CN101056963A

CN101056963A - Method for satisfying variable power demand

Info

Publication number: CN101056963A
Application number: CNA2005800384547A
Authority: CN
Inventors: S·D·巴尼基; N·W·莫克; W·L·特拉普
Original assignee: Eastman Chemical Co
Current assignee: Eastman Chemical Co
Priority date: 2004-11-10
Filing date: 2005-10-18
Publication date: 2007-10-17
Also published as: ZA200703105B

Abstract

A process for satisfying variable power demand and a method for maximizing the monetary value of a synthesis gas stream are disclosed. One or more synthesis gas streams (18; 20; 26) are produced by gasification of carbonaceous materials and passed to a power producing zone (38) to produce electrical power during a period of peak power demand or to a chemical producing zone (54) to produce chemicals such as, for example, methanol, during a period of off-peak power demand. The power-producing zone (38) and the chemical-production zone (54) which are operated cyclically and substantially out of phase in which one or more of the combustion turbines are shut down during a period of off-peak power demand and the syngas fuel diverted to the chemical producing zone. This out of phase cyclical operational mode allows for the power producing zone (38) to maximize electricity output with the high thermodynamic efficiency and for the chemical producing zone (54) to maximize chemical production with the high stoichiometric efficiency. The economic potential of the combined power and chemical producing zones is enhanced.

Description

The method that is used for satisfying variable power demand

Invention field

The present invention relates to a kind of being used for produces the electric energy of the amount that changes regularly and the method for chemical by synthetic gas.More particularly, the present invention relates to a kind of method that is used for producing off and on electric energy and chemical, wherein during the stage of off peak power demand, close down one or more gas turbines, and the synthetic gas that will supply with these turbines turns to the production of chemical.

Background of invention

Electrical energy production and distributed network can be reacted to time dependent power demand pattern particularly in needs usually.This demand model wants every day usually, weekly and even annual step cycle ground raise and reduce, wherein the levels of precision of Bian Huaing is distinct in each area.The energy value that produces under the maximum load often can be outer twice that produces of peak value or high power more.Uncommon different technologies and or the fuel of being to use for the base load of electric public service network and maximum load facility.

In order to make the economic potential maximization, when the system loading factor changed in time, variable loading factor is assigned, promptly is assigned to various electric energy generation units often with the requirement of minimum marginal cost within unitary given network.Network with dispatched mode operation generation unit can make the producer that the production cost of whole system is minimized.The generation unit of most worthy is those of cost allowance that have low marginal cost and change the ability of capacity coefficient significantly, apace and do not have essence.

Those skilled in the art are well-known to be, existing conventional electric power produces factory and often utilizes Sweet natural gas, oil fuel and hydrocarbon liquid as the energy source that is used to produce electric power.The most effective modern power station combines turbine (Brayton) circulation that high-temp combustion produces on the thermokinetics with turbine (Carnot) circulation that lesser temps water/steam produces.When will burning and steam turbine when being designed for frequent, this so-called mating type circulation factory is specially adapted to the circulating generation of dispatched mode.Hydrocarbon fuel and oil plant are liquid and are to store easily outside peak value or during the stage of not generating electricity.Alternatively for Sweet natural gas, existing and a large amount of long scope distributions and pipeline system provide and have been used to satisfy accumulating of requirement variation.

But, these fuel, it is attractive especially for the electric energy that increase was provided during the peak value requirement stage, no longer is the cheap and this sufficient supply as their past.Now, because crude oil, refined product and Sweet natural gas is expensive, and the limited reserves of the unreliability in source and these fuel, therefore explores new technology that the different energy and exploitation be used for effectively utilizing whole energy sources and become necessary.

Coal and other carbonaceous fuel (for example refinery coke, biological substance, paper pulp waste material) are very abundant and relatively cheap, and are rational material for research as the field of the main energy source of generating.Coal is used to produce the main raw material of the heat of electric energy and mechanical energy, initial because handle, transportation and store in the problem that relates to and owing to its content that can produce ash content, sulphur and other impurity of environment and other emission control problem has lost concern.But now because its lower cost and more reliable domestic supply, the coal concern of getting back, and studying more effective and more clean utilize mode.

