of 30 bar to 70 bar. In an exemplary embodiment of the present disclosure, the second predetermined pressure is 60 bar.
In an embodiment of the present disclosure, the second predetermined WHSV is in the range of 0.7 h-1 to 2 h-1. In an exemplary embodiment of the present disclosure, the second predetermined WHSV is 1 h-1.
In an embodiment of the present disclosure, the third predetermined temperature is in the range of 400 °C to 500 °C. In an exemplary embodiment of the present disclosure, the third predetermined temperature is 450 °C.
In an embodiment of the present disclosure, the third predetermined pressure is in the range of 1 bar to 5 bar. In an exemplary embodiment of the present disclosure, the third predetermined pressure is 2 bar.
In an embodiment of the present disclosure, the third predetermined WHSV is in the range of 1 h-1 to 2.5 h-1. In an exemplary embodiment of the present disclosure, the third predetermined WHSV is 2.0 h-1.
Furthermore, optionally, the first mixture and the second mixture are mixed to obtain a third mixture comprising paraffins and olefins.
In one embodiment of the present disclosure, the linear alkylbenzenes are produced from 100% renewable feedstock (vegetable oil). In another embodiment of the present disclosure, the linear alkylbenzenes are prepared from a mixture of the renewable feedstock (vegetable oil) and petroleum feedstock.
In an embodiment of the present disclosure, the first mixture is subjected to fractionation to obtain olefins having a desired carbon chain length of C10 to C13 hydrocarbons.
In an embodiment of the present disclosure, the predetermined amount of the first mixture is in the range of 5 wt% to 30 wt% with respect to the total amount of the third mixture. This amount of first mixture gives the average molecular weight of green LAB between 235 gm/mol to 244 gm/mol and carbon distribution of C12 LAB in LAB between 35 wt % to 85 wt%.
In an exemplary embodiment, the predetermined mass percentage of the first mixture is 15 wt%.
Finally, the olefins are reacted with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined weight hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins.
In an embodiment of the present disclosure, the olefins of the first mixture are reacted with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined weight hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins.
In another embodiment of the present disclosure, the olefins of the third mixture are reacted with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined liquid hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins.
In an embodiment of the present disclosure, the alkylation is carried out in the presence of an alkylation catalyst.
In an embodiment of the present disclosure, the alkylation catalyst is selected from the group consisting of fluorinated silica-alumina, hydrogen fluoride, supported sulphated zirconia, fluorinated alumina, aluminium chloride, Ionic liquids and zeolitic catalysts.
In an embodiment, the homogeneous catalyst is an ionic liquid such as hydrofluoric acid.
In another embodiment the heterogeneous catalyst is selected from a supported sulphated zirconia, fluorinated silica-alumina and a fluorinated alumina catalyst.
In an embodiment of the present disclosure, the homogeneous catalyst is used during the liquid phase alkylation. In another embodiment of the present disclosure the heterogeneous catalyst is used during the vapor phase alkylation.
In an exemplary embodiment of the present disclosure the alkylation catalyst is hydrogen fluoride. In another exemplary embodiment of the present disclosure the alkylation catalyst is supported sulphated zirconia, fluorinated silica-alumina, and fluorinated alumina.
In an embodiment of the present disclosure, the fourth predetermined temperature is in the range of 100 °C to 150 °C. In an exemplary embodiment of the present disclosure, the fourth predetermined temperature is 130 °C.
In an embodiment of the present disclosure, the fourth predetermined pressure is in the range of 5 bar to 15 bar. In an exemplary embodiment of the present disclosure, the fourth predetermined pressure is 10 bar.
In an embodiment of the present disclosure, the fourth predetermined WHSV is in the range of 1 h-1 to 2 h-1. In an exemplary embodiment of the present disclosure, the third predetermined WHSV is 1.5 h-1.
In an embodiment of the present disclosure, the crude coconut oil/ crude palm kernel oil is subjected to a controlled hydrodeoxygenation and a partial dehydration reaction by using Co-Mo supported highly porous ?-Al2O3 catalyst system at a reaction temperature in the range of 275 °C to 325 °C, at a reaction pressure in the range of 30 bar to 60 bar and at a WHSV in the range of 0.8 h-1 to 1.5 h-1 and hydrocarbon feed to hydrogen ratio of 1:1200 Sm3/Nm3, to obtain a mixture of paraffins and olefins mixture. The n-paraffin and olefin mixture is subjected to fractionation to obtain olefins having the desired chain length of C10 to C13 which is reacted with benzene to obtain green linear alkylbenzenes (LABs).
