CN103449365B - Process for converting high-concentration CO-tolerant sulfur and device thereof - Google Patents
Process for converting high-concentration CO-tolerant sulfur and device thereof Download PDFInfo
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- CN103449365B CN103449365B CN201310153504.2A CN201310153504A CN103449365B CN 103449365 B CN103449365 B CN 103449365B CN 201310153504 A CN201310153504 A CN 201310153504A CN 103449365 B CN103449365 B CN 103449365B
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- 238000000034 method Methods 0.000 title claims abstract description 66
- 230000008569 process Effects 0.000 title claims abstract description 58
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 14
- 239000011593 sulfur Substances 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 123
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000008859 change Effects 0.000 claims abstract description 42
- 239000002918 waste heat Substances 0.000 claims abstract description 32
- 239000003034 coal gas Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- AZSYUHSAQICHNK-UHFFFAOYSA-N [C]=O.[S] Chemical compound [C]=O.[S] AZSYUHSAQICHNK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 description 16
- 230000009466 transformation Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- 238000000844 transformation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910018575 Al—Ti Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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Abstract
The present invention relates to a kind of high-concentration carbon monoxide sulfur resistant conversion process and device thereof, described high-concentration carbon monoxide sulfur resistant conversion process, comprise at least Two Stages, raw water coal gas is divided into two strands, one is down to 0.2 ~ 0.5:1 through Low Pressure Waste Heat Boiler aqueous vapor mol ratio, heat up through gas-gas heat exchanger heat exchange after Separation of Water, then enter a change reactor and carry out transformationreation; One becomes reactor outlet process gas after removing heat, then enters two change reactors after mixing with another strand of raw water coal gas and carry out two-dimensional transform reaction.This technique ingenious control of energy and balance enter water-gas ratio and the heat of each shift-converter, first, second shift-converter can be reacted in the mode close to chemical reaction equilibrium, this technique need not arrange pre-reactor, can effectively prevent again shift-converter bed temperature too high; Under different load, the risk of the first shift-converter generation methanation reaction is minimum, is the sulfur resistant conversion process of a kind of high concentration CO, low water-gas ratio.
Description
Technical field
The present invention relates to a kind of high-concentration carbon monoxide sulfur resistant conversion process and device thereof, being specifically related to a kind of is raw material with raw gas, produces the high-concentration carbon monoxide sulfur resistant conversion process of oxo-synthesis gas, F-T synthetic gas, methane synthetic gas under low water-gas ratio condition.
Background technology
In the process gas that the coal gasification being representative with GSP, east stove, space flight stove, BGL etc., chilling technology produce, the butt composition (mole composition after deduction contained humidity) of CO is roughly 60% ~ 75%, and water-gas ratio (mol ratio of water and other gaseous fraction) is 0.8 ~ 1.2.CO enters shift-converter up to more than 60%, under same transformationreation condition, the temperature of reaction of reaction bed bottom generally can close to 500 DEG C, even more than 530 DEG C, so just special requirement is proposed to the material of reactor, add the cost of reactor, also increase the insecurity of device operation.
The method one of current solution high concentration CO conversion overtemperature adopts high water-gas ratio to reduce bed temperature, the temperature of bed bottom can be down to less than 460 DEG C as water-gas ratio brought up to about 1.8; Another kind increased a pre-reactor before main shift-converter, and pre-transform reaction product enters main shift-converter again after spray cooling or heat exchange cooling, also needs additionally to increase equipment; Also have a kind of method to be that the first shift-converter adopts very low water-gas ratio, as 0.2 ~ 0.4, limit the transformation efficiency of CO, but along with reaction to carry out water-gas ratio more and more lower, under high temperature, low water-gas ratio, there is the danger that methanation reaction occurs; And in actual production operating process, because the load of device can change, need constantly to carry out corresponding regulation and control to the parameter such as temperature, water-gas ratio of first, second shift-converter, bring difficulty to the steady running of device.
