CN104785296A - Liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal - Google Patents
Liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal Download PDFInfo
- Publication number
- CN104785296A CN104785296A CN201510117502.7A CN201510117502A CN104785296A CN 104785296 A CN104785296 A CN 104785296A CN 201510117502 A CN201510117502 A CN 201510117502A CN 104785296 A CN104785296 A CN 104785296A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- phthalocyanine
- cobalt
- liquid
- naoh solution
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000007788 liquid Substances 0.000 title claims abstract description 36
- -1 cobalt sulfonated phthalocyanine Chemical class 0.000 title claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- 239000010941 cobalt Substances 0.000 title claims abstract description 18
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 title abstract description 27
- 239000003915 liquefied petroleum gas Substances 0.000 title abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 claims abstract description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims abstract description 5
- IXROTFPQTYAPMU-UHFFFAOYSA-M [Co]Oc1ccccc1 Chemical compound [Co]Oc1ccccc1 IXROTFPQTYAPMU-UHFFFAOYSA-M 0.000 claims description 19
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003209 petroleum derivative Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 150000003254 radicals Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 7
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 235000013495 cobalt Nutrition 0.000 description 16
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [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 description 13
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- 238000006277 sulfonation reaction Methods 0.000 description 6
- 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 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006477 desulfuration reaction Methods 0.000 description 4
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- 229940124530 sulfonamide Drugs 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- KHAZIIVSIJPRGF-UHFFFAOYSA-N [Na].CCCS Chemical compound [Na].CCCS KHAZIIVSIJPRGF-UHFFFAOYSA-N 0.000 description 2
- OEBFEEOMRDUMIR-UHFFFAOYSA-N [S].C(CC)S Chemical compound [S].C(CC)S OEBFEEOMRDUMIR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BQYGCEWROWDDKH-UHFFFAOYSA-N butane-1-thiol;sodium Chemical compound [Na].CCCCS BQYGCEWROWDDKH-UHFFFAOYSA-N 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- QPUSANCBJDDXSA-UHFFFAOYSA-N ethanethiol;sodium Chemical compound [Na].CCS QPUSANCBJDDXSA-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YRZZLAGRKZIJJI-UHFFFAOYSA-N oxyvanadium phthalocyanine Chemical compound [V+2]=O.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 YRZZLAGRKZIJJI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal; the liquid catalyst is composed of an active component tetra-beta-p-sulfonic phenoxy phthalocyanine cobalt, a stabilizer propylene glycol dimethyl ether, one or a combination of N-methyl diethanolamine or triethanolamine, an emulsifier octadecyl dimethyl benzyl ammonium chloride and an NaOH solution. The invention also discloses a tetra-beta-p-sulfonic phenoxy phthalocyanine cobalt structure designed for the first time, and a catalytic conversion effect of the liquid catalyst on liquefied gas mercaptan. The catalyst active component tetra-beta-p-sulfonic phenoxy phthalocyanine cobalt has extremely good solubility in water and alkali liquids, and has higher mercaptan removal activity.
Description
Technical field
The invention belongs to PETROLEUM PROCESSING field, be specifically related to the application of a kind of liquid cobalt sulfonated phthalocyanine catalyst in liquid gas sweetening technique.
Background technology
Containing harmful components such as mercaptan in liquefied petroleum gas (LPG), because mercaptan has corrosivity, and the smell that gives out a foul smell, if do not removed, considerable influence can be produced to the following process of environment and liquefied gas.At present, the refining main employing Merox extracting-liquid phase catalytic oxidation technique of LPG removal of mercaptans or tunica fibrosa doctor process.The principle that these two kinds of techniques remove mercaptan in liquefied gas is substantially identical, first the mercaptan in liquefied gas is via catalyst-caustic extraction, then under the existence of oxygen and catalyst, the sodium mercaptides in extract is converted into disulphide, alkali lye and catalyst are regenerated simultaneously, and total chemical equation is:
In above-mentioned two kinds of LPG doctor processes, all need in advance by catalyst dissolution in alkali lye, obtain catalyst-alkali lye.But current normally used solid sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt catalyst dissolubility in alkali lye poor, affect the dispersion of catalyst in alkali lye, thus reduce the catalytic conversion efficiency of mercaptan in LPG doctor process, cause the waste of catalyst.