In another embodiment of the present disclosure, the petroleum feedstock of present disclosure is pre-fractionated to obtain light kerosene (below C10 hydrocarbons), heavy kerosene (above C14 hydrocarbons) and medium kerosene (C10 to C13 hydrocarbons). The medium kerosene is routed in a hydrotreater to remove sulphur compounds followed by removing raffinate (such as isoparaffins, naphthenes and aromatics) to obtain n-paraffins. The n-paraffins are pre-fractionated to obtain light n-paraffins (below C10 hydrocarbons), heavy n-paraffins (above C14 hydrocarbons) and medium n-paraffins (C10 to C13 paraffins). The light n-paraffins and the heavy n-paraffin’s are removed and the medium n-paraffins undergo dehydrogenation reaction which produces a mixture of n-paraffins and olefins. The mixture of n-paraffins and olefins having the desired chain length of C10 to C13 obtained from the petroleum feedstock and the mixture of n-paraffin and olefin mixture having the desired chain length of C10 to C13 obtained from the renewable feedstock (vegetable oil) are mixed to obtain a third mixture. The olefins from the third mixture are reacted with benzene which undergo alkylation to obtain the green linear alkylbenzenes (LABs).
In an embodiment of the present disclosure, the process is a continuous process.
In an embodiment of the present disclosure the product mixture is separated to obtain linear alkylbenzenes.
In an embodiment of the present disclosure, the paraffins from product mixture are separated by fractionation and recycled back to undergo dehydrogenation.
In an embodiment of the present disclosure, the linear alkyl benzene prepared by the process of the present disclosure is characterized by:
• average molecular weight in the range of 235 gm/mol to 244 gm/mol; and
• carbon distribution of C12 LAB with respect to total LAB in the range of 35 wt % to 85 wt%.
In an exemplary embodiment of the present disclosure, the linear alkyl benzene prepared by the considering step (a) in the process of the present disclosure is characterized by:
• average molecular weight of 242 gm/mol; and
• carbon distribution of C12 LAB with respect to total LAB 81 wt%.
In an exemplary embodiment of the present disclosure, the linear alkyl benzene prepared by the considering step (c) in the process of the present disclosure is characterized by:
• average molecular weight of 241 gm/mol; and
• carbon distribution of C12 LAB with respect to total LAB 39 wt%.
The process of the present disclosure deals with partially substituting fossil fuel derived kerosene with renewable feedstocks such as crude coconut oil/palm kernel oil to produce a mixture of paraffins and olefins. The mixture of paraffins and olefins can be used for the preparation of linear alkylbenzenes (LABs) and subsequently into green cleaning composition. As the cleaning composition has a fraction derived from renewable feedstocks hence, considered as a green cleaning composition which is a premier product as it has higher C12 LAB content. The green cleaning composition has superior cleaning and stain removing properties and has higher cost realization in market when compared with fossil fuel derived cleaning composition.
In accordance with the present disclosure, the so obtained linear alkylbenzenes (LABs) is used to produce linear alkylbenzene sulfonate (LABS) which is the largest primary surfactant used in the home care industries to make biodegradable laundry cleaning composition.
In one embodiment, the process of the present disclosure partially substitutes the use of kerosene with the crude coconut oil/Palm kernel oil that can produce green linear alkylbenzenes (LABs) thereby reducing the fossil fuel carbon footprint and make it sustainable. The addition of 5 wt% to 30 wt% of crude coconut oil derived n-paraffins and olefins mixture into kerosene based mixture of n-paraffins and olefins produces partially green mixture of n-paraffins and olefins with increase in the C12 carbon content in the green mixture of n-paraffins and olefins which can be subsequently used for alkylation reaction with benzene to produce the green linear alkylbenzenes. The so obtained green LAB can come under ISCC (International Sustainability and Carbon Certification) scheme, which assure sustainability in manufacturing process as the origin of the raw materials is renewable. The process of the present disclosure is drop-in solution in the existing petroleum based LAB manufacturing division to produce green LAB. Further, the process of the present disclosure is economical and environment friendly.