As can be seen here, for the transformation system of high concentration CO, solving overheated overtemperatute, at utmost reduce the risk of methanation reaction and reduce production load variations to the impact of transformationreation technique as far as possible, is the key reducing process cost, assurance device long-period stable operation.
Summary of the invention
The object of this invention is to provide water-gas ratio and heat that the ingenious control of a kind of energy and balance enter each shift-converter, making a change, two become reactors can react in the mode close to chemical reaction equilibrium; Both need not pre-reactor be set, and effectively can prevents again the sulfur resistant conversion process that shift-converter bed temperature is too high; The present invention provides the device realizing this sulfur resistant conversion process simultaneously.
High-concentration carbon monoxide sulfur resistant conversion process of the present invention, comprise at least Two Stages, raw water coal gas is divided into two strands, one is down to 0.2 ~ 0.5:1 through Low Pressure Waste Heat Boiler aqueous vapor mol ratio, be preferably 0.2 ~ 0.3:1, heat up through gas-gas heat exchanger heat exchange after Separation of Water, then enter a change reactor and carry out transformationreation; One becomes reactor outlet process gas after removing heat, then enters two change reactors after mix with another strand of raw water coal gas and carry out two-dimensional transform reaction, and in two change reactor outlet gas, CO content is 15-22mol%(butt).
According to requirement and the different target product of subsequent treatment process, described transformationreation may need secondary or multistage.As produced oxo-synthesis gas (raw material of methyl alcohol processed, ethylene glycol, F-T synthesis wet goods), methane etc., only needing part CO to carry out transformationreation, just can meet the demands through Two Stages at most; During to produce for the purpose of hydrogen, need CO to transform as far as possible completely, need through three grades, even level Four transformationreation.
In above-mentioned technique, gas-gas heat exchanger can become the heat supply of reactor outlet process gas by one, also can become the heat supply of reactor outlet process gas by two.
When becoming reactor outlet process gas heat supply by one, one becomes reactor outlet process gas removes heat through gas-gas heat exchanger and middle pressure waste heat boiler, then enters two change reactors after mixing with another strand of raw water coal gas and carry out two-dimensional transform reaction.
When becoming reactor outlet process gas heat supply by two, one become outlet process gas only through in press waste heat boiler to remove heat, then enter two change reactors after mixing with another strand of raw water coal gas and carry out two-dimensional transform reaction.
In more detail, the invention provides water-gas ratio and the high concentration CO of heat, low water-gas ratio sulfur resistant conversion process that the ingenious control of a kind of energy and balance enter each shift-converter, following two schemes can be divided into:
Scheme one: raw material coal gas is divided into two strands, one process gas is reduced to 0.2 ~ 0.5:1 through Low Pressure Waste Heat Boiler water-gas ratio, be preferably 0.2 ~ 0.3:1, after gas-liquid separator separates dewaters, reactor outlet process gas is become again by after gas-gas heat exchanger heat exchange heats up with one, enter a change reactor and carry out transformationreation, and reduce the tolerance entering a change reactor due to shunting action, thus ensure that one-stage transfor-mation reaction carries out under low aqueous vapor when lesser temps, react bed hot(test)-spot temperature when reaching balance and only have about 400 DEG C, can effectively prevent bed temperature too high.And a change reactor outlet process gas is removed after heat through gas-gas heat exchanger, waste heat boiler is pressed to remove heat further in passing through again, then enter two change reactors after mixing with another strand of raw material coal gas and carry out two-dimensional transform reaction, make CO content in two change reactor outlet gas reach 15-22mol%(butt).Because one becomes reactor outlet gas temperature very high (about 400 DEG C), give up after pot withdraws partial heat through gas-gas heat exchanger heat exchange and middle pressure, temperature of charge reduces, then after merging with another strand of raw material coal gas together with enter two change reactors, thus ensure that lower two change reactor inlet temperatures; On the other hand, because a water-gas ratio become in reactor outlet gas is very low, if make up water cannot not proceed two-dimensional transform reaction, and after merging with another strand of raw material coal gas of high water-gas ratio, improve water-gas ratio, make it the water-gas ratio requirement being suitable for two-dimensional transform reaction, avoid extremely incident methanation reaction under high temperature, low water-gas ratio condition from temperature and water-gas ratio two aspects like this.Even if also do not need when device load changes to carry out continuous regulation and control to a change, two parameters such as temperature, water-gas ratio becoming reactors, device can stably be run.Therefore the present invention is a kind of sulfur-resisting transformation novel process of applicable high concentration CO.
