CN102000505A - Novel middle-temperature carbonyl sulfide hydrolysis method - Google Patents
Novel middle-temperature carbonyl sulfide hydrolysis method Download PDFInfo
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- CN102000505A CN102000505A CN 201010545447 CN201010545447A CN102000505A CN 102000505 A CN102000505 A CN 102000505A CN 201010545447 CN201010545447 CN 201010545447 CN 201010545447 A CN201010545447 A CN 201010545447A CN 102000505 A CN102000505 A CN 102000505A
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- hydrolyst
- protective agent
- carbonyl sulfide
- catalyst
- antitoxin
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Abstract
The invention relates to a novel middle-temperature carbonyl sulfide hydrolysis method which adopts a measure of placing an antitoxic protective agent on the top of cheap active alumina hydrolysis catalysts to achieve the antitoxic and deoxidation effect and to prevent the poisoning of the hydrolysis catalysts. Trace carbonyl sulfide (COS) in various kinds of chemical raw material gases can be hydrolyzed at a temperature of 150 DEG C to 320 DEG C, the process is simple, and the price of the adopted catalysts can be reduced by more than 50 percent compared with the traditional molybdenum-containing middle-temperature surfer resistance hydrolysis catalysts (EH-2 and EH-3 types produced by Hubei Chemical Research Institute).
Description
Technical field
The present invention relates to temperature (150 ℃～320 ℃) method for hydrolysis in the middle cos of a kind of material gas (as conversion gas, synthesis gas, water-gas, propylene, liquefied gas).
Background technology
The present invention relates to a kind of novel in warm carbonyl sulfide hydrolysis method, in the material gas of producing with oil, coal, Jiao (as conversion gas, synthesis gas, water-gas, propylene, liquefied gas), cos (COS) is main organic sulfur composition, and contain a small amount of water vapor (dew point of gas＞30 ℃), and most downstream section are responsive especially to sulphur, and Determination of Trace Sulfur can cause the downstream catalyst poisoning and inactivation in the raw material.The activated alumina of industrial employing hydrolysis function (or the various metallic compounds of modified aluminas even load are to improve activity) catalyst promotes the reaction that is hydrolyzed of cos and water vapour:
COS+H
2O=CO
2+H
2S
Connect again after reaction activated carbon, iron oxide or Zinc oxide desulfurizer removes the H of generation
2S is as Chinese patent 92104524.7,95111160.4,97125340.4,200410074539.8 etc.Since contain oxygen in its unstripped gas, when it is applied to middle warm 150 ℃～320 ℃ (this moment, its steam content often was higher than low temperature or ordinary-temp hydrolysis technology, favourable hydrolysis), the H of hydrolytic catalyst of carbonyl sulfur absorption
2S and oxygen reaction generate SO
2, sulfation occurs and poison, cause the active decline of hydrolyst.So the oxytolerant hydrolyst of temperature (150 ℃～320 ℃) in the exploitation then must solve catalyst surface sulfation poisoning problem.Developed a kind of deoxidation catalyst abroad the earliest, be placed on the top of aluminium oxide catalyst, anti-block contacts with aluminium oxide.Chinese patent 03818595.4 discloses a kind of O
2Remove the upstream side that catalyst is placed in hydrolytic catalyst of carbonyl sulfur, do not poison with the protection hydrolytic catalyst of carbonyl sulfur.It is to pass through 2H
2S+2CO+O
2=2COS+2H
2The deoxygenation of O mode.Said method is with O
2With inorganic sulfur (H
2S) react away, change into cos (COS) again, increased the import reactant concentration of downstream hydrolytic catalyst of carbonyl sulfur, thereby increased the conversion load of hydrolyst.And this O
2Remove catalyst for containing Cr
2O
3Cellular TiO
2Catalyst, hydrolytic catalyst of carbonyl sulfur are the TiO of baric
2Catalyst.Chinese patent 200710062492.7 has adopted a kind of by adding V
2O
5The method that (its quality percentage composition 8%～12%) changes the catalyst composition improves catalyst sulfate resistance voltinism energy.Domestic commercially availablely have EH-2, EH-3 type medium temperature hydrolyzation catalyst (Hubei Prov. Chemical Research Inst produce, and contains quality percentage mark 6%～11%MoO
3).Above-mentioned catalyst all exists preparation complexity, contained metal oxide more valuable (for combination catalyst of the present invention), the shortcoming that cost is high.T504 type hydrolyst (Hubei Prov. Chemical Research Inst production), though low price, the sulfation phenomenon if use, can take place in serviceability temperature low (≤150 ℃) under middle temperature (150 ℃～320 ℃) condition, its service life is short.