The process of the present disclosure can use about 30 wt% of olefin content which makes the process cost- effective and subsequently increase the LAB production.
The conventional processes involve several unit operation/reaction steps such as 1) deoxygenation 2) separation 3) fractionation 4) dehydrogenation 5) alkylation, however the process of the present disclosure has the lesser unit operation steps to obtain the final product such as 1) deoxygenation 2) fractionation 3) alkylation. Also, the process of the present disclosure results in comparatively higher olefin content which makes the green LAB process cheaper as it reduces the step of dehydrogenation. About 30 wt% of olefin content in the mixture of n-paraffins and olefins is achieved by the process of the present disclosure, which subsequently increases the green LAB production. Also, in the present disclosure, the feedstock is free of any sulfiding agent.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following experiments which are set forth for illustration purposes only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.
EXPERIMENTAL DETAILS:
Experiment 1: A process for the preparation of linear alkylbenzene in accordance with the present disclosure
General process for the preparation of linear alkylbenzenes using renewable feedstock -vegetable oil (without using petroleum feedstock)
Controlled hydrodeoxygenation and partial dehydration of vegetable oil i.e. crude coconut oil was carried out in a continuous trickle bed reactor. The trickle bed reactor was used to produce linear alkylbenzene product from a vegetable oil as feed. The Crude coconut oil (feedstock) was free of any sulfiding agent.
Crude coconut oil was subjected to a controlled hydrodeoxygenation and a partial dehydration reaction by using Co-Mo supported highly porous ?-Al2O3 catalyst system at varying temperature, pressure and WHSV. Vegetable oil/H2 ratio was kept 1:1200 Sm3/Nm3 to obtain a first mixture of n-paraffins and olefins.
The first mixture (which was in the form of liquid) contains the mixture of only n-paraffins and a-olefins mixture as no aromatics and no iso-paraffins were observed (after GC analysis).
The first mixture was subjected to fractionation to obtain olefins having the desired carbon chain length of C10 to C13 which was then used in alkylation where benzene is alkylated to obtain green linear alkylbenzenes (LABs).
The alkylation of olefins was carried out by a liquid phase alkylation OR a vapor phase alkylation.
I. Alkylation method - Liquid phase alkylation
The mixture of paraffins and olefins was used for liquid phase alkylation wherein the reaction of olefin and benzene was carried out having benzene to olefin ratio of 6:1 at 45 °C, at an atmospheric pressure, for 45 min to obtain green linear alkylbenzenes (LABs). Hydrofluoric acid was used as a homogeneous catalyst (Ionic liquids) during the alkylation.
II. Alkylation method- Vapor phase alkylation
The mixture of paraffins and olefins was used for vapor phase alkylation wherein the reaction of olefin and benzene was carried out having benzene to olefin ratio of 6:1 at 130 oC, 10 bar of pressure, WHSV at 1.5 h-1 for 4 hours to produce green linear alkylbenzenes (LABs). Heterogeneous catalyst (supported sulphated zirconia, fluorinated silica-alumina, fluorinated alumina catalyst) was used for alkylation reaction.
Study of conversion percentage of the crude coconut oil into olefins.
The conversion percentage of the crude coconut oil into olefins (present in the mixture of paraffins and olefins) was studied and calculated based on HPLC analysis. Calibration curve was prepared by injecting standard coconut oil and area under the curve is used for conversion percentage curve which is used to calculate the conversion of coconut oil.
The first mixture comprising the paraffins and olefins was analysed by gas chromatography (GC) and two-dimensional gas chromatography (2D-GC). Further, the olefin quantification was performed by GC calibration curve method by injecting standard C8 to C18 paraffin and olefins and area under the curve was used to calculate percentage of olefin present in the samples. After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon layer was analyzed by using HPLC to find out conversion of coconut oil into the first mixture of olefins/paraffin and GC to find out n-paraffin, olefin, isoparaffin, aromatic content in the product (first mixture). The sample was injected into a gas chromatograph that was equipped with a fused silica capillary column, internally coated with DB-17* and with a flame ionization detector (FID). Gas sample collected after experiment was analyzed by RGA (refinery gas analyzer).
(*Agilent J&W DB-17 is a (50%-phenyl)-methylpolysiloxane column of mid polarity.)
Effect of process parameters on a conversion of the crude coconut oil to olefin (present in the first mixture containing olefins and paraffins).
