CN104445064A - Syngas CO combined conversion method and apparatus - Google Patents
Syngas CO combined conversion method and apparatus Download PDFInfo
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- CN104445064A CN104445064A CN201310424372.2A CN201310424372A CN104445064A CN 104445064 A CN104445064 A CN 104445064A CN 201310424372 A CN201310424372 A CN 201310424372A CN 104445064 A CN104445064 A CN 104445064A
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Abstract
The invention discloses a syngas CO combined conversion method. According to the method, CO in the syngas is successively subjected to water-cooling heat-exchange conversion and gas-cooling heat-exchange conversion; the low-temperature syngas is firstly subjected to heat exchange with a reaction gas in the process of gas-cooling heat-exchange conversion, then is subjected to water-cooling heat-exchange conversion reaction along with generation of a byproduct steam is generated, and then is subjected to gas-cooling heat-exchange conversion for deep conversion reaction; the reaction gas after being subjected to deep conversion reaction is subjected to heat recovery and condensate-liquid recovery and then is sent to a subsequent workshop section for processing; and one part of the water-cooling heat-exchange conversion byproduct steam is mixed with the syngas and the mixture is subjected to water-cooling heat-exchange conversion, or all of the steam are sent out. The invention also discloses an apparatus applied to the above syngas CO combined conversion method. The method and the apparatus can realize continuous reaction heat discharge in the reaction process, continuously transfers the reaction heat and maintains the reaction to be performed at a low temperature, equipment is less, investment is low, and the reaction-heat byproduct medium-pressure steam satisfies demands of conversion reaction, reduces or eliminates externally-supplied steam and realizes outward delivery.
Description
Technical field
The present invention relates to technical field of chemical engineering, particularly relate to a kind of synthetic gas CO combined transformation method and apparatus.
Background technology
In the crude synthesis gas obtained by various raw material and method, CO content is generally higher than the content produced needed for various Chemicals, such as, in gas maked coal, CO can up to more than 70% (butt), and produce the low < 10ppm that reaches of CO need in the synthetic gas of synthetic ammonia, need the requirement according to producing product that a large amount of CO is transformed into H for this reason
2, make it meet synthetic gas H
2, CO proportion requirement, such as synthesizing methanol hydrogen-carbon ratio is about 2, and synthesizing methane preparing natural gas hydrogen-carbon ratio is that 3, CO transformationreation is as follows: CO+H
2o (vapour)=H
2+ CO
2+ Q.This is a reversible exothermic reaction, and the reaction heat of releasing makes temperature of reaction raise, and CO equilibrium conversion reduces, and can not reach conversion requirements.
The multiple adiabatic shift-converter that existing CO conversion is generally repeatedly cooled by reaction gas completes, and by the difference of transformation temperature, has high temperature shift, middle temperature transformation (at 350 ~ 500 DEG C of down conversions, use Cr
2o
3series catalysts) and low temperature shift (at 180 ~ 250 DEG C of down conversions, using Cu-series catalyst), cobalt molybdenum resistant to sulfur wide temperature shift catalyzer (200 ~ 470 DEG C) is then used to the coal gas of sulfur compound.
CO conversion needs steam, and in synthetic gas, the ratio of steam and dry synthetic gas is commonly called as water-gas ratio.Water-gas ratio is high, inverse sulphureting reaction can occur first: MoS
2+ 2H
2o=MoO
2+ 2H
2s, makes cobalt-molybdenum catalyst inactivation, if second moisture content is too high, the steam lower than dew-point temperature can be condensed into liquid state again, and catalyst strength is reduced and efflorescence.And water-gas ratio is low, is unfavorable for first improving CO interconversion rate, second also methanation reaction can occurs under high temperature: CO+3H
2=CH
4+ H
2o, this strong exothermal reaction easy burn-out catalyzer, produces ammonia, methyl alcohol to synthetic gas, the CH generated
4that indifferent gas consumes useful in a large number CO, H in vain
2gas, therefore there is long flow path in multistage insulation conversion, equipment is many, energy consumption is high, invest large deficiency.