Summary of the invention
The object of the invention is to provide two kinds of catalyst combination that function is different, and hydrolytic catalyst of carbonyl sulfur is not poisoned, long service life, and do not increase the content of cos in the reactant, price is low, effective.
The present invention adopts at common, inexpensive hydrolyst top and places a kind of antitoxin protective agent (by Shuangxiong Catalyst Co., Ltd., Hubei's production, the patent No. be: ZL 200610125452.8), and it is to pass through 2H
2+ O
2=2H
2The deoxygenation of O mode, prevent that effectively hydrolyst poisons under middle temperature (150 ℃～320 ℃) condition.It is effective, price is low.Be placed on the common hydrolysis activated alumina and be used in combination, can be under 150 ℃～320 ℃ temperature conditions with various material gas in any traces of carbonyl sulfide (COS) hydrolysis, can be near the COS equilibrium conversion under actual condition, percent hydrolysis 〉=95%, promptly cos can be accomplished less than 0.1～3ppm.Can simplify fine desulfurizing technology greatly, needn't heat exchanger be set specially as low temperature or ordinary-temp hydrolysis technology and cool off, lower the temperature, heat up again ..., can directly go here and there in other workshop section.Convenient being suitable for avoided " malaria ", makes flow process simple.
The filling of activated alumina hydrolyst and antitoxin protective agent should be carried out under drying condition, avoids loading under the very big situation of rainy weather or ambient humidity, in order to avoid influence intensity.Before the loading catalyst, must be clean cleaning in the reactor earlier, with the grate plate installation in position, spread stainless steel cloth.
Reacting furnace should be established two sections and segmentation filling, attaches together one section as two kinds of catalyst, then must take off flat after, repave stainless steel cloth, flanging does not refill it.
The present invention is achieved in that
A kind of novel in warm carbonyl sulfide hydrolysis method, can under 150 ℃～320 ℃ conditions, be used for carbonyl sulfide hydrolysis, it is to be formed by two kinds of different catalyst combination of function, it is characterized in that adopting at the common, inexpensive hydrolyst top that is easy to get and place a kind of antitoxin protective agent, the product that described antitoxin protective agent adopts patent " preparation method of the counterpoison of protection cobalt molybdenum co surfer-resistant shift catalyst " to produce, its patent No. is ZL200610125452.8; Hydrolyst is traditional activated alumina cheap and easy to get.
A kind of novel in warm carbonyl sulfide hydrolysis method, it is characterized in that described antitoxin protective agent is a kind ofly can contain H
2Deoxidation catalyst under the S condition, it is by the mode of oxygen and hydrogen complete reaction oxygen to be removed.
A kind of novel in warm carbonyl sulfide hydrolysis method, the volume ratio that it is characterized in that described antitoxin protective agent and hydrolyst is 1:2～1:9, the best is 1:4.
Beneficial effect of the present invention:
1, provide a kind of common, inexpensive to be easy to get activated alumina as middle temperature (150 ℃～320 ℃) hydrolytic catalyst of carbonyl sulfur.Price is low.Prior art is the TiO that contains modified alumina catalysts such as molybdenum, vanadium or baric
2Catalyst.It prepares complicated, and contained metal oxide is more valuable, the cost height.
2, provide a kind of antitoxin protective agent, it is the product that adopts patent " preparation method of the counterpoison of protection cobalt molybdenum co surfer-resistant shift catalyst " to produce, and its patent No. is ZL200610125452.8.It is placed on the top of hydrolytic catalyst of carbonyl sulfur, hydrolytic catalyst of carbonyl sulfur is not poisoned, long service life.It is a kind ofly can contain H
2Deoxidation catalyst under the S condition is by the mode of oxygen and hydrogen complete reaction oxygen to be removed.And do not increase the content of cos in the reactant.Technology contains Cr for (1) now
2O
3Cellular TiO
2Catalyst, it is to pass through 2H
2S+2CO+O
2=2COS+2H
2The deoxygenation of O mode.Be with O
2With inorganic sulfur (H
2S) react away, change into cos (COS) again, increased the import reactant concentration of downstream hydrolytic catalyst of carbonyl sulfur, thereby increased the conversion load of hydrolyst.(2) contain noble metal (platinum, palladium etc.) deoxidation catalyst, though the deoxygenation mode is 2H
2+ O
2=2H
2O, but not anti-sulphur.
3, the best proportioning of antitoxin protective agent and hydrolyst is provided, effective.
Description of drawings
Fig. 1 is a warm carbonyl sulfide hydrolysis process schematic representation among the present invention.