For improving the dissolubility of metal phthalocyanine catalyst in alkali lye, the phthalocyanine derivates of software engineering researchers invent sulfonate or carboxylate is as the deodorization catalyst of light petroleum fraction, and the better catalytic activity of cobalt phthalocyanine and vanadyl phthalocyanine.Patent US 4885268 discloses the preparation method of four sulfonated phthalocyanine cobalts, and prepared four sulfonated phthalocyanine cobalts dissolubility in aqueous improves, but its catalytic oxidation thiol active is poor relative to two sulfonated phthalocyanine cobalts.Liquid-liquid deodorization catalyst that patent US 4248694 discloses single sulfonation, the mixed liquor of two sulfonation and four sulfonated phthalocyanine cobalts is used as light petroleum fraction, the activity of catalyst makes moderate progress, but because the low-solubility of single sulfonated phthalocyanine cobalt, the dissolubility making single sulfonation, two sulfonation and four sulfonated phthalocyanine cobalt mixtures total is still poor.
Patent US 6740619 discloses the preparation of Cobalt Phthalocyanine and the application in LPG deodorizing technology thereof of sulfanilamide (SN) replacement, with chlorosulfonic acid, Cobalt Phthalocyanine and ammonia are the Cobalt Phthalocyanine that the water-soluble four higher sulfanilamide (SN) of Material synthesis replace, its catalytic activity and stability suitable with industrial catalyst, but raw material chlorosulfonic acid has severe corrosive, dangerous large.
Patent CN 103755713A discloses a kind of preparation method and application thereof of eight sulfonic phthalocyanin; adopt the method synthesis title complex of large point of alite protection; be easy to separation and purification; this sulfonation's phthalocyanin metalic has higher water-soluble; can be used as sensitising agent, photodynamics medicament or photosensitive medicament; but this water-soluble metal phthalocyanine complex structure, preparation cost is high, and fails used as petroleum fraction desulfuration alcohol catalyst.
At present, although existing various metals phthalocyanine derivates is used for the report of petroleum fraction desulfuration alcohol technique, the problems such as the poorly soluble or activity of catalyst ubiquity is not high, therefore, the LPG mercaptan-eliminating catalyst of exploitation high activity and highly dissoluble is very necessary.
Summary of the invention
To be solved by this invention is the problem of existing petroleum gas sweetening catalyst solubility difference, and object is to provide a kind of liquid metals sulfonated phthalocyanine catalyst and the application in liquid gas sweetening.This liquid metals sulfonated phthalocyanine composition catalyst and water and alkali lye have good intersolubility, the advantages such as good stability, and it is active to have higher liquid gas sweetening.
The present invention adopts following technical scheme:
Cobalt sulfonated phthalocyanine complex provided by the invention, can called after four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine or 2 (3), 9 (10), 16 (17), 23 (24)-four-(4-sulfonic group-1-phenoxy group) Cobalt Phthalocyanines, its structure is designed first by the present invention, and its structural formula is as follows:
Wherein, substituted radical is all in the peripheral position of phthalocyanine ring, is called β position, i.e. 2 (3), 9 (10), 16 (17), 23 (24) positions, and R represents substituted radical
complex called after 2 (3), 9 (10), 16 (17), 23 (24)-four-(4-sulfonic group-1-phenoxy group) Cobalt Phthalocyanines, or be called four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine.
Four-β of the present invention-p-sulfonic acid phenoxyl cobaltphthalocyanines can be used as the active component of petroleum gas sweetening liquid catalyst, there is highly-water-soluble and alkali solubility, solve conventional industrial solid sulfonated phthalocyanine cobalt or the poorly soluble problem of poly-phthalocyanine cobalt catalyst, and it is active to have excellent removal of mercaptans.
