CN112138723A - Desulfurization catalyst and preparation method thereof - Google Patents

Desulfurization catalyst and preparation method thereof Download PDF

Info

Publication number
CN112138723A
CN112138723A CN202011146705.6A CN202011146705A CN112138723A CN 112138723 A CN112138723 A CN 112138723A CN 202011146705 A CN202011146705 A CN 202011146705A CN 112138723 A CN112138723 A CN 112138723A
Authority
CN
China
Prior art keywords
parts
desulfurization catalyst
desulfurization
product
product obtained
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011146705.6A
Other languages
Chinese (zh)
Inventor
田作林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202011146705.6A priority Critical patent/CN112138723A/en
Publication of CN112138723A publication Critical patent/CN112138723A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

Abstract

A desulfurization catalyst comprises the following components in parts by weight: 35-45 parts of sulfonated titanium cobalt cyanide, 15-24 parts of acetylsalicylic acid, 28-34 parts of manganese sulfate, 26-32 parts of hydroquinone, 16-23 parts of tannin extract, 7-13 parts of ammonium sulfate and 2-9 parts of vanadium pentoxide. The desulfurization catalyst overcomes the defect that the PDS desulfurization catalyst can not be used independently, and hydroquinone, ferrous sulfate and the like do not need to be added additionally when the catalyst is used, so that the comprehensive desulfurization cost is reduced. The desulfurization catalyst is quick in reaction and long in duration when in use, can ensure that the index meets the environmental requirement, and has a certain tower cleaning function, so that the blockage time is delayed, and the generation speed of secondary salt in the desulfurization solution is slowed down.

