Technical field
[0001]The present invention removes the hydrogen sulfide by the wet method from the hydrogen sulfide-containing gas, a hydrogen sulfide removal is recovered as a salt containing sulfur or sulfur with desulfurization catalyst, to a wet desulfurization process of hydrogen sulfide-containing gas.
BACKGROUND
[0002]The main method for removing hydrogen sulfide by the coke oven gas wet process from the beginning with hydrogen sulfide-containing gas, there is Takahakkusu method and Fumakkusu method. In either method, the equipment comprising an absorption tower 1 and the regenerator 2 as shown in FIG. 1 is often used. Absorption column 1 is provided with a hydrogen sulfide-containing gas 3, the desulfurization catalyst is brought into contact with a desulfurization catalyst solution 5 formed by dissolving in an alkaline solution. Regenerator 2 is contacted with an oxygen-containing gas 6 and the desulfurization catalyst solution 5.
[0003]
　In the absorption tower 1, by contacting the hydrogen sulfide-containing gas 3 and desulfurization catalyst solution 5, to dissolve hydrogen sulfide contained hydrogen sulfide-containing gas 3 to the desulfurization catalyst solution 5. Accordingly, the purified gas 4 by removing hydrogen sulfide from a hydrogen sulfide-containing gas 3. Hydrogen sulfide melted into the desulfurization catalyst solution 5 is oxidized by reacting with desulfurization catalyst dissolved in the desulfurization catalyst solution 5, the ion containing salt or sulfur containing solid sulfur or sulfur. In this case, desulfurization catalyst itself is reduced, changes to reduced form from oxidized form.
[0004]
　Further, in the regenerator 2, the oxygen-containing gas 6, by contacting the desulfurization catalyst solution 5 was dissolve hydrogen sulfide, to dissolve the oxygen contained in the oxygen-containing gas 6 in contact with the desulfurization catalyst solution 5 . Thus, oxygen melted into desulfurization catalyst solution 5 is contained in the desulfurization catalyst solution 5, it is reacted with desulfurization catalyst reductant after the reaction with hydrogen sulfide. As a result, it returns the desulfurization catalyst to oxidant, to reproduce a form that can again react with hydrogen sulfide dissolved in the desulfurization catalyst solution 5.
[0005]
　Desulfurization catalyst, by reacting the hydrogen sulfide or oxygen and alternating dissolved in the desulfurization catalyst solution 5, alternate between the reductant and the oxidant, is repeatedly used. Desulfurization catalyst solution 5 while circulated between the absorption tower 1 and the regenerator 2 is repeatedly used. Desulfurization catalyst solution 7 which ions dissolved including the generated sulfur or salt or sulfur containing sulfur is discharged out of the system.
[0006]
　In Takahakkusu method described in Patent Document 1 mainly naphthalene having two aromatic rings, quinones with anthracene or phenanthrene skeleton having three aromatic rings, with hydroquinones or their salts, the standard redox potential E 0 the substance exhibiting = 0.45 ~ 0.7 V is used as a desulfurization catalyst. At this time, since the solubility in water by an aromatic ring there are two or more in a molecule is reduced, materials having enhanced solubility in water by introducing an acidic group such as sulfonic acid and carboxylic acid and it is used as a desulfurization catalyst.
[0007]
　Conventionally, in the Takahakkusu method generally 1,4-naphthoquinone-2-sulphonate, or a reduced form it is used as a catalyst. Quinone group of the catalyst compound in the aqueous solution is repeatedly reducing and oxidizing, it alternates between the sodium 1,4-naphthoquinone-2-sulfonic acid and its reduced form, or 1,4-naphthoquinone-2-sulfonic by moving between the ammonium and its reduced form, and the hydrogen sulfide dissolved in the desulfurization catalyst solution was an aqueous solution containing salts or ions containing sulfur or sulfur solids.
[0008]
　At the time of the invention of Patent Document 1 is made primarily but the recovery by sulfur solids had been intended, it receives and fluctuations in the market value of the solid sulfur, more recently recovered as an aqueous solution containing a salt or ion containing sulfur the technology has been universal. In Non-Patent Document 1, the development of catalysts have been carried out in order to facilitate recovery from an aqueous solution, has only one aromatic ring or 1,2,4-trihydroxybenzene, consider the 4-methyl catechol It has been made. 1,2,4-trihydroxybenzene, while indicating good desulfurization activity in the steady state, the price is expensive, there is a practical problem. On the other hand, 4-methyl catechol, besides is expensive, since will decompose in air, stored under an inert gas atmosphere is required, cost of storage and transportation is increased.
[0009]
　Further, Fumakkusu method of Patent Document 2, an aromatic polynitro compounds or aromatic polyoxy compounds as a catalyst, a wet desulfurization process from hydrogen sulfide-containing gas, such as shown in FIG. 1, as its desulfurization catalyst, usually , it is using the picric acid. Recovery form of sulfur is not only sulfur solids is often recovered as an aqueous solution salts or ions are dissolved contains sulfur.
CITATION
Patent Document
[0010]
Patent Document 1: Japanese Patent Publication 39-001015 Patent Publication
Patent Document 2: Japanese Patent Publication 33-007084 discloses
Patent Document 3: Japanese Patent Laid-Open 8-059600 discloses
Patent Document 4: Japanese Patent 2012-25900 No.