The specific embodiment
Further specify below by comparative example and embodiment.
In the following embodiments, traditional activated alumina hydrolyst (spherical gamma-Al cheap and easy to get in the hydrolysis stove
2O
3Carrier, Jingjiang City, Jiangsu morning, sun chemical industry Co., Ltd produced) top places a kind of antitoxin protective agent (Shuangxiong Catalyst Co., Ltd., Hubei produces, the patent No. is: ZL 200610125452.8).
Comparative example
The laboratory comparative example carries out in glass reactor, and condition is a reaction tube diameter: 30mm, loadings: hydrolyst 30mL, catalyst grain size: diameter is the former particle sample of 4.0～5.0mm, normal pressure, air speed 2500h
-1, unstripped gas is formed (volume percentage mark): H
250%, CO 10%, CO
226%, O
20.5%, H
2S 6000ppm, COS 40ppm, surplus are water vapour, reaction temperature: 250 ℃, reaction time: 240h, unstripped gas measure the expression of its outlet COS content as its reactivity by the B catalyst, and test result sees Table 1.
Embodiment 1
The laboratory implementation example; in glass reactor, carry out; condition is a reaction tube diameter: 30mm; total filling amount: 30mL; antitoxin protective agent above hydrolyst, antitoxin protective agent and hydrolyst volume ratio 1:2, two kinds of catalyst grain sizes: diameter is the former particle sample of 4.0～5.0mm; normal pressure, air speed 2500h
-1, unstripped gas is formed (volume percentage mark): H
250%, CO 10%, CO
226%, O
20.5%, H
2S 6000ppm, COS 40ppm, surplus are water vapour, reaction temperature: 250 ℃, reaction time: 240h, unstripped gas measure the expression of its outlet COS content as its reactivity successively by antitoxin protective agent, hydrolyst, and test result sees Table 1.
Embodiment 2
The laboratory implementation example; in glass reactor, carry out; condition is a reaction tube diameter: 30mm; total filling amount: 30mL; antitoxin protective agent above hydrolyst, antitoxin protective agent and hydrolyst volume ratio 1:4, two kinds of catalyst grain sizes: diameter is the former particle sample of 4.0～5.0mm; normal pressure, air speed 2500h
-1, unstripped gas is formed (volume percentage mark): H
250%, CO 10%, CO
226%, O
20.5%, H
2S 6000ppm, COS 40ppm, surplus are water vapour, reaction temperature: 250 ℃, reaction time: 240h, unstripped gas measure the expression of its outlet COS content as its reactivity successively by antitoxin protective agent, hydrolyst, and test result sees Table 1.
Embodiment 3
The laboratory implementation example; in glass reactor, carry out; condition is a reaction tube diameter: 30mm; total filling amount: 30mL; antitoxin protective agent above hydrolyst, antitoxin protective agent and hydrolyst volume ratio 1:6.5, two kinds of catalyst grain sizes: diameter is the former particle sample of 4.0～5.0mm; normal pressure, air speed 2500h
-1, unstripped gas is formed (volume percentage mark): H
250%, CO 10%, CO
226%, O
20.5%, H
2S 6000ppm, COS 40ppm, surplus are water vapour, reaction temperature: 250 ℃, reaction time: 240h, unstripped gas measure the expression of its outlet COS content as its reactivity successively by antitoxin protective agent, hydrolyst, and test result sees Table 1.
Embodiment 4
The laboratory implementation example; in glass reactor, carry out; condition is a reaction tube diameter: 30mm; total filling amount: 30mL; antitoxin protective agent above hydrolyst, antitoxin protective agent and hydrolyst volume ratio 1:9, two kinds of catalyst grain sizes: diameter is the former particle sample of 4.0～5.0mm; normal pressure, air speed 2500h
-1, unstripped gas is formed (volume percentage mark): H
250%, CO 10%, CO
226%, O
20.5%, H
2S 6000ppm, COS 40ppm, surplus are water vapour, reaction temperature: 250 ℃, reaction time: 240h, unstripped gas measure the expression of its outlet COS content as its reactivity successively by antitoxin protective agent, hydrolyst, and test result sees Table 1.
Embodiment 5
The T504 hydrolyst that synthesis ammonia plant former use in Hebei is common lost efficacy after three months, and Fig. 1 new method is adopted in the back, and catalyst filling ratio adopts embodiment 2, and test is used 3 years, and is respond well.The concrete data of using see Table 2.
