CN1063152C - Purifying method with organosulfur conversion - Google Patents
Purifying method with organosulfur conversion Download PDFInfo
- Publication number
- CN1063152C CN1063152C CN98113477A CN98113477A CN1063152C CN 1063152 C CN1063152 C CN 1063152C CN 98113477 A CN98113477 A CN 98113477A CN 98113477 A CN98113477 A CN 98113477A CN 1063152 C CN1063152 C CN 1063152C
- Authority
- CN
- China
- Prior art keywords
- conversion
- organic sulfur
- sulfur
- hydrolyst
- organosulfur
- 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 - Lifetime
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 125000001741 organic sulfur group Chemical group 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 6
- 230000009466 transformation Effects 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 101000938681 Mus musculus Carboxylesterase 1F Proteins 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000009977 dual effect Effects 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AIOXPJUKHIPDKC-UHFFFAOYSA-N [C].[O].[S] Chemical compound [C].[O].[S] AIOXPJUKHIPDKC-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 methanation Chemical compound 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a purifying method with conversion and organic sulfur conversion. In a shift converter, organic sulfur hydrolyst is placed at the middle or the bottom of conversion catalysts; thereby, the organic sulfur content is decreased by about 90%; during the conversion, COS of the organic sulfur at the outlet is lowered to be below 1 ppm. The effect of the present invention is equivalent to the effect that a new desulphurization working section is additionally arranged; the present invention reduces the investment, and has the dual functions of conversion and organic sulfur conversion.
Description
The present invention relates to a kind of purifying method of synthesis ammonia plant, have the dual-use function that the organosulfur conversion is held concurrently in conversion.With coal and heavy oil is the synthesis ammonia plant of raw material, in its unstripped gas is to contain more various forms of organosulfurs in the semi-water gas, and it is H2S that this part organosulfur major part after semiwater gas desulphurizing, conversion has been converted into inorganic sulfur.But still have a spot of organosulfur, its principal mode is an oxygen sulphur carbon (COS), is generally 3～10ppm, and follow-up workshop section of process such as carbonization, dry method are taken off H
2S, wet method are taken off H
2Behind the S, still contain 2～5ppm, this works the mischief to the catalyzer in the follow-up workshop section such as methyl alcohol, methanation, ammonia synthesis catalyst, shortens its work-ing life.
Transform organosulfur for the head it off synthesis ammonia plant adopts such as ways such as organosulfur cobalt molybdenum hydrogenation, tempreture organic sulphur hydrolysis, low-temperature rectisol, liquid nitrogen washing usually behind conversion section, make the organosulfur＜0.3ppm of outlet, generally between 0.1～0.5ppm.These methods all will be set up a new desulfurization workshop section, increase investment, and investment is also very big sometimes.
The objective of the invention is in order to overcome the deficiency of aforesaid method, provide a kind of set transformation and tempreture organic sulphur hydrolysis function in the method for one, the best makes the organosulfur＜0.3ppm of outlet, generally between 0.1～0.5ppm, and need not increase new desulfurization workshop section, need not increase equipment and investment.
The objective of the invention is to adopt following method to realize, a kind of conversion purifying method that organosulfur transforms of holding concurrently, adopt the transformation catalyst product in the shift converter, transformation catalyst adopts the spherical sulphur resisting and low temp conversing catalyzer of B302Q, the spherical sulfur-resistant transformation catalyst of B303Q (Co-Mo sulfur-tolerant shift catalyst that the Hubei Prov. Chemical Research Inst produces), organic sulfur hydrolyst is placed in middle part or bottom in transformation catalyst in shift converter, hydrolytic catalyst of carbonyl sulfur 851-1 (northwest chemical industry research institute Kunshan joins pure factory and produces), hydrolytic catalyst of carbonyl sulfur TGH-2 (TaiYuan Industry University's product), T504 type normal tempreture organic sulphur hydrolysis catalyst (Hubei Prov. Chemical Research Inst production) or employing have the extraordinary aluminum oxide of activity of conversion to make catalyzer.Decide according to temperature in the stove position of placing organic sulfur hydrolyst in shift converter, and the laying temperature zone is generally 180～380 ℃, is preferably 200～300 ℃, and the best is 220～240 ℃.