The method that liquid cobalt sulfonated phthalocyanine catalyst of the present invention is used for petroleum gas sweetening is:
(1) preparation of liquid catalyst: with a small amount of water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine, add appropriate 5 ~ 15%NaOH solution again, add a certain amount of stabilizing agent and emulsifying agent, shake up, four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content is made to be 5 ~ 25%, stabilizing agent (one of Propylene Glycol Dimethyl Ether, N methyldiethanol amine or triethanolamine or compound) content is 0.5 ~ 1.5%, and emulsifying agent (stearyl dimethyl benzyl ammonium chloride) content is 0.5% ~ 1%.
(2) liquid catalyst of the present invention as the evaluation method of petroleum gas sweetening catalyst is: the key of liquefied petroleum gas thiols conversion catalyst is the catalytic conversion efficiency to sodium mercaptides, in order to evaluate the performance of catalyst of the present invention widely, first mix with appropriate 5 ~ 25%NaOH solution with liquid catalyst of the present invention, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 50 ~ 200 μ g/g, then in a certain amount of above-mentioned catalyst-alkali lye mixed liquor, add the sodium mercaptides solution of dissimilar variable concentrations, 40 DEG C of constant temperature stir, pass into the catalytic oxidation that air carries out sodium mercaptides, Potential Titration Analysis is carried out every sampling in 5 minutes, calculate the removal efficiency of mercaptan sulfur, thus the activity of catalyst of the present invention is evaluated.
Or, first mix with appropriate 5 ~ 25%NaOH solution with liquid catalyst of the present invention, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 50 ~ 200 μ g/g, then the liquefied petroleum gas that a certain amount of above-mentioned catalyst-alkali lye mixed liquor extracting contains mercaptan is got, agent hydrocarbon is than being 1:10 ~ 100, and extract is the sodium mercaptides catalyst alkali lye containing variable concentrations.This extract stirs at 40 DEG C of constant temperature, pass into air, carry out catalytic oxidation desulfurization alcohol, carry out Potential Titration Analysis every sampling in 5 minutes, calculate the removal efficiency of mercaptan sulfur, thus evaluate with the activity of liquefied petroleum gas to catalyst of the present invention containing mercaptan of reality.
Mercaptan removal rate calculates by formula (1):
X%=(C
0-C
1) × 100/C
0formula (1)
In formula:
The removal efficiency of X%-mercaptan sulfur;
C
0mercaptan sulfur concentration before-catalytic reaction, ppm;
C
1mercaptan sulfur concentration after-catalytic reaction, ppm.
The advantage that liquid cobalt sulfonated phthalocyanine composition catalyst of the present invention is used for petroleum gas sweetening is:
(1) sulfonation's phthalocyanin metalic complex active component of the present invention, phthalocyanine ring introduces four p-sulfonic acid phenoxyls, is prepared into tetrasulfonic acid base substituted phthalocyanine, water-soluble, alkali solubility is fabulous, can high degree of dispersion in alkali lye.
(2) preparation method of liquid catalyst of the present invention is simple, is easy to operation.
(3) liquid catalyst of the present invention has higher removal of mercaptans activity.
Accompanying drawing explanation
Fig. 1 is the conversion ratio contrast of two kinds of catalyst removal propanethiol sulphur, a catalyst of the present invention, the industrial solid cobalt sulfonated phthalocyanine of b.
Detailed description of the invention
Embodiment 1
Test the four-β of the present invention-solubility of p-sulfonic acid phenoxyl cobaltphthalocyanines respectively in water and 10%NaOH solution, and contrast with the solubility of the solid sulfonated phthalocyanine cobalt of current industrial use, the results are shown in table 1.
