WO2018173150A1 - Procédé de désulfuration par voie humide de gaz contenant du sulfure d'hydrogène - Google Patents

Procédé de désulfuration par voie humide de gaz contenant du sulfure d'hydrogène Download PDF

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WO2018173150A1
WO2018173150A1 PCT/JP2017/011444 JP2017011444W WO2018173150A1 WO 2018173150 A1 WO2018173150 A1 WO 2018173150A1 JP 2017011444 W JP2017011444 W JP 2017011444W WO 2018173150 A1 WO2018173150 A1 WO 2018173150A1
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hydrogen sulfide
desulfurization catalyst
desulfurization
containing gas
solution
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PCT/JP2017/011444
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English (en)
Japanese (ja)
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望都 樽見
憲治 中尾
鈴木　公仁
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新日鐵住金株式会社
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Priority to PCT/JP2017/011444 priority Critical patent/WO2018173150A1/fr
Priority to CN201780088427.3A priority patent/CN110446542A/zh
Priority to KR1020197028845A priority patent/KR20190120808A/ko
Publication of WO2018173150A1 publication Critical patent/WO2018173150A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/70—Non-metallic catalysts, additives or dopants

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  • the present invention relates to a wet desulfurization method from a hydrogen sulfide-containing gas, in which hydrogen sulfide is removed from the hydrogen sulfide-containing gas by a wet method, and the removed hydrogen sulfide is recovered as sulfur or a salt containing sulfur using a desulfurization catalyst.
  • the Takahax method and the Fumax method are the main methods for removing hydrogen sulfide from a hydrogen sulfide-containing gas such as coke oven gas by a wet method.
  • equipment including an absorption tower 1 and a regeneration tower 2 as shown in FIG. 1 is often used.
  • the absorption tower 1 brings the hydrogen sulfide-containing gas 3 into contact with a desulfurization catalyst solution 5 in which the desulfurization catalyst is dissolved in an alkaline solution.
  • the regeneration tower 2 brings the oxygen-containing gas 6 and the desulfurization catalyst solution 5 into contact with each other.
  • hydrogen sulfide contained in the hydrogen sulfide-containing gas 3 is dissolved in the desulfurization catalyst solution 5 by bringing the hydrogen sulfide-containing gas 3 into contact with the desulfurization catalyst solution 5. Thereby, hydrogen sulfide is removed from the hydrogen sulfide-containing gas 3 to obtain a purified gas 4.
  • the hydrogen sulfide dissolved in the desulfurization catalyst solution 5 is oxidized by reacting with the desulfurization catalyst dissolved in the desulfurization catalyst solution 5, and becomes solid sulfur or a salt containing sulfur or an ion containing sulfur. At this time, the desulfurization catalyst itself is reduced and changes from an oxidant to a reductant.
  • the oxygen-containing gas 6 and the desulfurization catalyst solution 5 in which hydrogen sulfide is dissolved are brought into contact with each other, so that oxygen contained in the contacted oxygen-containing gas 6 is dissolved in the desulfurization catalyst solution 5. .
  • the oxygen dissolved in the desulfurization catalyst solution 5 reacts with the desulfurization catalyst of the reductant after reacting with hydrogen sulfide contained in the desulfurization catalyst solution 5.
  • the desulfurization catalyst is returned to an oxidant and regenerated into a form capable of reacting again with hydrogen sulfide dissolved in the desulfurization catalyst solution 5.
  • the desulfurization catalyst is used repeatedly by going back and forth between the reductant and the oxidant by reacting alternately with hydrogen sulfide or oxygen dissolved in the desulfurization catalyst solution 5.
  • the desulfurization catalyst solution 5 is repeatedly used while circulating between the absorption tower 1 and the regeneration tower 2.
  • the generated sulfur or sulfur-containing salt or sulfur-containing ion-dissolved catalyst solution 7 is discharged out of the system.
  • 1,4-naphthoquinone-2-sulfonate or a reduced form thereof is generally used as a catalyst.
