CN102701149B - Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion - Google Patents
Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion Download PDFInfo
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- CN102701149B CN102701149B CN201210185731.9A CN201210185731A CN102701149B CN 102701149 B CN102701149 B CN 102701149B CN 201210185731 A CN201210185731 A CN 201210185731A CN 102701149 B CN102701149 B CN 102701149B
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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
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion. According to the process, a primary water heat-transfer shift converter and a secondary shift converter are adopted, CO in feed gas reacts with H2O to generate H2 and CO2 under the catalysis of a Co-Mo (copper-zinc) catalyst, and CO in shift gas coming out of a shift system is less than or equal to 0.1% (dry basis). In the process, CO is subject to deep conversion, the feed gas (containing water gas, semi-water gas, natural gas conversion gas or coke-oven gas conversion gas) utilization rate is high, the shift catalyst is not overheated, and the catalyst has a long service life; meanwhile, by-product saturated steam with the pressure of 0.5 to 9.0 MPa is generated, sensible heat and latent heat in the shift gas are further recovered by deoxygenated water and desalted water, low-grade heat energy is converted into high-grade heat energy, cooling water consumption is reduced, the temperature of` the shift gas coming out of a process system is lower than or equal to 40 DEG C, equipment is few, the flow is short, the investment is small, and the resistance is low (less than or equal to 0.05MPa).
Description
Technical field
The invention belongs to the unstripped gas CO conversion field in Coal Chemical Industry, gas chemical industry, coal-seam gas chemical industry, biogas chemical industry, relate in particular to the high CO conversion of the high water-gas ratio field of the pressurization pulverized coal continuous gasification furnace generations such as space flight, coal water slurry Texaco, GSP, multi-nozzle, shell (shell), the high CO conversion of the low water-gas ratio field that the gasification of fixed-bed intermittent formula produces low water-gas ratio high CO conversion field and the generation of normal pressure pulverized coal continuous gasification furnace.The particularly water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam.
Background technology
At present, make CO and H
2o generates CO
2and H
2reach CO and be converted into H
2object, ultimate principle is: under catalyzer (catalyst type has Fe-series catalyst, Cobalt molybdenum series catalyst, copper-zinc system catalyst) existence condition, possess suitable temperature and pressure, make CO and H
2o generates CO
2and H
2, its reaction equation is:
At present, there is following problem in the continuous coal gasification water-gas shift of pressurizeing:
(1) shift converter is adiabatic reaction, takes indirect heat exchange equipment to be set after reactor and reclaim sensible heat and the latent heat of conversion gas; The rank that reclaims heat is more, and special low grade heat energy is more.
(2) one sections of adiabatic shift converter loaded catalysts are difficult definite: be subject to " activity quotient (TF) " restriction: TF is an empirical value, need the data after practical application to go to check.Select when " one section of adiabatic shift converter " catalyst levels, if TF choosing is large, catalyst levels is just few, and " one section of adiabatic shift converter " transformation efficiency does not just reach requirement, gives that postorder shift converter brings that load increases, deviation is very large between system energy recovery and design load; If TF is little, " one section of adiabatic shift converter " catalyst levels is just many, just there is overtemperature (probably occur catalyzer burn phenomenon) in " one section of adiabatic shift converter ", what bring is that methanation side reaction increases thereupon, and operation brings very large potential safety hazard to system.
(3) also there is following defect in other existing adiabatic shift converter technique: equipment is many, operational path is long, construction investment is large, systemic resistance is large, the point of dew point corrosion is many, operation energy consumption is high, catalyzer is short work-ing life.
There are the following problems in the conversion of conversion of natural gas gas, coal-seam gas reforming gas and coke(oven)gas reforming gas:
(1) be transformed to two sections of heat-insulatings, all need that indirect heat exchange equipment is set after each shift converter and reclaim sensible heat and the latent heat of conversion gas; The rank that reclaims heat is more, and special low grade heat energy is more.
(2) because water-gas ratio is high, last step adiabatic reaction balance temperature is apart from little, and transformation system outlet CO >=0.25% (butt), is difficult to drop to CO≤0.10%, and unstripped gas utilization ratio is low, increases postorder load and energy consumption.