The effect of temperature, H2 pressure, WHSV, H2 purity, coconut oil purity, concentration of coconut oil in n-paraffin on conversion of crude coconut oil to olefin were studied.
• Effect of temperature
Examples 1 to 5
Examples 1 to 5 were carried out by the general procedure of Experiment 1 in the trickle bed reactor with varying temperature from 250 °C (Example 1), 275 °C (Example 2), 300 °C (Example 3), 315 °C (Example 4) and 325 °C (Example 5) at 60 bar H2 pressure and 1.25 h-1 WHSV to study the conversion percentage of the crude coconut oil to the first mixture of olefins and paraffins (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from aqueous layer and the separated hydrocarbon product was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas, aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 1.
Table 1 illustrates the effect of the temperature on the conversion percentage of the crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 1: Effect of temperature
Example No. Temperature (°C) % Conversion Olefin (wt%) Paraffin (wt%)
1 250 73.2 20.1 79.9
2 275 87.4 18.5 81.5
3 300 100 0.9 99.1
4 315 100 0.7 99.3
5 325 100 0 100
From Table 1 it is observed that with increasing reaction temperature from 250 °C to 325 °C at 60 bar H2 pressure and 1.25 h-1 WHSV; olefin content in the first mixture was reduced.
The complete hydrodeoxygenation and complete dehydration reaction occurs at 325 °C leads to the formation of only n-paraffin as a product whereas, below 325 oC olefin was obtained as another product which is due to controlled hydrodeoxygenation and a partial dehydration reaction.
Though higher content of olefin % was observed at 250 oC and at 275 °C, conversion rate of the feedstock is less thereby producing tar and undesirable products during the process. Therefore, complete conversion is also important along with the formation of olefin content. From Table 1 it is observed that the temperature 300 oC is an optimum temperature to achieve the desired result. Hence, further experiments were performed at 300 °C to optimize the further reaction conditions.
• Effect of H2 pressure
Examples 6 to 10
Examples 6 to 10 were carried out by the general procedure of Experiment 1 in the trickle bed reactor with varying H2 pressure from 20 bar (Example 6), 30 bar (Example 7), 40 bar (Example 8), 50 bar (Example 9), and 60 bar (Example 10) at 300 oC and at WHSV 1.25 h-1 to study the conversion percentage of the crude coconut oil to the first mixture of olefins and paraffins (hydrocarbon layer)
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas, aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 2.
Table 2 illustrates effect of H2 pressure on conversion percentage of the crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 2: Effect of hydrogen pressure
Example No H2 Pressure
(bar) % Conversion Olefin (wt%) Paraffin (wt%)
6 20 75.2 18 82
7 30 98.36 36 64
8 40 99.97 28 72
9 50 99.99 12 88
10 60 100 0.4 99.6
From Table 2 it is observed that, with increasing H2 pressure from 20 bar to 60 bar at 300 oC and 1.25 h-1 WHSV; olefin content in mixture was reduced. Though the amount of olefin % is high at 30 bar pressure, less conversion of coconut oil was observed at 30 bar H2 pressure. Since, substantial amount of unconverted crude coconut oil can lead to tar formation in alkylation reaction the optimum pressure is considered as 40 bar.
Further, the complete hydrodeoxygenation and complete dehydration reaction occurs at 60 bar which leads to only paraffin as product whereas, below 50 bar H2 pressure, olefin was obtained as another product which is due to controlled hydrodeoxygenation and partial dehydration reaction.
Therefore, further experiments were performed at 40 bar H2 pressure to optimize the further reaction conditions.
• Effect of WHSV
Examples 11 to 15
Examples 11 to 15 were carried out by the general procedure of Experiment 1 in the trickle bed reactor with varying WHSV from 0.7 h-1 (Example 11), 1.0 h-1 (Example 12), 1.25 h -1 (Example 13), 2.0 h-1 (Example 14) and 2.5 h-1 (Example 15) at 300 °C and at 40 bar pressure, to study the conversion percentage of the crude coconut oil, to the first mixture of olefins and paraffins (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 3.