  • the quinone group of the catalyst compound in the aqueous solution repeats oxidation and reduction, and moves back and forth between sodium 1,4-naphthoquinone-2-sulfonate and its reduced form, or 1,4-naphthoquinone-2-sulfone
  • hydrogen sulfide dissolved in the desulfurization catalyst solution is made into an aqueous solution containing solid sulfur or a salt or ion containing sulfur.
  • Patent Document 1 At the time when the invention of Patent Document 1 was made, it was mainly intended for recovery by solid sulfur, but recently, it was recovered as an aqueous solution containing salts or ions containing sulfur due to changes in the market value of solid sulfur. Technology to do so is becoming universal.
  • Non-Patent Document 1 a catalyst for facilitating recovery as an aqueous solution has been developed, and studies on 1,2,4-trihydroxybenzene having only one aromatic ring and 4-methylcatechol have been made. Has been done. 1,2,4-Trihydroxybenzene exhibits good desulfurization activity in the steady state, but is expensive and has practical problems.
  • 4-methylcatechol is not only expensive but also decomposes in the air, so that it needs to be stored in an inert gas atmosphere, which increases costs for storage and transportation.
  • the Fumax method of Patent Document 2 is a wet desulfurization method from a hydrogen sulfide-containing gas as shown in FIG. 1 using an aromatic polynitro compound or an aromatic polyoxy compound as a catalyst. Uses picric acid.
  • the sulfur recovery form is often recovered as an aqueous solution in which not only solid sulfur but also a salt or ion containing sulfur is dissolved.
  • picric acid which is a desulfurization catalyst for the Fmax method
  • Fmax method is explosive when dried and solidified, when storing and transporting a large amount of picric acid, it can be handled only in an aqueous solution for safety reasons.
  • the Takahax method desulfurization catalyst may be solidified, but once manufactured as an aqueous solution, it is necessary to cause salt precipitation to crystallize. Therefore, the process for crystallizing the desulfurization catalyst of the Takahax method is complicated and has a problem in terms of cost. Therefore, it is not currently used for production, and it is difficult to obtain a solidified product.
  • Non-Patent Document 1 1,2,4-trihydroxybenzene as discussed in Non-Patent Document 1 is sold in a solid state, but is expensive and has a practical problem. 4-Methylcatechol is also expensive and decomposes in the air, so that it needs to be stored in an inert gas atmosphere, which increases costs for storage and transportation.
  • the present invention is a desulfurization catalyst that can be handled in a solid state, has no safety problems such as explosive properties, is easily available at low cost, and has a desulfurization performance equivalent to a conventional desulfurization catalyst.
  • An object of the present invention is to provide a wet desulfurization method using hydrogen sulfide from a gas containing hydrogen sulfide.
  • the present inventors diligently studied a catalyst that is less explosive and solid. As a result, in the wet desulfurization method, it has been found that when one or both of methylhydroquinone and tolquinone are used as a desulfurization catalyst, the desulfurization ability is high.
  • Patent Document 1 it is essential to introduce an acidic group in order to ensure water solubility. However, if the compound has only one aromatic ring in the molecule, an acidic group must be introduced. It was found that it was possible to make it into an aqueous solution without. Further, 1,2,4-trihydroxybenzene, which has already been confirmed to be active in Non-Patent Document 1, etc., is expensive and difficult to put into practical use from the viewpoint of cost. Therefore, when examination was conducted with pyrogallol having the same substituent and different only in the position of the functional group, it was found that sufficient activity could not be obtained. Therefore, it was clarified that not only simple functional groups but also their positional relationships should be considered.
  • a compound in which one methyl group is substituted for hydroquinone or catechol can be handled in a solid state, like 1,2,4-trihydroxybenzene, and is excellent in terms of storage and transportation costs. I can say that.
  • 4-methylcatechol is studied, but 4-methylcatechol is an anxious compound and decomposes in the air, so it must be stored in an inert gas atmosphere. , Storage and transportation costs will increase.