There are the following problems in the conversion of intermittent type fixed bed and the low water-gas ratio of normal pressure continuous gasification:
(1) the conversion gas entrained steam amount that goes out last step beds causes greatly steam consumption high, brings certain difficulty to recovery conversion gas sensible heat and latent heat.
(2) conversion low grade heat energy is many, and overall operation cannot balance, causes a large amount of low grade heat energies wastes.
Summary of the invention
In order to solve the problem existing in background technology, the invention provides the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam, this technique CO deep conversion, unstripped gas (contains: water-gas, semi-water gas, conversion of natural gas gas or coke(oven)gas reforming gas) utilization ratio is high, transformation catalyst is overtemperature not, catalyzer long service life, the saturation steam of by-product 0.5～9.0MPa simultaneously, utilize deaerated water and de-salted water further to reclaim sensible heat and latent heat in conversion gas, low grade heat energy is converted into higher-grade heat energy, reduce cooling-water consumption, go out conversion gas≤40 ℃ of process system.Equipment is few, flow process is short, investment is supported, resistance low (≤0.05MPa).
For solving above technical problem, the technical scheme that the present invention takes is the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam, and this technique comprises the following step:
A. unstripped gas gas-water separation first, unstripped gas comprises: high water-gas ratio, high CO water-gas; Low water-gas ratio, high CO water-gas; High water-gas ratio conversion of natural gas gas, high water-gas ratio coke(oven)gas reforming gas and low water-gas ratio semi-water gas;
B. the heating of the unstripped gas after gas-water separation;
C. the unstripped gas after heating carries out detoxification and pre-change reaction;
D. unstripped gas completes part CO and is converted into H in one-level water shifting heat shift converter
2, CO
2, adopt water indirectly to reclaim catalyst bed reaction heat, by-product 2.5～9.0MPa higher-grade saturation steam;
E. conversion gas completes remaining CO and is converted into H in secondary water shifting heat shift converter
2, CO
2, adopt water indirectly to reclaim catalyst bed reaction heat, by-product 0.5～2.5MPa saturation steam;
F. adopt deoxygenation soft water to reclaim sensible heat and the latent heat in conversion gas, deaerated water is heated to 150～220 ℃;
G. adopt de-salted water to reclaim sensible heat and the latent heat in conversion gas, heated 104～230 ℃ of de-salted water;
H. adopt water coolant that conversion gas is cooled to below 40 ℃;
I. separating technology water of condensation;
J. the ammonia in de-mineralized water washing conversion gas;
K. adopt low-pressure steam by gas-entrained flashing off in process condensate water;
L. tail gas removes torch burning, degassing of process condensate water;
M. system design temperature 0.8～9.0MPa.
Further, unstripped gas gets off carrying harmful liquid separation in gas secretly in 1# gas-liquid separator (1).
Further, unstripped gas by exporting high-temperature gas heat exchange with one-level water shifting heat shift converter (4), is guaranteed into the unstripped gas temperature>=T of detoxification groove (3) in unstripped gas well heater (2)
water coal gas dew-point temperature+ 30 ℃, protection detoxifying agent and cobalt-molybdenum catalyst.
Further, the heavy metal oxide that contains in unstripped gas, dust and other are absorbed by detoxification groove (3) upper strata sorbent material catalyzer objectionable impurities; A small amount of cobalt-molybdenum series catalyst loads by part CO and H in unstripped gas in detoxification groove (3) lower floor
2o reaction is converted into H
2and CO
2, unstripped gas temperature increase to 250～300 ℃.Sorbent material is the sorbent material that the conventional CT series magnesium-aluminium spinel in this area is main component.
Further, unstripped gas completes part CO and is converted into H in one-level water shifting heat shift converter (4)
2, CO
2, CO≤2.0% (butt) in one-level water shifting heat shift converter (4) outlet conversion gas.Temperature of reaction at 180～400 ℃, pressure at 0.8～9.0MPa.
Further, conversion gas completes remaining part CO and is converted into H in secondary water shifting heat shift converter (6)
2, CO
2, and by-product 0.5～2.5MPa saturation steam; CO≤0.1% (butt) in secondary water shifting heat shift converter (6) outlet conversion gas, the water of removing one-level, secondary water shifting heat shift converter reaction heat is natural circulation, hot water parses higher-grade saturation steam in gas bag.Temperature of reaction at 180～300 ℃, pressure at 0.8～9.0MPa.