Coal often burns with air and utilizes the heat that produces to be formed on the high pressure steam that is inflated in the turbine, produces machinery or electric energy thus.Generator multiple scope, that can drive by expansion steam has efficiently been developed in power industry.But the steam driven generator of coal combustion is not to be applicable to very much the electric power that the noticeable change amount is provided, but often is designed for more basis (being substantially constant) load.Coal burner is not suitable for the demand of interruption yet.Usually, they are owing to lower fuel cost is preferred for the basic load operation.

As mentioned above, coal and other solid carbonaceous material further contain a large amount of sulphur compounds, and its burning produces serious environmental problem.Owing in the burning of coal of these sulfur-bearings, produced a large amount of low-pressure gases, removed contaminative sulfide such as SO after the burning ₂And SO ₃Be expensive.These and other problem has stimulated the research for the coal gasifying process that will produce clean fuel gas thus, has wherein removed sulphur compound from fuel before burning.

Coal and other solid carbonaceous material can be gasified, and the gasification product (synthetic gas) that obtains is cleaned and be used for generating electricity with the mixed cycle operating method.So-called integrated gasification mixed cycle (IGCC) power station is by fuel (often being coal or pet coke) gasification section and mixed cycle energy section.This mixed cycle is equal to circulation used when utilizing gas fuel basically.But the generation of synthetic gas is more complicated and take out from natural gas line.When using IGCC, solid abrasive and preparation, gasification, ash treatment, gas cooling and desulfurized step are that investment is expensive, and are difficult to often close down with the cost highland and start.Their designs adopting the limited capacity of closing to come operate continuously, and are helped successive basic load operation basically in essence.Even gasification section can be as easily closing down based on the Sweet natural gas of pipeline, the prohibitive economic punishment that the idle running of vaporizer section and causing under the utilization of assets subsequently produces for the energy.Thus, exist the variable energy of mixed cycle section to produce ability not matching between operating with the required basic load of gasification section.IGCC is considered to the basic load unit in the art, but does not have the ability of sending the shoulder load coefficient.

Proposed in the prior art that multiple variation pattern solves the problem variable power demand relevant with IGCC technology.Common approach is to operate gasification section under the basic capacity coefficient of substantially constant.The rough synthetic gas that generates is thus cleaned to go out a large amount of sulphur compounds and other impurity, synthetic gas with cleaning is fed in the chemosynthesis reaction of so-called part conversion, " once passing through " (no gas circulation) subsequently, burned direct basic load generating, the replacement fuel more expensive, that equate cleaning thus of being used for of wherein unconverted synthetic gas.This synthetic chemical is stored and uses subsequently the fuel that acts on gas turbine-steam turbine mixture circulatory system during the peak value requirement stage.The chemical of the common generation of enumerating in this area is ammonia, methyl alcohol, dme and fischer-tropsch product.

Regrettably, one-pass technology is subjected to the stoichiometry of chemical reaction and in the restriction of the process efficiency of the ratio of storable fuel, this fuel can be generated by synthetic gas.Gasification produces common H ₂Be 0.7/1～1.2/1 and have a CO of less amount with the CO ratio ₂, H ₂The synthetic gas of S, methane and other inert substance.Because methyl alcohol, dme and Fischer-Tropsch hydrocarbon synthetic consumed 2 moles of H ₂/ 1 mole of CO, what see easily is, even H ₂Conversion is completely, and this stoichiometry requires also will limit the conversion of synthetic gas steam.Because only effectively fractional, be generally about 50% obtainable hydrogen once being transformed by synthesis mode, this method will make and maximumly only be converted into storable liquid chemical fuel for about 25% obtainable hydrogen.Chemical equilibrium and kinetic limitation have further suppressed the attainable conversion of potential under composition, temperature and the pressure when actual the reaction.

This example that wherein generates the part method for transformation of chemical jointly is disclosed in US 4,566,267 (being used for the ammonia co-production), US 5,392,594 (being used for methyl alcohol), US 3,986,349 and 4,092,825 (being used for Fischer-Tropsch hydrocarbon) and US 4,341,069 (being used for the dme co-production).Weber etc. are at " MethanolCoproduction:Strategies for Effective Use of IGCC Power Plants ", Proceedings of the American Power Conference (1988), 50, the optimum that discloses the synthetic gas that is used for this methyl alcohol part method for transformation among the 288-93 is converted into about 20～35% obtainable synthetic gas.Thus, the output that is changed to 50～100% gasification section of average basis (peak value outer) and peak load, maximum is changed to 50～140%.