The solubility of table 1 cobalt phthalocyanine of the present invention in water and alkali lye also contrasts with solid sulfonated phthalocyanine cobalt
Application examples 2
With 1mL deionized water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.25g, add 10%NaOH solution 3.70g, add 0.025g stabilizing agent Propylene Glycol Dimethyl Ether, 0.025g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 5%, stabiliser content is 0.5%, and emulsifier content is 0.5%.Get this liquid catalyst 0.10g to join in 100g 5%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 50 μ g/g.Get the above-mentioned catalyst solution of 30mL, add micro-high concentration ethyl mercaptan sodium solution, make mercaptan sulfur concentration about 100 μ gg in reactant liquor
-1, 40 DEG C of constant temperature stir, and pass into air, react 50 minutes, mercaptan sulfur removal efficiency is 92.5%.
Application examples 3
With 2mL deionized water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.50g, add 5%NaOH solution 2.40g, add 0.050g stabilizing agent N methyldiethanol amine, 0.050g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 10%, stabiliser content is 1%, and emulsifier content is 1%.Get this liquid catalyst 0.10g to join in 100g 10%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 100 μ g/g.Get the above-mentioned catalyst solution of 30mL, add micro-high concentration ethyl mercaptan sodium solution, make mercaptan sulfur concentration about 120 μ gg in reactant liquor
-1, 40 DEG C of constant temperature stir, and pass into air, react 50 minutes, mercaptan sulfur removal efficiency is 95.8%.
Application examples 4
With 3mL deionized water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 1.25g, add 15%NaOH solution 0.625g, add 0.075g stabilizing agent triethanolamine, 0.050g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 25%, stabiliser content is 1.5%, and emulsifier content is 1%.Get this liquid catalyst 0.080g to join in 100g25%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 200 μ g/g.Get the above-mentioned catalyst solution of 30mL, add micro-high concentration propanethiol sodium solution, make mercaptan sulfur concentration about 120 μ gg in reactant liquor
-1, 40 DEG C of constant temperature stir, and pass into air, react 50 minutes, mercaptan sulfur removal efficiency is 98.8%.
Application examples 5
With 1mL water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.30g, add 12%NaOH solution 2.60g, add stabilizing agent triethanolamine 0.025g, Propylene Glycol Dimethyl Ether 0.050g, 0.025g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 6%, stabilizing agent total content is 1.5%, and emulsifier content is 0.5%.Get this liquid catalyst 0.200g to join in 100g 20%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 120 μ g/g.Get the above-mentioned catalyst solution of 30mL, add micro-high concentration butyl mercaptan sodium solution, make mercaptan sulfur concentration about 60 μ gg in reactant liquor
-1, 40 DEG C of constant temperature stir, and pass into air, react 50 minutes, mercaptan sulfur removal efficiency is 97.0%.
Application examples 6
With 1mL water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.30g, add 8%NaOH solution 2.60g, add stabilizing agent triethanolamine 0.025g, N methyldiethanol amine 0.050g, 0.025g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 6%, stabilizing agent total content is 1.5%, and emulsifier content is 0.5%.Get this liquid catalyst 0.200g to join in 100g 20%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 120 μ g/g.Get the above-mentioned catalyst solution of 30mL, add micro-high concentration butyl mercaptan sodium solution, make mercaptan sulfur concentration about 60 μ gg in reactant liquor
-1, 40 DEG C of constant temperature stir, and pass into air, react 50 minutes, mercaptan sulfur removal efficiency is 97.3%.
Application examples 7
With 1.5mL water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine 0.80g, add 5%NaOH solution 2.625g, add 0.040g stabilizing agent triethanolamine, 0.035g emulsifying agent stearyl dimethyl benzyl ammonium chloride, shakes up, and makes four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine content be 16%, stabiliser content is 0.8%, and emulsifier content is 0.7%.Get this liquid catalyst 0.100g to join in 100g 15%NaOH solution, controlling catalyst activity concentration of component in this catalyst-alkali lye mixed liquor is 160 μ g/g.Then liquefied petroleum gas (the mercaptan sulfur concentration about 40 μ gg that a certain amount of above-mentioned catalyst-alkali lye mixed liquor extracting contains mercaptan is got
-1), agent hydrocarbon is than being 1:20, and stirred at 40 DEG C of constant temperature by extract, pass into air, carry out catalytic oxidation desulfurization alcohol, react 50 minutes, mercaptan sulfur removal efficiency is 96.6%.