  • methylhydroquinone which is a compound in which one methyl group is substituted for other hydroquinone or catechol.
  • the reaction mechanism is similar to that of the conventional Takahax catalyst.
  • H 2 S dissolved hydrogen sulfide
  • O 2 oxygen
  • methylhydroquinone is generally marketed as a solid powder and is very easy to obtain.
  • Conventional applications include polymer raw materials, polymerization inhibitors, polymerization inhibitors, stabilizers, etc., so that market value is ensured and a relatively stable supply can be expected. It is also mass-produced and can be obtained at a low price at a price that is less than 1/10 of 1,2,4-trihydroxybenzene and about 1/4 of 4-methylcatechol.
  • toluquinone which is an oxidized form of methylhydroquinone
  • a polymerization inhibitor and an oxidizing agent can be used as a polymerization inhibitor and an oxidizing agent and is generally available, so it is also possible to obtain a desulfurization catalyst as an oxidant, making it easier to obtain a desulfurization catalyst. I have to.
  • the hydrogen sulfide-containing gas is brought into contact with a desulfurization catalyst solution in which the desulfurization catalyst is dissolved in an alkaline solution.
  • ammonia may be used as an alkali source of the alkali solution.
  • the desulfurization catalyst solution contains at least one of the methylhydroquinone and the toluquinone in the solid state, and the alkaline solution It is also possible to manufacture by dissolving it in the solution.
  • the desulfurization catalyst may be replenished by charging the catalyst.
  • Hydrogen is dissolved in the desulfurization catalyst solution to remove the hydrogen sulfide from the hydrogen sulfide-containing gas to obtain a purified gas, and the desulfurization catalyst solution in which the hydrogen sulfide is dissolved from the absorption tower to the regeneration tower.
  • an oxygen-containing gas is brought into contact with the desulfurization catalyst solution to produce sulfur, a salt containing sulfur, or an ion containing sulfur, and the sulfur, the salt containing sulfur, or the sulfur. Include ON collected, then circulating the desulfurization catalyst solution to the absorption tower.
  • each aspect of the present invention by using one or both of methylhydroquinone and toluquinone as a desulfurization catalyst, it can be handled in a solid state, has no safety problems such as explosive properties, and can be obtained at low cost. It is easy to provide a wet desulfurization method from a hydrogen sulfide-containing gas using a desulfurization catalyst having desulfurization performance equivalent to that of a conventional desulfurization catalyst.
  • FIG. 1 is a schematic diagram of a desulfurization catalyst activity evaluation test apparatus used in Examples 1 and 2 and Comparative Examples 1 to 7.
  • FIG. FIG. 3 is a schematic view of a desulfurization test apparatus used in Examples 3 to 5 and Comparative Examples 8 and 9.
  • the wet desulfurization method of this embodiment is composed of two main steps, an absorption step and a regeneration step, as in the conventional wet desulfurization method.
  • the first absorption step is a step in which hydrogen sulfide contained in the hydrogen sulfide-containing gas 3 is brought into contact with the alkaline desulfurization catalyst solution 5 and hydrogen sulfide is dissolved in the desulfurization catalyst solution 5. Is done.
  • the hydrogen sulfide-containing gas 3 is an exhaust gas mainly discharged from various types of dry distillation furnaces, heating furnaces, power plants, etc., and is a gas containing about 10 ppm to 10,000 ppm of hydrogen sulfide.
  • the hydrogen sulfide-containing gas 3 can achieve a higher hydrogen sulfide removal rate in a gas containing a high concentration of hydrogen sulfide to some extent due to the problem of dissolution equilibrium of hydrogen sulfide in an alkaline solution. More preferred is a gas containing hydrogen sulfide.
  • the hydrogen sulfide-containing gas 3 may include hydrogen, methane, carbon monoxide, carbon dicarbon, nitrogen, ammonia, hydrogen cyanide, and the like in addition to hydrogen sulfide.