In addition, the generating thermo-efficiency by mixed cycle factory is owing at first generate chemical fuel, be lowered with this fuel of afterfire.Usually the overall thermal efficient of measured with respect to the BTU content of the feed carbon material of clean generating IGCC is 38～46%.By synthetic gas generate the chemistry of fuel product and with this fuel of afterfire with this IGCC technology of the invalid introducing of extra thermokinetics.The fuel that is obtained (being methyl alcohol, dme and hydrocarbon) is in lower energy state with respect to original synthetic gas, and produces still less energy when when burning with respect to original synthetic gas per unit quantity.

Attempted being rich in H by circulation ₂Or the CO fluid improves the conversion of synthetic gas, and for example US 4,946,477,5,284,878 and 5,392,594 examples like that, but disclosed maximum synthetic gas transformation efficiency is less than 75%.The equilibrium-limited that forms for DME is greater than for methyl alcohol, and is so that the transformation efficiency that can realize is to the maximum is about 77%, for example as US 4,341, disclosed such in 069.But the common gaseous component of DME and must be cooled and compress and store is accompanied by higher cost of investment thus.

Proposed for having multiple other change of effective basis to the basic theme of the partial synthesis cyclostrophicization of peak load capacity, comprise and increase another chemosynthesis step, heat integration is configured to improve thermo-efficiency (correspondingly having higher cost of investment) and synthetic gas stores.For example, can prepare acetate by methyl alcohol in the tail gas and carbon monoxide.Realized the extra conversion of synthetic gas, but the product (acetate) that obtains is applicable to no longer as the peak value fuel in the gas turbine formula generator.In another example, the partial synthesis cyclostrophic can be turned to methyl-formiate.Can realize about 68% transformation efficiency, but need significant extra investment to be used for independently gas turbine system of the hydrogenation (hydrogenalysis), methyl-formiate disassociation of carbon monoxide enrichment, methyl-formiate and two.

Other idea comprises that the storage synthetic gas is to be used as peak value fuel subsequently.But the synthetic gas that contains a large amount of hydrogen can not be liquefied.Thus, needs are large-scale and expensive gaseous state storing unit is used to have consumption synthetic gas peak value fuel storage.Be integrated in the IGCC steam cycle by will partly transforming the steam that produces in the methanol process, can realize improved thermodynamic efficiency.Also can utilize the outer energy of peak value that electrolysis is hydrogen and oxygen.With hydrogen and CO or CO ₂Mixing stores the methyl alcohol that is used as peak value fuel with preparation.This method suffers the two low ripe aerodynamic efficiency of electrolysis and methyl alcohol synthesis step.

Above-mentioned disclosed method and technology are failed to solve fully and are changed the problem that is used for based on the energy charge in the power station of gasification.Depend on continuously the common chemical that produces with energy and subsequently for the scheme of the common chemical that produces of peak energy load burning, allow variation relatively limited in the energy loading coefficient, be generally 50～140% basis and arrive the peak load coefficient." once by " chemical method can be produced more a spot of chemical.For example, once amount to carbon monoxide/hydrogen feeding gas of 12～30%, and can not use this gas effectively thus by methanol production.Owing to lack the economical efficiency of scale that is used for chemicals production, once have the higher cost of investment that is used for chemicals production usually by the chemical method.When the chemical of burning co-production was used for the peak value generating, for per 10% the synthetic gas that transforms thus, the steam heat efficient of energy cycle had been lowered several percentage points.Thus, the method that needs variable energy to produce has kept the high thermal efficiency of energy cycle during energy produces, and measures with maximum during chemical produces simultaneously and efficiency of investment is converted into chemical with untapped gaseous fuel.