Further, the sensible heat and the latent heat that reclaim conversion gas by deoxygenation soft water heater (8) and de-salted water well heater (9) two-stage drop to below 40 ℃ conversion gas temperature, and the deoxygenation soft water of heating supplies with 1
#gas bag (5), 2
#gas bag (7).
Further, transformation system process condensate water is realized gas-liquid separation by 2# gas-liquid separator (10), and liquid directly degassing is recycled; Gas is washed tower (11) at ammonia and is completed washing, purifying, and after purifying, gas removes subsequent processing, and washings completes flash distillation in stripping tower (12), and temperature is 25～160 ℃.Flash off the gas torch that reduces internal heat, liquid goes gasification process to recycle.
Further, water shifting heat shift converter is the transformation task that two-stage just completes CO; One-level, secondary water shifting heat shift converter are full radial structure, gas upper entering and lower leaving, air-flow ecto-entad radially passes through beds, what in cobalt molybdenum or copper-zinc system catalyst bed, setting was convenient to lift by crane moves hot-water line unit, CO≤0.1% (butt) in secondary water shifting heat shift converter outlet conversion gas; The water of removing I and II water shifting heat shift converter reaction heat is natural circulation, and 1
#, 2
#in gas bag, parse saturation steam.
Further, system catalyst sulfuration is separate unit sulfuration in parallel, changes detoxification groove (3) wherein when detoxifying agent and catalyzer and sulfuration, under system normal operating condition, completes.
Further, normal drive to adopt steam supply thermal source, the natural cycle system of driving steam heating I and II water shifting heat shift converter, the circulation by water is by beds preheating, catalyzer also reaches more than 180 ℃ light-off temperature, supplies with thermal source without electric heater is set in addition.
The invention has the beneficial effects as follows:
(1) detoxification groove is designed to two of A, B, be used alternatingly, the not only poisonous substance in planar water coal gas, during simultaneously to each driving, katalysis by the inner loading catalyst of detoxification groove makes saturation water in water-gas change superheated vapour into, while stopping to drive, because saturation steam causes " dew point corrosion " to follow-up equipment, guarantee shift converter catalyzer work-ing life >=8 year.
(2) shift converter adopts two, First shift converter (one-level water shifting heat shift converter) beds inside is embedded with the heat transfer tube of water shifting heat, one-level water shifting heat shift converter reaction heat and detoxification groove reaction heat all shift out by being embedded in one-level water shifting heat shift converter beds inner water tube, and by-product 2.56～9.0MPa saturation steam; Second shift converter (secondary water shifting heat shift converter) beds inside is also embedded with the heat transfer tube of water shifting heat, secondary water shifting heat shift converter reaction heat shifts out by being embedded in secondary water shifting heat shift converter beds inner water tube, and by-product 0.5～2.5MPa saturation steam, because the reaction heat of shift converter is removed in time by inner water tube, shift converter temperature out is easy to control, and catalyzer can fill more.
(3) furnace temperature of one-level water shifting heat shift converter and secondary water shifting heat shift converter beds regulates by shift converter byproduct steam pressure, guarantees that adjusting aspect is flexible, easy to control; Also while guaranteeing to drive, take to add steam to the natural water circulation system of one-level water shifting heat shift converter, secondary water shifting heat shift converter, rapidly shift converter temperature rise is got up, with restart up simultaneously.
(4) natural circulation is taked in one-level water shifting heat shift converter and secondary water shifting heat shift converter water route, suddenly while parking, the CO of the inner nubbin of shift converter continues reaction, water route also still keeps circulation, and beds internal heat is shifted out, guarantee also can not surpass in the furnace temperature of unexpected dead ship condition shift converter.
(5) reclaim 200～210 ℃ of conversion gas sensible heats of secondary water shifting heat shift converter outlet and latent heat and adopt deaerated water and de-salted water to reclaim, guarantee not use under recirculated cooling water prerequisite conversion gas temperature out≤40 ℃.
