CN1336253A - Production method of binuclear phthalocyanine cobalt sulfone desulfurization and decyanation catalyst - Google Patents
Production method of binuclear phthalocyanine cobalt sulfone desulfurization and decyanation catalyst Download PDFInfo
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- CN1336253A CN1336253A CN 00122431 CN00122431A CN1336253A CN 1336253 A CN1336253 A CN 1336253A CN 00122431 CN00122431 CN 00122431 CN 00122431 A CN00122431 A CN 00122431A CN 1336253 A CN1336253 A CN 1336253A
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- desulfurization
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- sulfone
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 18
- 230000023556 desulfurization Effects 0.000 title claims abstract description 18
- 238000007255 decyanation reaction Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title claims abstract description 11
- -1 phthalocyanine cobalt sulfone Chemical class 0.000 title claims description 4
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 7
- CHCFOMQHQIQBLZ-UHFFFAOYSA-N azane;phthalic acid Chemical compound N.N.OC(=O)C1=CC=CC=C1C(O)=O CHCFOMQHQIQBLZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 5
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000007791 liquid phase Substances 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 7
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 4
- 239000007789 gas Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 125000001741 organic sulfur group Chemical group 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 abstract 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 238000012824 chemical production Methods 0.000 abstract 1
- 238000010668 complexation reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract 1
- 229960004889 salicylic acid Drugs 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- 231100000331 toxic Toxicity 0.000 abstract 1
- 230000002588 toxic effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for producing a desulfurization and decyanation catalyst by a liquid phase catalytic oxidation method in chemical production. Salicylic acid, ammonium phthalate sulfonate, pyromellitic dianhydride, cobalt chloride and the like are used as raw materials, and processes of sulfonation, condensation, complexation, drying, crushing and the like are adopted. It is suitable for desulfurizing and decyanating various low and high sulfur gases and low viscosity liquids by liquid phase catalytic oxidation. Is a new process for replacing the international ADA method and the domestic TV method which are commonly used. The method overcomes the defects that the ADA method and the TV method can not remove organic sulfur, the removal rate of hydrogen cyanide is low, the solution components are complex, the method still belongs to a toxic process, the tower is easy to block, the operation cost is high and the like.
Description
The present invention is the production method of the desulfurization and decyanation catalyst of liquid phase catalytic oxidation in the Chemical Manufacture.
In liquid phase catalytic oxidation desulfurization technology category, external commonly used is the ADA method, and domestic except that the ADA method, some enterprises also adopt tannin extract (TV) method, and these methods can not removal of organic sulfur from, and the prussic acid decreasing ratio is low, and the solution compolision more complicated needs and V
2O
5, tartrate first sodium etc. is used, so running cost height; Contain NaVO in the doctor solution
3, still belonging to poisonous technology, side reaction produces a large amount of waste liquids, carries under the situation of salt device (carry salt make running cost higher) in nothing and needs discharging in a large number, and serious environment pollution, and easily stifled tower are unfavorable for operation." investigation of middle scale nitrogenous fertilizer plant desulfurization technology applicable cases, nitrogen association emphasis investigation in 1996 project in the Ministry of Chemical Industry ".
The objective of the invention is in liquid phase catalytic oxidation desulfurization category, it is good to seek a kind of technique effect, and remarkable in economical benefits is the desulfurization and decyanation catalyst and the production method thereof of nontoxic pollution-free especially.
The quality standard of this desulfurization and decyanation catalyst product is: outward appearance: Lan Se or blue grey powder (aqueous solution is blue look); Water-insoluble :≤5.0% catalytic activity: 〉=0.04min
-1
This desulfurization and decyanation catalyst production process route is: sulfonation → condensation → complexing → oven dry → pulverizing → finished product.Main production raw material is: Whitfield's ointment, ammonium phthalate ammonium sulphonate, pyromellitic acid anhydride, cobalt chloride, sulfuric acid etc.This desulfurization and decyanation catalyst controlling of production process condition is: raw material Whitfield's ointment in the sulfonation reaction and vitriolic mol proportioning are 1: 1; The mol proportioning of the raw material ammonium phthalate ammonium sulphonate in the condensation reaction, pyromellitic acid anhydride, cobalt chloride is 1: 1: 2; The raw material binuclear phthalocyanine cobalt (condensation product) in the complex reaction and the weight proportion of sulphosalicylic acid (sulfonated products) are 1: 6; The sulfonation reaction temperature is controlled at 140～180 ℃, and the reaction times was controlled at 4～5 hours; Setting-up point is controlled at 210～240 ℃, and the reaction times was controlled at 2～4 hours; Complex reaction is finished in the short period of time at normal temperatures; Oven dry was carried out 2～6 hours at 120 ℃～160 ℃, and final powder is broken to 20～60#.