For this reason, in recent years isothermal converter technique is developed, if isothermal low-temperature CO shift reactor by name (CN101721956) is to be provided with many suspension heat exchanging water pipes, the outer reaction heat byproduct steam of absorption tube, after byproduct steam goes out reactor to drum, enter again the inverted U-shape pipe absorption reaction heat in shift-converter, after improving vapor temperature, be mixed into catalyst layer with unreacting gas and carry out transformationreation, the successful implementation on full scale plant of this technology, obtain than the better effect of aforementioned multiple adiabatic reactor series connection conversion, but this technology structure of reactor is complicated, heat transfer effect owes strong, catalyst loading and unloading is inconvenient, and temperature of reaction is higher, the corresponding equilibrium constant reduces, for for the low requirement of ammonia synthesis gas CO content requirement, catalyst levels need be increased large, improve water-gas ratio.
Summary of the invention
The technical problem to be solved in the present invention is the defect existed for prior art, provide a kind of synthetic gas CO combined transformation method and apparatus, it can in reaction process, sustained reaction heat release, continue through other medium reaction heat is shifted out, maintain reaction and carry out at low temperatures.
A kind of synthetic gas CO combined transformation method, CO in synthetic gas converts through water-cooled heat exchange conversion and air cooling heat exchange first, reaction gas heat exchange during low temperature synthetic gas first converts with air cooling heat exchange, then through water-cooled heat exchange transformationreation, and byproduct steam, afterwards reaction gas degas cold heat exchange conversion carry out further CO depth conversion reaction, low temperature synthetic gas is heated simultaneously, through the reacted reaction gas of depth conversion through heat recuperation, phlegma reclaim Hou Songhou workshop section process; A byproduct steam part for described water-cooled heat exchange conversion mixes laggard water-cooled heat exchange with synthetic gas and converts, and rest part steam is sent outside; Or steam is all sent outside.
Preferred as one, described synthetic gas CO combined transformation method also comprises adiabatic conversion, reaction gas heat exchange during described low temperature synthetic gas first converts with air cooling heat exchange, then adiabatic conversion is gone to carry out pre-transform reaction, to anhydrate cold heat exchange transformationreation, and byproduct steam, the depth conversion reaction of CO is carried out in reaction gas cold heat exchange conversion of degassing afterwards further again, and low temperature synthetic gas is heated, reclaim the process of Hou Songhou workshop section through the reacted reaction gas of depth conversion through heat recuperation, phlegma; A byproduct steam part for described water-cooled heat exchange conversion mixes laggard water-cooled heat exchange with the synthetic gas after adiabatic conversion and converts, and rest part steam is sent outside; Or all steam is sent outside.
Preferred as one, fill into steam in the reaction gas after described water-cooled transformationreation.
Above-mentioned water-gas ratio when adding steam requires to calculate according to Practical Project condition.
During described water-cooled heat exchange conversion and air cooling heat exchange convert, when reactor carries out transformationreation on a catalyst, gas temperature is higher than dew-point temperature 20 ~ 30 DEG C.
When described synthetic gas is sulfide content high synthetic gas, water-cooled heat exchange conversion, air cooling heat exchange conversion and adiabatic conversion all adopt Co-Mo sulfur resistant catalyst.
The pressure of the steam of described water-cooled heat exchange conversion by-product is higher than reacting gas pressure.Described water-cooled heat exchange conversion removes reaction heat by the water evaporation byproduct steam in heat transfer tube, general water vapor temperature is lower than temperature of reaction 5 ~ 20 DEG C, regulate and maintain temperature of reaction, reach and control evaporation of water pressure higher than reacting gas pressure, the system self-produced steam of making can refill in the reaction gas before water-cooled heat exchange conversion.
The temperature out of described air cooling heat exchange conversion is lower than balanced loss functions 5 ~ 19 DEG C.
A kind of device for above-mentioned synthetic gas CO combined transformation method, gas converting heat is had to restrain in described air cooling shift-converter, water-cooled heat-exchanging tube bundle is had in described water-cooled shift-converter, described water-cooled heat-exchanging tube bundle is communicated with drum, the inlet pipe of described drum outlet connection water-cooled shift-converter, the gas converting heat tube bank outlet of described air cooling shift-converter is connected successively with before and after water-cooled shift-converter shell side and air cooling shift-converter shell side, and the shell side of each reactor is all equipped with transformation catalyst.