Description

Desulfurization catalyst and preparation method thereof
Technical Field
The invention relates to the field of desulfurization catalysts, and particularly relates to a desulfurization catalyst and a preparation method thereof.
Background
In recent years, the requirements of various environmental regulations on the emission of atmospheric pollutants are increasingly strict, so that the upgrading of the quality of domestic oil products is accelerated, and in order to meet the production requirements of ultra-low-sulfur clean diesel, the existing diesel desulfurization technology needs to be improved to improve the desulfurization efficiency. Coke oven gas is one of the main by-products of coking enterprises and contains a large amount of chemical products. With the extension of coal chemical product lines, the recycling of chemical products in coke oven gas is more and more extensive. Hydrogen sulfide and hydrogen cyanide in coke oven gas can cause great harm to the recovery of chemical products and must be removed. The desulfurization process of domestic large-scale coke-oven plants generally adopts ammonia process gas desulfurization technology (i.e. HPF desulfurization process), and the HPF desulfurization process utilizes ammonia water as absorbent, and adds catalyst to convert acidic gases in coal gas, such as hydrogen sulfide and hydrogen cyanide, into salts, such as ammonium thiocyanate, and the like, so that the coke oven gas is purified.
At present, the catalysts used in the HPF process in China areThe ten more species can be roughly classified into two types, the first is phenol-quinone conversion (active group conversion) catalyzed by valence-changing ions, such as: ADA, hydroquinone, tannin extract, picric acid (PIA) in the F/R process, and sodium 1, 4-naphthoquinone 2-sulfonate in the TAKAHAX process. Although the said desulfurizing catalyst can meet some technological requirements, it has some demerits, such as incapable of eliminating organic sulfur, low desulfurizing efficiency, less separation of sulfur foam, blocking equipment and adaptability to H2Small S content range, high desulfurization cost and the like. The second type is a sulfonated cobalt phthalocyanine and metal ion type desulfurization catalyst developed in recent years, and the desulfurization catalyst is different from the first type in that the desulfurization catalyst is an oxygen carrier and performs oxidation regeneration action through atomic oxygen carried by the desulfurization catalyst. In the prior art, a PDS desulfurization catalyst is a commonly used second-type desulfurization catalyst, but the PDS desulfurization catalyst cannot be used alone, and substances such as ferrous sulfate and the like need to be added, so that the desulfurization cost is high, more secondary salts are generated, and a secondary salt extraction system needs to be arranged independently, so that a more complete desulfurization catalyst is needed in the desulfurization process.
Disclosure of Invention
In order to solve the problems, the invention provides a desulfurization catalyst and a preparation method thereof, which overcome the defect that a PDS desulfurization catalyst cannot be used independently, do not need to add ferrous sulfate and other substances, and have lower desulfurization cost.
The technical scheme of the invention is as follows:
a desulfurization catalyst consists of sulfonated titanium cobalt cyanide with a special space structure and a cocatalyst, and comprises the following components in parts by weight: 35-45 parts of sulfonated titanium cobalt cyanide, 15-24 parts of acetylsalicylic acid, 28-34 parts of manganese sulfate, 26-32 parts of hydroquinone, 16-23 parts of tannin extract, 7-13 parts of ammonium sulfate and 2-9 parts of vanadium pentoxide.
The preparation method of the desulfurization catalyst comprises the following steps:
(1) and (3) performing phthalic anhydride sulfonation treatment, adding 15-22 parts of phthalic anhydride, 17-23 parts of fuming sulfuric acid and 1-4 parts of catalyst into a stirring kettle, stirring and heating to 120-150 ℃, keeping the temperature for 0.5-2 hours, slowly heating to 200-300 ℃, and keeping the temperature for 4-7 hours to obtain the sulfophthalic acid product. Preferably, the catalyst is anhydrous sodium sulfate, and the concentration of the fuming sulfuric acid is 62-68%.
(2) Synthesizing in a reactor, namely adding 20-50 parts of ammonia water into the reactor, then adding 1-3 parts of pyromellitic dianhydride, 14-18 parts of urea, 2-6 parts of cobalt chloride, 7-10 parts of sulfophthalic acid and 0.1-0.5 part of ammonium molybdate, and heating and melting;
