CN101155757A

CN101155757A - Integration of gasification and ammonia production

Info

Publication number: CN101155757A
Application number: CN 200680011836
Authority: CN
Inventors: C·A·施米德特
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2005-04-11
Filing date: 2006-04-05
Publication date: 2008-04-02
Also published as: ZA200707435B

Abstract

A method and system are described for making ammonia using hydrogen from a gasification process and for integrating the steam systems of the two processes. The gasification process provides high-pressure, purified hydrogen and high-pressure, saturated steam. The high pressure hydrogen lowers the overall compression requirement for the ammonia process. In addition, the high-pressure, saturated steam can be converted into superheated steam by recovering heat from ammonia synthesis and used to power steam turbines for compression and refrigeration needs.

Description

It is integrated that gasification and ammonia are produced

The mutual reference of related application

[0001] relate generally to ammonia of the present invention is synthetic.More specifically, the present invention relates to by produce the novel method of the steam system of hydrogen system ammonia and integrated these 2 kinds of technologies with gasifying process.The present invention can provide enough steam to drive existing turbine drives and so and the cost of reduction operation ammonia synthesis technology of drawing gas.

Background of invention

[0002] reaction of nitrogen and hydrogen generation ammonia is known.Just developed the industrial production of ammonia as far back as 20 beginnings of the century.The production method of ammonia is to make hydrogen and nitrogen at the catalyst surface direct reaction based on iron:

3H ₂+N ₂→2NH ₃

The building-up reactions of ammonia is heat release; Therefore, balance will move right with the decline of temperature of reaction.But in fact, temperature of reaction must maintain sufficiently high degree, but could synthesize the product of quantities received in the rationally short time.Even use catalyzer to come accelerated reaction speed usually, also be like this.Thermodynamic study is also supported under high pressure, generally under 15～346 crust, carries out this reaction.This class high pressure needs big energy, with the form of steam or electricity, is used for compression usually.

[0003] industry of ammonia is synthesized generally 3 key steps.The first, preparation ammonia-synthesizing material gas body.This step comprises generation hydrogen, removes impurity in the hydrogen and catalyzer poison and mixes nitrogen and hydrogen with stoichiometric ratio.Catalyzer poison mainly is carbonic acid gas and carbon monoxide, but sulphur also can poison catalyzer.In history, with water gas shift reaction the carbon monoxide in the gas is converted into hydrogen and carbonic acid gas, this relates to carbon monoxide and steam reacts on catalyzer.Carbonic acid gas can be removed with the multiple gases purification technique.Nitrogen generally is fed to the suction side of ammonia synthesis loop compressor.The second, make the ammonia-synthesizing material gas body pass through ammonia synthesis reactor.The 3rd, the ammonia product gas that cooling is come out from ammonia synthesis reactor reclaims the ammonia product and loops back unreacted ammonia synthesis gas.

[0004] steam methane conversion (SMR) is the traditional hydrogen source that is applicable to ammonia synthesis always.Based on the ammonia industrial natural gas of Sweet natural gas as raw material and can (fuel) source.But the rise of Gas Prices has made some ammonia producers or has for good and all stopped production, and perhaps looks for another way and produces hydrogen economically.

[0005] gasification is becoming the tempting method of producing the required hydrogen amount of world-class ammonia production unit.Gasification can provide and not be subjected to the stable of the rapid influence of fluctuations in market and reliable raw material.Gasification can be used for from hydrocarbon feed, as coal, refinery coke, Residual oil and other material, produces synthesis gas for many years.Hydrocarbon feed is gasified in the presence of aerobic.Oxygen produces with air separation equipment usually, in this equipment, removes airborne nitrogen to form purifying oxygen.

[0006] nitrogen from air separation has caused with gasification as the method that hydrogen and nitrogen raw material are provided for ammonia synthesis with the validity of coming the hydrogen containing synthesis gas body of autopneumatolysis.Can make the synthesis gas that in gasifier, produces pass to the transformationreation section, here, on catalyzer, react and CO is converted into H by CO and steam ₂And CO ₂Conversion gas can further be made with extra care, and method commonly used is to separate, to form the purified hydrogen air-flow.For example, the conversion synthetic air can sour gas remove and purification section in purifying, and the purified hydrogen product can be conducted to the ammonia synthesis reaction loop.Synthetic air can be processed, to obtain the hydrogen stream that purity is higher than 99.9mol%.By product nitrogen can take out from oxygen equipment, and is purified, mixes with hydrogen then, to form the ammonia-synthesizing material gas body.

[0007] gasification and new and existing ammonia process based on Sweet natural gas is integrated, generally is not that Energy Efficient and cost are effective always.Especially, the design in past does not produce enough steam always and has caused and need replace the turbine drives of drawing gas with electric motor.But, use electric motor will increase the initial investment of integrated project, also can cause higher Operation and maintenance cost.Therefore, preferably solve the integrated problem that enters into new and existing ammonia equipment based on Sweet natural gas of gasification, so that there is enough power to drive processing unit and need not electric motor with vapor form.

Summary of the invention

[0008] production technique of ammonia can be effectively integrates with gasifying process as High Pressure Hydrogen and vapour source.Therefore, in first inventive point, the present invention relates to the method for a kind of integrated hydrogen manufacturing technology and Ammonia Process.This method comprises:

(a) make the reaction of carbonaceous material and oxygen in gasifying process, gasifying process comprises high pressure gasifier and has the CO transformationreation section of transformationreation section product stream;

(b) make from the hydrogenous high pressure synthetic air of the bag of gasifying process and pass to Ammonia Process as feeding, Ammonia Process comprises the ammonia convertor section that contains ammonia product stream;

(c) be used to heat generation high pressure-saturation steam that transformation into itself's conversion zone product flows;

(d) make all or part of high pressure saturated vapo(u)r and all or part of ammonia product stream from step (c) carry out heat exchange, to produce superheated vapour, wherein, at least 50% superheated vapour total amount that is used for ammonia process produces by described heat exchange; With

(e) make described superheated vapour pass to the steamer driving mechanism of steamer driving mechanism, ammonia refrigerating compressor of hydrogen and nitrogen feed compressor or both.

Gasifying process produces the hydrogenous high pressure draft of bag, and the compression energy that its needs is lacking from traditional hydrogen raw material of conversion of natural gas recently.In addition, gasifying process provides high-pressure saturated steam, and it can make up the heat that ammonia plant produces effectively, and producing superheated vapour, the latter can be used for the steam turbine of driving gas compression and other energy requirement.

[0009] in second inventive point, the present invention relates to the integral process of a kind of hydrogen manufacturing and system ammonia.This technology comprises:

(a) in high pressure gasifier, make the reaction of carbonaceous material and oxygen, comprise the high pressure gasifier product stream of hydrogen, carbonic acid gas, carbon monoxide and water with generation;

(b) make gasifier product be circulated to CO transformationreation section, comprise the high pressure conversion conversion zone product stream of other hydrogen and carbonic acid gas with generation;

(c) be used to the heat generation high-pressure saturated steam that transformation into itself's conversion zone product flows;

(d) make transformationreation section product be circulated to purification section, to remove CO ₂And H ₂S, and form the hydrogenous high pressure purifying gasification product stream of bag;

(e) make high pressure purifying gasification product stream and nitrogen pass to hydrogen and nitrogen feed compressor, to produce ammonia convertor feeding stream;

(f) make ammonia convertor feeding be circulated to ammonia convertor section, to form ammonia product stream;

(g) make ammonia product stream and high-pressure saturated steam from the transformationreation section carry out heat exchange, to form superheated vapour, wherein at least 50% superheated vapour total amount that is used for ammonia process produces by heat exchange; With

(h) make superheated vapour pass to the steamer driving mechanism of steamer driving mechanism, ammonia refrigerating compressor of hydrogen and nitrogen feed compressor or both.