(6) festoon of one-level water shifting heat shift converter and secondary water shifting heat shift converter catalyzer internal heat transfer is an one-piece construction, can hang out smoothly, is convenient to maintenance and the catalyzer self-unloading of tube bank; Meanwhile, be provided with access opening at top end socket, bottom head is provided with catalyzer self-unloading hole, catalyst loading, press filler and unload the details such as catalyzer and also can complete in the time not hanging on portion's end socket.
(7) conversion corrosion is mainly " hydrogen-type corrosion " and " dew point corrosion ", the water-gas of water-gas well heater, detoxification groove, one-level water shifting heat shift converter, secondary water shifting heat shift converter inside and the " H that conversion gas inside is contained
2o " be superheated vapour, these equipment will solve " hydrogen-type corrosion " problem; " H in deaerated water well heater, de-salted water well heater, air water separator conversion gas
2o " become liquid state from saturated mode, easily form " acidic solution ", these equipment will solve " dew point corrosion " problem.
(8) one-level water shifting heat shift converter, secondary water shifting heat shift converter bed temperature are by Steam pressure control, transformationreation balance temperature is apart from large, impellent is large, adopt two shift converters just can realize transformation system outlet CO≤0.1% (butt), gas flow process is short, and major equipment is only 8 (detoxification groove is out that one is standby).Change that original conversion process long flow path, equipment are many, " dew point corrosion " is many, construction investment is large, maintenance cost is high, working cost is high and easily occur the defects such as security incident.
(9) we are applied in shift converter reactor fine reactors for synthesis of ammonia radial distribution principle, inside and outside be equipped with gas distributor and surge drum, gas distributor inner side and surge drum outside are equipped with bridge-type grid distributor again, between inside and outside, adopt two compensation, make radial gas distribution error≤5.0%, guarantee that gas distribution is even; Shift converter overall resistance≤0.01MPa, two shift converters can meet 20～600,000 tons/year of synthesis capabilities; Not only solve a transportation difficult problem, reduce construction investment simultaneously.
(10) the present invention is practical, can meet all unstripped gas conversion process.Patent of the present invention can be for new project, also can be for old plant modification.
Accompanying drawing explanation:
Accompanying drawing 1 is the process flow sheet of space flight stove and the conversion of pressurization shell (shell) pressurization fine coal pressurization continuous gasification;
Accompanying drawing 2 is the conversion process flow process of the pressurization fine coal pressurization continuous gasifications such as coal water slurry Texaco, GSP, multi-nozzle;
Accompanying drawing 3 is the technical process of the conversion of the low water-gas ratio of fine coal atmosphere intermission formula fixed bed gasification.
Embodiment
Below in conjunction with accompanying drawing, invention embodiment is described further:
Embodiment 1:
As shown in Figure 1, the unstripped gas that carrys out self-gasifying device enters 1# gas-liquid separator 1-1 inside and carries out lower eddy flow (the downward eddy flow of gas is convenient to separate), 180 ° of separated rear reversions of dust and water enter pipe core, then enter Stainless Steel Cloth and further filter, and guarantee that gas is clean.
The unstripped gas that goes out 1# liquid/gas separator 1-1 enters unstripped gas well heater 1-2 heat exchange, after temperature to 240 ℃ (30 ℃ of feeding temperature >=dew-point temperatures), enter detoxification groove 1-3, gas directly enters a small amount of beds in bottom and reacts after the detoxifying agent detoxification of top, temperature is elevated to 300 ℃ (controlling temperature of reaction≤300 ℃ by loaded catalyst), utilizes this partially catalyzed agent further to adsorb under hot conditions and removes the objectionable impurities in water-gas.The gas that goes out detoxification groove 1-3 enters one-level water shifting heat shift converter 1-4 and reacts, temperature is controlled at 240～350 ℃, the gas that goes out 240～350 ℃ of one-level water shifting heat shift converter 1-4 removes unstripped gas well heater 1-2 heating water coal gas, temperature enters secondary water shifting heat shift converter 1-6 and reacts after dropping to 230～250 ℃, temperature is controlled at 190～210 ℃.The gas that goes out 190～210 ℃ of secondary water shifting heat shift converter 1-6 enters deaerated water well heater 1-8 and heats the deoxygenation soft water (water temp. heating to 190～220 ℃) that enters 1#, 2# gas full (1-5,1-7), gas temperature enters de-salted water well heater 1-9 after dropping to 152～154 ℃, de-salted water is heated to 104 ℃ and directly removes thermal de-aeration.After gas temperature drops to 40 ℃, through 2# gas-liquid separator 1-10, system process water of condensation is separated, conversion gas H completes washing in ammonia is washed tower 1-11, goes rear operation after washing.Process condensate water and washing water complete flash distillation in stripping tower 1-12, the tail gas I flashing off, degassing of process condensate water K.