When said apparatus runs, containing the low temperature synthetic gas of CO, first through air cooling heat transfer reactor tube side by air preheat in the catalyst layer outside pipe, the temperature of the outer catalyzer of control tube.Gas after heat exchange regulates after water-gas ratio by adding steam, is introduced into water-cooled heat transfer reactor, most CO is carried out transformationreation, the hot byproduct steam of simultaneous reactions.Go out the shell side that water-cooled heat transfer reactor enters air cooling heat transfer reactor more afterwards, in catalyst layer, carry out the CO transformationreation of the degree of depth, limit coronite heat exchange, reduce bottom catalyst temperature, promote the carrying out of CO transformationreation.
Preferred as one, described device also comprises pre-transform reactor, and the gas converting heat tube bank outlet of described air cooling shift-converter is connected successively with before and after pre-transform reactor shell side, water-cooled shift-converter shell side and air cooling shift-converter shell side.Low temperature synthesizer enters in pre-transform reactor after the preheating of air cooling heat transfer reactor, carries out a small amount of transformationreation, then regulates water-gas ratio by adding steam, and reaction gas enters water-cooled heat transfer reactor successively afterwards, air cooling heat transfer reactor carries out transformationreation.
Combination unit of the present invention has 2 committed step equipment, and First is water-cooled isothermal shift-converter, and its process characteristic adopts saturated feedwater to move heat to shift-converter, by-product middle pressure steam simultaneously.Second is air cooling heat exchange shift-converter, adopting low temperature synthetic gas for moving thermal medium, moving heat to shift-converter.
Pipeline between described water-cooled heat transfer reactor and air cooling heat transfer reactor is provided with steam and fills into mouth.
Described water-cooled shift-converter is water pipe reactor, is preferably around pipe type water pipe reactor.
Described water-cooled shift-converter more preferably radial water pipe reactor, i.e. reaction gas radial flow in water-cooled shift-converter.
The inventive method and device have following characteristics:
1) air cooling heat transfer reactor can reduce the temperature of reaction of depth conversion, is equivalent to again an interchanger simultaneously, reduces facility investment.
2) latter end temperature of reaction is lower, and the equilibrium constant is large, reduces catalyst levels.
3) reaction is carried out at low temperature (21O ~ 260 DEG C between), and the water-gas ratio of needs is low, and consume steam few, follow-up phlegma is few, and phlegma treatment scheme shortens and equipment minimizing.
4) reaction heat by-product middle pressure steam, meets transformationreation needs, reduces or does not need outer for steam, and can send steam needs outside.
5) coal gas of different CO content and different velocity of variation transformationreation is gone for.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method.
Fig. 2 is the schematic flow sheet of the another kind of scheme of the inventive method, wherein also comprises adiabatic conversion, all fills into steam before and after water-cooled heat exchange conversion, fills into steam from drum before water-cooled heat exchange conversion, fills into steam from outer confession after water-cooled heat exchange conversion.
Fig. 3 is the schematic flow sheet of the another kind of scheme of the inventive method, wherein also comprises adiabatic conversion, all fills into steam, fill into steam all from drum before and after water-cooled heat exchange conversion.
Fig. 4 is the schematic diagram of apparatus of the present invention, is wherein provided with between drum export pipeline and water-cooled heat exchange shift-converter inlet ductwork and fills into vapour line.
Fig. 5 is the schematic diagram of the another kind of scheme of apparatus of the present invention, wherein be provided with between drum export pipeline and water-cooled heat exchange shift-converter inlet ductwork and fill into vapour line, be provided with between drum export pipeline and water-cooled heat exchange shift-converter export pipeline and fill into vapour line.
Fig. 6 is the schematic diagram of the another kind of scheme of apparatus of the present invention, wherein also comprises pre-transform reactor, is provided with and fills into vapour line between drum export pipeline and water-cooled heat exchange shift-converter inlet ductwork.
Fig. 7 is the schematic diagram of the another kind of scheme of apparatus of the present invention, wherein also comprise pre-transform reactor, be provided with between drum export pipeline and water-cooled heat exchange shift-converter inlet ductwork and fill into vapour line, wherein water-cooled heat exchange shift-converter is radial water pipe reactor, and catalyzer is contained between pipe.
Fig. 8 is the schematic diagram of a kind of embodiment of apparatus of the present invention.
Description of reference numerals:
1-air cooling heat exchange shift-converter 2-water-cooled heat exchange shift-converter 3-drum
4-raw gas strainer 5-pre-transform reactor D1-first steam fills into pipeline
D2-discharge of steam pipeline D3-second steam fills into pipeline
Embodiment
Be described in detail of the present invention below in conjunction with drawings and Examples.