Table 3 illustrates effect of different WHSV on the conversion percentage of crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 3: Effect of WHSV
Example No. WHSV
(h-1) % Conversion Olefin (wt%) Paraffin (wt%)
11 0.7 h-1 100 8 92
12 1 h-1 99.97 16 84
13 1.25 h-1 100 27 73
14 2 h-1 97 36 64
15 2.5 h-1 83 21 79
From Table 3 it is observed that change in WHSV affect the crude coconut oil conversion drastically. Increasing the WHSV from 0.7 h-1 to 2 h-1, the amount of olefin content also increases, however the conversion of feedstock is less. Since the substantial amount of unconverted crude coconut oil can lead to tar formation in alkylation reaction, WHSV at 1.25 h-1 was considered as optimum based on olefin requirement in paraffin and olefin mixture.

• Effect of H2 purity
The conversion percentage of crude coconut oil was studied in respect of H2 purity (50%, 75%, 90% and 100%).
Examples 16 to 19
Examples 16 to 19 were carried out by the general procedure of Experiment 1 in the trickle bed reactor with varying H2 purity from 50 % (Example 16), 75 % (Example 17), 90 % (Example 18), and 100 % (Example 19) at 300 °C, 40 bar pressure and 1.25 h-1 WHSV to study the conversion percentage of the crude coconut oil to the first mixture of olefins and paraffins (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 4.
Table 4 illustrates effect of different H2 purity on the conversion percentage of crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 4 : Effect of H2 purity
Example No. H2 Purity (V%) % Conversion Olefin (wt%) Paraffin (wt%)
16 50 67 9 91
17 75 81 16 84
18 90 85 21 79
19 100 100 29 71
From Table 4 it is observed that decrease in H2 purity affect the conversion of the crude coconut oil conversion drastically. Olefin percentage (present in the mixture of paraffin and olefin) was reduced by reducing the H2 purity. Therefore, 100% pure H2 purity is desirable.
• Effect of coconut oil purity
The conversion percentage of the crude coconut oil was studied by using different concentrations of impurities in the crude coconut oil such as impurity of free fatty acid (FFA) with FFA 0.1 wt%, FFA 5 wt %, FFA 15 wt %, FFA 30 wt %.
Examples 20 to 23 were carried out by the general procedure of Experiment 1 in the trickle bed reactor with varying free fatty acid (FFA) with FFA 0.1 wt%, (Example 20), FFA 5 wt %, (Example 21), FFA 15 wt %, (Example 22), and FFA 30 wt %. (Example 23) at 300 °C, at 40 bar, 1.25 h-1 WHSV and 100% purity of H2 to study the conversion percentage of the crude coconut oil, to the first mixture of olefins and paraffins (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in the hydrocarbon mixture are tabulated below in Table 5.
Table 5 illustrates effect of the crude coconut oil having various concentration of impurity on the conversion percentage of the crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 5: Effect of the crude coconut oil purity

Example No. FFA content in coconut oil (wt%) % Conversion Olefin (wt%) Paraffin (wt%)
20 0.1 100 30 70
21 5 100 28 72
22 15 100 27 73
23 30 100 26 74
From Table 5 it is observed that purity of coconut oil having varying free fatty acid (FFA) content such 0.1 wt%, FFA 5 wt%, FFA 15 wt%, FFA 30 wt% has no effect on conversion percentage of crude coconut oil to olefin (present in the mixture of paraffin and olefin) i.e. leads to 100% conversion irrespective of varying free fatty acid (FFA) content. However, olefin content was marginally changed i.e., 26 wt%, 27 wt%, 28 wt%, 30 wt% for the crude coconut oil having FFA content 30 wt%, FFA 15 wt%, FFA 5 wt%, FFA 0.1 wt% respectively.
Experiment 2: Process for the preparation of linear alkylbenzenes using vegetable oil (renewable feedstock) and kerosene (petroleum feedstock).
Controlled hydrodeoxygenation and partial dehydration of vegetable oil was carried out in a continuous trickle bed reactor. The feedstock was free of any sulfiding agent. Crude coconut oil was subjected to controlled hydrodeoxygenation and partial dehydration reaction by using Co-Mo supported on highly porous ?-Al2O3 catalyst system at reaction temperature at 300°C and reaction pressure at 40 bar. Vegetable oil/H2 ratio 1:1200 Sm3/Nm3 and WHSV at 1.25 h-1 to obtain a first mixture of paraffins and alpha olefins. The liquid product contains only n-paraffins and a-olefins mixture whereas, no aromatics and no iso-paraffins were observed. The first mixture was subjected to fractionation to obtain olefins having the desired carbon chain length of C10-C13.