Scheme two: similar with scheme one, difference is just that gas-gas heat exchanger becomes the heat supply of reactor outlet process gas by two, and at this moment a change reactor outlet process gas presses waste heat boiler to remove heat in only passing through.
The butt composition of coal gasification CO is general more than 60%, no matter be that high water-gas ratio enters shift-converter, or before entering one-stage transfor-mation reactor, water-gas ratio is adjusted to about 0.25, the bed hot(test)-spot temperature of one-stage transfor-mation reactor all can reach 400 DEG C, even more than 400 DEG C, therefore one-stage transfor-mation reactor outlet gas can as producing 4.0MPa, the thermal source of middle pressure steam of about 250 DEG C, and the middle pressure steam produced can be incorporated to the middle pressure steam pipe network of plant area.Simultaneously one-stage transfor-mation reactor outlet gas through in press waste heat boiler after temperature be minimized, contribute to reduction two-dimensional transform reactor inlet temperature.
Transformationreation (CO+H
2o → CO
2+ H
2) be thermopositive reaction, along with the carrying out of reaction, reaction bed temperature raises gradually.Water is reactant, and water-gas ratio is large, is conducive to the transformation efficiency improving transformationreation; Simultaneously because specific heat of water is larger, therefore water is also the carrier of heat, and water-gas ratio is conducive to greatly reducing reaction bed temperature.Water-gas ratio also has impact to the temperature that process gas enters beds, and for preventing liquid water from entering beds, general requirement temperature in is higher than dew-point temperature more than 20 DEG C; Water-gas ratio is higher, and dew-point temperature is higher, and corresponding requirements bed inlet temperatures is higher.
From the process gas (raw gas) that gasification unit is come, before entering shift-converter, prioritizing selection is first through being equipped with the container of detoxifying agent, sorbent material, and the ash in removing process gas grades impurity, plays a protective role to the catalyzer in shift-converter.
Raw material coal gas after purification, be divided into two strands, the wet basis flow wherein entering one water-gas of Low Pressure Waste Heat Boiler is 30 ~ 70% of total water-gas flow, specifically according to raw material composition and downstream process, the conversion requirements of conversion process is determined, first Low Pressure Waste Heat Boiler cooling is entered, gas-liquid separator dewaters, water-gas ratio is down to 0.2 ~ 0.5:1, heat up through gas-gas heat exchanger heat exchange again, then enter one-stage transfor-mation reactor and carry out transformationreation, the dry gas air speed entering a change reactor is 2000 ~ 12000h-1, initial stage temperature in 190 ~ 230 DEG C, preferably 205 ~ 225 DEG C, latter stage temperature in 220 ~ 270 DEG C, preferably 240 ~ 260 DEG C, but temperature in must under relevant pressure, water-gas ratio state process gas dew point more than 20 DEG C.One becomes reactor outlet process gas after removing heat, then enters two change reactors after mix with another strand of raw material coal gas and carry out two-dimensional transform reaction, and the dry gas air speeds of two change reactors are 2000 ~ 5000h
-1, initial stage temperature in 200 ~ 240 DEG C, preferably 210 ~ 235 DEG C; Latter stage temperature in 240 ~ 290 DEG C, preferably 260 ~ 280 DEG C.The gaseous tension entering converter unit is generally 3.5 ~ 6.5MPa.