Summary of the invention

We find, by closing down one or more energy-producing gas turbines and use synthetic gas fuel is used for chemicals production during the off peak power demand stage, can satisfy variable power demand effectively.Therefore, proposed a kind of method that is used for producing off and on electric energy and chemical, it comprises:

(a) oxidant stream that will comprise at least 90 volume % oxygen is fed in one or more gasifiers continuously;

(b) oxidant stream and carbonaceous material are reacted in one or more gasifiers, produce one or more synthetic airs that comprise carbon monoxide, hydrogen, carbonic acid gas and sulfocompound thus;

(c) during the stage of peak power requirement, make at least one synthetic air lead to the power-producing zone that comprises at least one gas turbine, produce electric energy thus;

(d) during the stage of off peak power demand, make at least one synthetic air lead to chemical and produce the district, produce chemical thus; With

(e) during the stage of off peak power demand, close down at least one gas turbine.

This gas comprises carbon monoxide, carbonic acid gas and hydrogen (being abbreviated as " synthetic gas " herein), and it is being consumed circularly and in the power-producing zone of the operation mutually that is different in essence and the chemical generation district.During the stage of off peak power demand, close down the gas turbine of one or more generation electric energy, and its synthetic gas fuel is introduced chemical generation district.By this way, the turnout of synthetic gas remains on the numerical value of basic load basically, utilize expensive synthetic gas generation device fully, allow the assignment of round-robin and variable energy charge coefficient simultaneously, and make and utilize the chemicals production maximization that need not the synthetic gas that is used to generate electricity.This new combination provides the energy of unusual handiness to produce operation, has given abundant economical advantage, and especially in response to current energy variation requirement that electrical production person faced.For example, in one embodiment of the invention, the power station can produce 100% time operation of capacity by day at its beta maximum energy under the peak power requirement, and come fueling by synthetic gas fully.Synthetic gas can provide by well known to a person skilled in the art any means, still, usually, can be supplied with by the gasification of coal or other carbonaceous material.For example, in another embodiment of the present invention, power-producing zone can comprise integrated-type gasification mixed cycle (being abbreviated as " IGCC " herein) power station.This point is different fully with existing power station layout, wherein operates this energy generation apparatus with the basic load pattern with very little load-following capacity.

Our method provides at the most 100% synthetic gas to be introduced into chemical and has produced the district, so that in hydrogen, carbon monoxide or the carbonic acid gas one or more are converted into reaction product.For example, in a kind of embodiment of present method, can utilize this synthetic gas to produce methyl alcohol, alkyl formate, ammonia, dme, hydrogen, fischer-tropsch product or its combination.In another embodiment, this chemical produces the district and produces the district for methyl alcohol, and it can comprise fixed bed or liquid slurry phase methanol reactor.In still another embodiment of the present invention, this method further comprises step: by gradually synthetic gas being transferred to methyl alcohol generation district or being produced from methyl alcohol generation district, simultaneously methyl alcohol is co-fed in the gas turbine with the electric power output capacity that keeps them at 50% of their maximum capacities effectively start and close down methyl alcohol and produce district and gas turbine outside peak value and during the transitory stage between the peak power requirement at least.

Description of drawings

Fig. 1 has described the block diagram of a kind of embodiment that is used for producing jointly variable energy and methyl alcohol.

Describe in detail

In general embodiment, the invention provides a kind of novel method that is used for producing off and on electric energy and chemical, it comprises:

In the method for the invention, can be with the reaction continuously in one or more gasifiers of carbonaceous material and oxygen, thus with on constant speed produce synthetic gas.Within the scope of the invention " peak power requirement " as used herein, its implication is to the peak power requirement of power-producing zone in 24 hour given time period." stage of peak power requirement " used herein implication is the one or more time periods within above-mentioned 24 hour stage, and wherein the power demand to power-producing zone is at least 90% of a peak power requirement." stage of off peak power demand " used herein implication is the one or more time periods within 24 hour given stage, wherein to the power demand of power-producing zone be as defined above the peak power requirement less than 90%.Used herein belonging to, " speed of substantially constant " was interpreted as meaning, provided this gas continuously with continual mode and constant level.But, " speed of substantially constant " and do not lie in eliminating may be owing to for example safeguarding, start or the regular normal stoppage that takes place of the stage of closing down.For purposes of the present invention, sulphur refers to and is essentially organic or inorganic any sulfocompound.The example of this sulfocompound is enumerated as: hydrogen sulfide, sulfurous gas, sulphur trioxide, sulfuric acid, elementary sulfur, carbonyl sulfide, mercaptan etc.It is the required fuel in operation power station under its maximum capacity that phrase used herein " maximum capacity demand for fuel " should be connected to implication.Such as used herein, maximum capacity is intended to represent the amount of energy of the maximum possible that can be produced by the power station.Maximum capacity can, but and not necessarily equal design capacity because the improvement that the design capacity in power station can be by tooling and fixing a breakdown is improved.Usually, the power station will be by day time durations under its maximum capacity, operating under the peak power requirement.Gaseous fuel of the present invention or synthetic gas comprise carbonic acid gas, carbon monoxide and hydrogen, can provide by in the several different methods well known in the art any, comprise the steam or the CO 2 reformation of carbonaceous material such as Sweet natural gas or petroleum derivative; The partial oxidation or the gasification of carbonaceous material such as petroleum residue, bituminous matter, subbituminous coal and hard coal and coke, brown coal, resinous shale, oil-sand, mud coal, biomass, petroleum refining residue or coke etc.