Comparison study example
With propanethiol sodium solution (sulfur content about 100 μ gg
-1) be model compound, controlling Kaolinite Preparation of Catalyst of the present invention, equal with the concentration of cobalt ions of solid cobalt sulfonated phthalocyanine in reaction system (cobalt ions is concentration about 10 μ gg in reaction system
-1), under the same terms, catalytic reaction is after 50 minutes, and the removal of mercaptans contrasting catalyst of the present invention and industrial solid cobalt sulfonated phthalocyanine is active, and result such as Fig. 1 shows.Be the conversion ratio contrast of two kinds of catalyst removal propanethiol sulphur in figure, a catalyst of the present invention, the industrial solid cobalt sulfonated phthalocyanine of b.
Catalyst of the present invention is used as LPG mercaptan-eliminating catalyst, has higher catalytic activity, and it is active suitable with industrial solid cobalt sulfonated phthalocyanine.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (8)
1., for a petroleum gas sweetening liquid cobalt sulfonated phthalocyanine catalyst, be made up of active component four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine, stabilizing agent, emulsifying agent and NaOH solution.
2. liquid catalyst activity component as claimed in claim 1 is for having highly-water-soluble and an alkali-soluble cobalt sulfonated phthalocyanine complex, it is characterized in that: it is as follows that the present invention designs its structure first:
Wherein, R represents substituted radical
substituted radical is all in the peripheral position of phthalocyanine ring, be called β position, namely 2 (3), 9 (10), 16 (17), 23 (24) positions, called after 2 (3), 9 (10), 16 (17), 23 (24)-four-(4-sulfonic group-1-phenoxy group) cobaltphthalocyanines, or be called four-β-p-sulfonic acid phenoxyl cobaltphthalocyanines.
3. liquid catalyst according to claim 1, its stabilizing agent is one or the compound of Propylene Glycol Dimethyl Ether, N methyldiethanol amine or triethanolamine.
4. liquid catalyst according to claim 1, its emulsifying agent is stearyl dimethyl benzyl ammonium chloride.
5. liquid catalyst according to claim 1, it is also made up of NaOH solution.
6. according to claim 2,3,4,5, it is characterized in that the preparation method of liquid catalyst: with a small amount of water for solvent, dissolve four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine, then add appropriate NaOH solution, add a certain amount of stabilizing agent and emulsifying agent, shake up.
7. according to claim 6, it is characterized in that: in liquid catalyst, the mass concentration of four-β-p-sulfonic acid phenoxyl Cobalt Phthalocyanine is 5 ~ 25%, and stabiliser content is 0.5 ~ 1.5%, and emulsifier content is 0.5% ~ 1%, all the other are NaOH solution, and the mass concentration of NaOH solution is 5 ~ 15%.