Deaerated water C heating procedure: the water yield that native system 1#, 2# gas bag (1-5,1-7) need is～1311.313kg/tNH
3, after deaerated water well heater 1-8, temperature is elevated to 190～220 ℃, and the deaerated water C of heating meets not outer confession of self needs;
25 ℃ of de-salted water D are after de-salted water well heater 1-9 heating, and temperature raises 104 ℃ can directly remove system for deoxidizing by heat power, does not need additional steam, and the de-mineralized water G amount of heating is :～6388.78kg/tNH
3.
After the washing of the total water of condensation of de-salted water well heater 1-9 and deaerated water well heater 1-8, flash distillation, be transported to gasification process.
Existing 4 the adiabatic shift converter Technology economical operation index contrast table look-ups of the present invention and space flight stove are as follows:
Embodiment 2,
As shown in Figure 2, the unstripped gas that carrys out self-gasifying device enters 1# gas-liquid separator 2-1 inside and carries out lower eddy flow (the downward eddy flow of gas is convenient to separate), 180 ° of separated rear reversions of dust and water enter pipe core, then enter Stainless Steel Cloth and further filter, and guarantee that gas is clean.
The unstripped gas that goes out 1# liquid/gas separator 2-1 enters unstripped gas well heater 2-2 heat exchange, after temperature to 300 ℃ (30 ℃ of feeding temperature >=dew-point temperatures), enter detoxification groove 2-3, gas directly enters a small amount of beds in bottom and reacts after the detoxifying agent detoxification of top, temperature raises～300 ℃, utilizes this partially catalyzed agent further to adsorb under hot conditions and removes the objectionable impurities in water-gas.The gas that goes out detoxification groove 2-3 enters one-level water shifting heat shift converter 2-4 and reacts, the water that reaction heat is embedded in beds pipe absorbs by-product 2.5～9.0MPa saturation steam, reaction bed temperature is controlled at 300～350 ℃, the gas that goes out 4300～350 ℃ of one-level water shifting heat shift converters removes unstripped gas well heater 2-2 heating water coal gas, temperature drops to～and entering the adiabatic shift converter 2-13 of secondary after 260 ℃ reacts, and temperature is controlled at 250～270 ℃.The gas that goes out 250～270 ℃ of the adiabatic shift converter 2-13 of secondary divides two-way, and a road enters deaerated water well heater 2-8 and heats the deoxygenation soft water (water temp. heating to 190～220 ℃) that enters the full 2-5 of 1# gas and waste heat boiler 2-13; Waste heat boiler 2-13 by-product 0.5～2.5MPa saturation steam is removed on another road.After two-way gas mixes temperature drop to～178 ℃, enter de-salted water well heater 2-9 complete gas-liquid separation in 3# gas-liquid separator 2-15 after, de-salted water is heated to 104 ℃ and directly removes thermal de-aeration.After gas temperature drops to 40 ℃, through 2# gas-liquid separator 2-10, system process water of condensation is separated, conversion gas H completes washing in ammonia is washed tower 2-11, goes rear operation after washing.Process condensate water and washing water complete flash distillation in stripping tower, the tail gas I flashing off, degassing of process condensate water K.
Deaerated water C heating procedure: deaerated water is heated to 190～220 ℃Fen tri-tunnels in deaerated water well heater inside, the first via enters 1# gas bag 2-5, by-product 2.5～9.0MPa saturation steam, waste heat boiler 2-13 by-product 0.5～2.5MPa saturation steam is removed on the second tunnel; Third Road is outward for gasification;
25 ℃ of de-salted water D are after de-salted water well heater 2-9 heating, and temperature raises 104 ℃ can directly remove system for deoxidizing by heat power, does not need additional steam.