Table 1 laboratory COS conversion data
| Project | Inlet COS content (ppm) | Outlet COS content (ppm) |
| Comparative example | 40.42 | 32.83 |
| Embodiment 1 | 40.35 | 2.09 |
| Embodiment 2 | 40.12 | 1.51 |
| Embodiment 3 | 40.23 | 2.52 |
| Embodiment 4 | 40.33 | 2.98 |
Table 2 factory uses data
| Embodiment 5 | Inlet COS content (ppm) | Outlet COS content (ppm) |
| The driving initial stage | 23.85 | 1.20 |
| After test is used 1 year | 28.57 | 1.22 |
| After test is used 2 years | 26.69 | 1.33 |
| After test is used 3 years | 27.77 | 1.45 |
Claims (4)
- One kind novel in warm carbonyl sulfide hydrolysis method, can under 150～320 ℃ of conditions, be used for carbonyl sulfide hydrolysis, it is to be formed by two kinds of different catalyst combination of function, it is characterized in that adopting at the common, inexpensive hydrolyst top that is easy to get and place a kind of antitoxin protective agent, the product that described antitoxin protective agent adopts patent " preparation method of the counterpoison of protection cobalt molybdenum co surfer-resistant shift catalyst " to produce, its patent No. is ZL200610125452.8; Hydrolyst is traditional activated alumina cheap and easy to get.
- 2. as claimed in claim 1 a kind of novel in warm carbonyl sulfide hydrolysis method, it is characterized in that described antitoxin protective agent is a kind ofly can contain H 2Deoxidation catalyst under the S condition, it is by the mode of oxygen and hydrogen complete reaction oxygen to be removed.
- 3. as claimed in claim 1 a kind of novel in warm carbonyl sulfide hydrolysis method, the volume ratio that it is characterized in that described antitoxin protective agent and hydrolyst is 1:2～1:9.
- 4. as claimed in claim 1 a kind of novel in warm carbonyl sulfide hydrolysis method, the volume ratio that it is characterized in that described antitoxin protective agent and hydrolyst is 1:4.
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|---|---|---|---|
| CN 201010545447 CN102000505A (en) | 2010-11-16 | 2010-11-16 | Novel middle-temperature carbonyl sulfide hydrolysis method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350122A (en) * | 2016-08-31 | 2017-01-25 | 武汉科林精细化工有限公司 | Fine desulfurization process for coke-oven gas |
| CN110643395A (en) * | 2019-10-15 | 2020-01-03 | 北京北科环境工程有限公司 | Blast furnace gas fine desulfurization process |
| CN112899041A (en) * | 2021-01-15 | 2021-06-04 | 中国神华煤制油化工有限公司 | Water gas shift system and preheating method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153580A (en) * | 1977-12-09 | 1979-05-08 | United Catalysts Inc. | CO conversion catalyst |
| CN1675337A (en) * | 2002-08-09 | 2005-09-28 | 三菱重工业株式会社 | Apparatus for treating COS for gas produced by gasification and method for treating COS |
| CN1986057A (en) * | 2006-12-13 | 2007-06-27 | 湖北双雄催化剂有限公司 | Preparing method of counterpoison for protecting Co-Mo Co of anti-sulfur change catalyst |
| CN101797477A (en) * | 2010-03-24 | 2010-08-11 | 太原理工大学 | Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer |
-
2010
- 2010-11-16 CN CN 201010545447 patent/CN102000505A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4153580A (en) * | 1977-12-09 | 1979-05-08 | United Catalysts Inc. | CO conversion catalyst |
| CN1675337A (en) * | 2002-08-09 | 2005-09-28 | 三菱重工业株式会社 | Apparatus for treating COS for gas produced by gasification and method for treating COS |
| CN1986057A (en) * | 2006-12-13 | 2007-06-27 | 湖北双雄催化剂有限公司 | Preparing method of counterpoison for protecting Co-Mo Co of anti-sulfur change catalyst |
| CN101797477A (en) * | 2010-03-24 | 2010-08-11 | 太原理工大学 | Method for reducing concentration of carbonyl sulfide on outlet of hydrogen sulfide (H2S) desulfurizer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106350122A (en) * | 2016-08-31 | 2017-01-25 | 武汉科林精细化工有限公司 | Fine desulfurization process for coke-oven gas |
| CN106350122B (en) * | 2016-08-31 | 2019-05-10 | 武汉科林精细化工有限公司 | A kind of oven gas fine desulfurizing technology |
| CN110643395A (en) * | 2019-10-15 | 2020-01-03 | 北京北科环境工程有限公司 | Blast furnace gas fine desulfurization process |
| CN112899041A (en) * | 2021-01-15 | 2021-06-04 | 中国神华煤制油化工有限公司 | Water gas shift system and preheating method thereof |
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Application publication date: 20110406 |