Non-patent literature
[0011]
Non-Patent Document 1: Hiroshi Uchida, Tsuru defined communication, Tatsuya Kawada, Terasaki FutoshiJiro, Miyuki Kojima, KazuIchiro Izutsu al "2-nitroso-1-wet oxidation desulfurization method using naphthol-4-sulfonic acid" fuel societies, 60 winding, 1981, p. 58-64
Summary of the Invention
Problems that the Invention is to Solve
[0012]
　Takahakkusu method, Fumakkusu method are both due form when the form and transport during the storage of desulfurization catalyst is an aqueous solution, have boasts the problem of costly when and transport when stored in capacitance piling up It was. Therefore, rather than the desulfurization catalyst comprising an aqueous solution form when and transport during the storage, desulfurization catalyst comprising the solid has been desired.
[0013]
　However, since the picric acid which is a desulfurization catalyst Fumakkusu methods dried Explosive and solidifying, store large amounts of picric acid, in the case of transport, not handled only in aqueous solution for safety reasons.
[0014]
　On the other hand, the desulfurization catalyst Takahakkusu method, as described in Patent Document 3, there is a possibility of solidification, once, those prepared as an aqueous solution by salt precipitation required to be crystallized is present. Therefore, because the process to crystallize the desulfurization catalyst Takahakkusu methods have a complex and a cost problem, not used for the production at present, that is solidified is difficult to come by.
[0015]
　Further, 1,2,4-trihydroxybenzene, such as those discussed in Non-Patent Document 1 is expensive but are sold in solid form, there is a practical problem. Besides being expensive for the 4-methyl catechol, since will decompose in air, it must be stored under an inert gas atmosphere, cost of storage and transportation is increased.
[0016]
　In view of the above problems, the present invention can be handled in solid form, there is no safety problem, such as explosive, easy to come at a lower cost, desulfurization catalyst having a conventional desulfurization catalyst equivalent desulfurization performance It was used, and an object thereof is to provide a wet desulfurization method from hydrogen sulfide-containing gas.
Means for Solving the Problems
[0017]
　In view of the above problems, the catalyst of the present invention have studied intensively in a solid state with a small explosive. As a result, in the wet desulfurization method, it was found to be high either or using both the desulfurization ability of methylhydroquinone or toluquinone as desulfurization catalyst.
[0018]
　The present inventors in view of the cost of storage and transportation, it is possible to handle as a solid and studying with a small compound with an aromatic ring. In order to ensure Patent Document 1, water-soluble, it has been required to introduce an acidic group, if aromatic ring is only one of the compounds in the molecule, particular, the introduction of acidic groups without, it was found that it is possible to aqueous solutions of. Also, already 1,2,4-trihydroxybenzene which has been confirmed to be active in Non-Patent Document 1, it is difficult practical in terms of cost expensive. Therefore, was examined in the same have a substituent and only the position of the functional groups are different pyrogallol was found that a sufficient activity can not be obtained. Therefore, not only the kind of simple functional groups, it became clear that must also be discussed considering its positional relationship.
[0019]
　Compounds having a methyl group is one substituted hydroquinone or catechol, as well as the 1,2,4-trihydroxybenzene is capable of handling a solid and is excellent in terms of storage and transportation costs it can be said. In Non-Patent Document 1, 4-but considering the methyl catechol is being performed, 4-methyl catechol are anxious compounds, since will decompose in air, it must be stored under an inert gas atmosphere , cost of storage and transportation is increased.
[0020]
　Therefore, a methyl group was examined methylhydroquinone a compound which is one substituted with other hydroquinone or catechol. As a result, it was found that methyl hydroquinone has sufficient activity. As the reaction mechanism shown in FIG. 2, as in the conventional Takahakkusu catalyst, the portion of the quinone group, hydrogen sulfide (H dissolved 2 and reduction by S) 11, an oxygen (O 2 and oxidation)
[0021]
　Therefore, the reaction system, toluquinone, even by using only either one of methylhydroquinone, repeated that quinone groups of the catalyst is oxidized and reduced, will be back and forth between the oxidant and reductant , exist both in the reaction system, desulfurization was also found to proceed.
[0022]
　Further, methylhydroquinone are generally commercially available as a solid powder, availability is extremely easy. The conventional applications, the polymer of the raw material and a polymerization inhibitor, a polymerization inhibitor, because of like stabilizers, market value is secured, relatively stable supply can be expected. Mass production has also been, 1,2,4-trihydroxybenzene-tenth of 1 or less, in about one price quarter of the 4-methyl catechol, can be inexpensively get. Moreover, since the circulation generally find use as well a polymerization inhibitor or oxidation agents toluquinone is oxidation of methyl hydroquinone, it is also possible to obtain a desulfurization catalyst as an oxidant, easier to obtain desulfurization catalyst I have to.
[0023]
　Thus, in the wet desulfurization process, by using one or both of methylhydroquinone or toluquinone as desulfurization catalyst, can solve the problem of the present invention, the present invention has been accomplished.
[0024]
(1) according to one embodiment of the present invention, the wet desulfurization method from hydrogen sulfide-containing gas, a desulfurization catalyst solution desulfurization catalyst is dissolved in an alkaline solution, by contacting the hydrogen sulfide-containing gas, wherein the hydrogen sulfide a wet desulfurization process of performing desulfurization containing gas, as the desulfurization catalyst, using at least one of methyl hydroquinone and toluquinone.