[0010] in the 3rd inventive point, the present invention relates to the integral system of a kind of hydrogen manufacturing and system ammonia.This system comprises:

(a) high pressure gasifier is used for making the reaction of carbonaceous material and oxygen, comprises the high pressure gasifier product stream of hydrogen, carbonic acid gas, carbon monoxide and water with generation;

(b) CO transformationreation section is used for transforming carbon monoxide and water in the gasifier product stream, comprises the high pressure conversion conversion zone product stream of other hydrogen and carbonic acid gas with generation;

(c) first heat exchange segments is used for being used to the heat generation high-pressure saturated steam that transformation into itself's conversion zone product flows;

(d) purification section is used for removing CO ₂And H ₂S, and form the hydrogenous high pressure purifying gasification product stream of bag;

(e) nitrogen and hydrogen feed compressor are used for compressing high pressure purifying gasification product stream and nitrogen, to produce ammonia convertor feeding stream;

(f) ammonia convertor section is used for making hydrogen and nitrogen reaction in the ammonia convertor feeding stream, to generate the ammoniated product stream of bag;

(g) second heat exchange segments is used for the high-pressure saturated steam of giving from the thermal exchange of ammonia product stream from the transformationreation section, to form superheated vapour; With

(h) be used for the steamer driving mechanism of nitrogen and hydrogen feed compressor or be used for the steamer driving mechanism of ammonia refrigerating compressor, it is accepted to the described superheated vapour of small part.

The accompanying drawing summary

[0011] Fig. 1 is that signal is according to gasifier of the present invention and the incorporate feel flow draw of block of existing ammonia equipment.Fig. 2 is the simplification process flow sheet according to ammonia plant of the present invention and integrated steam system.

Detailed Description Of The Invention

[0012] gasification of carbonaceous material can be used to produce High Pressure Hydrogen and the steam that is applicable to that ammonia is produced.The integrated of gasification and ammonia process can method effective with cost and Energy Efficient be realized, and provided attractive economically another kind of method to the hydrogen from conversion of natural gas.Therefore, in general embodiment, the invention provides the method for a kind of integrated hydrogen manufacturing technology and Ammonia Process, comprising:

(a) make the reaction of carbonaceous material and oxygen in gasifying process, described gasifying process comprises high pressure gasifier and has the CO transformationreation section of transformationreation section product stream;

(b) make from the hydrogenous high pressure synthetic air of the bag of described gasifying process and pass to Ammonia Process as feeding, described Ammonia Process comprises the ammonia convertor section that contains ammonia product stream;

(d) make all or part of high pressure saturated vapo(u)r and all or part of ammonia product stream from step (c) carry out heat exchange, to produce superheated vapour, wherein at least 50% superheated vapour total amount that is used for ammonia process produces by heat exchange; With

Gasifier produces the air-flow that comprises carbon monoxide, carbonic acid gas and hydrogen, can be converted into other hydrogen and carbonic acid gas with water gas shift reaction.The pressure of consequent hydrogen is higher than the pressure from the hydrogen of traditional natural gas conversion process, therefore, only needs less compression as the ammonia synthesis raw material time.In addition, water gas shift reaction provides high-pressure saturated steam, can utilize the heat that produces in the ammonia plant to improve temperature, and producing superheated vapour, the latter can be used for the steam turbine of driving gas compression and other energy requirement.

[0013] except as otherwise noted, the numeral of the quantity of the character of used all expressions components, molecular weight and so on, reaction conditions etc. all is interpreted as all being modified with in all cases " pact " word in this specification sheets and the claim.Therefore, unless opposite explanation is arranged, the digital parameters of mentioning in following specification sheets and the claims all is an approximation, and they can change according to the expected performance of the pursuit that obtains with the present invention.At least, should regard each digital parameters at least as according to the significant figure of report and the value that obtains with common rounding-off method.And the scope described in the disclosure and the claim is intended to comprise entire area particularly and not merely be end value.For example, described 0～10 scope is intended to disclose all integers between 0～10, as 1,2,3,4 etc.; All marks between 0～10 are as 1.5,2.3,4.57,6.113 etc.; And end points 0 and 10.The scope relevant with chemical substituting group, for example, " C ₁～C ₅Hydrocarbon ", be intended to comprise particularly and disclose C ₁And C ₅Hydrocarbon and C ₂, C ₃And C ₄Hydrocarbon.

[0014] although providing the numerical range and the parameter of wide region of the present invention all is approximation, the numerical value that provides in specific embodiment is all reported accurately as far as possible.Yet, any numerical value all contain inherently the standard deviation that exists in the experimental measurement separately at them certain error that must cause.

[0015] used as this specification sheets and claim, singulative " " and " this " comprise their plural things, unless clearly illustrate that in the literary composition.For example, so-called " turbine " or " pump " is intended to comprise a lot of platform turbines or pump.What is called contains or comprises the composition of " a kind of component " or " a kind of compound ", is intended to also comprise other component or other compound respectively except that proposing.

[0016] so-called " comprising " or " containing " or " comprising "; we are meant in composition or goods or method; at least there are compound, element, particle or the method steps etc. that proposed; there are not other compound, catalyzer, material, particle, method steps etc. but do not get rid of; even other compound of this class, material, particle, method steps etc. and the identical function that has that has proposed are unless clearly be left out in the claims.

[0017] should also be understood that mentioning one or more method stepss does not repel also have other method steps or the insertion method steps between these steps of clearly mentioning before and after described combination step.And the coding of processing step and component is a convenient tool of differentiating activity separately or component, and described coding can arrange with any order, except as otherwise noted.In addition, except as otherwise noted, all force value and scope all are meant absolute pressure.

[0018] the present invention includes the gasification of carbonaceous material, to generate the mixture (also being called synthesis gas) of hydrogen, carbon monoxide and carbonic acid gas.Term " carbonaceous ", as used herein, describe various suitable carbonaceous raw materials, and be intended to comprise gaseous state, liquid state and solid hydrocarbons, hydrocarbonaceous material and their mixture.Any combustible carbonaceous organic material matter or its slurry all can be included in the definition of term " carbonaceous " basically.Solid-state, gaseous state and liquid raw material can mix or use simultaneously; And can comprise paraffin, alkene, alkynes, cycloalkanes and aromatic substance in any ratio.In the definition of term " carbonaceous ", the carbonaceous organic material matter that also comprises oxidation comprises carbohydrate, cellulose materials, aldehyde, organic acid, alcohol, ketone, oxidation fuel oil, waste liquid and from the by product that contains oxidation carbonaceous organic material matter of chemical technology and their mixture.In gasification reaction coal commonly used, comprise refinery coke and other carbonaceous material, useless hydrocarbon, Residual oil and from the raw material based on oil of the by product of heavy crude.

[0019] the present invention produces synthesis gas with high pressure gasifier.Any in several known gasifying process can both be merged into technology of the present invention.In high-pressure gasified reactor, make the reaction of carbonaceous fuel and oxygen-containing gas, randomly, carry out having in the presence of temperature regulato such as the steam, with the generation synthesis gas.This class gasifying process generally all drops on as in the big class of being divided in the 5th chapter of " Gasification " (C.Higman and M.van der Burgt, Elsevier, 2003).The example of moving-bed gasification device such as Lurgi dry ashing technology, British Gas/Lurgi slag tap gasifier, Ruhr 100 gasifiers; Fluidized-bed gasifier is carried gasifier, Lurgi circulating fluidized bed gasifier, U-Gas agglomeration fluidized bed process and Kellogg Rust Westinghouse agglomeration fluidized bed process as Winkler and high temperature Winkler method, KelloggBrown and Root (KBR); And entrained flow gasifiers, as Texaco, Shell, Prenflo, Noell, E-Gas (or Destec), CCP, Eagle, Koppers-Totzek method.Plan is used for the gasifier of present method and can operates in the scope of 1～104 crust absolute pressure (hereinafter being referred to as " crust ") and 400 ℃～2000 ℃.The working pressure scope of high pressure gasifier is generally 22～84 crust.Other example of working pressure is 42～84 crust and 67～77 crust.Gasification temperature is generally in 900 ℃～1700 ℃ scopes, and is more general, in 1100 ℃～1500 ℃ scopes.

[0020] depend on wherein used carbon raw material and be used for producing the gasifier type of gaseous state carbon monoxide, carbonic acid gas and hydrogen, the preparation of raw material can comprise grindings, dry, make the one or more unit operations in the pulping of grinding raw material in suitable fluid (as water, organic liquid, overcritical or liquid carbon dioxide).Carbonaceous fuel and reactive oxygen-containing gas as air, contain the basic pure oxygen of the above oxygen of 90mol% or contain the oxygen-rich air of the above oxygen of 21mol%, react.Industrial preferred basic pure oxygen.For obtaining basic pure oxygen, air is wanted compressed basic pure oxygen and the basic purity nitrogen of being separated into then in air separation equipment.This kind equipment is industrial known.

[0021] oxygen flow and carbon containing or the hydrocarbon-containing feedstock made are introduced one or more gasifiers, oxygen is consumed and raw material is converted into the crude synthesis gas body that generally comprises carbon monoxide, hydrogen, carbonic acid gas and water basically therein.Oxygen and raw material introduce gasifier really the butt formula in the art technology scope.The crude synthesis gas body can comprise other impurity, as hydrogen sulfide, carbonyl sulfide, methane, ammonia, prussic acid, hydrogenchloride, mercury, arsenic and other metal, depends on raw material source and gasifier type.Beyond the degassifying device, gasifying process of the present invention can comprise water-gas shift, high-temperature gas cooling apparatus, ash/slag treatment facility; Carbonic acid gas, sulphur and sour gas are removed section; Gas filter and scrubber.

[0022] except that high pressure gasifier, gasifying process of the present invention comprises CO transformationreation section.This paper refers to one or more technique units with term " section ", as reactor, condenser, heat exchanger etc.Come out from gasifier with synthesis gas, pass to CO transformationreation section, here, it and water or steam react having in the presence of the catalyzer, to increase the mark of hydrogen.Especially to make synthesis gas and water (being generally steam) and suitable catalyst reaction, so that carbon monoxide is converted into carbonic acid gas and hydrogen in the mode of water gas shift reaction.The CO transformationreation also is called " steam reforming " and is described in, for example, and in the U.S. patent 5,472,986.The transformationreation of CO except that the mark that increases hydrogen, also reduces the carbon monoxide in the gaseous mixture, and CO may be the ammonia synthesis catalyst poisonous substance, as previously mentioned.

[0023] the CO transformationreation is generally carried out on catalyzer with methods known in the art.The CO catalyst for water-gas shift reaction can be the VIII of one or more families metal on heat-resistant carriers.Can be the catalyst plate of carrier with traditional random filling pottery, as used in second convertor, but produce tangible pressure drop because of they make gas, Chang Youxuan be with containing the monoblock catalyzer that generally is parallel to reactant flow direction passage.

[0024] transformationreation is a reversible, and lesser temps helps hydrogen and carbonic acid gas.But speed of reaction is slow at low temperatures.Therefore, Chang Youxuan carries out high temperature and low temperature shift reaction successively.Gas temperature in the high temperature shift reaction is generally 350 ℃～1050 ℃.High temperature catalyst often is the ferric oxide that is mixed with a small amount of chromic oxide.The gas temperature of low temperature shift reactor is 150 ℃～300 ℃, and is more general, 200 ℃～250 ℃.Low temperature shift catalyst generally is a cupric oxide, can be loaded on zinc oxide and the aluminum oxide.Some catalyst for water-gas shift reaction can have in the presence of the sulphur operation, and other then can not the catalyzer of copper (for example, based on).The design of preferred transformationreation section and operation will make pressure drop as far as possible little, so that can keep the pressure of synthesis gas.

[0025] or, when gas temperature was higher than 900 ℃, water gas shift reaction also can be realized down in that catalyst-free is auxiliary.Because the characteristic of a large amount of heat releases of water gas shift reaction, steam can be discharged the heat of gas and produces from water-gas shift by retrieving.The CO transformationreation can control thermopositive reaction rejected heat known in the art any reactor pattern carry out.The example of suitable reactor pattern is the single-stage insulation fix bed reactor; The multistage insulation fix bed reactor that has interstage cooling, vapor generation or quenching (cold-shotting); Have vapor generation or refrigerative tubular fixed-bed reactor; Or fluidized-bed.

[0026] discharges from CO transformationreation section with synthesis gas, usually make it to stand cooling and cleaning operation, comprise scrubbing technology, gas is introduced into scrubber and contact with water spray therein, and the water spray cools off this gas and removes particle and ion component in the synthesis gas.Effluent liquid from one or more shift-converters can contain 4～50mol% carbonic acid gas, CO ₂May need to be reduced.

What [0027] minimizing of carbonic acid gas can be with in all multi-methods of removing carbonic acid gas from air-flow known in the art is any, intends in technology of the present invention carrying out under any pressure of usefulness.For example, carbonic acid gas can be removed with chemical absorption method, for example, and with caustic soda, salt of wormwood or other inorganic base aqueous solution, or alkanolamine.These methods can be carried out as follows: make synthesis gas and liquid absorbing medium in any suitable liquid known in the art-gas contactor, and as in the tower that tower tray or filler are housed, contact.The example that is applicable to alkanolamine of the present invention comprise contain at the most 10 carbon atoms and normal boiling point be lower than 250 ℃ primary, secondary amino group alcohol.Specific examples comprises primary amino alcohols, as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 1-amino-Ding-2-alcohol, 2-amino-Ding-1-alcohol, 3-amino-3-methyl-2-amylalcohol, 2,3-dimethyl-3-amino-1-butanols, 2-amino-2-ethyl-1-butanols, 2-amino-2-methyl-3-amylalcohol, 2-amino-2-methyl-1-butanols, 2-amino-2-methyl-1-amylalcohol, 3-amino-3-methyl isophthalic acid-butanols, 3-amino-3-methyl-2-butanols, 2-amino-2,3-dimethyl-1-butanols, with secondary amino group alcohol, as diethanolamine (DEA), 2-(ethylamino)-ethanol (EAE), 2-(methylamino-)-ethanol (MAE), 2-(third amino)-ethanol, 2-(isopropylamino)-ethanol, 2-(fourth amino)-ethanol, 1-(ethylamino)-ethanol, 1-(methylamino-)-ethanol, 1-(third amino)-ethanol, 1-(isopropylamino)-ethanol and 1-(fourth amino)-ethanol.Merchandise sales are much all arranged in this class amino alcohol.

[0028] or, the carbonic acid gas in the synthesis gas also can be removed with the physical absorption method.The example that is suitable for the physical absorption solvent is methyl alcohol (" Rectisol ") and other alkanol, propylene carbonate and other alkyl carbonate, and the dimethyl ether of the polyoxyethylene glycol of 2～12 ethylene glycol unit and their mixture are generally with trade(brand)name Selexol ^TMThe solvent common name, n-methyl-pyrrolidone (" Purisol "); And tetramethylene sulfone (" Sulfinor ").Physics and chemical absorption method can couplings, for example, use tetramethylene sulfone and the alkanolamine Sulfinol as absorption agent ^TMMethod, or be the Amisol of absorption agent with monoethanolamine and carbinol mixture ^TMMethod.Other example of the carbon dioxide removal method of having set up comprises " Amine Guard ", " Benfield ", " Benfield-DEA ", " Vetrocoke " and " Catacarb " method.

[0029] outside the removing carbon dioxide, sulphur usually with sulfocompound, is present in the synthesis gas as the form of hydrogen sulfide and other sour gas, also can remove with method well known in the art.For example, can use chemical absorption method in the sulphur removal district, for example, with caustic soda, salt of wormwood or other mineral alkali, or alkanolamine, from synthesis gas, reclaim sulfocompound.The example that is used for suitable alkanolamine of the present invention comprise contain at the most 10 the total number of carbon atoms and normal boiling point be lower than 250 ℃ primary, secondary amino group alcohol.Specific examples comprises primary amino alcohols, as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), 1-amino-Ding-2-alcohol, 2-amino-Ding-1-alcohol, 3-amino-3-methyl-2-amylalcohol, 2,3-dimethyl-3-amino-1-butanols, 2-amino-2-ethyl-1-butanols, 2-amino-2-methyl-3-amylalcohol, 2-amino-2-methyl-1-butanols, 2-amino-2-methyl-1-amylalcohol, 3-amino-3-methyl isophthalic acid-butanols, 3-amino-3-methyl-2-butanols, 2-amino-2,3-dimethyl-1-butanols, with secondary amino group alcohol, as diethanolamine (DEA), 2-(ethylamino)-ethanol (EAE), 2-(methylamino-)-ethanol (MAE), 2-(third amino)-ethanol, 2-(isopropylamino)-ethanol, 2-(fourth amino)-ethanol, 1-(ethylamino)-ethanol, 1-(methylamino-)-ethanol, 1-(third amino)-ethanol, 1-(isopropylamino)-ethanol and 1-(fourth amino)-ethanol.

[0030] or, also can remove sulfocompound with the physical absorption method.The example that is suitable for the physical absorption solvent is methyl alcohol and other alkanol, propylene carbonate and other alkyl carbonate, and the dimethyl ether of the polyoxyethylene glycol of 2～12 ethylene glycol unit and their mixture are generally with trade(brand)name Selexol ^TMSolvent common name, n-methyl-pyrrolidone and tetramethylene sulfone.Physics and chemical absorption method can couplings, for example, are the Sulfinol of absorption agent with tetramethylene sulfone and alkanolamine ^TMMethod, or be the Amisol of absorption agent with monoethanolamine and carbinol mixture ^TMMethod.Synthesis gas and solvent are contacted in any class solution-air contactor that comprises packed tower and tower that tower tray is housed and so on known in the art.The operation of this class deacidification contactor is known in the art.Synthesis gas also can be used methods known in the art, concentrates as membrane separation process and/or transformation absorption process.

[0031] containing the sulfurous compound and also can remove described solid such as zinc titanate, zinc ferrite, stannic oxide, zinc oxide, ferric oxide, cupric oxide, strontium oxide or their mixture in the synthesis gas with the solid absorption method of using solid fixed bed, fluidized-bed or moving-bed.Before sulphur removal equipment, one or more gas cooling steps can be arranged, to press the wherein temperature of the needs reduction synthesis gas of used concrete sulfur removal technology.From the sensible heat energy of synthesis gas, can use methods known in the art, reclaim by in the cooling tandem arrangement, producing steam.In the general feeding gas at least 90%, more general, at least 98% sulphur can be removed with previously described process for sulfur removal.

[0032] the hydrogenous high pressure synthetic air of bag is passed to Ammonia Process as feeding from gasifying process.High pressure H from gasifying process ₂The pressure of air-flow is generally 49～63 crust.For example, the pressure of air-flow can be 56 crust.Therefore, for the general pressure that are generally 25～32 crust that method provided that all surpass based on Sweet natural gas of hydrogen pressure from gasifying process of the present invention.Estimate that the pressure of hydrogen product is brought up to 49～63 crust can reduce 30～40% to the power requirement to typical ammonia synthesis loop compressor.Purity by the hydrogen that above gasifying process produced is generally 96～99.99mol%, is more generally 99～99.9mol%.

[0033] the transformationreation section of above-mentioned gasifying process can produce the high pressure steam of different pressures and different degrees of superheat.Term " high pressure ", as used herein, be interpreted as being meant 22 crust or higher pressure.The example of the saturated vapor pressure that can be produced by the transformationreation section is 22 crust～63 crust, 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.For example, can produce 42 crust saturation steams from the CO transforming section.This 42 crust saturation steam provides handiness and effective and integrative for the ammonia steam system.For example, steam is directly repeatedly kicked into the ammonia synthesis loop steam system.This point is shown among Fig. 1 and Fig. 2.

[0034] Ammonia Process generally comprises the ammonia conversion zone that produces ammonia product stream.The high pressure synthesis gas is generally introduced ammonia process by the ammonia synthesis loop compressor.This gas is mixed with nitrogen and circulation ammonia-synthesizing material gas body, thus the hydrogen and the nitrogen unstripped gas of generation more volume.The general hydrogeneous and nitrogen reactant of gained ammonia-synthesizing material gas body, their mol ratio was generally 2.7: 1～3.2: 1, was more generally 2.8: 1～3.1: 1, and was generally most 2.9: 1～3.0: 1.The scope that exists of rare gas element is 1～30mol%, is more generally 5～20mol%.

[0035] compression ammonia raw gas mixture and it is used for the synthetic of ammonia.In traditional ammonia equipment, generally cling to～346 pressure that cling to 15.More general, pressure is 42 crust～346 crust, and is the most general, is 56 crust～167 crust.Making the ammonia-synthesizing material gas body is to pass through on the ammonia synthesis catalyst of ammonia in the hydrogenation of catalysis nitrogen.Catalyzer can be contained in one or more tubular types or the hearth reactor, and these reactors can be formed by one or more reactors in series.Under this class situation, the equipment of cooling gas can be set between ammonia synthesis reactor.Ammonia synthesis catalyst can be a known any type in the ammonia synthesizing industry, and as U.S. patent 5,846,507 is described.

[0036] ammonia reclaims from product gas, and a part of residual ammonia-synthesizing material gas body is recycled.Ammonia generally reclaims by condensation method, but also can comprise water or solvent scrubbing with any method known in the art.Condensation can be by making gas expansion or with refrigeration, water coolant or auxiliary from the method for cooling of the liquid nitrogen of oxygen equipment.Compress the poor-ammonia product gas of gained then, and most of poor-the ammonia product gas is as the recycle of ammonia-synthesizing material gas body.Hydrogen and nitrogen by ammonia reactor, reclaim the ammonia product and loop back the passage of unreacted nitrogen and ammonia, this paper is referred to as ammonia synthesis loop.The order of compression, mixing hydrogen-rich synthetic gas body and nitrogen and recovery ammonia is unimportant.

[0037] hydrogenation of nitrogen is heat release, and in order to reclaim ammonia, must remove the heat of effusive ammonia product stream.Therefore, in one embodiment of the invention, all or part of ammonia product stream can with all or part of high-pressure saturated steam generation heat exchange that comes the transformationreation section of autopneumatolysis, to generate superheated vapour.Term " overheated ", as used herein, be interpreted as being meant that steam is heated to more than the dew point under its setting pressure.Cross heat and be generally at least 40 ℃.Other example of superheated is at least 45 ℃, at least 50 ℃, and at least 60 ℃ and at least 70 ℃.For example, can make a part pass to the ammonia process vapor header from the saturation steam of CO transforming section.Perhaps, can change into superheated vapour to whole high-pressure saturated steams from the CO transforming section.According to the present invention, at least 35% superheated vapour total amount that is used for ammonia synthesis technology can produce by the heat exchange with ammonia product stream.The superheated vapour total amount is interpreted as being meant the superheated vapour total amount that is used for ammonia synthesis technology in the unit time, for example, is used to drive the superheated vapour of turbine, pump, heating or other arts demand.Can lean on other example of superheated that provides with the heat exchange of ammonia product stream to comprise at least 40%, at least 50%, at least 60% and 100% of overheated total amount.Product ammonia stream and can be with any suitable superheater from the heat exchange between the high-pressure saturated steam of transformationreation, promptly the heat-exchanging part of in the boiler temperature of saturation steam being brought up to superheated vapour is realized.Heat exchanger can be an any type well-known to those skilled in the art, for example, and run-in index, reverse-flow, intersection streaming interchanger.This class interchanger can, for example, shell-and-tube interchanger form constitutes.

[0038] can pass to one or more steamer driving mechanisms to superheated vapour, the latter can be used for driving one or more compressors used in the ammonia process again.For example, can pass to hydrogen and nitrogen feed compressor, ammonia refrigerating compressor or both steamer driving mechanisms to superheated vapour.In order to be complementary with the vapor pressure that is produced by the CO transformationreation, it is that specified vapour pressure is the condensing-type turbine of 22～63 crust that at least one steamer driving mechanism is preferably arranged.Other example of rated value that is applicable to the condensing-type turbine of the inventive method includes, but not limited to 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.Term " condensing steam turbine ", as used herein, be meant following simple steam turbine: therein, high pressure steam is expanded by condensing steam turbine, with produce power or, exhaust steam is generally discharged and condensation from one or more levels under low pressure (being lower than 2 crust) simultaneously, needs for heating, apparatus and process or feed-water heater.For example, in one embodiment of the invention, the steamer driving mechanism of hydrogen and nitrogen feed compressor is that nominal steam pressure is the condensing-type turbine of 22～63 crust.Hydrogen and nitrogen feed compressor can be used single turbine, perhaps, and also can be with an above turbine.In another embodiment, the steamer driving mechanism that is applicable to hydrogen and nitrogen feed compressor and ammonia refrigerating compressor all is 42 crust condensing-type turbines.In another embodiment, superheated vapour can also be used to driving other steam turbine, as condensing steam turbine and pump except that being used for driving the turbine of hydrogen and nitrogen feed compressor and ammonia refrigerating compressor.

[0039] in another embodiment of the invention, the heat that can be used to transformation into itself's reaction or the purification section crude synthesis gas body that gasifier produced stream before produces other high pressure superheated steam.The method of the hot crude synthesis gas body heat content of the row's of recovery autopneumatolysis device reaction chamber is known in the art, and includes, but not limited to quenching, full recovery of heat and their combination.For example, in synthesis gas quenching method, the water quenching is from the crude synthesis gas body of gasifier.Be called among the embodiment of full recovery of heat at another, with syngas cooler cooling crude synthesis gas body.In also having an embodiment, can use the combination of quenching and radiation synthesis gas cooler.In the quenching method, the crude synthesis gas body leaves gasifier via quench tube, and the lower submerged of quench tube is in the pond.When this water, unstripped gas is cooled to the water saturation temperature and by flush away slag and soot particulates.Should discharge from gasifier/quench vessel via the conduit on the sidewall through overcooled saturated synthesis gas then.

[0040] in full recovery of heat method mutation, the crude synthesis gas body leaves the gasifier conversion zone and at radiation synthesis gas cooler internal cooling.The heat that reclaims is used to overheated and produces high pressure steam.The radiation synthesis gas cooler is known in the art and can comprise, and for example, at least one ring of vertical water cooling tube is as U.S. patent 4,310,333 and 4,377, shown in 132 and described.

[0041] used compressor can be any kind of using always and knowing in this area in the Ammonia Process of the present invention.For example, hydrogen and nitrogen feed compressor can comprise a casing, mean compressing mechanism and are enclosed in the housing.In another embodiment, the compressor of Ammonia Process can be reciprocation compressor, radial compressor, rotary compressor or their combination.A plurality of factors are depended in the selection of concrete type of compressor, and as compression ratio and gas volume, these are in those of ordinary skills' general knowledge scope.

[0042] by behind the superheater, ammonia product stream also can be used to produce high-pressure saturated steam by the passage of the heat exchanger by boiler water supply.This high-pressure saturated steam can be conducted to the process steam collector or also can with from the combination of the high-pressure saturated steam of CO transformationreation section and then with the heat exchange of ammonia product stream.Perhaps, other if desired high-pressure saturated steam then can make a part of ammonia product stream flow through around superheater, and is used for producing the other high-pressure saturated steam from boiler water supply.

[0043] method of the present invention can be used for ammonia/equipment for gasification newly developed, or can be applicable to dispose the existing ammonia equipment that gasifying process is the high pressure hydrogen source.For example, typically can transform as follows based on the ammonia synthesis loop of the ammonia equipment of Sweet natural gas: replace existing for performance gasify and ammonia process between the integrated advantage of steam the vapor expansion turbine drives and the compressor that design.Therefore, in one embodiment, the present invention comprises also that the compressor that comprises a casing with a steamer driving mechanism and is replaced and is used for the existing steamer driving mechanism and the compressor of compressed hydrogen and nitrogen raw material in the Ammonia Process.

[0044] in ammonia equipment, generally uses 2 main steam collectors, i.e. 104 crust and 42 crust steam collectors based on Sweet natural gas.104 crust superheated vapour collectors are commonly used to drive the preposition turbine of ammonia synthesis loop.Exhaust steam from this turbine can enter 42 crust steam collectors.42 crust steam collectors can be used to drive the processing units of condensing steam turbine and pump and so on.

[0045] typical case can comprise based on the existing steamer driving mechanism of the ammonia equipment of Sweet natural gas, for example, and 104 crust～42 preposition turbines of crust and 42 crust condensing-type turbines.Term " preposition turbine ", as used herein, with " high-order turbine " and " back pressure turbine " synonym, and be intended to have the meaning of often being understood in this area, that is, can be added to new installation or be configured to the middle non-condensing-type turbine of high pressure of pressing on the used equipment.Preposition turbine is accepted the exhaust steam of high pressure steam and generation and old boiler uniform pressure and is used for supplying with old turbine.These existing turbines will be replaced by the condensing-type turbine of the specified vapour pressure of appropriate size by 22～63 crust.Other example of rated value that is applicable to the condensing-type turbine of the inventive method includes, but not limited to 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.Waste gas from this condensing-type turbine can pass to surface condenser.

[0046] vapor generation in existing ammonia synthesis loop can be transformed and be produced 22 crust～63 crust superheated vapours.As mentioned above, the saturation steam that in ammonia synthesis technology and gasifying process, produces can organize be incorporated in the ammonia synthesis technology overheated.As mentioned above, the used superheated vapour total amount of at least 35% ammonia process can be by producing with the heat exchange of ammonia product stream.Other example of superheated that can provide by the heat exchange with ammonia product stream comprises always crosses at least 40%, at least 50%, at least 60% and 100% of heat.For example, can replace 104 crust vapour generators with 22 crust～63 crust vapour generators and vapor superheater.Other example of vapour generator includes, but not limited to 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.22 crust～63 crust saturation steams that produce in ammonia synthesis loop and the gasifying process can be by overheated in this superheater.Superheated vapour can be used as supplies with ammonia synthesis loop and/or refrigeration compressor or other vapour source.Embodiment of the present invention are shown in Fig. 2.

[0047] except that ammonia synthesis loop compressor and refrigeration compressor, the superheated vapour of Chan Shenging can be used to start other processing unit in the ammonia synthesis loop in the above described manner.Other purposes of superheated vapour comprises the turbine expansion driving mechanism that is used for the boiler water supply pump, the turbine expansion driving mechanism that is used for other pump and compressor, or generating.The balance that is used for other user's superheated vapour will depend on the specific steam needs of concrete equipment.

[0048] except that the displacement turbine, the existing hydrogen of ammonia equipment and nitrogen feed compressor generally comprise 2 separation vessel casees, i.e. low-pressure cabinet and high-voltaghe compartment.The suction side that low-pressure cabinet sucks fresh feeding and directly discharges high-voltaghe compartment.According to the present invention,, can cancel the low-pressure cabinet compressor by the hydrogen raw material being pressurized to 49～63 crust and transforming the high-voltaghe compartment compressor.This embodiment also is shown in Fig. 2.Cancellation stage compressor and driving mechanism can reduce total power requirement, investment, the Operation and maintenance cost of ammonia synthesis compression step.

[0049] as mentioned above, may need the advanced compression machine is transformed a little, so that suck and be disposed to desired synthesis loop working pressure at 49～63 crust.For example, in this technological design, can reduce by 40 ～60  to the high-grade suction temperature, be generally 40 .In typical ammonia equipment, extremely rudimentary suction temperature is 40 , and the high-grade that arrives is up to 120 .Because it is rudimentary that the present invention need not, so colder synthesis gas can directly enter senior and can reduce the power requirement of compressor.

[0050] except that method mentioned above, the present invention also provides the integral process of hydrogen manufacturing and system ammonia, comprising:

(g) make ammonia product stream and high-pressure saturated steam from the transformationreation section carry out heat exchange, to form superheated vapour, wherein at least 50% superheated vapour total amount that is used for described ammonia process produces by described heat exchange; With

(h) make described superheated vapour pass to the steamer driving mechanism of steamer driving mechanism, ammonia refrigerating compressor of hydrogen and nitrogen feed compressor or both.

The integrated various embodiments of gasifying process, transformationreation, ammonia process, steamer driving mechanism, compressor, steam and heat as previously mentioned.For example, the working pressure scope of high pressure gasifier can be 42～84 crust, or, in another embodiment, be 67～77 crust.Make gas pass to CO transformationreation section and arrive purification section from gasifier, as previously mentioned, here, all or part of CO ₂And sulfocompound, as H ₂S is removed, or their concentration is lowered, to generate the hydrogenous high pressure purifying gasification product stream of bag.This technology can contain and is useful on the heat exchanger of generation from the high-pressure saturated steam of CO transformationreation.Pressure can contain H for the purifying of 49～63 crust ₂Gasification product stream and nitrogen can make up with the unreacting material that loops back, and pass to hydrogen and nitrogen feed compressor, to produce fresh ammonia converter raw material.Can make compressed hydrogen and nitrogen raw material pass to the ammonia converter section then, here, hydrogen and nitrogen react, to produce the ammoniated product stream of bag.Can pass to superheater and be used for producing high pressure superheated steam from the high-pressure saturated steam of transformationreation section by heat exchange with ammonia product stream.At least 35% superheated vapour total amount that is used for ammonia process can be leaned on the heat exchange of ammonia product stream and produce.Other example of superheated that can provide by the heat exchange with ammonia product stream comprises always crosses at least 40%, at least 50%, at least 60% and 100% of heat.As previously mentioned, can make this superheated vapour pass to hydrogen and nitrogen feed compressor, ammonia refrigerating compressor or both steamer driving mechanisms.The nominal steam pressure of steamer driving mechanism is generally 22 crust～63 crust, but other rated value also is possible, for example, and 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.As mentioned above, can use various type of compressor and pattern by the understanding of this area.Superheated vapour can be used to drive other steam turbine.

[0051] by behind the superheater, ammonia product stream also can be used to produce high-pressure saturated steam by the passage of the heat exchanger by boiler water supply.High-pressure saturated steam can be conducted to the process steam collector, perhaps also can with from the combination of the high-pressure saturated steam of CO transformationreation section and then with the heat exchange of ammonia product stream.Perhaps,, part ammonia product stream is flow through around superheater, and be used for producing other high-pressure saturated steam from boiler water supply if wish that other high-pressure saturated steam is arranged.

[0052] the present invention also provides the integral system of a kind of hydrogen manufacturing and system ammonia, and this system comprises:

(f) ammonia convertor section is used for making hydrogen and nitrogen in the ammonia convertor feeding stream to react, to generate the ammoniated product stream of bag;

(h) be used for the steamer driving mechanism of nitrogen and hydrogen feed compressor or be used for the steamer driving mechanism of ammonia refrigerating compressor, it is accepted to the small part superheated vapour.