Further, separately a Pre-fractionated kerosene (C10 to C13 hydrocarbons) was hydrotreated at 300 °C, at 60 bar of hydrogen pressure, and at 1.0 h-1 (WHSV) by using Co-Mo supported on highly porous ?-Al2O3 catalyst to remove sulphur compounds followed by removing raffinate (such as isoparaffins, naphthenes and aromatics) to obtain n-paraffins which further undergo dehydrogenation at 450 0C, at 2 bar of hydrogen pressure, and at 2.0 h-1 (WHSV) by using Pt/Al2O3 catalyst to produce a second mixture of n-paraffins and olefins.
The second mixture obtained from the kerosene (petroleum feedstock) and the first mixture obtained from the crude coconut oil (renewable feedstock) was mixed to obtain a third mixture.
The Alkylation of olefins was carried out by liquid phase alkylation OR vapor phase alkylation.
I. Alkylation method - Liquid phase alkylation
The third mixture of paraffins and olefins was used for liquid phase alkylation wherein the reaction of olefin and benzene was carried out having a benzene to olefin ratio 6:1 at 45 °C, at atmospheric pressure, for 45 min to obtain green linear alkylbenzenes (LABs). Hydrofluoric acid was used as a homogeneous catalyst during the alkylation.
II. Alkylation method- Vapor phase alkylation
The third mixture of paraffins and olefins was also used for vapor phase alkylation wherein the reaction of olefin and benzene was carried out having benzene to olefin ratio of 6:1 at 130 0C, at 10 bar of pressure, WHSV at 1.5 h-1 to obtain green linear alkylbenzenes (LABs). Heterogeneous catalyst (supported sulphated zirconia/ fluorinated silica-alumina/fluorinated alumina) was used for alkylation reaction.
• Various concentration of coconut oil in n-paraffin
The conversion percentage of crude coconut oil was studied at different concentration of crude coconut oil in n-paraffin (5 wt%, 10 wt%, 15 wt%, 15 wt% and 100 wt%). Crude coconut oil in n-paraffin was subjected to controlled hydrodeoxygenation and partial dehydration reaction by using Co-Mo supported on highly porous ?-Al2O3 catalyst, reaction temperature at 300 ?C, reaction pressure at 40 bar, vegetable oil/H2 ratio 1:1200 Sm3/Nm3 and WHSV at 1.25 h-1 to obtain a first mixture of paraffins and olefins mixture (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas, aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 6.
Table 6 illustrates effect of different concentration of crude coconut oil in n-paraffin on the conversion percentage of crude coconut oil to olefin (present in the mixture of paraffin and olefin).
Table 6: Effect of coconut oil content in n-paraffin as feed
Sr. No. Coconut oil content in n-paraffin
(wt%) Coconut oil Conversion (%) Olefin (wt%) Paraffin (wt%)
1 5 100 2 98
2 10 100 3 97
3 15 100 5 95
4 40 100 14 86
5 100 100 30 70
From Table 6 it is observed that the concentration of crude coconut oil in the n-paraffin when increased from 5 wt%, 10 wt%, 15 wt%, 40 wt% and 100 wt% has no effect on conversion percentage of crude coconut oil to olefin. The olefin content represented in table shows increasing trend as coconut oil content is increased in n-paraffin content. The paraffin content mentioned in the table is combination of n-paraffin added along with feed and n-paraffin produce during reaction from the crude coconut oil. Hence, it can be blended with n-paraffin or kerosene for olefin preparation.

Experiment 3:
Carbon composition study between the crude coconut oil and the crude palm kernel oil
The carbon composition of the crude coconut oil and the crude palm kernel oil was carried out at 60 bar H2 pressure at 300 °C temperature and at 1.25 h-1 WHSV to obtain n-paraffin compositions. The complete hydrodeoxygenation and complete dehydration reaction occurs at 300 °C and 60 bar H2 pressure which leads to only formation of n-paraffin as product.
Table 7 illustrates the carbon composition of the crude coconut oil and the crude palm kernel oil.