(2) according to the above (1), the wet desulfurization method from hydrogen sulfide-containing gas, ammonia may be used as the alkali source in the alkaline solution.
(3) In the above (1) or (2) a wet desulfurization method from hydrogen sulfide-containing gas according to the desulfurization catalyst solution, at least one of the methyl hydroquinone and the toluquinone, in the solid state, the alkaline solution may be prepared by dissolving was poured into.
(4) above (1) to according to any one of (3), the wet desulfurization method from hydrogen sulfide-containing gas, at least one of the methyl hydroquinone and the toluquinone, the desulfurization catalyst solution in the solid state was charged into, it may be supplemented with the desulfurization catalyst.
(5) above (1) to according to any one of (4), the wet desulfurization method from hydrogen sulfide-containing gas, may be employed the following: using the absorption tower and the regeneration tower, the absorbing perform desulfurization while circulating the desulfurization catalyst solution between the tower and the regeneration tower, in the absorption tower, by contacting the hydrogen sulfide-containing gas into the desulfurization catalyst solution, sulfide of the hydrogen sulfide-containing gas by dissolving hydrogen in the desulfurization catalyst solution, said removing the hydrogen sulfide from the hydrogen sulfide-containing gas as a purified gas, the regenerator from the absorption tower, the desulfurization catalyst solution prepared by dissolving the hydrogen sulfide is circulated in the regenerator, said desulfurization catalyst solution is contacted with an oxygen-containing gas, sulfur, salts containing sulfur or to generate ions containing sulfur, the sulfur, salts containing the sulfur or the sulfur include ON collected, then circulating the desulfurization catalyst solution to the absorption tower.
(6) In the wet desulfurization method from hydrogen sulfide-containing gas described in (5), in the regeneration tower, at least one of the methyl hydroquinone and the toluquinone, was put into the desulfurization catalyst solution in solid form, wherein the desulfurization catalyst may be replenished.
The invention's effect
[0025]
　According to the above aspect of the present invention, by using one or both of methylhydroquinone or toluquinone as desulfurization catalyst, can be handled in solid form, there is no safety issues such as explosive, to come at a low cost easy, using the desulfurization catalyst having a conventional desulfurization catalyst equivalent desulfurization performance, it is possible to provide a wet desulfurization method of the hydrogen sulfide-containing gas.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026]
FIG. 1 is a schematic configuration diagram of a wet desulfurization method from hydrogen sulfide-containing gas using a general desulfurization catalyst.
[Figure 2] and methyl hydroquinone and toluquinone, hydrogen sulfide (H 2 S) and oxygen (O 2 is an estimated reaction equation between).
3 is a schematic diagram of a desulfurization with regenerator inlet of the solid desulfurization catalyst is provided.
Is a schematic diagram of FIG. 4 absorption tower desulfurization equipment that combines the function of the regenerator.
[5] used in Comparative Examples 1-7 and Examples 1 and 2, a schematic diagram of a desulfurization catalytic activity evaluation test apparatus.
[6] used in Comparative Examples 8 and 9 and Examples 3-5 is a schematic diagram of a desulfurization test device.
DESCRIPTION OF THE INVENTION
[0027]
　The following describes an embodiment of the present invention. As shown in FIG. 1, a wet desulfurization method of the present embodiment, as in the conventional wet desulfurization method, and a large two steps of the absorption step and the regeneration step.
[0028]
　The first absorption step, the hydrogen sulfide contained in a hydrogen sulfide-containing gas 3 is brought into contact with the desulfurizing catalyst solution 5 alkaline, a step of dissolve hydrogen sulfide to the desulfurization catalyst solution 5, run in the absorption tower 1 It is.
[0029]
　Hydrogen sulfide-containing gas 3, mainly various dry distillation furnace, a heating furnace, a flue gas discharged from the power plant or the like, a gas containing hydrogen sulphide of about 10000ppm from 10 ppm. Further, the hydrogen sulfide-containing gas 3 from the problem of the dissolution equilibrium of hydrogen sulfide in alkaline solution, to some extent, since the direction of gas containing a high concentration of hydrogen sulphide can be achieved with high hydrogen sulfide removal ratio, 1000 ppm or more 10000ppm or less and more preferably gas containing hydrogen sulfide. Hydrogen sulfide-containing gas 3 is, in addition to hydrogen sulfide, hydrogen, methane, One carbide carbon, Two carbide carbon, nitrogen, may include ammonia, hydrogen cyanide and the like. Coke oven gas discharged from the coke oven generally includes a hydrogen sulphide of about above, it is a good example of the hydrogen sulfide-containing gas 3 to apply the present embodiment.
[0030]
　By contacting the hydrogen sulfide-containing gas 3 and desulfurization catalyst solution 5, but is dissolved hydrogen sulfide contained in the hydrogen sulfide-containing gas 3 into the desulfurization catalyst solution 5, this time, is included in the hydrogen sulfide-containing gas 3 other acidic gases such as hydrogen cyanide, not may be dissolved into the desulfurization catalyst solution 5, no problem for the purpose of removing particular hydrogen cyanide at the same time.
[0031]
　Desulfurization catalyst solution 5 which dissolve hydrogen sulfide by contacting the hydrogen sulfide-containing gas 3 is obtained by dissolving in an alkaline solution of one or both of methylhydroquinone or toluquinone as desulfurization catalyst. At this time, the concentration of the desulfurization catalyst or 0.01 mmol / L is preferred in order to obtain a sufficient activity. Moreover, since solubility in water of toluquinone is not large, the upper limit is preferably not more than 100 mmol / L.