2#, 3# gas-liquid separator (2-10,2-15) and ammonia are transported to gasification process after washing the process condensate water flash distillation of tower 2-11.
The unstripped gas conversion process technical operation economic target contrast table look-up that the present invention and coal slurry gasifier are produced is as follows:
The present invention and conventional water-gas gasification converter technique is different in flow setting, and also difference to some extent of operation energy consumption and every economic and technical norms, is listed as follows with regard to two kinds of processing parameters and the contrast of economical operation index below:
Converter technique of the present invention has following advantage as can be seen from the above table:
1,, from operation, conversion process of the present invention, can be down to 0.6% by the CO of transformation system outlet, has also just been equivalent to increase by 1% H
2, not only reduce the load of gas sweetening, increased effectively synthetic tolerance simultaneously, produce the changing device of 400Kt/a per year, can be increased to synthesizer H
2amount is 1810NM
3/ h, by ton ammonia hydrogen consumption 1988NM
3calculate, can every little increase output 0.91t product ammonia.
2, the technique of the present invention conversion, can improve the quality of byproduct steam, not only the steam grade of former by-product 4.0MPa is increased to 6.3Mpa, but also the amount of by-product middle pressure steam is increased to 790Kg/tNH3 by 430Kg/tNH3.
3, reduce cooling water amount 3.81M
3/ tNH
3.
4, can find out that from upper comparison converter technique of the present invention can, by improving the transformation efficiency of CO, increase effective tolerance of entering synthesis system, thereby reach the effect of energy-saving and production-increase, has not only improved the grade of byproduct steam, and can save the cooling water inflow of system.
5, converter technique of the present invention is not only applicable to newly-built changing device, is applicable to existing changing device yet and transforms, and only need increase a water shifting heat shift converter when transformation, and part pipeline is adjusted, and about half a year, can recoup capital outlay.
Embodiment 3
As shown in Figure 3: the unstripped gas that carrys out self-gasifying device enters 1# gas-liquid separator 3-1 inside and carries out lower eddy flow (the downward eddy flow of gas is convenient to separate), 180 ° of separated rear reversions of dust and water enter pipe core, then entered Stainless Steel Cloth and further filtered, guaranteed that gas was clean.
The unstripped gas separating after profit enters saturator 3-24 and enters tower hot water heat exchange humidification, going out saturator 3-24 gas is heated to 300～350 ℃ at unstripped gas well heater 3-2 and enters one section of bed 3-28 of middle change stove reaction, and then enter middle change two-section batch 3-29 reaction, 420～440 ℃ of incoming stock hot-air heater 3-2 of conversion gas after reaction, temperature enters one section of water cooler 3-30 after being down to 260～290 ℃, temperature enters secondary water shifting heat shift converter 3-6 and continues reaction after being down to 220 ℃, the water that reaction heat is embedded in the inner tube bank of beds absorbs, and flash off in 2# gas bag 3-7, 0.5～2.5MPa steam F, reacted gas enters one section of bed 3-32 reaction of low change stove, the conversion gas that goes out one section of bed 3-32 of low change stove enters and enters low change stove two-section batch 3-32 after two-step cooling device 3-31 cooling again and react, reacted gas enters the first water heater 3-27 heating cycle water, temperature is down to and after 140 ℃, is entered hot-water tower 3-25 and reclaim latent heat and the sensible heat in conversion gas, go out the conversion gas of hot-water tower 3-25 through water, water cooler 3-22 is cooled to 40 ℃ to enter subsequent processing conversion gas,
Hot water circulation: the hot water that goes out hot-water tower 3-25 is heated to 142 ℃ and enters saturator 3-24 humidification unstripped gas through the first water heater 3-27, one section of water cooler 3-30, two-step cooling device 3-31 successively, circulating hot water is down to～and to enter the second water heater 3-23 after 93 ℃ cooling, and temperature is down to 60 ℃ and is entered hot-water tower 3-25 and reclaim sensible heat and the latent heat in conversion gas.104 ℃ of deaerated water replenish hot-water tower 3-25 middle part.