(3) after the reactants in the reactor are heated and melted, continuously adding 7-9 parts of urea, 1-3 parts of cobalt chloride and 3.5-5 parts of sulfophthalic anhydride and stirring to fully mix the reactants, wherein the reaction can be carried out more completely, and continuously observing the reactants during stirring until the reactants are observed to be viscous;
(4) taking out the product obtained in the step (3), putting the product into a metal disc, uniformly distributing the product to ensure uniform heating, ensuring the metal disc to have good heat conduction effect, then putting the metal disc into a drying box with the temperature of 250-400 ℃ for drying for 1-4 hours, and evaporating the water in the metal disc to obtain the desulfurization catalyst raw powder;
(5) adding 9-15 parts of salicylic acid and 8-13 parts of 95% sulfuric acid into a reaction kettle, heating to 100 ℃ and 200 ℃, and reacting for 2-4 hours;
(6) transferring the product obtained in the step (5) into a mixer, adding 34-43 parts of ammonium bicarbonate, 6-13 parts of ammonium sulfate, 8-15 parts of hydroquinone and 25-33 parts of desulfurization catalyst raw powder, and uniformly stirring and mixing;
(7) transferring the product obtained in the step (6) into a metal disc, uniformly distributing the product to facilitate water evaporation, and drying the product in a drying box at the temperature of 150-;
(8) and (4) taking out the product obtained in the step (7), crushing and packaging the product to finally obtain a blue-black powdery desulfurization catalyst finished product, wherein the granularity after crushing is less than 20 meshes.
Compared with the prior art, the invention has the advantages that:
1. the desulfurization catalyst is suitable for coke oven gas with different sulfur contents, and has the advantages of high desulfurization and decyanation speed and high efficiency, wherein the desulfurization efficiency can reach more than 98 percent, and the decyanation efficiency can reach more than 90 percent.
2. The desulfurization catalyst can remove inorganic sulfur and organic sulfur at the same time.
3. Compared with other catalysts, the desulfurization catalyst disclosed by the invention can be used independently, has the characteristics of large sulfur foam particles, easiness in separation and no blockage of equipment, is low in consumption, does not need to add hydroquinone and ferrous sulfate, and is low in operation cost.
4. The desulfurization catalyst has good selectivity for the generation of sulfur, so that the growth speed of the secondary salt is slow, the discharge amount of waste liquid is small, the treatment cost is low, and the environmental pollution is small.
5. The desulfurization catalyst disclosed by the invention has the advantages that no waste residue is generated in the production process, the operation is simple, the equipment energy consumption is low, the product stability is more outstanding, and compared with the production process of other catalysts, complicated procedures and equipment such as neutralization and precipitation are omitted, so that the consumption of manpower and raw materials is reduced.
Catalytic oxidation principle of desulfurization catalyst
1. Absorption reaction
Hydrogen sulfide (H)2S), mercaptan (RSH), carbonyl sulfide (COS), carbon disulfide (CS)2) And reacting with alkaline solution to generate corresponding compound:
H2S+NH3·H2O→NH4HS+H2O……………………………(1)
RHS+NH3·H2O→RSNH4+H2O……………………………(2)
COS+NH3·H2O→(NH4)2CO2S+H2O…………………………(3)
CS2+NH3·H2O→(NH4)2COS2+H2O…………………………(4)
as is clear from the above absorption reaction, the reaction proceeds in a certain stepUnder technological conditions, if the absorption reaction is carried out completely, S in the system needs to be reacted2－Oxidized into elemental sulfur and separated.
2. Desulfurization reaction
Because the special molecular structure of the invention has oxygen carrying capacity, atomic oxygen with higher oxidation activity is continuously released in the desulfurization process, and S in the system can be quickly absorbed2－Oxidized into elemental sulfur, greatly strengthening the desulfurization effect, and the main reaction process is as follows:
Figure BDA0002739911410000031
Figure BDA0002739911410000032
Figure BDA0002739911410000033
Figure BDA0002739911410000041
3. regeneration reaction
In the desulfurization reaction, the oxygen carried by the invention is consumed, and air is blown to regenerate the oxygen:
ZL(On)+O2→ZL(On+2)…………………………………(9)
the research shows that the action mechanism of the invention is as follows.
a: the desulfurization catalyst dissolves O in alkaline solution2Adsorbing and activating to form high-activity macroions;
b: when H is met2S and other sulfur-containing compounds are adsorbed onto the microscopic surface of high-activity macroion to make H react under the condition of production2Sulfur in sulfur-containing compounds such as S is oxidized into elemental sulfur or polysulfide;