[0032]
　Furthermore, in order to absorb the hydrogen sulfide from the hydrogen sulfide-containing gas 3, it is necessary to maintain the pH value of the desulfurization catalyst solution 5 alkaline, leading to reduced activity of becomes too the desulfurization catalyst to highly alkaline. Therefore, pH value of the desulfurization catalyst solution 5 is preferably maintained in the range from 7.5 to 11.0.
[0033]
　By using one or both of methylhydroquinone or toluquinone as desulfurization catalyst, for example, when compared with the case of using 1,4-naphthoquinone-2-sodium sulfonate is a desulfurization catalyst Takahakkusu method, 1,4-naphthoquinone - in 2-sulfonic acid existing sales form of sodium (1mol / L aqueous sodium salt solution), while including 1,4-naphthoquinone-2-sodium sulfonate of about 1mol per 1kg, the 8mol per 1kg in methylhydroquinone powder including methyl hydroquinone. Also in molecule of any of the desulfurization catalyst, for having one active site for one molecule, the active sites per unit weight is better methyl hydroquinone powder, generally available 1,4-naphthoquinone-2-sulfonic is 8 times the aqueous solution of sodium can be reduced cost of storage and transportation. Considering from this point of view, fewer rings, those less substituted group. One or both of methyl hydroquinone and toluquinone used in the present invention is one in the number of aromatic rings, substituent is only one methyl group, is effective in reducing storage and transport costs.
[0034]
　As the alkali source of the alkaline solution constituting the desulfurization catalyst solution 5, sodium hydroxide, sodium carbonate, such as ammonia is used. In this embodiment, one or both of methyl hydroquinone or toluquinone does not contain the alkali metal is desulfurization catalyst. Therefore, by using the particular ammonia as the alkali source it can be effective to desulfurize the desulfurization catalyst solution without alkali metal. This, after the process in the step of processing the steps or desulfurization catalyst solution 5 to recover the sulfuric acid ion or a salt thereof from the desulfurization catalyst solution 5 as waste, it is not necessary to consider the Guaranteed damage by alkali metals. Therefore, since it is advantageous will be to relax the restrictions on the equipment and operation, it is preferable to use ammonia alkali source.
[0035]
　The method of contacting the desulfurization catalyst solution 5 with hydrogen sulfide-containing gas 3, by introducing hydrogen sulfide-containing gas 3 from the lower portion of the absorption tower 1, and sprayed desulfurization catalyst solution 5 from the upper part of absorption tower 1, the desulfurization catalyst solution 5 or a method of absorbing hydrogen sulphide. Or, pooled desulfurization catalyst solution 5 to the absorption tower 1, the hydrogen sulfide-containing gas 3 to the desulfurization catalyst solution 5 pooled may be blown method. Furthermore, it may be contacted by a method other than these methods. From the bottom of the absorption tower 1 by introducing hydrogen sulfide-containing gas 3, when in the form of spraying desulfurization catalyst solution 5 from the top of the absorption tower 1, more contact area between the hydrogen sulfide-containing gas 3 and desulfurization catalyst solution 5 in order to increase, it may be utilized, such as fillers.
[0036]
　The regeneration step will be described mainly with reference to FIG. 3, in order to clearly show correspondence between FIG. 1, reference numeral in Figure 1 there are cases indicated by parenthesis in the following description. Incidentally, FIG. 3 is a schematic diagram of a desulfurization with regenerator inlet of the solid desulfurization catalyst is provided.
　Regeneration step, salt in the desulfurization catalyst solution 5 was absorbed hydrogen sulfide, including with regenerating the desulfurization catalyst by blowing an oxygen-containing gas 20 (6), the hydrogen sulfide dissolved in the desulfurization catalyst solution 5 sulfur or sulfur or a process of the ions containing sulfur. Regeneration step is carried out in the regenerator 19 (2). Oxygen-containing gas 20 is necessary in order to oxidize the methyl hydroquinone toluquinone, it can be used air, oxygen, or the like oxygen-enriched air.
[0037]
　And toluquinone is oxidized product of desulfurization catalyst desulfurization catalyst solution 5, it referred the role of methyl hydroquinone as a reducing material. In the absorption tower 16 (1), when dissolved hydrogen sulfide in an alkaline solution containing a desulfurization catalyst, toluquinone desulfurization catalyst solution 5 is reacted with hydrogen sulfide, the methyl hydroquinone. The amount of hydrogen sulfide dissolved in the alkaline solution in the absorption tower 16, to become higher than the concentration of the desulfurization catalyst, most of the desulfurization catalyst is a methyl hydroquinone in the desulfurization catalyst solution 5 withdrawn from the absorption tower 16, sulfur of the total amount while the processing of the hydrogen is not completed, it is fed to the regenerator 19. In the regenerator 19, as described above, by blowing an oxygen-containing gas 20, for methyl hydroquinone is toluquinone react with oxygen in the oxygen-containing gas, it is possible to react again hydrogen sulfide.