  • the coke oven gas discharged from the coke oven generally contains hydrogen sulfide of the above degree, and is a good example of the hydrogen sulfide-containing gas 3 to which this embodiment is applied.
  • the hydrogen sulfide contained in the hydrogen sulfide-containing gas 3 is dissolved into the desulfurization catalyst solution 5.
  • the hydrogen sulfide-containing gas 3 is included.
  • Other acidic gases such as hydrogen cyanide may be dissolved in the desulfurization catalyst solution 5, and there is no problem particularly for the purpose of simultaneously removing hydrogen cyanide.
  • the desulfurization catalyst solution 5 in which hydrogen sulfide is dissolved by contacting with the hydrogen sulfide-containing gas 3 is obtained by dissolving one or both of methylhydroquinone and tolquinone in an alkaline solution as a desulfurization catalyst.
  • the concentration of the desulfurization catalyst is preferably 0.01 mmol / L or more in order to obtain sufficient activity.
  • the upper limit is preferably 100 mmol / L or less.
  • the pH value of the desulfurization catalyst solution 5 is preferably maintained in the range of 7.5 to 11.0.
  • methylhydroquinone and tolquinone as a desulfurization catalyst, for example, 1,4-naphthoquinone-, compared with the case of using sodium 1,4-naphthoquinone-2-sulfonate, which is a desulfurization catalyst of Takahax method, is used.
  • the existing sales form of sodium 2-sulfonate (1 mol / L sodium salt aqueous solution) contains approximately 1 mol of sodium 1,4-naphthoquinone-2-sulfonate per kg, whereas methylhydroquinone powder contains 8 mol of 1 mol / kg sodium salt. Contains methylhydroquinone.
  • 1,4-naphthoquinone-2-sulfone which is generally available for methylhydroquinone powder, is the active site per unit weight.
  • the cost is 8 times that of an aqueous sodium acid solution, and storage and transportation costs can be reduced. From this viewpoint, those having a small number of rings and few substituents are preferable.
  • One or both of methylhydroquinone and tolquinone used in the present invention have one aromatic ring and only one methyl group, and are effective in reducing storage and transportation costs.
  • Sodium hydroxide, sodium carbonate, ammonia, etc. are used as the alkali source of the alkaline solution constituting the desulfurization catalyst solution 5.
  • one or both of methylhydroquinone and tolquinone which are desulfurization catalysts do not contain an alkali metal. Therefore, the effect of desulfurization with a desulfurization catalyst solution not containing an alkali metal can be exhibited by using ammonia as an alkali source.
  • ammonia as an alkali source because it is advantageous in that restrictions on facilities and operations are eased.
  • the hydrogen sulfide-containing gas 3 is introduced from the lower part of the absorption tower 1, and the desulfurization catalyst solution 5 is sprayed from the upper part of the absorption tower 1, thereby desulfurization catalyst solution.
  • 5 may absorb hydrogen sulfide.
  • the desulfurization catalyst solution 5 may be stored in the absorption tower 1 and the hydrogen sulfide-containing gas 3 may be blown into the stored desulfurization catalyst solution 5. Furthermore, you may make it contact by methods other than these.
  • the contact area between the hydrogen sulfide-containing gas 3 and the desulfurization catalyst solution 5 is further increased.
  • a filler or the like may be used.
  • FIG. 3 is a schematic diagram of a desulfurization facility having a regeneration tower provided with an inlet for a solid desulfurization catalyst.
  • the regeneration step regenerates the desulfurization catalyst by blowing the oxygen-containing gas 20 (6) into the desulfurization catalyst solution 5 that has absorbed hydrogen sulfide, and converts the hydrogen sulfide dissolved in the desulfurization catalyst solution 5 into sulfur or a salt containing sulfur. Or it is the process of making it ion containing sulfur.
  • the regeneration step is performed in the regeneration tower 19 (2).
  • the oxygen-containing gas 20 is necessary for oxidizing methylhydroquinone to tolquinone, and air, oxygen, oxygen-enriched air, or the like can be used.