Table 7: n-paraffin with different carbon composition produced from the crude coconut oil and the crude palm kernel oil

Sr. No. n-paraffin with Carbon number Crude coconut oil (wt%) Crude palm kernel oil (wt%)
1 C6 0.2 0
2 C8 5.9 0.3
3 C10 4.9 3.4
4 C11 1.5 2
5 C12 46.1 46.8
6 C13 1.3 1
7 C14 20.5 15.5
8 C15 0.2 0.6
9 C16 8.2 10.4
10 C18 11.1 0
11 C20 0.1 0
From Table 7 it is observed that the complete hydrodeoxygenation and complete dehydration reaction of the crude coconut oil and the crude palm kernel oil produced n-paraffin with similar carbon composition. Hence, the crude palm kernel oil can also be used as feedstock for producing desired olefins and further for producing desired linear alkylbenzenes.
• Conversion of the Crude palm kernel oil to olefin (present in the mixture of paraffin and olefin).
Crude palm kernel oil was subjected to controlled hydrodeoxygenation and partial dehydration reaction by using Co-Mo supported on highly porous ?-Al2O3 catalyst, reaction temperature at 300 ?C, various reaction pressure (20, 30, 40, 50 60 bar), vegetable oil/H2 ratio 1:1200 Sm3/Nm3 and WHSV at 1.25 h-1 to obtain a first mixture of paraffins and olefins (hydrocarbon layer).
After experiments, the hydrocarbon layer was separated from the aqueous layer and the separated hydrocarbon product layer was analyzed by using HPLC to calculate % conversion of feedstocks. GC was used to calculate percentage of n-paraffin, olefin, iso-paraffin, aromatic present in it.
Upon analysis, it is observed that the liquid hydrocarbon product contains only n-paraffins and a-olefins mixture whereas aromatics and iso-paraffins were below detection limit. Hence, only paraffin and olefin present in hydrocarbon mixture are tabulated below in Table 8.
Table 8 illustrates effect of H2 pressure on the conversion percentage of the crude palm kernel oil to olefin (present in the mixture of paraffin and olefin).
Table 8: Study of crude palm kernel oil to olefin
Sr. No. H2 Pressure (bar) % Conversion Olefin (wt%) Paraffin (wt%)
1 20 76 9 91
2 30 93 34 66
3 40 99.5 29 71
4 50 100 8 92
5 60 100 0 100
From Table 8 it is observed that with increasing H2 pressure from 20 to 60 bar at 300 oC and 1 h-1 WHSV; olefin content in the first mixture reduced. Less conversion of the crude palm kernel was observed at 30 bar H2 pressure whereas, 40 bar H2 pressure gives better conversion of the crude palm kernel oil to olefin (present in the mixture of paraffin and olefin). It is further observed that 60 bar of H2 pressure gives only n-paraffin and no olefin present in the mixture of paraffin and olefin. The complete hydrodeoxygenation and complete dehydration reaction occurs at 60 bar which leads to only n-paraffins as product whereas, below 50 bar olefin was obtained as another product which is due to a controlled hydrodeoxygenation and a partial dehydration reaction. As substantial amount of unconverted crude oil can lead to tar formation in alkylation section hence, 40 bar H2 pressure can be considered as optimal pressure during the preparation of olefins from the crude palm kernel oil feedstock.
Therefore, it is evident that the crude palm kernel oil and the crude coconut oil provides better amount of olefins by using controlled hydrodeoxygenation and a partial dehydration process of the present disclosure.
TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of a process for the preparation of linear alkylbenzenes (LABs) that;
• is simple, economic and an environment friendly;
• employs renewable feedstock;
• produces green LAB, which can be used in the preparation of biodegradable laundry cleaning compositions and detergents; and
• can reduce the fossil fuel carbon footprint.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The foregoing description of the specific embodiments so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired object or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the components and component parts of the preferred embodiments, it will be appreciated that many embodiments can be made and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other changes in the preferred embodiment as well as other embodiments of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation.