8. an application for liquid cobalt sulfonated phthalocyanine composition catalyst as claimed in claim 1, is characterized in that: described liquid cobalt sulfonated phthalocyanine catalyst is used for liquid gas sweetening technique.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510117502.7A CN104785296B (en) | 2015-04-17 | 2015-04-17 | A kind of liquid cobalt sulfonated phthalocyanine catalyst for petroleum gas sweetening |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510117502.7A CN104785296B (en) | 2015-04-17 | 2015-04-17 | A kind of liquid cobalt sulfonated phthalocyanine catalyst for petroleum gas sweetening |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104785296A true CN104785296A (en) | 2015-07-22 |
| CN104785296B CN104785296B (en) | 2017-03-08 |
Family
ID=53550750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510117502.7A Expired - Fee Related CN104785296B (en) | 2015-04-17 | 2015-04-17 | A kind of liquid cobalt sulfonated phthalocyanine catalyst for petroleum gas sweetening |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104785296B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212216A (en) * | 2017-12-05 | 2018-06-29 | 中国石油天然气股份有限公司长庆石化分公司 | A kind of more cobalt sulfonated phthalocyanines for petroleum gas sweetening |
| CN108579812A (en) * | 2018-04-18 | 2018-09-28 | 山东澳润化工科技有限公司 | A kind of compound desulfuration of liquefied gas catalyst and its preparation method |
| CN110724150A (en) * | 2019-10-29 | 2020-01-24 | 武汉科林精细化工有限公司 | Preparation method of liquid binuclear cobalt phthalocyanine ammonium sulfonate desulfurization catalyst |
| CN114956118A (en) * | 2022-04-08 | 2022-08-30 | 大连理工大学 | Method for reducing nitrogen into ammonia by visible light photocatalysis |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805562A (en) * | 1956-03-14 | 1958-12-10 | Ici Ltd | New phthalocyanine compounds |
| US4803170A (en) * | 1985-05-09 | 1989-02-07 | Ultra Diagnostics Corporation | Competitive immunoassay method, device and test kit |
| CN1267238A (en) * | 1997-06-20 | 2000-09-20 | 卡内基梅隆大学 | Homogeneous oxidation catalyst using metal complexes |
| JP2002212471A (en) * | 2001-01-17 | 2002-07-31 | Canon Inc | Ink, color filter and its manufacturing method, liquid crystal panel, computer and image display device |
| CN1935378A (en) * | 2006-11-07 | 2007-03-28 | 北京三聚环保新材料有限公司 | Method for preparing catalyst for converting mercaptan in gasoline |
| CN1935377A (en) * | 2006-11-07 | 2007-03-28 | 北京三聚环保新材料有限公司 | Method for preparing catalyst for converting mercaptan in liquefied gas |
| US20120068123A1 (en) * | 2009-05-26 | 2012-03-22 | Basf Se | Use of phthalocyanine compounds with aryl or hetaryl substituents in organic solar cells |
-
2015
- 2015-04-17 CN CN201510117502.7A patent/CN104785296B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB805562A (en) * | 1956-03-14 | 1958-12-10 | Ici Ltd | New phthalocyanine compounds |
| US4803170A (en) * | 1985-05-09 | 1989-02-07 | Ultra Diagnostics Corporation | Competitive immunoassay method, device and test kit |
| CN1267238A (en) * | 1997-06-20 | 2000-09-20 | 卡内基梅隆大学 | Homogeneous oxidation catalyst using metal complexes |
| JP2002212471A (en) * | 2001-01-17 | 2002-07-31 | Canon Inc | Ink, color filter and its manufacturing method, liquid crystal panel, computer and image display device |
| CN1935378A (en) * | 2006-11-07 | 2007-03-28 | 北京三聚环保新材料有限公司 | Method for preparing catalyst for converting mercaptan in gasoline |
| CN1935377A (en) * | 2006-11-07 | 2007-03-28 | 北京三聚环保新材料有限公司 | Method for preparing catalyst for converting mercaptan in liquefied gas |
| US20120068123A1 (en) * | 2009-05-26 | 2012-03-22 | Basf Se | Use of phthalocyanine compounds with aryl or hetaryl substituents in organic solar cells |
Non-Patent Citations (1)
| Title |
|---|