[0038]
　Desulfurization catalyst desulfurization catalyst solution 5 is introduced into the regenerator 19 is fed from the absorption tower 16, as described above, but mostly a methyl hydroquinone, and reacted with hydrogen sulfide and oxygen in the regeneration tower 19 repeating the reaction, the amount of hydrogen sulfide desulfurization catalyst solution 5 decreases, toluquinone can not be reacted with hydrogen sulfide. On the other hand, oxygen since only reaction methylhydroquinone supplied from time to time is toluquinone progresses, the proportion of toluquinone rises in desulfurization catalyst desulfurization catalyst solution 5. Desulfurization catalyst solution 5 ratio of toluquinone rises is fed from the regeneration tower 19 to the absorption tower 16, is reused. Thus, the hydrogen sulfide in the desulfurization catalyst solution 5, the a part is oxidized in the absorption tower 16, the majority is oxidized in the regeneration tower 19, the ions containing salts or sulfur containing sulfur or sulfur.
[0039]
　Further, since the mechanism as described above, as the desulfurization catalyst to be dissolved in the desulfurization catalyst solution 5, even either the methyl hydroquinone or toluquinone, or it may be a both. The reaction, the absorption tower 16, in each of the regenerator 19, in order to settle the present embodiment as described above.
[0040]
　Method of contacting desulfurization catalyst solution 5 and the oxygen-containing gas 20, reservoir desulfurization catalyst solution 5 to the regenerator 19, the oxygen-containing gas 20 may be blown method for desulfurization catalyst solution 5 pooled. Or take in oxygen-containing gas 20 from the lower portion of the regenerator 19, and sprayed desulfurization catalyst solution 5 from the top of the regenerator 19, a method of absorbing the hydrogen sulfide in the desulfurization catalyst solution 5, further may be in any other way Absent.
[0041]
　The equipment for performing the absorption step and the regeneration step, as described above, do not matter absorber 16 (1) and the regeneration tower 19 and (2) as a separate structure, as shown in FIG. 4, blown sulfide if it is considered not to mix the hydrogen-containing gas 24 and oxygen-containing gas 30, may be implemented in one facility that combines the functions of the absorption tower and the regeneration tower (e.g., Patent Document 4 and the like, see ).
[0042]
　In Figure 4, upper than partition 27 installed in the tower functions as an absorption column, the absorption step is carried out at the top. The lower functions as regenerator than the partition wall 27, the reproduction process is performed.
　The upper than partition 27, a hydrogen sulfide-containing gas 24 is blown from a position close to the partition wall 27. Then, a desulfurization catalyst solution 28, 31 which was dissolved desulfurization catalyst that is recycled by spraying from the top of the tower, is contacted with a hydrogen sulfide-containing gas 24. As a result, hydrogen sulfide in hydrogen sulfide-containing gas 24 is absorbed in the desulfurization catalyst solution 28 and 31, the hydrogen sulfide-containing gas 24 which hydrogen sulphide has been removed is recovered from the vicinity overhead as the purified gas 25. At this time, between the contact area to increase, deriving portion of the introduction portion and the purified gas 25 hydrogen sulfide-containing gas 24 of the tower top between the hydrogen sulfide-containing gas 24 desulfurized catalyst solution 28, 31, a filler layer 26 may be provided. Desulfurization catalyst solution 28, 31 which has absorbed hydrogen sulfide down along the septum 27, through the seal pot 29, are stored in the lower portion of the column. Oxygen-containing gas 30 to the desulfurization catalyst solution 28 stored in the bottom of the tower blowing rare, regeneration of the desulfurization catalyst is performed. Oxygen-containing gas 30 is passed through the desulfurization catalyst solution 28, and is discharged as an exhaust gas 33. Desulfurization catalyst solution 28, 31 stored in the bottom of the column, by being introduced from the top of the column by the liquid feed pump 32 is withdrawn from a lower portion of the column, is recycled. The partition wall 27 and the seal pot 29, are not mixed with blown hydrogen sulfide-containing gas 24 and oxygen-containing gas 30.
[0043]
　When turning on the solid desulfurization catalyst of this embodiment in the desulfurization catalyst solution 5,28,31 in equipment, advance desulfurization catalyst solution dissolved in water or an alkaline solution facility after an aqueous solution form 5 , it may be charged to 28 and 31. Or, a solid desulfurization catalyst may be directly charged to the desulfurization catalyst solution 5,28,31 in facilities. When you put the solid desulfurization catalyst directly to the desulfurization catalyst solution 5,28,31 in equipment, it eliminates the need for a solid desulfurization catalyst to the aqueous solution form, preferably for prevent the complication of the process.
[0044]
　Desulfurization catalyst, the deterioration, or from being lost gradually in the step of collecting the ions containing salts or sulfur containing sulfur or sulfur by partial discharge of the desulfurization catalyst solution, during the equipment operation, continuously or intermittently it is preferred to replenish the. Replenishment In considers emissions desulfurization catalyst solution 5,28,31 which is circulated, the components of the discharged solution, and oxidation-reduction potential of the desulfurization catalyst solution 5,28,31 circulating, the desulfurization catalyst added amount, and the timing may be suitably determined.