The integrated various embodiments of gasifying process, transformationreation, ammonia process, steamer driving mechanism, compressor, steam and heat as previously mentioned.For example, the working pressure scope of high pressure gasifier can be 42～84 crust, or, in another embodiment, be 67～77 crust.Make gas pass to CO transformationreation section and arrive purification section from gasifier, as previously mentioned, here, all or part of CO ₂And sulfocompound, as H ₂S is removed, or their concentration is lowered, to generate the hydrogenous high pressure purifying gasification product stream of bag.Pressure can contain H for the purifying of 49～63 crust ₂Gasification product stream and nitrogen can make up with the unreacting material that loops back, and pass to hydrogen and nitrogen feed compressor, to produce fresh ammonia converter raw material.Can make compressed hydrogen and nitrogen raw material pass to the ammonia converter section then, here, hydrogen and nitrogen react, to produce the ammoniated product stream of bag.This technology can have one first heat exchanger, is used for producing the high-pressure saturated steam from the CO transformationreation.This high-pressure saturated steam can pass to one second heat exchanger or superheater, and changes into high pressure superheated steam by the heat exchange with ammonia product stream.At least 35% superheated vapour total amount that is used for ammonia process can be by producing with the heat exchange of ammonia product stream.Can comprise by other example of superheated that provides with the heat exchange of ammonia product stream and always cross at least 40%, at least 50%, at least 60% and 100% of heat.As previously mentioned, can make this superheated vapour pass to hydrogen and nitrogen feed compressor, ammonia refrigerating compressor or both steamer driving mechanisms.The nominal steam pressure of these steamer driving mechanisms is generally 22 crust～63 crust, but other rated value also is possible, for example, and 22 crust～60 crust, 22 crust～55 crust, 22 crust～50 crust and 22 crust～45 crust.As mentioned above, can use various type of compressor and pattern by the understanding of this area.Superheated vapour can be used to drive other steam turbine.

[0053] this technology also can comprise other heat exchanger that is used for retrieving to flow from ammonia process unnecessary heat.For example, as previously mentioned, can also produce high-pressure saturated steam as described below: make ammonia product stream afterwards, again the passage by the 3rd heat exchanger by boiler water supply by aforementioned second heat exchanger (or superheater) with ammonia product stream.This technology also can comprise conduit, is used for making up from the high-pressure saturated steam of first heat exchange segments and high-pressure saturated steam from the 3rd heat exchange segments, and to form the combined high pressure saturated steam flowing, it can feed into second heat exchanger, produces superheated vapour.All or part of high-pressure saturated steam from the 3rd heat exchanger also can be conducted to ammonia process steam collector, generally uses for whole ammonia process.Perhaps, other if desired high-pressure saturated steam then can make part ammonia product stream flow through around superheater, and is used for producing the other high-pressure saturated steam from boiler water supply.

[0054] one embodiment of the invention can specifically illustrate with reference to feel flow draw of block shown in Figure 1, and this illustrates the integrated of meaning gasifier and existing ammonia equipment.In Fig. 1, aeriferous stream 10 is fed air gas separation unit (ASU) 1.This ASU1 becomes air separation based on the stream 11 of oxygen with based on the stream 20 of nitrogen.Stream 11 based on oxygen is used as the part feeding that enters gasifier 2, at gasifier, and oxygen and hydrocarbons 12 and steam or the combination of water (not shown).Partial oxidation takes place in gasifier 2, forms crude synthesis gas body 13 and particulate matter 22.Make crude synthesis gas stream 13 pass to CO transforming section 3, here, CO is converted into H having in the presence of the steam ₂And CO ₂Chemical reaction in CO transforming section 3 is heat release, and heat is recovered with the form of high-pressure saturated steam 19.Make this high-pressure saturated steam 19 pass to ammonia synthesis loop 6, for further steam combination.The synthetic air 14 of using from CO transforming section 3 is cooled by heat exchanger 4, passes to sour gas then and removes section 5.In this section, refrigerative crude synthesis gas stream 15 is purified as with H ₂Be main product stream 17, be fed to ammonia synthesis loop 6.Contain CO ₂Stream 18 and contain H ₂The stream 16 of S is removed section 5 from sour gas and is discharged, and is used for other technology.In acid gas removal section 5, H ₂Product can also utilize the common technology of transformation absorption, film or methanation reaction and so on to be further purified.In ammonia synthesis technology 6, mix H with stoichiometry ₂Product stream 17 and nitrogen stream 20, this point is described in down among Fig. 2, to form ammonia synthesis raw material 21.

[0055] another embodiment of the invention can be shown in Fig. 2, and this figure describes the technical process of ammonia plant.In Fig. 2, from the H of acid gas removal and purification section 5 (from Fig. 1) ₂ Product stream 17 mixes with the stream 20 based on nitrogen from air gas separation unit 1 (from Fig. 1) with stoichiometry.These mix flows constitute ammonia synthesis fresh feed 40.Ammonia synthesis fresh feed 40 is cooled off by heat exchanger 31.Fresh feed 40 and ammonia synthesis reactor recycle gas 44 are subjected to the compression of monotubular ammonia synthesis circulation loop compressor 32 and are fed to ammonia synthesis loop gas processing sections 37.

[0056] section 37 representatives known in the art be used for preparing be applicable to the ammonia synthesis feeding gas stream 41 that ammonia transforms and be used for ammonia convertor section product is flowed the 43 many processing step/equipment that separate ammonification product 21 and circulating current 44.This class processing step comprises that condensation goes out ammonia product 21 to heating ammonia synthesis feeding air-flow 41 with separating also from ammonia convertor section product stream 43.

[0057] feed ammonia synthesis convertor 34 ammonia synthesis gas of making 41, the ammonia of heat release therein forms reaction and elevates the temperature.Ammonia synthesis reaction can be finished with integrated heat exchange in one or more ammonia synthesis transmodulators.Hot effluent 42 from last ammonia synthesis convertor passes to vapor superheater 35 and boiler water supply (BFW) preheater/vapour generator 36.Vapor superheater 35 and BFW preheater/vapour generator 36 cooling ammonia convertor effluents 42 form refrigerative ammonia convertor and flow out logistics 43.The further cooling of flowing out logistics 43 occurs in synthesis loop gas processing sections 37.Provide bypass 43A around BFW preheater/vapour generator 36 to flow out the temperature of logistics 43 for controlled chilling ammonia convertor more significantly.

[0058] in synthesis loop gas processing sections 37, ammonia product 21 is separated from refrigerative ammonia convertor outflow logistics 43, and unreacted synthesis gas 44 is looped back ammonia synthesis compressor 32.

[0059] boiler water supply 45 is conducted to BFW preheater/vapour generator 36, and produces the BFW or the high-pressure saturated steam 46 of heating, depend on after superheater 35 from ammonia synthesis convertor gas 42 obtainable heats.Make the BFW or the saturation steam 46 of heating pass to ammonia synthesis section steam collector 30 then.Saturation steam can be input into or export ammonia synthesis section steam collector 30 via pipeline 56.

[0060] can mix with high-pressure saturated steam 19 via pipeline 47 from the high-pressure saturated steam of ammonia synthesis section steam collector 30 from CO shift-converter section 3.Make the high-pressure saturated steam 48 of combination pass to vapor superheater 35 then, to produce high pressure superheated steam 49.A part of high-pressure saturated steam from CO shift-converter section 3 can be crossed vapor superheater 35 via pipeline 48A, is used for equipment starting and/or temperature control.

[0061] depend on the steam requirement of ammonia productive unit 6 (Fig. 1), the superheated vapours in the pipeline 49 can export other purposes to via pipeline 50, or import from donkey boiler via pipeline 51.High pressure superheated steam from pipeline 49 is conducted to the turbine 33 that draws gas via pipeline 53, driving ammonia synthesis compressor 32, and/or via pipeline 52 to the turbine 39 that draws gas, to drive ammonia refrigerating compressor 38.Waste gas from draw gas turbine drives 33 and 39 can be delivered to the condenser (not shown), and condensation product then is recovered via

pipeline

54 and 55.

[0062] in the ammonia synthesis technology based on methane, most of vapor generation realizes in process for making hydrogen.When replacing, do not have enough steam to drive existing installation process steam expansion turbine, thereby will replace the vapor expansion turbine with electric motor with gasifying process.As therefore, the present invention can be with flying colors advances to have now ammonia equipment energy is integrated, can utilize steam turbine rather than electric drive to drive major equipment again.

[0063] above-mentioned embodiment intends being used for illustrating the present invention.Those of ordinary skill in the field of chemical engineering will appreciate that the detail of any specific embodiments can be different, and will depend on the position and the needs of institute's taking into account system.All these can realize that planning of the present invention, design alternative and embodiment all are considered in those skilled in the art's limit of power, and therefore within the scope of the invention.

Claims

1. process for making hydrogen and the incorporate method of Ammonia Process, described method comprises:

(d) make all or part of described high pressure saturated vapo(u)r and all or part of described ammonia product stream from step (c) carry out heat exchange, to produce superheated vapour, wherein at least 50% superheated vapour total amount that is used for described Ammonia Process produces by described heat exchange; With

2. according to the process of claim 1 wherein that the working pressure scope of high pressure gasifier is 42～84 crust.

3. according to the method for claim 2, wherein high pressure gasifier is operated under 67～77 crust.

4. according to the process of claim 1 wherein that the pressure of the hydrogenous high pressure draft of bag is 49～63 crust.

5. according to the process of claim 1 wherein that one of described at least steamer driving mechanism is that nominal steam pressure is the condensing-type turbine of 22～63 crust.

6. according to the method for claim 5, the described steamer driving mechanism of wherein said hydrogen and nitrogen feed compressor is that nominal steam pressure is the condensing-type turbine of 22～63 crust.

7. according to the method for claim 6, wherein said hydrogen and nitrogen feed compressor comprise a casing.

8. according to the method for claim 7, wherein said hydrogen and nitrogen feed compressor are reciprocation compressor, radial compressor or rotary compressor.

9. according to the method for claim 1, comprise also that the compressor that comprises a casing with a steamer driving mechanism and replaces to be used for the existing steamer driving mechanism and the compressor of compressed hydrogen and nitrogen feeding in the described Ammonia Process.

10. according to the method for claim 9, wherein existing steamer driving mechanism comprises 104 preposition turbines of crust and 42 crust condensing-type turbines.

11. according to the method for claim 9, wherein existing compressor comprises 2 or more a plurality of casing.

12., also comprise with described superheated vapour driving other steam turbine according to the method for claim 1.

13., comprise that also the heat that is used to from crude synthesis gas solids gasifier stream produces other high pressure superheated steam according to the method for claim 1.

14. the method according to claim 1 also comprises the following steps:

(f) be used to produce high-pressure saturated steam from the heat of ammonia product stream; With

(g) before, combination is from the high-pressure saturated steam of step (c) with from the high-pressure saturated steam of step (f) in step (d).

15. the integral process of hydrogen manufacturing and system ammonia, described technology comprises:

(b) make described gasifier product be circulated to CO transformationreation section, comprise the high pressure conversion conversion zone product stream of other hydrogen and carbonic acid gas with generation;

(d) make described transformationreation section product be circulated to purification section, to remove CO ₂And H ₂S, and form the hydrogenous high pressure purifying gasification product stream of bag;

(e) make described high pressure purifying gasification product stream and nitrogen pass to hydrogen and nitrogen feed compressor, to produce ammonia convertor feeding stream;

(f) make described ammonia convertor feeding be circulated to ammonia convertor section, to form ammonia product stream;

(g) make described ammonia product stream and described high-pressure saturated steam from the transformationreation section carry out heat exchange, to form superheated vapour, wherein at least 50% superheated vapour total amount that is used for described ammonia process produces by described heat exchange; With

(h) make described superheated vapour pass to the steamer driving mechanism of steamer driving mechanism, ammonia refrigerating compressor of described hydrogen and nitrogen feed compressor or both.

16. according to the method for claim 15, the working pressure scope of wherein said high pressure gasifier is 42～84 crust.

17. according to the method for claim 15, the operation under 67～77 crust of wherein said high pressure gasifier.

18. according to the method for claim 15, wherein said high pressure purifying gasification H ₂The pressure of product stream is 49～63 crust.

19. according to the method for claim 15, the nominal steam pressure of wherein said steamer driving mechanism is 22～63 crust.

20., wherein drive other steam turbine with described superheated vapour according to the method for claim 15.

21. according to the method for claim 15, wherein said hydrogen and nitrogen feed compressor are reciprocation compressor, radial compressor or rotary compressor.

22. according to the method for claim 21, wherein said hydrogen and nitrogen feed compressor comprise a casing.

23. the method according to claim 15 also comprises the following steps:

(i) be used to produce high-pressure saturated steam from the heat of ammonia product stream; With

(j) before, combination is from the high-pressure saturated steam of step (c) with from the high-pressure saturated steam of step (i) in step (g).

24. the integral system of hydrogen manufacturing and system ammonia, described system comprises

(b) CO transformationreation section is used for transforming carbon monoxide and water in the described gasifier product stream, comprises the high pressure conversion conversion zone product stream of other hydrogen and carbonic acid gas with generation;

(e) nitrogen and hydrogen feed compressor are used for compressing described high pressure purifying gasification product stream and nitrogen, to produce ammonia convertor feeding stream;

(f) ammonia convertor section is used for making hydrogen and nitrogen reaction in the described ammonia convertor feeding stream, to generate the ammoniated product stream of bag;

(g) second heat exchange segments is used for the described high-pressure saturated steam of giving from the thermal exchange of described ammonia product stream from the transformationreation section, to form superheated vapour; With

(h) be used for the steamer driving mechanism of described nitrogen and hydrogen feed compressor or be used for the steamer driving mechanism of ammonia refrigerating compressor, it is accepted to the described superheated vapour of small part.

25. according to the system of claim 24, wherein the working pressure scope of high pressure gasifier is 42～84 crust.

26. according to the system of claim 24, wherein the working pressure of high pressure gasifier is 67～77 crust.

27. according to the system of claim 24, wherein the nominal steam pressure of steamer driving mechanism is 22～63 crust.

28. the system according to claim 24 also comprises:

(i) the 3rd heat exchange segments is used for giving boiler water supply from the thermal exchange of described ammonia product stream, to produce high-pressure saturated steam; With

(j) conduit, be used for making up from the described high-pressure saturated steam of described first heat exchange segments with from the described high-pressure saturated steam of described the 3rd heat exchange segments, to form the combined high pressure saturated steam flowing that to feed described second heat exchanger, to produce superheated vapour.