Organic sulfur hydrolyst 851-1, TGH-2, T504 and the extraordinary aluminium oxide catalyst of activity of conversion is arranged all is the commercially available prod are COS γ-Al
2O
3Be carrier, flooded the liquid metallic compound, add extraordinary stablizer and make.
Employing in the middle part of transformation catalyst or the bottom method of placing organic sulfur hydrolyst, makes the oxygen sulphur carbon (COS) in the coal gas with water vapor in the conversion gas following hydrolysis reaction take place in shift converter:
Thereby reduce the content about 90% of organosulfur, the organosulfur COS of outlet is dropped to below the 1ppm, greatly improved the catalyzer result of use in the follow-up workshop section, its effect is with to set up a new removal of organic sulfur from workshop section suitable.
The embodiment of factory
There is the transformation system of two cover same capabilities in certain factory, all adopts low temperature shifting process (is 90103262.X with application number), and the transformation catalyst filling is identical, pressure 0.8MPa, semi-water gas flow 18000NM
3/ h, the outlet carbon monoxide is 1.4%.First cover is unkitted organic sulfur hydrolyst, and second is enclosed within the low furnace bottom that becomes has adorned 5M
3The extraordinary aluminium oxide catalyst of tempreture organic sulphur hydrolysis, two cover analytical data are as follows: the initial stage data of driving: the first cover outlet COS is 2ppm
The second cover outlet COS is after 0.2ppm uses half a year: the first cover outlet COS is 3.1ppm
The second cover outlet COS is after 0.22ppm uses 1 year: the first cover outlet COS is 3.5ppm
The second cover outlet COS is a 0.21ppm laboratory implementation example
1. sulfur-resistant transformation catalyst 30ml, steam-to-gas ratio 1.0,180～380 ℃ of probe temperatures, semi-water gas flow 30000ml/h, pressure are normal pressure, the content of test outlet CO.
2. condition adds the organic sulfur hydrolyst of the extraordinary aluminum oxide of 5ml with 1 in the middle part of 180 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
3. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 180 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
4. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 200 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
5. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 220 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
6. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 240 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
7. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 260 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
8. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 280 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
9. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 300 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
10. condition adds the organic sulfur hydrolyst of 5ml T504 with 1 in the middle part of 320 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
11. condition with 1, adds the organic sulfur hydrolyst of 5ml T504 in the middle part of 340 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
12. condition with 1, adds the organic sulfur hydrolyst of 5ml T504 in the middle part of 360 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
13. condition with 1, adds the organic sulfur hydrolyst of 5ml T504 in the middle part of 380 ℃ of the probe temperatures, sulfur-resistant transformation catalyst.
Detected result under each condition
| The group number | Detected temperatures ℃ | Outlet CO%, outlet COS (ppm) | ||
| Do not add | T504 | Extraordinary aluminum oxide | ||
| 1 | 180 | 2.5 4.8 | 2.5 0.36 | 2.5 0.37 |
| 2 | 200 | 2.0 4.2 | 2.0 0.31 | |
| 3 | 220 | 1.6 2.2 | 1.6 0.23 | |
| 4 | 240 | 1.0 2.3 | 1.0 0.25 | |
| 5 | 260 | 0.8 1.8 | 0.8 0.36 | |
| 6 | 280 | 0.5 1.8 | 0.5 0.37 | |
| 7 | 300 | 0.3 1.7 | 0.3 0.37 | |
| 8 | 320 | 0.35 1.7 | 0.35 0.4 | |
| 9 | 340 | 0.39 1.7 | 0.39 0.4 | |
| 10 | 360 | 0.42 1.7 | 0.42 0.4 | |
| 11 | 380 | 0.45 1.7 | 0.45 0.4 | |
Claims (3)
1. the conversion purifying method that organosulfur transforms of holding concurrently, adopt the transformation catalyst product in the shift converter, transformation catalyst adopts the spherical sulphur resisting and low temp conversing catalyzer of B302Q, the spherical sulfur-resistant transformation catalyst of B303Q, it is characterized in that organic sulfur hydrolyst is placed in middle part or the bottom in transformation catalyst in the shift converter, organic sulfur hydrolyst adopts hydrolytic catalyst of carbonyl sulfur 851-1, hydrolytic catalyst of carbonyl sulfur TGH-2, T504 or employing to have the extraordinary aluminum oxide of activity of conversion to make catalyzer, 180-380 ℃ of organic sulfur hydrolyst regional temperature.