[0045]
　In addition, when introducing it in a solid state of the desulfurization catalyst, it is necessary to provide the inlet for introducing into the equipment. For example, Figure 3 in which the regenerator 19 and absorber 16 is made as a separate equipment, reservoir desulfurization catalyst solution 5 in the regeneration tower 19, to implement the blown method an oxygen-containing gas 20 to the desulfurization catalyst solution 5 pooled If you like, directly on top of the regenerator 19, it is preferable to provide the inlet 21 to inject solids desulfurization catalyst. Desulfurization catalyst solution 5 pooled in the regenerator 19 is the majority of the desulfurization catalyst solution 5 in circulation equipment, also by the oxygen-containing gas 20 is blown in a state where agitation is promoted for efficiently dissolving the desulfurization catalyst to the desulfurization catalyst solution 5 can be diffused.
[0046]
　Further, the solid desulfurization catalyst of this embodiment, when put into the desulfurization catalyst solution 5 in facilities, the desulfurization catalyst solution 5, may also include other catalysts. For example, using the existing wet desulfurization apparatus, when carrying out the method of the present embodiment, the already desulfurization catalyst solution 5 is used in the conventional Takahakkusu method is hydrodesulfurization catalyst are 1,4-naphthoquinone -2 - Although sulfonate and its reduced form is included, to the solution, so we continue to add solid desulfurization catalyst according to the present embodiment may be implemented.
Example
[0047]
Comparative Example 1
　As shown in FIG. 5, put the simulated reaction liquid 35 of 400mL to 500mL beaker 34, while stirring the simulated reaction 35 with a magnetic stirrer 36, the air through a cylindrical gas injection pipe 37 0 I saw the reaction by blowing in .3L / min. Simulating the composition of the reaction solution 35, the NaSH as an alternative of the dissolved hydrogen sulfide to a concentration of 10 mmol / L, the concentration of 1,4-naphthoquinone-2-sodium sulfonate is hydrodesulfurization catalyst 0.2 mmol / L of Takahakkusu method and the. Hydrogen sulfide is, when dissolved in an alkaline solution, to become the hydrogen sulfide ion, with NaSH to ionizing sodium ion and hydrogen sulfide ions upon aqueous solution as an alternative to hydrogen sulfide. The alkaline NaSH, to become a simulated reaction liquid 35 within the Adjustment pH value from 7.5 to 11.0, the pH value adjustment by alkali source was not carried out. To evaluate the activity by desulfurization catalyst is constant, the temperature of the reaction solution was kept constant for 30 ° C. using a hot water bath 40. The present study is a batch test, hydrogen sulfide ion concentration in the simulated reaction mixture 35 was performed under the conditions continue to decline.
[0048]
　It performed a plurality of times sampling of the simulated reaction liquid 35 during a reaction time of 1 hour 30 minutes, to measure the hydrogen ion concentration sulfide by capillary electrophoresis apparatus. The reduction rate 1.50 mmol · L hydrogen sulfide ions from aging of the hydrogen sulfide ion concentration -1 · hr -1 was obtained. Incidentally, when the negative by linear approximation of the gradient search of magnitude, resulting the same experiment from magnitude without a catalyst slope was performed by the least squares method the relationship for the reaction time of the hydrogen sulfide ion concentration the value obtained by subtracting the amount of inclination to be obtained and the decrease rate of the hydrogen sulfide ion.
[0049]
Example 1
　The same experiment as in Comparative Example 1, in place of sodium 1,4-naphthoquinone-2-sulfonic acid, put a solid methylhydroquinone was performed by dissolving in simulated reaction solution 35. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At this time, 1.81 mmol · L as the reduction rate of the hydrogen sulfide ion -1 · hr -1 was obtained. This indicates that methyl hydroquinone may have certain 1,4-naphthoquinone-2-sulfonic acid sodium least equivalent hydrogen sulphide ions capacity in conventional Takahakkusu catalyst.
[0050]
Example 2
　The same experiment as in Comparative Example 1 was carried put toluquinone in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At this time, 1.63 mmol · L as the reduction rate of the hydrogen sulfide ion -1 · hr -1 was obtained. This shows that that can have toluquinone 1,4-naphthoquinone-2-sulfonic acid sodium least equivalent hydrogen sulphide ion capacity is in the conventional Takahakkusu catalyst is the oxidation of methyl hydroquinone, in reduced form there methylhydroquinone, be charged to the system in any form of toluquinone is oxidant, indicating that can be used as a desulfurization catalyst.
[0051]
Comparative Example 2
　The same experiment as in Comparative Example 1 was carried put hydroquinone in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At that time, the reduction rate of hydrogen sulphide ions, 1.02 mmol · L -1 · hr -1 became. This is because is one hydroquinone simplest compound having a quinone group, shows that not get certain 1,4-naphthoquinone-2-sulfonic acid sodium equivalent performance with conventional Takahakkusu catalyst.
[0052]
Comparative Example 3
　The same experiment as in Comparative Example 1 was carried put catechol instead of sodium 1,4-naphthoquinone-2-sulfonic acid. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At that time, the reduction rate of hydrogen sulphide ions, 0.87 mmol · L -1 · hr -1 became. This is because is one catechol of the simplest compounds having a quinone group, shows that not get certain 1,4-naphthoquinone-2-sulfonic acid sodium equivalent performance with conventional Takahakkusu catalyst.