  • toluquinone which is an oxidant of the desulfurization catalyst
  • methylhydroquinone which is a reductant
  • the amount of hydrogen sulfide dissolved in the alkaline solution in the absorption tower 16 is higher than the concentration of the desulfurization catalyst, most of the desulfurization catalyst in the desulfurization catalyst solution 5 taken out from the absorption tower 16 is methylhydroquinone, and the entire amount of sulfidation.
  • the liquid is sent to the regeneration tower 19 without finishing the hydrogen treatment.
  • methylhydroquinone reacts with oxygen in the oxygen-containing gas to become tolquinone, so that it can react with hydrogen sulfide again.
  • the desulfurization catalyst solution 5 in which the proportion of tolquinone is increased is sent from the regeneration tower 19 to the absorption tower 16 and reused. Therefore, a part of the hydrogen sulfide in the desulfurization catalyst solution 5 is oxidized in the absorption tower 16, but most of it is oxidized in the regeneration tower 19 and becomes sulfur or a salt containing sulfur or an ion containing sulfur.
  • the desulfurization catalyst dissolved in the desulfurization catalyst solution 5 may be either methylhydroquinone or tolquinone, or both. This is because, due to the reaction, each of the absorption tower 16 and the regeneration tower 19 settles into the existence form as described above.
  • the contact method between the desulfurization catalyst solution 5 and the oxygen-containing gas 20 may be a method of storing the desulfurization catalyst solution 5 in the regeneration tower 19 and blowing the oxygen-containing gas 20 into the stored desulfurization catalyst solution 5.
  • the oxygen-containing gas 20 is taken in from the lower part of the regeneration tower 19, the desulfurization catalyst solution 5 is sprayed from the upper part of the regeneration tower 19, and hydrogen sulfide is absorbed by the desulfurization catalyst solution 5. Absent.
  • the absorption tower 16 (1) and the regeneration tower 19 (2) may be configured separately, and as shown in FIG. As long as it is considered that the hydrogen-containing gas 24 and the oxygen-containing gas 30 are not mixed, the hydrogen-containing gas 24 and the oxygen-containing gas 30 may be implemented with one facility having both functions of a regeneration tower and an absorption tower (see, for example, Patent Document 4). ).
  • the upper part of the partition wall 27 installed in the tower functions as an absorption tower, and the absorption process is carried out in this upper part.
  • the lower part than the partition 27 functions as a regeneration tower, and a regeneration process is implemented.
  • the hydrogen sulfide-containing gas 24 is blown from a position close to the partition wall 27. Then, the desulfurization catalyst solutions 28 and 31 in which the desulfurization catalyst used in circulation is dissolved are sprayed from the upper part in the tower, thereby contacting the hydrogen sulfide-containing gas 24.
  • a filler layer 26 may be provided.
  • the desulfurization catalyst solutions 28 and 31 that have absorbed hydrogen sulfide pass through the partition wall 27 and are stored in the lower part of the tower via the seal pot 29.
  • the oxygen-containing gas 30 is blown into the desulfurization catalyst solution 28 stored in the lower part of the tower, and the desulfurization catalyst is regenerated.
  • the oxygen-containing gas 30 passes through the desulfurization catalyst solution 28 and is then discharged as exhaust gas 33.
  • the desulfurization catalyst solutions 28 and 31 stored in the lower part of the tower are extracted from the lower part of the tower and introduced from the upper part of the tower by the liquid feed pump 32, thereby being recycled.
  • the partition wall 27 and the seal pot 29 prevent the hydrogen sulfide-containing gas 24 and the oxygen-containing gas 30 from being mixed.
  • the desulfurization catalyst solution 5 in the equipment is dissolved in water or an alkali solution in advance to form an aqueous solution. , 28, 31.
  • the solid desulfurization catalyst may be put into the desulfurization catalyst solution 5, 28, 31 in the equipment as it is.