Embodiment 1
Adopt device as shown in Figure 8, this device comprises the raw gas strainer 4 connected successively, air cooling heat exchange shift-converter 1, pre-transform reactor 5 and water-cooled heat exchange shift-converter 2, the pneumatic outlet of raw gas strainer 4 is connected with the tube side import of air cooling heat exchange shift-converter 1, the tube side outlet of air cooling heat exchange shift-converter 1 is connected with the import of pre-transform reactor 5, the outlet of pre-transform reactor 5 is connected with the shell side import of water-cooled heat exchange shift-converter 2, the shell-side outlet of water-cooled heat exchange shift-converter 2 is connected with the shell side import of air cooling heat exchange shift-converter 1, the tube side two ends of described water-cooled heat exchange shift-converter 2 connect the import and export of drum 3 respectively, be provided with the first steam between the vapour outlet of drum 3 and the inlet ductwork of water-cooled heat exchange shift-converter 2 and fill into pipeline D1.
The water-gas come from gasifying powder coal device enters changing device, and pressure is about 3.72MPa (g), temperature about 198 DEG C, and water-gas ratio is about 0.68.After raw gas strainer 4 oil removing dust removal and filtration, the tube side of the cold shift-converter of air inlet 1 by the reaction heat and sensible heat of managing the gas of outer catalyst layer be heated to ~ 230 DEG C, enter pre-transform reactor 5 afterwards, carry out the purification of coal gas and a small amount of CO transformationreation.
Go out gas temperature temperature ~ 254 DEG C of pre-transform reactor 5, water-gas ratio is reduced to 0.62.Added 3.8MPa (g) the saturation steam D1 of water-cooled heat exchange shift-converter 2 by-product by variable valve, make water-gas ratio reach 1.1, temperature is reduced to about 249 DEG C, enters in water-cooled heat exchange shift-converter 2 and carries out transformationreation.Gas flows axially through the catalyst layer in water-cooled heat exchange shift-converter 2 from the top down.Reaction heat is taken away by the feedwater evaporation byproduct steam be distributed in the spiral tube of catalyst layer, then removes drum 3.
Go out reaction gas temperature ~ 255 DEG C of water-cooled heat exchange shift-converter 2, CO content about 0.64% (wet basis), enter the transformationreation that air cooling heat exchange shift-converter 1 carries out the degree of depth.Simultaneously catalyst reaction temperatures gradually by the coal gas in cold pipe be cooled to ~ 220 DEG C, now export reaction gas CO content and be reduced to ~ 0.30% (wet basis).The process of Hou Songhou workshop section is reclaimed through heat recuperation, phlegma through the reacted reaction gas of depth conversion.
Claims (13)
1. a synthetic gas CO combined transformation method, it is characterized in that: the CO in synthetic gas converts through water-cooled heat exchange conversion and air cooling heat exchange first, reaction gas heat exchange during low temperature synthetic gas first converts with air cooling heat exchange, then water-cooled heat exchange transformationreation is carried out, and byproduct steam, afterwards reaction gas degas cold heat exchange conversion carry out further CO depth conversion reaction, low temperature synthetic gas is heated simultaneously, the reacted reaction gas of depth conversion through heat recuperation, phlegma reclaim Hou Songhou workshop section process; A byproduct steam part for described water-cooled heat exchange conversion mixes laggard water-cooled heat exchange with synthetic gas and converts, and rest part steam is sent outside; Or all steam is sent outside.
2. synthetic gas CO combined transformation method as claimed in claim 1, it is characterized in that: described synthetic gas CO combined transformation method also comprises adiabatic conversion, reaction gas heat exchange during described low temperature synthetic gas first converts with air cooling heat exchange, then adiabatic conversion is gone to carry out pre-transform reaction, to anhydrate again cold heat exchange transformationreation, and byproduct steam, afterwards reaction gas degas cold heat exchange conversion carry out further CO depth conversion reaction, and low temperature synthetic gas is heated, reclaim the process of Hou Songhou workshop section through the reacted conversion gas of depth conversion through heat recuperation, phlegma; A byproduct steam part for described water-cooled heat exchange conversion mixes laggard water-cooled heat exchange with the synthetic gas after adiabatic conversion and converts, and rest part steam is sent outside; Or all steam is sent outside.