The embodiment of the present invention is mainly carried out reducing energy consumption to existing " in low " conversion process, not only by-product 0.5～2.5MPa steam F, reduce conversion energy consumption simultaneously, and existing " in low " conversion process mainly implemented following three transformations and just can be realized the object of by-product higher-grade steam, energy-conservation and deep conversion:
1, between " one section of water cooler 3-30 " and " one section of bed 3-32 of low change stove " import, increase by one can byproduct steam " secondary water shifting heat shift converter 3-6 " and " 2# gas bag 3-7 ", unnecessary heat is converted into 1.2MPa saturation steam, can by-product 239.55kg/tNH after transformation
3saturation steam.
2, original " the second water heater 3-23 " changes saturator 3-24 into hot water cooler use between hot-water tower 3-25.
3, a liquid distributor 3-26 of the inner increase of hot-water tower 3-25, supplemental heat water level is put and is changed between two sections of fillers of hot-water tower 3-25.
We are according to 65000Nm3/h unstripped gas, and " in the low " changing device that has that connection alcohol generates adopts the economical operation index of example of the present invention transformation front and back to be listed in the table below:
When the present invention is applied to the water-gas shift of high water-gas ratio, high C0, detoxification groove is that A, two of B are used alternatingly, in detoxification groove, filling magnesia-alumina spinel structure detoxifying agent and cobalt molybdenum are pre-change catalyzer, and detoxifying agent and the separately filling of pre-change catalyzer, as accompanying drawing 1, accompanying drawing 2.Secondary water shifting heat shift converter can be adiabatic reactor layer shift converter, and adiabatic bed shift converter postorder will configure waste heat boiler and deaerated water well heater and reclaim out sensible heat and the latent heat of adiabatic bed shift converter gas; When the conversion of natural gas gas of high water-gas ratio or the conversion of coke(oven)gas reforming gas, become in advance stove into one, inner filling Fe-series catalyst; When low water-gas ratio semi-water gas conversion, become in advance stove into one, top filling detoxifying agent, hypomere filling cobalt-molybdenum series catalyst, separate with end socket between two sections.Secondary water shifting heat shift converter can be adiabatic reactor layer shift converter, and cobalt-molybdenum series catalyst divides two sections of fillings, separates, and adopt cycling hot water shifting heat between two sections; When the transformation of low water-gas ratio semi-water gas " in low " conversion process, become in advance stove into one, catalyzer divides two sections, and as shown in Figure 3, two sections all load Fe-series catalyst, between two sections, separate with end socket.
Claims (11)
1. a water shifting heat conversion process for the energy-conservation deep conversion of by-product higher-grade steam, this technique comprises the following step:
A. unstripped gas gas-water separation first, unstripped gas comprises: high water-gas ratio, high CO water-gas; Low water-gas ratio, high CO steam; High water-gas ratio conversion of natural gas gas, high water-gas ratio coke(oven)gas reforming gas and low water-gas ratio semi-water gas;
B. the heating of the unstripped gas after gas-water separation;
C. the unstripped gas after heating carries out detoxification and pre-change reaction;
D. unstripped gas completes part CO and is converted into H in one-level water shifting heat shift converter
2, CO
2, adopt water indirectly to reclaim catalyst bed reaction heat, by-product 2.5～9.0MPa higher-grade saturation steam;
E. conversion gas completes remaining CO and is converted into H in secondary water shifting heat shift converter
2, CO
2, adopt water indirectly to reclaim catalyst bed reaction heat, by-product 0.5～2.5MPa saturation steam;
F. adopt deoxygenation soft water to reclaim sensible heat and the latent heat in conversion gas, deoxygenation soft water is heated to 150～220 ℃;
G. adopt de-salted water to reclaim sensible heat and the latent heat in conversion gas, heated 104～230 ℃ of de-salted water;
H. adopt water coolant that conversion gas is cooled to below 40 ℃;
I. separating technology water of condensation;
J. the ammonia in de-mineralized water washing conversion gas;
K. adopt low-pressure steam by gas-entrained flashing off in process condensate water;
L. tail gas removes torch burning, degassing of process condensate water;
M. system design temperature 0.8～9.0MPa.
2. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, is characterized in that: unstripped gas gets off carrying harmful liquid separation in gas secretly in 1# gas-liquid separator (1).
3. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, it is characterized in that: unstripped gas by exporting high-temperature gas heat exchange with one-level water shifting heat shift converter (4), is guaranteed into the unstripped gas temperature>=T of detoxification groove (3) in unstripped gas well heater (2)
water-gas dew-point temperature+ 30 ℃, protection detoxifying agent and cobalt-molybdenum catalyst.
4. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, is characterized in that: the heavy metal oxide that contains in unstripped gas, dust and other are absorbed by detoxification groove (3) upper strata sorbent material catalyzer objectionable impurities; The cobalt-molybdenum catalyst of detoxification groove (3) lower floor filling part is by part CO and H in unstripped gas
2o reaction is converted into H
2and CO
2, unstripped gas temperature increase to 250～300 ℃.
5. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, is characterized in that: unstripped gas completes part CO and is converted into H in one-level water shifting heat shift converter (4)
2, CO
2, butt CO≤2.0% in one-level water shifting heat shift converter (4) outlet conversion gas, temperature of reaction is that 180～400 ℃, pressure are 0.8～9.0MPa.
6. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, is characterized in that: conversion gas completes remaining part CO and is converted into H in secondary water shifting heat shift converter (6)
2, CO
2, and by-product 0.5～2.5MPa saturation steam; Butt CO≤0.1% in secondary water shifting heat shift converter (6) outlet conversion gas, the water of removing one-level, secondary water shifting heat shift converter reaction heat is natural circulation, hot water parses higher-grade saturation steam in gas bag, temperature of reaction at 180～300 ℃, pressure at 0.8～9.0MPa.
7. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, it is characterized in that: the sensible heat and the latent heat that reclaim conversion gas by deoxygenation soft water heater (8) and de-salted water well heater (9) two-stage drop to below 40 ℃ conversion gas temperature, and the deoxygenation soft water of heating supplies with 1
#gas bag (5), 2
#gas bag (7).
8. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, it is characterized in that: transformation system process condensate water is realized gas-liquid separation by 2# gas-liquid separator (10), liquid directly degassing is recycled; Gas is washed tower (11) at ammonia and is completed washing, purifying, and after purifying, gas removes subsequent processing, and washings completes flash distillation in stripping tower (12), and temperature is 25～160 ℃; Flash off the gas torch that reduces internal heat, liquid goes gasification process to recycle.
9. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, is characterized in that: water shifting heat shift converter is the transformation task that two-stage just completes CO; Gas upper entering and lower leaving in one-level, secondary water shifting heat shift converter, air-flow ecto-entad radially passes through beds, what in cobalt molybdenum or copper-zinc system catalyst bed, setting was convenient to lift by crane moves hot-water line unit, butt CO≤0.1% in secondary water shifting heat shift converter outlet conversion gas, the water of removing I and II water shifting heat shift converter reaction heat is natural circulation, and 1
#, 2
#in gas bag, parse saturation steam.
10. the water shifting heat conversion process of the energy-conservation deep conversion of a kind of by-product higher-grade steam according to claim 1, it is characterized in that: system catalyst sulfuration is separate unit sulfuration in parallel, change detoxification groove (3) wherein when detoxifying agent and catalyzer and sulfuration, under system normal operating condition, complete.
The water shifting heat conversion process of the energy-conservation deep conversion of 11. a kind of by-product higher-grade steam according to claim 1, it is characterized in that: the normal employing steam supply thermal source of driving, the natural cycle system of driving steam heating I and II water shifting heat shift converter, circulation by water is by beds preheating, catalyzer also reaches more than 180 ℃ light-off temperature, supplies with thermal source without electrically heated is set in addition.
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| CN103881767B (en) * | 2014-03-24 | 2015-05-13 | 中石化宁波工程有限公司 | Circulating CO shift process of saturation tower |
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| CN106838854B (en) * | 2017-03-21 | 2019-03-08 | 灵谷化工有限公司 | A kind of transformation system and its application method of by-product high-grade steam |
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Application publication date: 20121003 Assignee: Nanjing Dun Xian Chemical Industry Science Co., Ltd Assignor: Wang Lanyue Contract record no.: 2015320000016 Denomination of invention: Water heat-transfer shift process for by-product high-grade steam energy-saving deep conversion Granted publication date: 20140528 License type: Exclusive License Record date: 20150128 |
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