[0053]
Comparative Example 4
　The same experiment as in Comparative Example 1 was carried out 1,4-naphthoquinone-2-sulfonic instead of sodium 1,2-naphthoquinone-4-sulfonic acid sodium put. Concentration, alkalinity sources, the reaction temperature are all the same manner as in Comparative Example 1. At that time, the reduction rate of hydrogen sulphide ions, 1.46 mmol · L -1 · hr -1 became. This 1,2-naphthoquinone-4-sodium sulfonate have shown that may have a certain 1,4-naphthoquinone-2-sulfonic acid sodium equivalent hydrogen sulphide ions capacity in conventional Takahakkusu catalyst. However, the amount of active sites per unit weight for a 0.477 fold methylhydroquinone, it is possible towards methylhydroquinone used in the present invention achieve the same activity as the conventional at a lower weight.
[0054]
Comparative Example 5
　The same experiment as in Comparative Example 1 was carried put 1,4-naphthoquinone-2-sulfonic 1,2,4-trihydroxybenzene instead of sodium. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At that time, the reduction rate of hydrogen sulphide ions · L 1.53 mmol -1 · hr -1 became. This, 1,2,4-trihydroxybenzene is shown that may have a 1,4-naphthoquinone-2-sulfonic acid sodium equivalent hydrogen sulphide ion capacity is in the conventional Takahakkusu catalyst. However, since it is expensive when compared to methyl hydroquinone, can be towards methylhydroquinone used in the present invention is obtained more cheaply conventional similar activity.
[0055]
Comparative Example 6
　The same experiment as in Comparative Example 1 was carried put 4-methyl catechol in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At that time, the reduction rate of hydrogen sulphide ions · L 1.72 mmol -1 · hr -1 became. This 4-methyl catechol indicates that may have a certain 1,4-naphthoquinone-2-sulfonic acid sodium equivalent hydrogen sulphide ions capacity in conventional Takahakkusu catalyst. However, since it is expensive when compared to methyl hydroquinone, can be towards methylhydroquinone used in the present invention is obtained more cheaply conventional similar activity. Further, 4-methyl catechol, must be stored under an inert gas atmosphere by stability problems, storage cost is increased.
[0056]
Comparative Example 7
　The same experiment as in Comparative Example 1 was carried put pyrogallol in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Concentration, alkalinity sources, the reaction temperature is the same as Comparative Example 1 none. At that time, the reduction rate of hydrogen sulphide ions · L 0.03 mmol -1 · hr -1 became. This pyrogallol indicates that no hydrogen sulfide ion capacity, 1,2,4 Compared with the results of trihydroxybenzene, also have the same functional groups, hydrogen sulfide ion by its position It indicates that there is a difference in processing capability.
[0057]
Comparative Example 8
　shown in FIG. 6 an experimental apparatus. Absorption tower 42, column diameter 60mm, has a packed column that takes up to a height of 750mm the Rahishiringu of height 900mm 10mmφ in a glass tower. Regenerator 48 a column diameter 80 mm, glass bubble column height 1300 mm, the gas blowing inlet using a cylindrical gas injection pipe, the effective solution height was 1000 mm. Also, it was used glass bottles 10L as the circulating liquid tank 45 for experiments.
[0058]
　The composition of the simulation gas 41, ammonia 10000 ppm, prepared nitrogen gas containing hydrogen sulfide 5000 ppm, 0.8 Nm from the lower portion of the absorption tower 42 3 was blown in / hr. The flow rate of the blown air 49 from the bottom of the regenerator 48 was 50 NL / hr. Simulated reaction 46, it was circulated in the system by the liquid feed pump 47 at a flow rate of 45L / hr. Simulated reaction 46 sodium 1,4-naphthoquinone-2-sulfonic acid concentration is desulfurization catalyst Takahakkusu Method and 2 mmol / L, it was with aqueous ammonia to adjust the initial pH value to 9.0 as alkali source . Alkali source after start of the test was only ammonia contained in the simulated gas 41, adjustment of the other pH values was not carried out.
[0059]
　The hydrogen sulfide concentration in the purified gas 43 after treatment comes out from the top of the absorption column 42 was measured every predetermined time, a flame photometric detector with a gas chromatograph 44, the removed hydrogen sulfide concentration in the introduced hydrogen sulfide was determined hydrogen sulfide removal ratio is a ratio of. As a result, 100.0% hydrogen sulfide removal rate at 5 hours after start of the test, was the 99.2% hydrogen sulfide removal rate after 15 hours.
[0060]
Example 3
　The same experiment as in Comparative Example 8 were carried put methylhydroquinone in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Laboratory equipment, concentration, alkalinity sources, the reaction temperature is the same as in Comparative Example 8 none. At that time, to obtain a respectively 99.8% rate hydrogen sulfide removal 99.4% in the 5 hours after the 15 hours after the start of the test. This is the methyl hydroquinone shows that there is a conventional is Takahakkusu catalyst 1,4-naphthoquinone-2-sulfonic acid sodium equivalent hydrogen sulphide ion capacity.
[0061]
Comparative Example 9
　was carried put hydroquinone The same experiment as in Comparative Example 8 in place of sodium 1,4-naphthoquinone-2-sulfonic acid. Laboratory equipment, concentration, alkalinity sources, the reaction temperature is the same as in Comparative Example 8 none. At that time, to give a 62.8% hydrogen sulfide removal ratio 87.3%, respectively, in 5 hours and after 15 hours after the start of the test. This is because hydroquinone has shown that not obtained 1,4-naphthoquinone-2-sulfonic acid sodium equivalent performance are conventional Takahakkusu catalyst. Hydrogen sulfide dissolved in the alkaline solution is a simulated reaction solution is not sufficiently treated by the catalyst, the results had accumulated in the alkaline solution, presumably because it is no longer able to fully absorb the hydrogen sulphide.