Adopt technique of the present invention, at end-of-run, by suitably reducing to enter the tolerance of a change or suitably improving the water-gas ratio that becomes reactor inlet, higher CO transformation efficiency can be maintained, make device still can steady running.
Catalyzer of the present invention is cobalt-molybdenum type sulfur-resistant transformation catalyst, is preferably Mg-Al-Ti ternary support C o-Mo catalyzer, QCS-11, QCS-04 catalyzer of preferred applicant's development and production.The loadings that catalyzer becomes in reactors in a change and two determine according to adopted Process flow and unstripped gas tolerance.
One-stage transfor-mation reactor catalyst bed exit gas removes heat drop temperature by middle pressure waste heat boiler, and middle pressure waste heat boiler has then reclaimed heat, can produce middle pressure steam, and this steam can be incorporated to the middle pressure steam pipe network of plant area.Current coal gasification produce the pressure of process gas lower than 4.0MPa, in can controlling, the pressure of the useless pot of pressure is about 4.0MPa, produce middle pressure steam temperature be about 250 DEG C.
The device of the sulfur resistant conversion process described in realization, in scheme one:
Comprise connect successively the first gas inlet, Low Pressure Waste Heat Boiler, gas-liquid separator, gas-gas heat exchanger, one become reactor and two become reactors, wherein, one becomes reactor outlet is also connected with gas-gas heat exchanger, gas-gas heat exchanger and two becomes on the pipeline between reactor inlet and arranges middle pressure waste heat boiler, and middle pressure waste heat boiler and two becomes on the pipeline between reactor inlet and arranges the second gas inlet.
Feed coal air pipe is divided into two-way: a road is connected by pipeline with Low Pressure Waste Heat Boiler, gas-gas heat exchanger, an entrance becoming reactor, one outlet becoming reactor is connected by pipeline with gas-gas heat exchanger and middle pressure waste heat boiler, and then be connected with two-dimensional transform reactor inlet, and merged with another road before passing into two-dimensional transform reactor.
Scheme two is with the difference of scheme one: two become reactor outlet is connected with gas-gas heat exchanger, one becomes on pipeline that reactor outlet and two becomes between reactor inlet and arranges middle pressure waste heat boiler, and middle pressure waste heat boiler and two becomes on the pipeline between reactor inlet and arranges the second gas inlet.
Gas-gas heat exchanger becomes reactor outlet by pipeline and two and is connected, and an outlet becoming reactor is directly connected by pipeline with middle pressure waste heat boiler without gas-gas heat exchanger.
The present invention can also provide a kind of temperature rise control method of process for converting high-concentration CO-tolerant sulfur, comprises multi-stage transformation, at least Two Stages.First raw water coal gas is divided into two strands, and one is lowered the temperature through Low Pressure Waste Heat Boiler, and water-gas ratio is reduced to 0.2 ~ 0.5:1, is preferably 0.2 ~ 0.3:1, is separated after dewatering and heats up through gas-gas heat exchanger heat exchange, then enter a change reactor and carry out one-stage transfor-mation reaction; One becomes reactor outlet process gas after removing heat, then enters two change reactors after mix with another strand of raw material coal gas and carry out two-dimensional transform reaction, and in two change reactor outlet gas, CO content is 15-22mol%(butt).Can become the bed hot(test)-spot temperature of reactor by one and control at about 400 DEG C like this.
Compared with prior art, the present invention has following positively effect:
(1) one to become, two skills of exchanging work all design according to close to molecular balance, do not need adjustment during operating load change, make device energy long-period stable operation;
(2) both need not pre-reactor be set, can effectively prevents again shift-converter bed temperature too high, react bed hot(test)-spot temperature when reaching balance and only have about 400 DEG C;
(3), under different load, one becomes reactor generation methanation reaction, and there is very little risk.