This catalyzer is applicable to various low, the high-sulfur (H of liquid phase catalytic oxidation
2S content is at 0.3～500g/Nm
3) desulfurization, the decyanation of gas and low-viscosity (mobile) liquid, be mainly used in industries such as nitrogenous fertilizer, coking, town gas, Sweet natural gas, land and marine oil.Can simultaneously, at a high speed, efficiently remove H
2S (can reach more than 99%), HCN (can reach 97%), part organosulfur (to decreasing ratio 〉=98% of mercaptan, other is more than 60%).Compare with ADA, tannin extract method, this desulfurization and decyanation technology has remarkable advantages, and higher removal efficiency (can remove the part organosulfur simultaneously) is promptly arranged, the solution component is simple, need not add any auxiliary agent (except that alkali lye), running cost is lower by about 70% than ADA method, than TV method low about 50%; No toxic substance exists in the solution, and side reaction can be controlled, under the situation of not carrying salt, do not need to discharge waste liquid in a large number, belongs to nontoxic, pollution-free technology.In liquid phase catalytic oxidation desulfurization category, be that the desulfurization technology of core can be referred to as domestic initiation, technology leading in the world fully with this desulfurization and decyanation catalyst.Its obvious characteristic is (1) pollution-free, nonpoisonous craft; (2) desulphurization cost is low, and economic results in society are remarkable; (3) can remove H simultaneously
2S, HCN and part organosulfur, technique effect is good; (4) not stifled tower is easy to operation.
Optimum implementation of the present invention is: with Whitfield's ointment and dense H
2SO
4By 1: 1 (mol ratio, H
2SO
4Excessive 5%) mix, under agitation, controlled temperature is at 170 ℃, about 4 hours.Cooling neutralizes respectively with liming and ammoniacal liquor, removes unnecessary H
2SO
4The back is standby; Ammonium phthalate ammonium sulphonate, pyromellitic acid anhydride, cobalt chloride are mixed by 1: 1: 2 (mol ratio), 230 ℃ of reactions 3 hours, with standby behind the solvent evaporate to dryness; Condensation product binuclear phthalocyanine cobalt and sulfonated products sulphosalicylic acid were mixed by weight 1: 6, after fully stirring, the product that obtains is changed in the drying plant in 140 ℃ of oven dry 4 hours, promptly obtain the finished product.
Claims (2)
1, a kind of production method of desulfurization and decyanation catalyst of binuclear phthalocyanine cobalt sulfone, it is characterized in that: production process route is sulfonation → condensation → complexing → oven dry → pulverizing → finished product, main raw material is Whitfield's ointment, ammonium phthalate ammonium sulphonate, pyromellitic acid anhydride, cobalt chloride, sulfuric acid, Whitfield's ointment and vitriolic proportioning are that mol was than 1: 1 in the sulfonation reaction, 140～180 ℃ of temperature, the time is 4～5 hours, cooling, neutralize respectively with liming and ammoniacal liquor, remove unnecessary sulfuric acid; In the condensation reaction ammonium phthalate ammonium sulphonate, pyromellitic acid anhydride, cobalt chloride proportioning be mol than 1: 1: 2,210～240 ℃ of temperature, 2～4 hours time; In the complex reaction, condensation reaction products binuclear phthalocyanine cobalt and sulfonated products sulphosalicylic acid were mixed at normal temperatures by weight 1: 6,120～160 ℃ of oven dry 2～6 hours, final powder was broken to 20～60# then.
2, according to the production method of the described desulfurization and decyanation catalyst of binuclear phthalocyanine cobalt sulfone of claim 1, it is characterized in that: the sulfonation reaction temperature is 170 ℃, 4 hours time, 230 ℃ of condensation reactions, 3 hours, complex reaction was carried out at normal temperatures, complexing product bake out temperature is 140 ℃, 4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00122431 CN1103238C (en) | 2000-08-01 | 2000-08-01 | Production method of binuclear phthalocyanine cobalt sulfone desulfurization and decyanation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00122431 CN1103238C (en) | 2000-08-01 | 2000-08-01 | Production method of binuclear phthalocyanine cobalt sulfone desulfurization and decyanation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1336253A true CN1336253A (en) | 2002-02-20 |
| CN1103238C CN1103238C (en) | 2003-03-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00122431 Expired - Fee Related CN1103238C (en) | 2000-08-01 | 2000-08-01 | Production method of binuclear phthalocyanine cobalt sulfone desulfurization and decyanation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1103238C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138723A (en) * | 2020-10-23 | 2020-12-29 | 田作林 | Desulfurization catalyst and preparation method thereof |
| CN115006775A (en) * | 2022-05-27 | 2022-09-06 | 内蒙古金陶股份有限公司 | Cyanide tailing decyanation treatment method and decyanation agent composition |
-
2000
- 2000-08-01 CN CN 00122431 patent/CN1103238C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112138723A (en) * | 2020-10-23 | 2020-12-29 | 田作林 | Desulfurization catalyst and preparation method thereof |
| CN115006775A (en) * | 2022-05-27 | 2022-09-06 | 内蒙古金陶股份有限公司 | Cyanide tailing decyanation treatment method and decyanation agent composition |
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| Publication number | Publication date |
|---|---|
| CN1103238C (en) | 2003-03-19 |
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| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Northeast Normal University Document name: Certificate of invention patent; patent specification of invention |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030319 Termination date: 20120801 |