CLAIMS:WE CLAIM:

1. A process for the preparation of linear alkylbenzenes, said process comprising the following steps:
(a) subjecting a renewable feedstock in a reactor to a controlled hydrodeoxygenation and a partial dehydration in the presence of a first catalyst system in a hydrogen rich environment at a first predetermined temperature, at a first predetermined pressure and at a first predetermined weight hourly space velocity (WHSV) to obtain a first mixture of paraffins and olefins;
(b) optionally, separately, hydrotreating a petroleum feedstock in the presence of a second catalyst system in a hydrogen rich environment at a second predetermined temperature, at a second predetermined pressure and at a second predetermined weight hourly space velocity (WHSV) followed by dehydrogenating in the presence of a third catalyst under hydrogen environment at a third predetermined temperature, at a third predetermined pressure and at a third predetermined weight hourly space velocity (WHSV) to obtain a second mixture of paraffins and olefins;
(c) optionally, mixing said first mixture and said second mixture to obtain a third mixture comprising paraffins and olefins;
(d) reacting said olefins selected from said first mixture and said third mixture with benzene which undergo alkylation at a fourth predetermined temperature, at a fourth predetermined pressure and at a fourth predetermined weight hourly space velocity (WHSV) to obtain a product mixture comprising linear alkylbenzenes and paraffins; and
(e) separating said product mixture to obtain linear alkylbenzenes.
2. The process as claimed in claim 1, wherein said renewable feedstock is at least one selected from the group consisting of crude coconut oil, palm kernel oil, and babassu oil.
3. The process as claimed in claim 1, wherein said first catalyst system and said second catalyst system are independently selected from the group consisting of Ni-Mo supported highly porous ?-Al2O3 catalyst, and Co-Mo supported highly porous ?-Al2O3 catalyst.
4. The process as claimed in claim 1, wherein said third catalyst system is selected from Pt/Al2O3 and Ni/Al2O3.
5. The process as claimed in claim 1, wherein said first predetermined temperature is in the range of 275 °C to 325 °C.
6. The process as claimed in claim 1, wherein said first predetermined pressure is in the range of 30 bar to 60 bar.
7. The process as claimed in claim 1, wherein said first predetermined WHSV is in the range of 0.7 h-1 to 2 h-1.
8. The process as claimed in claim 1, wherein said petroleum feedstock is kerosene.
9. The process as claimed in claim 1, wherein said petroleum feedstock is a pre-fractionated kerosene containing C10 to C13 hydrocarbons.
10. The process as claimed in claim 1, wherein said second predetermined temperature is in the range of 275 °C to 325 °C.
11. The process as claimed in claim 1, wherein said second predetermined pressure is in the range of 30 bar to 70 bar.
12. The process as claimed in claim 1, wherein said second predetermined WHSV is in the range of 0.7 h-1 to 2 h-1.
13. The process as claimed in claim 1, wherein said third predetermined temperature is in the range of 400 °C to 500 °C.
14. The process as claimed in claim 1, wherein said third predetermined pressure is in the range of 1 bar to 5 bar.
15. The process as claimed in claim 1, wherein said third predetermined WHSV is in the range of 1 h-1 to 2.5 h-1.
16. The process as claimed in claim 1, wherein said fourth predetermined temperature is in the range of 100 °C to 150 °C.
17. The process as claimed in claim 1, wherein said fourth predetermined pressure is in the range of 5 bar to 15 bar.
18. The process as claimed in claim 1, wherein said fourth predetermined WHSV is in the range of 1 h-1 to 2 h-1.
19. The process as claimed in claim 1, wherein a ratio of said renewable feedstock to hydrogen is in the range of 1:800 Sm3/Nm3 to 1:2000 Sm3/Nm3.
20. The process as claimed in claim 1, wherein said first mixture is subjected to fractionation to obtain olefins having a carbon chain length of C10 to C13 hydrocarbons.
21. The process as claimed in claim 1, wherein a predetermined amount of said first mixture is in the range of 5 wt% to 30 wt% with respect to the total amount of the third mixture.
22. The process as claimed in claim 1, wherein said alkylation is carried out in the presence of an alkylation catalyst.
23. The process as claimed in claim 1 is a continuous process.
24. The process as claimed in claim 1, wherein said paraffins from said product mixture are separated by fractionation and recycled back to a dehydrogenation reactor.
25. Linear alkyl benzene prepared by the process as claimed in claim 1 is characterized by:
• average molecular weight in the range of 235 g/mol to 244 g/mol; and
• carbon distribution of C12 LAB with respect to total LAB in the range of 35 wt% to 85 wt%.

Dated this 28th day of August, 2024

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
OF R. K. DEWAN & CO.
AUTHORIZED AGENT OF APPLICANT

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, AT MUMBAI