(4) process of the present invention is simple, equipment is few, has taken into account temperature control and water-gas ratio requirement that a change, two becomes reactors, has both controlled the hot(test)-spot temperature of a change reactor well, and made again two change reactor inlet gases improve water-gas ratio while cooling.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present invention 1;
Fig. 2 is the process flow sheet of the embodiment of the present invention 2;
In figure: 1, middle pressure waste heat boiler; 2, two become reactor; 3, one becomes reactor; 4, gas-gas heat exchanger; 5, steam separator; 6, Low Pressure Waste Heat Boiler; 7, the first gas inlet; 8, the second gas inlet.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described further:
QCS-11, QCS-04 trade mark Mg-Al-Ti ternary support C o-Mo catalyzer that in embodiment becomes, two change catalyzers adopt the applicant commercially available respectively, loadings is respectively 45m
3, 89m
3.
Embodiment 1:
As shown in accompanying drawing 1 and table 1 data: raw material coal gas (A) is entered by the first gas inlet 7 and is divided into two strands (B and G), one raw material coal gas (B) is lowered the temperature through Low Pressure Waste Heat Boiler 6, gas-liquid separator 5 dewaters, aqueous vapor mol ratio is reduced to 0.25:1, become gas (D) heat exchange of reactor 3 outlet process again to heat up rear (C) with one, enter a change reactor 3 and carry out transformationreation.And one becomes reactor 3 outlet process gas (D) after gas-gas heat exchanger 4 removes heat (E), waste heat boiler 1 is pressed to remove heat drop temperature (F) further in passing through again, then after another burst of raw material coal gas (G) entered with the second gas inlet 8 mixes, (H) enters two change reactors 2 and carries out two-dimensional transform reaction, makes CO content in two change exit gass (I) reach 20.4mol%(butt).A, B, C, D, E, F, G, H, I are the logistics numbering of gas.
The main operating parameters of table 1 embodiment 1 and logistics composition table
Embodiment 2:
As shown in accompanying drawing 2 and table 2 data: raw material coal gas (a) is divided into two gangs of (b and g) after being entered by the first gas inlet 7, one raw material coal gas (b) is lowered the temperature through Low Pressure Waste Heat Boiler 6, gas-liquid separator 5 dewaters, aqueous vapor mol ratio is reduced to 0.31:1, become reactor 2 outlet process gas more (i) to be heated up rear (c) by gas-gas heat exchanger 4 heat exchange with two, enter a change reactor 3 and carry out transformationreation.And change reactor 3 outlet process gas (d) is removed after heat drop temperature (f) through middle pressure waste heat boiler 1, after another burst of raw material coal gas (g) entered with the second gas inlet 8 mixes, (h) enters two change reactors 2 and carries out two-dimensional transform reaction, and in making two change reactor 2 exit gass (i), CO content reaches 17.8mol%(butt).A, b, c, d, f, g, h, i, j are the logistics numbering of gas.
The main operating parameters of table 2 embodiment 2 and logistics composition table
Claims (6)
1. a high-concentration carbon monoxide sulfur resistant conversion process, comprise at least Two Stages, it is characterized in that: raw water coal gas is divided into two strands, one is down to 0.2 ~ 0.5:1 through Low Pressure Waste Heat Boiler (6) aqueous vapor mol ratio, heat up through gas-gas heat exchanger (4) heat exchange after Separation of Water, then enter a change reactor (3) and carry out transformationreation; One becomes reactor (3) outlet process gas after removing heat, then enters two change reactors (2) after mixing with another strand of raw water coal gas and carry out two-dimensional transform reaction;
The one dry gas air speed becoming reactor (3) is 2000 ~ 12000 h
-1, initial stage temperature in 190 ~ 230 DEG C, latter stage temperature in 220 ~ 270 DEG C; The two dry gas air speeds becoming reactor (2) are 2000 ~ 5000 h
-1, initial stage temperature in 200 ~ 240 DEG C; Latter stage temperature in 240 ~ 290 DEG C.