3. synthetic gas CO combined transformation method as claimed in claim 1 or 2, is characterized in that: fill into steam in the reaction gas after described water-cooled transformationreation.
4. synthetic gas CO combined transformation method as claimed in claim 1 or 2, is characterized in that: during described water-cooled heat exchange conversion and air cooling heat exchange convert, when reactor carries out transformationreation on a catalyst, gas temperature is higher than dew-point temperature 20 ~ 30 DEG C.
5. synthetic gas CO combined transformation method as claimed in claim 2, is characterized in that: when described synthetic gas is sulfide content high synthetic gas, adopt Co-Mo sulfur resistant catalyst.
6. synthetic gas CO combined transformation method as claimed in claim 1 or 2, is characterized in that: the pressure of the steam of described water-cooled heat exchange conversion by-product is higher than reacting gas pressure.
7. synthetic gas CO combined transformation method as claimed in claim 1 or 2, is characterized in that: the temperature out of described air cooling heat exchange conversion is lower than balanced loss functions 11 ~ 19 DEG C.
8. a synthetic gas CO combined transformation device, comprise water-cooled heat transfer reactor, air cooling heat transfer reactor, drum, it is characterized in that: in described air cooling shift-converter, have gas converting heat to restrain, water-cooled heat-exchanging tube bundle is had in described water-cooled shift-converter, described water-cooled heat-exchanging tube bundle is communicated with drum, the inlet pipe of described drum outlet connection water-cooled shift-converter, the gas converting heat tube bank outlet of described air cooling shift-converter is connected successively with before and after water-cooled shift-converter shell side and air cooling shift-converter shell side, the shell side of each reactor is all equipped with transformation catalyst.
9. synthetic gas CO combined transformation device as claimed in claim 8, it is characterized in that, described device also comprises pre-transform reactor, and the gas converting heat tube bank outlet of described air cooling shift-converter is connected successively with before and after pre-transform reactor shell side, water-cooled shift-converter shell side and air cooling shift-converter shell side.
10. synthetic gas CO combined transformation device as claimed in claim 8 or 9, is characterized in that: the pipeline between described water-cooled heat transfer reactor and air cooling heat transfer reactor is provided with steam and fills into mouth.
11. synthetic gas CO combined transformation devices as claimed in claim 8 or 9, is characterized in that: described water-cooled shift-converter is water pipe reactor.
12. synthetic gas CO combined transformation devices as claimed in claim 11, is characterized in that: described water-cooled shift-converter is around pipe type water pipe reactor.
13. synthetic gas CO combined transformation devices as claimed in claim 11, is characterized in that: described water-cooled shift-converter is radial water pipe reactor.
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| CN106115700A (en) * | 2016-08-19 | 2016-11-16 | 南京聚拓化工科技有限公司 | Beam tube type water bed moves hot compound CO converting means and conversion process |
| CN109181782A (en) * | 2018-09-30 | 2019-01-11 | 中石化宁波工程有限公司 | A kind of air cooling of mating coal water slurry gasification and water cooling isothermal conversion process |
| CN109264668A (en) * | 2018-09-30 | 2019-01-25 | 中石化宁波工程有限公司 | The CO conversion process of mating methanol-fueled CLC |
| CN109280568A (en) * | 2018-09-30 | 2019-01-29 | 中石化宁波工程有限公司 | A kind of isothermal conversion process of mating coal gasification |
| CN110803681A (en) * | 2019-10-24 | 2020-02-18 | 中石化宁波工程有限公司 | Gas-cooled conversion series isothermal conversion hydrogen production process matched with coal water slurry gasification and isothermal conversion furnace |
| CN115196590A (en) * | 2022-06-22 | 2022-10-18 | 上海富禧友好能源科技有限公司 | Process for co-producing hydrogen by capturing blast furnace gas carbon |
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| CN110803681A (en) * | 2019-10-24 | 2020-02-18 | 中石化宁波工程有限公司 | Gas-cooled conversion series isothermal conversion hydrogen production process matched with coal water slurry gasification and isothermal conversion furnace |
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| CN115196590A (en) * | 2022-06-22 | 2022-10-18 | 上海富禧友好能源科技有限公司 | Process for co-producing hydrogen by capturing blast furnace gas carbon |
| CN115196590B (en) * | 2022-06-22 | 2024-02-09 | 上海富禧友好能源科技有限公司 | Process for co-production of hydrogen by capturing carbon in blast furnace gas |
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