  • the solid desulfurization catalyst is directly added to the desulfurization catalyst solution 5, 28, 31 in the facility, it is not necessary to make the solid desulfurization catalyst into an aqueous solution, which is preferable because the process can be prevented from becoming complicated.
  • the desulfurization catalyst gradually disappears due to deterioration or partial discharge of the desulfurization catalyst solution in the process of recovering sulfur or sulfur-containing salts or sulfur-containing ions, continuous or intermittent during operation of the equipment It is preferable to replenish.
  • the amount of the desulfurized catalyst solution 5, 28, 31 being circulated, the components of the discharged solution, the redox potential of the desulfurized catalyst solution 5, 28, 31 being circulated are taken into consideration. What is necessary is just to determine an addition amount and timing suitably.
  • the regeneration tower 19 and the absorption tower 16 are formed as separate facilities, and the desulfurization catalyst solution 5 is stored in the regeneration tower 19 and the oxygen-containing gas 20 is blown into the stored desulfurization catalyst solution 5.
  • the desulfurization catalyst solution 5 stored in the regeneration tower 19 is the majority of the desulfurization catalyst solution 5 circulating in the facility, and the stirring is promoted by blowing in the oxygen-containing gas 20. Therefore, the desulfurization catalyst can be efficiently dissolved and diffused into the desulfurization catalyst solution 5.
  • the desulfurization catalyst solution 5 may contain another catalyst.
  • 1,4-naphthoquinone-2 which is a desulfurization catalyst already used in the conventional Takahax method, is added to the desulfurization catalyst solution 5.
  • 1,4-naphthoquinone-2 which is a desulfurization catalyst already used in the conventional Takahax method
  • the solution may be implemented so that the solid desulfurization catalyst according to the present embodiment is added to the solution.
  • the composition of the simulated reaction liquid 35 is such that NaSH is used as a substitute for dissolved hydrogen sulfide at a concentration of 10 mmol / L, and 1,4-naphthoquinone-2-sulfonate sodium, which is a desulfurization catalyst for Takahax method, is used at a concentration of 0.2 mmol / L. It was.
  • the simulated reaction solution 35 was sampled a plurality of times, and the hydrogen sulfide ion concentration was measured by a capillary electrophoresis apparatus.
  • the hydrogen sulfide ion reduction rate of 1.50 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 was obtained from the change with time in the hydrogen sulfide ion concentration.
  • the relationship between the hydrogen sulfide ion concentration and the reaction time was linearly approximated by the method of least squares to determine the magnitude of the negative slope, the same experiment was conducted without adding a catalyst from the magnitude of the obtained slope. The value obtained by subtracting the magnitude of the obtained slope was taken as the hydrogen sulfide ion reduction rate.
  • Example 1 An experiment similar to that in Comparative Example 1 was carried out by adding solid methylhydroquinone instead of sodium 1,4-naphthoquinone-2-sulfonate and dissolving it in the simulated reaction solution 35.
  • the concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1.
  • 1.81 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 was obtained as the reduction rate of hydrogen sulfide ions.
  • This indicates that methylhydroquinone can have a hydrogen sulfide ion treatment capacity equal to or higher than sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • Example 2 The same experiment as in Comparative Example 1 was carried out by adding tolquinone instead of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, 1.63 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 was obtained as the reduction rate of hydrogen sulfide ions. This indicates that toluquinone, which is an oxidized form of methylhydroquinone, can have a hydrogen sulfide ion treatment capacity equal to or higher than sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst. It is shown that it can be used as a desulfurization catalyst even if it is put into the system in any form of a certain methylhydroquinone and an oxidized form of tolquinone.
  • Comparative Example 2 An experiment similar to that of Comparative Example 1 was performed by adding hydroquinone instead of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the reduction rate of hydrogen sulfide ions was 1.02 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 . This indicates that hydroquinone, which is one of the simplest compounds having a quinone group, cannot achieve performance equivalent to that of sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • Comparative Example 3 The same experiment as in Comparative Example 1 was carried out by adding catechol in place of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the reduction rate of hydrogen sulfide ions was 0.87 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 . This indicates that catechol, which is one of the simplest compounds having a quinone group, cannot achieve the same performance as that of sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • Comparative Example 4 An experiment similar to that of Comparative Example 1 was conducted by adding sodium 1,2-naphthoquinone-4-sulfonate in place of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the decrease rate of hydrogen sulfide ions was 1.46 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 .