2. sulfur resistant conversion process according to claim 1, is characterized in that: gas-gas heat exchanger (4) becomes the heat supply of reactor (3) outlet process gas by one; One becomes reactor (3) outlet process gas removes heat through gas-gas heat exchanger (4) and middle pressure waste heat boiler (1).
3. sulfur resistant conversion process according to claim 1, is characterized in that: gas-gas heat exchanger (4) becomes the heat supply of reactor (2) outlet process gas by two; Waste heat boiler (1) is pressed to remove heat during one change reactor (3) outlet process gas passes through.
4. the sulfur resistant conversion process according to claim 1,2 or 3, is characterized in that: in two change reactor (2) exit gass, CO content is 15-22 mol%, in butt.
5. the sulfur resistant conversion process according to claim 1,2 or 3, is characterized in that: the aqueous vapor mol ratio of one raw water coal gas through Low Pressure Waste Heat Boiler (6) is down to 0.2 ~ 0.3:1.
6. the sulfur resistant conversion process according to claim 1,2 or 3, is characterized in that: the wet basis flow entering one water-gas of Low Pressure Waste Heat Boiler (6) is 30 ~ 70% of total water-gas flow.
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| CN104176705B (en) * | 2014-08-08 | 2016-05-25 | 山东齐鲁科力化工研究院有限公司 | A kind of sulfur resistant conversion process of producing synthesis gas |
| CN104591084B (en) * | 2014-12-29 | 2016-08-31 | 南京敦先化工科技有限公司 | The method and system that a kind of carbon monoxide either shallow converts |
| CN105969435B (en) * | 2016-05-28 | 2018-12-21 | 重庆化工设计研究院有限公司 | It is a kind of using raw gas as the process for synthesizing methane method and its system of raw material |
| CN107777664B (en) * | 2016-08-29 | 2020-03-20 | 中国石油化工股份有限公司 | Shift reaction process for regulating shift system temperature |
| CN110894061B (en) * | 2018-09-12 | 2021-11-05 | 中国石化工程建设有限公司 | Sulfur-tolerant shift method and device for multi-stage adjustment of water-gas ratio |
| CN110237680A (en) * | 2019-06-17 | 2019-09-17 | 中国华能集团有限公司 | A uniform temperature system and process for reducing sulfur dioxide by syngas |
| CN112708478A (en) * | 2020-11-23 | 2021-04-27 | 中石化南京工程有限公司 | Low water-gas ratio CO conversion device and method |
| CN115340888A (en) * | 2022-09-02 | 2022-11-15 | 云南水富云天化有限公司 | Automatic control system and method for reaction temperature of adiabatic shift converter |
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| EP1167282B1 (en) * | 1999-12-28 | 2007-04-04 | Daikin Industries, Ltd. | Shift reactor with heat-exchanger |
| US6821494B2 (en) * | 2001-07-31 | 2004-11-23 | Utc Fuel Cells, Llc | Oxygen-assisted water gas shift reactor having a supported catalyst, and method for its use |
| CN1204038C (en) * | 2001-12-30 | 2005-06-01 | 中国石化集团齐鲁石油化工公司 | CO isothermal sulfur resistant conversion process |
| DE102006032104A1 (en) * | 2006-07-11 | 2008-01-24 | Linde Ag | Process for the production of hydrogen and hydrogen-containing gas mixtures |
| CN101050391B (en) * | 2007-03-30 | 2011-04-13 | 青岛联信化学有限公司 | Sulfur resisting transform technique under low water / gas for gasifying powdered coal |
| CN102887480B (en) * | 2012-10-08 | 2014-06-04 | 中国石油化工集团公司 | CO shift technique by connecting isothermal shift and thermal insulation shift in series |
| CN202898012U (en) * | 2012-11-12 | 2013-04-24 | 山东齐鲁科力化工研究院有限公司 | High-concentration CO sulfur-tolerance conversion device sufficiently utilizing reaction heat |
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