| GAUTAM DAS等: "Synthesis, characterization and catalytic activity of cobalt phthalocyanine tetrasulphonamide in sweetening of LPG", 《CATALYSIS TODAY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212216A (en) * | 2017-12-05 | 2018-06-29 | 中国石油天然气股份有限公司长庆石化分公司 | A kind of more cobalt sulfonated phthalocyanines for petroleum gas sweetening |
| CN108212216B (en) * | 2017-12-05 | 2020-11-20 | 中国石油天然气股份有限公司长庆石化分公司 | Poly-sulfonated cobalt phthalocyanine catalyst for liquefied petroleum gas sweetening |
| CN108579812A (en) * | 2018-04-18 | 2018-09-28 | 山东澳润化工科技有限公司 | A kind of compound desulfuration of liquefied gas catalyst and its preparation method |
| CN108579812B (en) * | 2018-04-18 | 2020-11-06 | 山东澳润化工科技有限公司 | Composite liquefied gas desulfurizing catalyst and its preparing process |
| CN110724150A (en) * | 2019-10-29 | 2020-01-24 | 武汉科林精细化工有限公司 | Preparation method of liquid binuclear cobalt phthalocyanine ammonium sulfonate desulfurization catalyst |
| CN110724150B (en) * | 2019-10-29 | 2021-07-16 | 武汉科林化工集团有限公司 | Preparation method of liquid binuclear cobalt phthalocyanine ammonium sulfonate desulfurization catalyst |
| CN114956118A (en) * | 2022-04-08 | 2022-08-30 | 大连理工大学 | Method for reducing nitrogen into ammonia by visible light photocatalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104785296B (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104785296A (en) | Liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal | |
| Lü et al. | Deep catalytic oxidative desulfurization (ODS) of dibenzothiophene (DBT) with oxalate-based deep eutectic solvents (DESs) | |
| CN101513584B (en) | New method for desulfurization by oxidation based on alkaline ionic liquid catalyst | |
| CN113166049A (en) | Oxidized disulfide oil solvent compositions | |
| EP2970795B1 (en) | Process for removing sulphur compounds from hydrocarbons | |
| US7914669B2 (en) | Reactive extraction of sulfur compounds from hydrocarbon streams | |
| CN104117275B (en) | The method of one-step method process sulfide hydrogen and ammonia gaseous mixture | |
| CN103347587A (en) | Process for removing mercaptans from a gas stream | |
| Tao et al. | Oxidative desulfurization by oxygen using amphiphilic quaternary ammonium peroxovanadium polyoxometalates | |
| CN104789290A (en) | Method for deep desulfurization of liquefied petroleum gas | |
| CN102218260B (en) | Absorbent used for removing sulfides in malodorous gases | |
| CN106433835A (en) | Oil-gas desulfurizing agent and application | |
| RU2230096C1 (en) | Method of removing sulfur compounds from light hydrocarbon fractions | |
| CN105195222B (en) | A kind of eight carboxyl phthalocyanine cobalt catalysts for selexol process alcohol | |
| Zhan et al. | Kinetics of catalytic oxidation of sodium ethyl mercaptide | |
| CN105688645A (en) | Ultrahigh-sulfur-capacity desulfurizing agent as well as preparation method and application of ultrahigh-sulfur-capacity desulfurizing agent | |
| CN104371781B (en) | The sulfur method of liquefied petroleum gas and device | |
| CN105126768A (en) | Light-weight oil desulfurizing agent based on supra-molecular inclusion effect and application method thereof | |
| CN104371786B (en) | Alkali lye desulfurization method and device of liquefied petroleum gas | |
| CN108212216A (en) | A kind of more cobalt sulfonated phthalocyanines for petroleum gas sweetening | |
| Ahmed et al. | Efficient non-catalytic oxidative and extractive desulfurization of liquid fuels using ionic liquids | |
| CN110819378B (en) | Method for removing organic sulfur in liquid hydrocarbon | |
| Akopyan et al. | Extraction of mercaptans from light hydrocarbon mixtures with aqueous ammonia | |
| CN104371782A (en) | Liquefied petroleum gas alkali solution desulfurization method and device | |
| CN114699882B (en) | Ether amine compound for efficiently absorbing and removing organic sulfur compound, and design method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170308 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |