CN1042636C - Preparation method of cobalt phthalocyanine sulfonate desulfurizer - Google Patents
Preparation method of cobalt phthalocyanine sulfonate desulfurizer Download PDFInfo
- Publication number
- CN1042636C CN1042636C CN95102638A CN95102638A CN1042636C CN 1042636 C CN1042636 C CN 1042636C CN 95102638 A CN95102638 A CN 95102638A CN 95102638 A CN95102638 A CN 95102638A CN 1042636 C CN1042636 C CN 1042636C
- Authority
- CN
- China
- Prior art keywords
- sulfonate
- preparation
- phthalic anhydride
- intermediate product
- cobalt phthalocyanine
- 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.)
- Expired - Fee Related
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 12
- 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 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000013067 intermediate product Substances 0.000 claims abstract description 9
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004202 carbamide Substances 0.000 claims abstract description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract 1
- 125000001741 organic sulfur group Chemical group 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 235000003599 food sweetener Nutrition 0.000 description 10
- 239000003765 sweetening agent Substances 0.000 description 10
- 239000003513 alkali Substances 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class 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 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of cobalt phthalocyanine sulfonate, which comprises the steps of carrying out sulfonation reaction on phthalic acid under the action of concentrated sulfuric acid to generate phthalic anhydride sulfonate, separating and concentrating to obtain a solid intermediate product, and adding calcium oxide, cobalt chloride and urea into the intermediate product to carry out condensation reaction to obtain the cobalt phthalocyanine sulfonate. The invention has simple process and convenient operation, and the product has high activity, high selectivity, high solubility, easy regeneration and long service cycle, can simultaneously remove organic sulfur and inorganic sulfur, and has the desulfurization rate of more than 98 percent.
Description
The present invention relates to a kind of preparation method of sweetening agent, the preparation of special phthalocyanine cobalt sulfonate belongs to the Sulfonates synthesis technical field.
Coal and oil are the basic raw materials of Chemical Manufacture; and all contain a certain amount of sulphur (comprising organosulfur and inorganic sulfur); when being that raw material production water-gas is when synthesizing other products with them; must the composition of institute's sulfur-bearing be removed by quality index; desulfurization itself promptly protected equipment; also protected physical environment; at present; the sulfur method that adopts in China's Chemical Manufacture mainly is: APA; MSQ; methods such as gac and oxidation molecular sieve, aforesaid method can only remove inorganic sulfur, can not remove organosulfur; though; recent development goes out to gather metal phthalocyanine compounds such as phthalocyanine cobalt and is used for organic sulfide removal, but still shortcoming such as it is little to exist solubleness, and desulfuration efficiency is low.
The object of the present invention is to provide a kind of sweetening agent preparation method, its product is organic sulfide removal and inorganic sulfur simultaneously, has high reactivity, highly selective, characteristics such as it is easy to regenerate.
Task of the present invention is finished like this: make Tetra hydro Phthalic anhydride carry out sulfonation reaction under the strong acid effect, generate Tetra hydro Phthalic anhydride sulfonate, separate then to concentrate and obtain solid intermediate product, with intermediate product add calcium oxide/cobalt chloride and urea under 180 ℃ through condensation reaction, promptly generate phthalocyanine cobalt sulfonate.
The sweetening agent molecular formula of the present invention's preparation is:
C
32H
12O
12N
8CoNa
2Ca
2CL
2
Molecular weight is 1085, and the aperture is 0.2 millimeter, deep blue green crystallite, sweetening power 〉=300 grams.Structural formula is:
Adopt the present invention to prepare sweetening agent, technology is simple, and is easy to operate, its product has high reactivity, highly selective, and solubleness is big, regeneration easily, life cycle is long, simultaneously organic sulfide removal and inorganic sulfur, nontoxicity, etching apparatus not, desulphurization cost is low, be used for wet desulphurization factory, need do not change former technical process and increase equipment, desulfurization degree can reach more than 98%.
Further narrate the present invention below in conjunction with embodiment:
Embodiment 1:
Get Tetra hydro Phthalic anhydride 320 grams, the vitriol oil 100 grams, sodium sulfate 32 grams, 200 ℃ of following sulfonation reactions 10 hours, add 20 gram calcium oxide separation then and obtain the sulfonation intermediate product, get intermediate product 200 grams, urea 200 grams again, cobalt chloride 40 grams generate phthalocyanine cobalt sulfonate through condensation reaction under 180 ℃, product is deep blue green crystallite.
Embodiment 2:
With Tetra hydro Phthalic anhydride 320 grams, the vitriol oil 100 gram was 160～230 ℃ of following sulfonation reactions 10 hours, separate then to concentrate and obtain solid intermediate product, get intermediate product 200 gram, urea 200 grams, cobalt chloride 40 grams, calcium oxide 20 grams, sodium sulfate 32 grams again and generate phthalocyanine cobalt sulfonate through condensation reaction under 180 ℃, product is blue green crystallite.
Embodiment 3:
The sodium hydroxide alkaline solution of preparation 8-17% concentration, adding sweetening agent is that the content 100PPm of system recycles, treated gasoline doctor test percent of pass is low before using sweetening agent, the alkali lye usage period is short, treated gasoline doctor test percent of pass obviously is increased to more than 60% after adding sweetening agent, the corresponding prolongation of alkali lye life cycle, its detailed sweetening effectiveness sees the following form:
| Project | Concentration of lye % | Alkali lye amount M | The gasoline doctor test is by degree % | Steam-operating mercaptans content PPm | The alkali lye life cycle (my god) |
| Before adding sweetening agent | 8-10 | 15 | 10 | 8-15 | 25-30 |
| After adding sweetening agent | 8-10 | 15 | ＞60 | ＜5 | 10-35 |
Claims (1)
1, a kind of preparation method of phthalocyanine cobalt sulfonate, it is characterized in that: under vitriol oil effect, make Tetra hydro Phthalic anhydride carry out sulfonation reaction, generate Tetra hydro Phthalic anhydride sulfonate, wherein the ratio of Tetra hydro Phthalic anhydride, the vitriol oil, sodium sulfate is 320: 100: 32, temperature of reaction is 160 ℃-230 ℃, carry out sulfonation reaction, add then 20 parts in calcium oxide separate the sulfonation intermediate product, get its 200 parts again and add 40 parts in 200 parts in urea, cobalt chloride 180 ℃ of following condensation reactions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95102638A CN1042636C (en) | 1995-03-11 | 1995-03-11 | Preparation method of cobalt phthalocyanine sulfonate desulfurizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95102638A CN1042636C (en) | 1995-03-11 | 1995-03-11 | Preparation method of cobalt phthalocyanine sulfonate desulfurizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1117049A CN1117049A (en) | 1996-02-21 |
| CN1042636C true CN1042636C (en) | 1999-03-24 |
Family
ID=5074417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95102638A Expired - Fee Related CN1042636C (en) | 1995-03-11 | 1995-03-11 | Preparation method of cobalt phthalocyanine sulfonate desulfurizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1042636C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116637656A (en) * | 2023-05-15 | 2023-08-25 | 南京金炼科技有限公司 | Catalyst for regenerating high-efficiency sulfur-containing alkali liquor and preparation process |
Citations (1)
| 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 |
-
1995
- 1995-03-11 CN CN95102638A patent/CN1042636C/en not_active Expired - Fee Related
Patent Citations (1)
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1117049A (en) | 1996-02-21 |
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