2. a kind of conversion as claimed in claim 1 purifying method that organosulfur transforms of holding concurrently is characterized in that 200～300 ℃ of organic sulfur hydrolyst regional temperatures.
3. a kind of conversion as claimed in claim 1 purifying method that organosulfur transforms of holding concurrently is characterized in that 220～240 ℃ of organic sulfur hydrolyst regional temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113477A CN1063152C (en) | 1998-03-20 | 1998-03-20 | Purifying method with organosulfur conversion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113477A CN1063152C (en) | 1998-03-20 | 1998-03-20 | Purifying method with organosulfur conversion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1195640A CN1195640A (en) | 1998-10-14 |
| CN1063152C true CN1063152C (en) | 2001-03-14 |
Family
ID=5223198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113477A Expired - Lifetime CN1063152C (en) | 1998-03-20 | 1998-03-20 | Purifying method with organosulfur conversion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1063152C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR066682A1 (en) | 2007-05-25 | 2009-09-02 | Shell Int Research | A PROCESS TO REMOVE SULFUR FROM FUEL GAS, LESS REAGENT AND MORE REAGENT CONTAINS CONTAINING ORGANIC SULFUR AND LIGHT OLEFINS |
| AR066680A1 (en) * | 2007-05-25 | 2009-09-02 | Shell Int Research | A PROCESS TO REMOVE SULFUR FROM A FUEL GAS CURRENT, WHICH ALSO CONTAINS CARBON DIOXIDE AND LIGHT OLEFINS |
| CN113265275A (en) * | 2021-05-31 | 2021-08-17 | 中冶东方工程技术有限公司 | Coke oven gas purification device and method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5613022A (en) * | 1979-07-14 | 1981-02-07 | Toyo Eng Corp | Gas desulfurizing method |
| JPS58150521A (en) * | 1982-03-03 | 1983-09-07 | Agency Of Ind Science & Technol | Method for removing carbonyl sulfide from gas containing olefin |
| CN1081424A (en) * | 1993-06-28 | 1994-02-02 | 湖北省化学研究所 | The constant temperature fine desulfurizing production technique |
-
1998
- 1998-03-20 CN CN98113477A patent/CN1063152C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5613022A (en) * | 1979-07-14 | 1981-02-07 | Toyo Eng Corp | Gas desulfurizing method |
| JPS58150521A (en) * | 1982-03-03 | 1983-09-07 | Agency Of Ind Science & Technol | Method for removing carbonyl sulfide from gas containing olefin |
| CN1081424A (en) * | 1993-06-28 | 1994-02-02 | 湖北省化学研究所 | The constant temperature fine desulfurizing production technique |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1195640A (en) | 1998-10-14 |
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| C06 | Publication | ||
| PB01 | Publication | ||
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| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HUASHUO SCIENCE CO., LTD. Free format text: FORMER OWNER: HUBEI PROV. CHEMICAL RESEARCH INST. Effective date: 20090605 |
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| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090605 Address after: No. 30 Guan Shan Road, Wuhan, Hubei, Wuchang Patentee after: Huashuo Technology Co., Ltd. Address before: No. 30 Guan Shan Road, Wuhan, Hubei, Wuchang Patentee before: Hubei Research Institute of Chemistry |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Purifying method with organosulfur conversion Effective date of registration: 20100907 Granted publication date: 20010314 Pledgee: Bank of Hankou, Limited by Share Ltd, Optics Valley branch Pledgor: Huashuo Technology Co., Ltd. Registration number: 2010990000869 |
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| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20151106 Granted publication date: 20010314 Pledgee: Bank of Hankou Limited by Share Ltd Optics Valley branch Pledgor: Huashuo Technology Co., Ltd. Registration number: 2010990000869 |
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| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PM01 | Change of the registration of the contract for pledge of patent right |
Change date: 20151106 Registration number: 2010990000869 Pledgee after: Bank of Hankou Limited by Share Ltd Optics Valley branch Pledgee before: Bank of Hankou, Limited by Share Ltd, Optics Valley branch |
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| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20010314 |