c: the elemental sulfur or polysulfide desorbs from the surface of the desulfurization catalyst and leaves;
d: the desulfurization catalyst is regenerated by recovering oxygen the reaction process is as follows:
NH4HS+NH3·H2O+(x-1)S→(NH4)2Sx+H2O……………(10)
Figure BDA0002739911410000042
4. side reactions
2NH4HS+2O2→(NH4)2S2O3+H2O………………………(12)
NH4CN+(NH4)2Sx→NH4SCN+(NH4)2Sx-1………………(13)
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below. It should be noted that these embodiments are provided so that this disclosure can be more completely understood and fully conveyed to those skilled in the art, and the present disclosure may be implemented in various forms without being limited to the embodiments set forth herein.
Example 1
In this embodiment, the preparation method of the desulfurization catalyst comprises the following steps:
(1) and (3) performing phthalic anhydride sulfonation, adding 15 parts of phthalic anhydride, 17 parts of fuming sulfuric acid with the concentration of 62% and 1 part of anhydrous sodium sulfate into a stainless steel stirring kettle, stirring, heating to 120 ℃, keeping the temperature for 0.5 hour, slowly heating to 200 ℃, and keeping the temperature for 4 hours to obtain a sulfophthalic acid product.
The preparation method of the oleum comprises the following steps: introducing sulfur trioxide into the concentrated sulfuric acid solution to prepare fuming sulfuric acid.
(2) Synthesizing in a hemispherical reactor, adding 20 parts of ammonia water into the reactor, and then adding 1 part of pyromellitic dianhydride, 14 parts of urea, 2 parts of cobalt chloride, 7 parts of sulfophthalic acid and 0.1 part of ammonium molybdate to heat and melt;
(3) after the reactants in the reactor are heated and melted, continuously adding 7 parts of urea, 1 part of cobalt chloride and 3.5 parts of sulfophthalic anhydride dicarboxylic acid, and stirring until the reactants are viscous;
(4) taking out the product obtained in the step (3), putting the product into a metal disc for uniform distribution, and then putting the metal disc into a drying box at 250 ℃ for drying for 1 hour to obtain desulfurization catalyst raw powder;
(5) adding 7 parts of salicylic acid and 9 parts of 95% sulfuric acid into a reaction kettle, and heating to 100 ℃ for reacting for 2 hours;
(6) transferring the product obtained in the step (5) into a mixer, adding 18 parts of ammonium bicarbonate, 37 parts of ammonium sulfate, 9 parts of hydroquinone, 8 parts of desulfurization catalyst raw powder, and 26 parts of stirring and mixing uniformly;
(7) transferring the product obtained in the step (6) into a metal disc again, and drying the metal disc in a drying box at the temperature of 150 ℃ for 10 hours;
(8) and (4) taking out the product obtained in the step (7), and crushing and packaging the product to finally obtain a finished product of the desulfurization catalyst.
The desulfurization catalyst prepared by the preparation method consists of sulfonated titanium cobalt cyanide with a special space structure and a cocatalyst, and comprises the following components in parts by weight: 35 parts of sulfonated titanium cobalt cyanide, 15 parts of acetylsalicylic acid, 28 parts of manganese sulfate, 26 parts of hydroquinone, 16 parts of tannin extract, 7 parts of ammonium sulfate and 2 parts of vanadium pentoxide.
Example 2
In this embodiment, the preparation method of the desulfurization catalyst comprises the following steps:
(1) and (3) performing phthalic anhydride sulfonation, adding 20 parts of phthalic anhydride, 20 parts of fuming sulfuric acid with the concentration of 65% and 3 parts of anhydrous sodium sulfate into a stainless steel stirring kettle, stirring, heating to 130 ℃, keeping the temperature for 1 hour, slowly heating to 270 ℃, and keeping the temperature for 5 hours to obtain a sulfophthalic acid product.
The preparation method of the oleum comprises the following steps: introducing sulfur trioxide into the concentrated sulfuric acid solution to prepare fuming sulfuric acid.
(2) Synthesizing in a hemispherical reactor, adding 30 parts of ammonia water into the reactor, and then adding 2 parts of pyromellitic dianhydride, 16 parts of urea, 4 parts of cobalt chloride, 8 parts of sulfophthalic acid and 0.3 part of ammonium molybdate to heat and melt;
(3) after the reactants in the reactor are heated and melted, continuously adding 8 parts of urea, 2 parts of cobalt chloride and 4 parts of sulfophthalic anhydride dicarboxylic acid, and stirring until the reactants are viscous;
(4) taking out the product obtained in the step (3), putting the product into a metal disc for uniform distribution, and then putting the metal disc into a drying box at 300 ℃ for drying for 3 hours to obtain desulfurization catalyst raw powder;
(5) adding 11 parts of salicylic acid and 10 parts of 95% sulfuric acid into a reaction kettle, heating to 160 ℃, and reacting for 3 hours;
(6) transferring the product obtained in the step (5) into a mixer, adding 20 parts of ammonium bicarbonate, 40 parts of ammonium sulfate, 10 parts of hydroquinone and 10 parts of desulfurization catalyst raw powder, and uniformly stirring and mixing 30 parts of the mixture;
(7) transferring the product obtained in the step (6) into a metal disc again, and drying the metal disc in a drying box at 175 ℃ for 12 hours;
(8) and (4) taking out the product obtained in the step (7), and crushing and packaging the product to finally obtain a finished product of the desulfurization catalyst.
The desulfurization catalyst prepared by the preparation method consists of sulfonated titanium cobalt cyanide with a special space structure and a cocatalyst, and comprises the following components in parts by weight: 40 parts of sulfonated titanium cobalt cyanide, 20 parts of acetylsalicylic acid, 31 parts of manganese sulfate, 28 parts of hydroquinone, 20 parts of tannin extract, 10 parts of ammonium sulfate and 5 parts of vanadium pentoxide.
Example 3
In this embodiment, the preparation method of the desulfurization catalyst comprises the following steps:
(1) and (3) performing phthalic anhydride sulfonation, adding 22 parts of phthalic anhydride, 23 parts of fuming sulfuric acid with the concentration of 68% and 4 parts of anhydrous sodium sulfate into a stainless steel stirring kettle, stirring, heating to 130 ℃, keeping the temperature for 1 hour, slowly heating to 270 ℃, and keeping the temperature for 5 hours to obtain a sulfophthalic acid product.
The preparation method of the oleum comprises the following steps: introducing sulfur trioxide into the concentrated sulfuric acid solution to prepare fuming sulfuric acid.
(2) Synthesizing in a hemispherical reactor, adding 50 parts of ammonia water into the reactor, and then adding 3 parts of pyromellitic dianhydride, 18 parts of urea, 6 parts of cobalt chloride, 10 parts of sulfophthalic acid and 0.5 part of ammonium molybdate to heat and melt;
(3) after the reactants in the reactor are heated and melted, continuously adding 9 parts of urea, 3 parts of cobalt chloride and 5 parts of sulfophthalic anhydride dicarboxylic acid, and stirring until the reactants are viscous;
(4) taking out the product obtained in the step (3), putting the product into a metal disc for uniform distribution, and then putting the metal disc into a drying box at 300 ℃ for drying for 3 hours to obtain desulfurization catalyst raw powder;
(5) adding 15 parts of salicylic acid and 13 parts of 95% sulfuric acid into a reaction kettle, and heating to 200 ℃ for reacting for 4 hours;
(6) transferring the product obtained in the step (5) into a mixer, and then adding 22 parts of ammonium bicarbonate, 42 parts of ammonium sulfate, 13 parts of hydroquinone, 12 parts of desulfurization catalyst raw powder and 33 parts of desulfurization catalyst raw powder, and uniformly stirring and mixing;
(7) transferring the product obtained in the step (6) into a metal disc again, and drying the metal disc in a drying box at the temperature of 200 ℃ for 15 hours;
(8) and (4) taking out the product obtained in the step (7), and crushing and packaging the product to finally obtain a finished product of the desulfurization catalyst.
The desulfurization catalyst prepared by the preparation method consists of sulfonated titanium cobalt cyanide with a special space structure and a cocatalyst, and comprises the following components in parts by weight: 45 parts of sulfonated titanium cobalt cyanide, 24 parts of acetylsalicylic acid, 34 parts of manganese sulfate, 32 parts of hydroquinone, 23 parts of tannin extract, 13 parts of ammonium sulfate and 8 parts of vanadium pentoxide.
Examples of the experiments
The PDS desulfurization catalyst and the invention were used simultaneously, and the experimental three-month test was carried out, and the results are reported in Table 1.
TABLE 1 comparison of the use of two desulfurization catalysts (average)
Desulfurization effect Content of accessory salt (g/l) Alkali consumption (ton/day)
Example 1 98.5％ 178 1.7
Example 2 97.9％ 169 1.8
Example 3 98.3％ 172 1.6
PDS desulfurization catalyst 89.3％ 301 3.9
As can be seen from Table 1, compared with the PDS desulfurization catalyst, the desulfurization method has the advantages that the desulfurization effect is better, and less secondary salt is generated, so that a secondary salt extraction system is not required to be arranged in the production process, the manpower and material resources are saved, the consumed soda ash amount is obviously reduced, and the production cost is greatly saved.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or additions or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (9)

1. The desulfurization catalyst is characterized by comprising the following components in parts by weight: 35-45 parts of sulfonated titanium cobalt cyanide, 15-24 parts of acetylsalicylic acid, 28-34 parts of manganese sulfate, 26-32 parts of hydroquinone, 16-23 parts of tannin extract, 7-13 parts of ammonium sulfate and 2-9 parts of vanadium pentoxide.
2. A method for preparing the desulfurization catalyst according to claim 1, characterized by comprising the steps of:
(1) performing phthalic anhydride sulfonation treatment, adding 15-22 parts of phthalic anhydride, 17-23 parts of fuming sulfuric acid and 1-4 parts of catalyst into a stirring kettle, and reacting to obtain a sulfophthalic acid product;
(2) synthesizing in a hemispherical reactor, adding 20-50 parts of ammonia water into the reactor, then adding 1-3 parts of pyromellitic dianhydride, 14-18 parts of urea, 2-6 parts of cobalt chloride, 7-10 parts of sulfophthalic acid and 0.1-0.5 part of ammonium molybdate, and heating and melting;
(3) after the reactants in the reactor are heated and melted, continuously adding 7-9 parts of urea, 1-3 parts of cobalt chloride and 3.5-5 parts of sulfophthalic anhydride and stirring until the reactants are viscous;
(4) taking out the product obtained in the step (3), putting the product into a metal disc, uniformly distributing the product, and then putting the metal disc into a drying box for drying to obtain desulfurization catalyst raw powder;
(5) adding 7-11 parts of salicylic acid and 9-13 parts of 95% sulfuric acid into a reaction kettle, and heating the mixture during reaction;
(6) transferring the product obtained in the step (5) into a mixer, and then adding 18-22 parts of ammonium bicarbonate, 37-42 parts of ammonium sulfate, 9-13 parts of hydroquinone, 8-12 parts of desulfurization catalyst raw powder and 26-33 parts of desulfurization catalyst raw powder, stirring and mixing uniformly;
(7) transferring the product obtained in the step (6) into the metal disc again, and drying the metal disc in a drying box;
(8) and (4) taking out the product obtained in the step (7), and crushing and packaging the product to finally obtain a finished product of the desulfurization catalyst.
3. The method for preparing a desulfurization catalyst according to claim 2, wherein the catalyst used in the step (1) is anhydrous sodium sulfate, and the stirring is continuously performed during the temperature rising process.
4. The method for preparing a desulfurization catalyst according to claim 2, wherein the concentration of the aqueous ammonia in the step (2) is 15 to 18%.
5. The method as claimed in claim 2 or 4, wherein the temperature of the reactor is raised to 150 ℃ with stirring and maintained for 0.5-2 hours, and then slowly raised to 200 ℃ with temperature maintained for 4-7 hours after the reactants are added into the reactor in the step (2).
6. The method as claimed in claim 2, wherein in the step (4), the product obtained in the step (3) is taken out, placed in a metal disc for uniform distribution, and then placed in a drying oven for drying at 250 ℃ and 400 ℃ for 1-4 hours to obtain the desulfurization catalyst raw powder.
7. The method as claimed in claim 2, wherein the step (5) comprises adding 7-11 parts of salicylic acid and 9-13 parts of 95% sulfuric acid into the reaction kettle, and heating to 200 ℃ for reaction at 100 ℃ for 2-4 hours.
8. The method as claimed in claim 2, wherein in the step (7), the product obtained in the step (6) is taken out, put into a metal disc again for uniform distribution, and put into a drying oven for drying at 150 ℃ and 200 ℃ for 10-15 hours.
9. The method of claim 2, wherein the size of the pulverized product obtained in step (8) is less than 20 mesh.
CN202011146705.6A 2020-10-23 2020-10-23 Desulfurization catalyst and preparation method thereof Pending CN112138723A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011146705.6A CN112138723A (en) 2020-10-23 2020-10-23 Desulfurization catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011146705.6A CN112138723A (en) 2020-10-23 2020-10-23 Desulfurization catalyst and preparation method thereof

Publications (1)

Publication Number Publication Date
CN112138723A true CN112138723A (en) 2020-12-29

Family

ID=73954793

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011146705.6A Pending CN112138723A (en) 2020-10-23 2020-10-23 Desulfurization catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112138723A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088959A (en) * 1993-11-29 1994-07-06 太原煤炭汽化总公司焦化厂 Phthalocyanine cobalt sulfonate doctor solution and the sulfur removal technology in coke-oven gas thereof
CN1336253A (en) * 2000-08-01 2002-02-20 东北师范大学 Production process of desulfurization and decyanation catalyst of binuclear phthalocyanine cobalt sulfone
CN1689995A (en) * 2004-04-28 2005-11-02 北京城市排水集团有限责任公司 Digestion tank desulfurization method
CN1724162A (en) * 2005-06-07 2006-01-25 天门市天宝化工科技有限公司 Multicomponent composite desulfate catalyst
CN105032487A (en) * 2015-06-11 2015-11-11 吉林市环喜科技有限公司 Preparation method of PDS desulfurization catalyst

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088959A (en) * 1993-11-29 1994-07-06 太原煤炭汽化总公司焦化厂 Phthalocyanine cobalt sulfonate doctor solution and the sulfur removal technology in coke-oven gas thereof
CN1336253A (en) * 2000-08-01 2002-02-20 东北师范大学 Production process of desulfurization and decyanation catalyst of binuclear phthalocyanine cobalt sulfone
CN1689995A (en) * 2004-04-28 2005-11-02 北京城市排水集团有限责任公司 Digestion tank desulfurization method
CN1724162A (en) * 2005-06-07 2006-01-25 天门市天宝化工科技有限公司 Multicomponent composite desulfate catalyst
CN105032487A (en) * 2015-06-11 2015-11-11 吉林市环喜科技有限公司 Preparation method of PDS desulfurization catalyst

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
吉亚祉等: "脱硫催化剂OTS在栲胶法煤气脱硫工艺中的应用", 《新技术新工艺》 *
屈撑囤: "《精细有机合成反应与工艺》", 30 September 2000 *
陈霞: "焦炉煤气湿式氧化法脱硫工艺技术研究", 《中国优秀硕士学位论文全文数据库》 *

Similar Documents

Publication Publication Date Title
CN102381687B (en) Method for preparing acid by using sulfur containing waste material and wet method desulphurization process containing method thereof
CN105600990B (en) Method for recycling sulfur, ammonium sulfate and catalyst by utilizing coke oven gas desulfurization and decyanation waste liquid
CN106268219B (en) A kind of iron oxide fine desulfurizer and its preparation and application method
CN102398909B (en) Method for producing ammonium sulfate by using high-ammonium-nitrogen sulfur-containing high-salinity wastewater
CN101890286B (en) Method and device for removing hydrogen sulfide from gas by using suspension of ferric oxide powder
CN102910590A (en) Method of sulfur recovery through sulfur dioxide flue gas cleaning and catalyzing and application of catalyst
CN103274381B (en) A kind of vacuum carbonation coke-oven-gas desulfurization and decyanation effluent resource method and device
CN114620692A (en) Process for preparing sulfuric acid by carrying out salt extraction and co-firing on coking desulfurization foam sulfur melting and desulfurization waste liquid melting method
CN102658002A (en) Method for absorbing and purifying hydrogen sulfide with EDTA (ethylene diamine tetraacetic acid) chelated iron copper compound system
CN1192814C (en) Method for urea catalyst simultaneously processing flue gas and desulfurizing denitrification
CN103846003A (en) Method of removing hydrogen sulfide
CN102489150B (en) Preparation method for load type iron-based sulfureted hydrogen removal agent under room temperature
CN111592474A (en) Preparation method of complex iron catalyst for wet desulphurization
CN104119947B (en) A kind of catalytic cracking flue gas desulfurization and aftertreatment technology
CN102872798A (en) Preparation method for normal-temperature iron series hydrogen sulfide removal agent
CN101549298A (en) Activated carbon catalyst
CN112138723A (en) Desulfurization catalyst and preparation method thereof
CN102218260B (en) Absorbent used for removing sulfides in malodorous gases
CN101143746A (en) Method for processing sulfur-containing waste lye
CN105289608A (en) Preparation method for catalyst capable of simultaneously removing carbonyl sulfide and carbon disulfide
KR101657244B1 (en) The Desulfurization catalyst using Hydroxy magnesium and a method of manufacturing it
CN110252090B (en) Method for improving absorption capacity and utilization rate of sodium sulfite desulfurization process by using triethanolamine
CN102329689B (en) Additive and process for regeneration of waste oil for automobile engine
CN111056612B (en) Treatment method and application of sulfur-containing wastewater
CN112570033B (en) Wet desulphurization catalyst, desulphurization solution and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20201229