Unless point out on the contrary, the digital parameters that provides in following specification sheets and the claims is the approximation that can change according to the performance of the expectation that is intended to obtain by the present invention.At least, each digital parameters should constitute according to the numeral of the significant figure of being reported with by using common rounding method at least.In addition, the scope described in the disclosure content and the claim is intended to comprise particularly and is not the four corner of end points.For example, described is that 0～10 scope should disclose the whole integers between 0～10, for example 1,2,3,4 etc., and the whole marks between 0～10, for example 1.5,2.3,4.57,6.113 etc. and end points 0 and 10.In addition, 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.

Although having illustrated the digital scope and the parameter of wide region of the present invention is approximation, the numerical value that provides in specific embodiment is as far as possible accurately to provide.But any number contains some errors that must be caused by the standard deviation of finding in they thermometricallies separately in essence.

As employed in specification sheets and the claims, unless clearly point out in addition, singulative " (a) ", " one (an) " and " this (the) " include their plural object.Be intended to comprise one or more turbines or chemical when for example, mentioning " turbine " or " chemical ".Mention when containing or comprising " a kind of (an) composition " or " (a) step " and be intended to comprise respectively other composition or other step, except specified.

" comprise (comprising) " or " containing (containing) " or " comprising (including) " implication in composition or goods or method, having specified compound, element, goods or method steps etc. at least, but be not the existence of getting rid of other compound, catalyzer, material, goods, method steps etc., even these other compounds, material, goods, method steps etc. have and those specified identical functions, unless got rid of in the claims clearly.

Will be appreciated that also described one or more method steps is not the existence of other method steps of eliminating before or after the described step of combination, perhaps inserts method steps between clear those steps of determining.In addition, processing step or composition be labeled as the convenient manner that is used to discern different behaviors or composition, and unless otherwise noted, otherwise can arrange described mark with any order.

Method of the present invention comprises that the oxidant stream that will comprise at least 90 volume % oxygen is fed in one or more gasifiers continuously, and oxidant stream and carbonaceous material are reacted in one or more gasifiers, produce one or more synthetic airs that comprise carbon monoxide, hydrogen, carbonic acid gas and sulfocompound thus.In the multiple known gasification process any can be attached in the method for the present invention.These gasification process fall within the broad variety that provides in " Gasification " the 5th chapter (C.Higman and M.van der Burget, Elsevier, 2003) usually.Example is movable bed gasifier, as Lurgi dry ash division technique, and the BritishGas/Lurgi gasifier that removes the gred, Ruhr 100 gasifiers; The liquid bed gasifier, as Winkler and high temperature Winkler technology, Kellogg Brown and Root (KBR) transports gasifier, Lurgi circulating fluid bed gasifier, U-Gas assembles the fluid bed process and Kellogg Rust Westinghouse assembles the fluid bed process; With the moving gasifier of entrained flow, as Texaco, Shell, Prenflo, Noell, E-Gas (or Destec), CCP, Eagle and Koppers-Totzek technology.Expection is used for the gasifier of this method can be operated under the pressure and temperature scope of about 1～about 103bar absolute value (being abbreviated as " bara " herein) and 400 ℃～2000 ℃, and the preferred value scope is that about 21～about 83bara and temperature are between 500 ℃～1500 ℃.According to carbonaceous or the charging of hydrocarbon matter as used herein be used to produce the gasifier type of gaseous state carbon monoxide, carbonic acid gas and hydrogen, the preparation of charging can comprise grinding and one or more drying, in suitable fluid (for example water, organic liquid, overcritical or Liquid carbon dioxide) with the unit operation of ground charging slurrying.Can be oxidized comprise with the conventional carbonaceous material of preparation synthetic gas but be not to be defined in petroleum residue, bituminous matter, subbituminous coal and hard coal and coke, brown coal, resinous shale, oil-sand, mud coal, biomass, petroleum refining residue or refinery coke etc.For the economic worth and the thermodynamic efficiency of maximum, advantageously design the gasifier size and lack 90% to be supplied to, perhaps in another embodiment, the maximum capacity demand for fuel of at least 95% power-producing zone.