[0062]
Example 4
　The composition of the model gas in the same experiment as in Example 3, ammonia 12000 ppm, hydrogen sulfide 4000 ppm, hydrogen cyanide 1000 ppm, carbon dioxide, 25000 ppm, when a nitrogen gas containing methane 3000 ppm, hydrogen sulfide after 5 hours removal rate was 99.2%. This is another hydrogen cyanide and carbon dioxide is an acidic gas contained like coke oven gas, or methane hydrocarbon gas contained in the coke oven gas or the like shows that do not affect the desulfurization performance.
[0063]
Example 5
　In a similar experiment as in Example 3, once 5 hours after start of the test, the circulation of the circulation and fluid model gas, stopping the blowing of air, the simulated reaction extracted 2L from the circulating liquid tank, pH value was fed ammonia water 2L was diluted to 9.0. Further, while more solid desulfurization catalyst inlet 50 of the regeneration tower top methylhydroquinone 497mg solid powder was charged to the solution stored in the regenerator. Then, again, the circulation of the circulation and fluid simulation gas starts blowing of air, hydrogen sulfide removal rate 2 hours after resumption became 99.5%. This be charged in a solid state powder shows that do not affect the desulfurization performance.
Industrial Applicability
[0064]
　According to the present invention, it can be handled in solid form, there is no safety issues such as explosive, easy to come at a low cost, using a conventional desulfurization catalyst and desulfurization catalyst with equivalent desulfurization performance, sulfide possible to provide a wet desulfurization method of the hydrogen-containing gas.
DESCRIPTION OF SYMBOLS
[0065]
　1,16,42: absorption column
　2,19,48: regeneration tower
　3,15,24: hydrogen sulfide-containing gas
　4,17,25,43 Purification Gas
　5,28,31: desulfurization catalyst solution
　6,20,30 : oxygen-containing gas
　7, 23: sulfur or desulfurization catalyst solution containing ions salts or sulfur containing sulfur is dissolved
　8,22,33,51: exhaust gas
　9: toluquinone
　(oxidant) 10: methyl hydroquinone (reductant)
　11 : hydrogen sulfide
　12: sulfur
　13: oxygen
　14: water
　18,32,47: liquid feed pump
　21,50: solid desulfurization catalyst inlet
　26: filler
　27: partition wall
　29: seal pot
　34: 500 mL beaker
　35 and 46 : simulated reaction
　36: magnetic stirrer
　37: a cylindrical gas injection pipe
　38: pH / ORP meter
　39: dissolved oxygen meter
　40: water bath
　41: a hydrogen-containing gas (model
　gas) sulfide 44: Flame Photometric Detector with a gas chromatograph
　45: circulating liquid tank
　49: Air

The scope of the claims

[Requested item 1]The desulfurization catalyst solution desulfurization catalyst is dissolved in an alkaline solution, by contacting the hydrogen sulfide-containing gas, a wet desulfurization method of performing desulphurization of the hydrogen sulfide-containing gas,
　as the desulfurization catalyst, methyl hydroquinone and toluquinone wet flue gas desulfurization process of the hydrogen sulfide-containing gas, which comprises using at least one of.
[Requested item 2]
　Wet flue gas desulfurization process of the hydrogen sulfide-containing gas according to claim 1, characterized in that ammonia is used as the alkali source in the alkaline solution.
[Requested item 3]
　The desulfurization catalyst solution, sulfide according to at least one of the methyl hydroquinone and the toluquinone, in the solid state, to claim 1 or claim 2, characterized in that prepared by dissolving was charged into the alkali solution wet flue gas desulfurization process of the hydrogen-containing gas.
[Requested item 4]
　At least one of the methyl hydroquinone and the toluquinone, was put into the desulfurization catalyst solution in the solid state, the hydrogen sulfide according to any one of claims 1 to 3, wherein the replenishing said desulfurization catalyst wet flue gas desulfurization method from containing gas.
[Requested item 5]
　Using an absorption tower and the regeneration tower,
　performing desulfurization while circulating the desulfurization catalyst solution between the absorption tower and the regeneration tower, according to any one of claims 1 to 4, a hydrogen-containing gas sulfide a wet desulfurization process from,
　in the absorption tower, wherein by contacting the hydrogen sulfide-containing gas into the desulfurization catalyst solution and the hydrogen sulfide of the hydrogen sulfide-containing gas is dissolved in the desulfurization catalyst solution, the hydrogen sulfide-containing gas to remove the hydrogen sulfide as a purified gas,
　the regenerator from the absorption tower to circulate the desulfurization catalyst solution prepared by dissolving the hydrogen sulfide in the regeneration tower, the desulfurization catalyst solution by contacting an oxygen-containing gas, sulfur, salts containing sulfur or to generate ions containing sulfur, the sulfur, salts containing the sulfur or recovered ions containing the sulfur, then the removal Circulating the catalyst solution to the absorption tower,
the wet desulfurization method of the hydrogen sulfide-containing gas, characterized in that.
[Requested item 6]
　The regeneration tower, at least one of the methyl hydroquinone and the toluquinone, a solid and charged into the desulfurization catalyst solution, hydrogen sulfide-containing gas according to claim 5, characterized in that replenishing the desulfurization catalyst wet desulfurization method of.