  • sodium 1,2-naphthoquinone-4-sulfonate can have a hydrogen sulfide ion treatment capacity equivalent to sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • the amount of the active site per unit weight is 0.477 times that of methylhydroquinone, the methylhydroquinone used in the present invention can obtain the same activity as the conventional one at a lower weight.
  • Comparative Example 5 An experiment similar to that of Comparative Example 1 was conducted by adding 1,2,4-trihydroxybenzene in place of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the reduction rate of hydrogen sulfide ions was 1.53 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 . This indicates that 1,2,4-trihydroxybenzene can have a hydrogen sulfide ion treatment capacity equivalent to that of sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst. However, since it is more expensive than methylhydroquinone, methylhydroquinone used in the present invention can obtain the same activity as the conventional one at a lower cost.
  • Comparative Example 6 An experiment similar to that of Comparative Example 1 was performed by adding 4-methylcatechol in place of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the reduction rate of hydrogen sulfide ions was 1.72 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 . This indicates that 4-methylcatechol can have a hydrogen sulfide ion treatment capacity equivalent to that of sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • methylhydroquinone used in the present invention can obtain the same activity as the conventional one at a lower cost.
  • 4-methylcatechol needs to be stored in an inert gas atmosphere due to stability problems, which increases storage costs.
  • Comparative Example 7 The same experiment as in Comparative Example 1 was carried out by adding pyrogallol instead of sodium 1,4-naphthoquinone-2-sulfonate. The concentration, alkali source, and reaction temperature are all the same as in Comparative Example 1. At that time, the decrease rate of hydrogen sulfide ions was 0.03 mmol ⁇ L ⁇ 1 ⁇ hr ⁇ 1 . This indicates that pyrogallol does not have the ability to treat hydrogen sulfide ions. Compared with the results of 1,2,4-trihydroxybenzene, even if it has the same functional group, hydrogen sulfide ions are It shows that there is a difference in processing capacity.
  • the experimental apparatus is shown in FIG.
  • the absorption tower 42 is a packed tower in which a 10 mm ⁇ laching ring is put to a height of 750 mm in a glass tower having a tower diameter of 60 mm and a height of 900 mm.
  • the regeneration tower 48 was a glass bubble tower having a tower diameter of 80 mm and a height of 1300 mm, a cylindrical gas injection pipe was used for the gas inlet, and the effective liquid height was 1000 mm. Further, a 10 L glass bottle was used as the experimental circulating fluid tank 45.
  • composition of the simulated gas 41 nitrogen gas containing 10000 ppm of ammonia and 5000 ppm of hydrogen sulfide was prepared, and blown at 0.8 Nm 3 / hr from the lower part of the absorption tower 42.
  • the flow rate of the air 49 blown from the lower part of the regeneration tower 48 was 50 NL / hr.
  • the simulated reaction solution 46 was circulated in the system by a liquid feed pump 47 at a flow rate of 45 L / hr.
  • the simulated reaction solution 46 was adjusted to an initial pH value of 9.0 by using sodium 1,4-naphthoquinone-2-sulfonate, which is a desulfurization catalyst of Takahax method, at a concentration of 2 mmol / L and using ammonia water as an alkali source. .
  • the alkali source after the start of the test is only ammonia contained in the simulated gas 41, and other pH values are not adjusted.
  • the concentration of hydrogen sulfide in the purified gas 43 after the treatment coming out from the upper part of the absorption tower 42 is measured at regular intervals with a gas chromatograph 44 with a flame photometric detector, and the concentration of hydrogen sulfide removed in the introduced hydrogen sulfide is measured.
  • the hydrogen sulfide removal rate which is the ratio of As a result, the hydrogen sulfide removal rate was 100.0% after 5 hours from the start of the test, and the hydrogen sulfide removal rate was 99.2% after 15 hours.
  • Example 3 An experiment similar to that in Comparative Example 8 was conducted by adding methylhydroquinone instead of sodium 1,4-naphthoquinone-2-sulfonate.
  • the experimental equipment, concentration, alkali source, and reaction temperature are all the same as in Comparative Example 8.
  • hydrogen sulfide removal rates of 99.8% and 99.4% were obtained 5 hours and 15 hours after the start of the test, respectively. This indicates that methylhydroquinone has the same ability to treat hydrogen sulfide ions as the conventional Takahax catalyst sodium 1,4-naphthoquinone-2-sulfonate.
  • Comparative Example 9 An experiment similar to that in Comparative Example 8 was conducted by adding hydroquinone instead of sodium 1,4-naphthoquinone-2-sulfonate.
  • the experimental equipment, concentration, alkali source, and reaction temperature are all the same as in Comparative Example 8.
  • hydrogen sulfide removal rates of 87.3% and 62.8% were obtained 5 hours and 15 hours after the start of the test, respectively. This indicates that hydroquinone cannot achieve the same performance as that of sodium 1,4-naphthoquinone-2-sulfonate, which is a conventional Takahax catalyst.
  • Example 4 In the same experiment as in Example 3, when the composition of the simulated gas was nitrogen gas containing 12000 ppm of ammonia, 4000 ppm of hydrogen sulfide, 1000 ppm of hydrogen cyanide, carbon dioxide, 25000 ppm, and 3000 ppm of methane, the hydrogen sulfide removal rate after 5 hours was 99. 2%. This indicates that hydrogen cyanide and carbon dioxide, which are other acid gases contained in coke oven gas, and methane, which is a hydrocarbon gas contained in coke oven gas, do not affect the desulfurization performance.
  • Example 5 In the same experiment as in Example 3, 5 hours after the start of the test, once the simulated gas flow, liquid circulation, and air blowing were stopped, 2 L of the simulated reaction liquid was withdrawn from the circulating liquid tank, and the pH value was 9.0. 2 L of ammonia water diluted so as to become was added. Further, 497 mg of methylhydroquinone was charged as a solid powder from the solid desulfurization catalyst charging port 50 at the top of the regeneration tower into the solution stored in the regeneration tower. Thereafter, the circulation of simulated gas, the circulation of liquid, and the blowing of air were started again, and the hydrogen sulfide removal rate became 99.5% 2 hours after the restart. This indicates that the desulfurization performance is not affected even when the solid powder is added.
  • the sulfuration using a desulfurization catalyst that can be handled in a solid state has no safety problems such as explosive properties, is easily available at low cost, and has a desulfurization performance equivalent to that of a conventional desulfurization catalyst.
  • a wet desulfurization method from a hydrogen-containing gas can be provided.

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Abstract

Ce procédé de désulfuration par voie humide de gaz contenant du sulfure d'hydrogène effectue la désulfuration d'un gaz contenant du sulfure d'hydrogène par mise en contact de ce gaz avec une solution de catalyseur de désulfuration qui est obtenue par dissolution d'un catalyseur de désulfuration dans une solution alcaline. Au moins l'une entre la méthyl hydroquinone et la toluquinone est utilisée en tant que catalyseur de désulfuration.
PCT/JP2017/011444 2017-03-22 2017-03-22 Procédé de désulfuration par voie humide de gaz contenant du sulfure d'hydrogène WO2018173150A1 (fr)

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CN113518663A (zh) 2019-09-30 2021-10-19 株式会社Lg化学 用于氢化反应的催化剂及其制造方法
CN114672020B (zh) * 2022-03-10 2023-10-20 天津科技大学 一种苯并噁嗪基共轭梯形聚合物的制备方法及其在硫化氢检测当中的应用

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