Oxygen or another suitable gaseous stream of containing capacity oxygen are injected gasifier with carbonaceous or the charging of hydrocarbon matter.Oxidant stream can prepare by any means well known in the art, and as the low-temperature distillation of air, pressure oscillating absorbs, membrane sepn, or its arbitrary combination.The purity of oxidant stream is generally the oxygen of at least 90 volume %; For example, oxidant stream can comprise the oxygen of at least 95 volume %, perhaps is the oxygen of at least 98 volume % in another embodiment.

One or more gasifiers are introduced in oxidant stream and the carbonaceous or the charging of hydrocarbon matter that make, wherein oxygenant is consumed and charging fully is converted into one or more synthetic gas (synthetic stream, it comprises for example sulfocompound of carbon monoxide, hydrogen, carbonic acid gas, water and various impurity.For example, synthetic gas can comprise water and other impurity, and for example hydrogen sulfide, carbonyl sulfide, methane, ammonia, prussic acid, hydrogenchloride, mercury, arsenic and other metal depend on feed source and gasifier type.Gasification section comprises one or more gasifiers, high-temperature gas refrigerating unit, ash content/slag treatment device and gas filter, washer.With the accurate mode of oxygenant and charging introducing gasifier is the technology of this area, and preferably this method will be moved continuously and with the speed of substantially constant.

At least one synthetic air is led to power-producing zone during the stage of peak power requirement, produce electric energy thus.Power-producing zone comprises and is used for the equipment that chemical energy and kinetic energy with the synthetic gas charging are converted into electric energy or mechanical energy, is generally the form of at least one turbo-expander, hereinafter is also referred to as " gas turbine ".Usually, this power-producing zone will comprise that as being used for the synthetic gas Conversion of energy be the mixed cycle system of the most effectual way of electric energy, and it comprises Brayton circulation and the Carnot circulation that is used to generate electricity.In the mixed cycle operation, gaseous fuel is mixed with the gas with oxygen, burning, and be fed in one or more gas turbines to produce electric energy or mechanical energy.Hot waste gas in gas turbine or a plurality of turbine is delivered in one or more heat recovery steam generators (HRSG), wherein with a part of heat recuperation in the hot waste gas as steam.Before residual low-level heat is discharged in the concentrated medium arbitrarily in turbine exhaust gas, the various steam (that is, by reclaiming the heat release of chemical reaction) that steam among one or more HRSG produces in these method other parts are delivered in one or more steam turbine decompressors to produce electric energy or mechanical energy.Various changes for the elementary mixing cycles operation are well known in the art.Example is HAT (wet air turbine) circulation and Tophat circulation.All be suitable for, for power-producing zone of the present invention and unrestricted.

Turn down the energy of the capacity coefficient of gas turbine and represent, comprise the thermodynamic efficiency, mechanical efficiency and the disposal of pollutants that depend on load by many coefficients, and economic motivating force.Usually, gas turbine is valuably at least 50% time of full capacity operation at them.For example, gas turbine can be at least 60% time of full capacity operation, typically they at least 70% time of full capacity and more typically in their at least 80% time of full capacity.According to method of the present invention, during the stage of off peak power demand, can close down at least one gas turbine, and can starch at least one synthetic air and lead to chemical and produce the district to produce chemical.The stage that for example, in 24 hour stage, may have more than one peak value external power requirement.Thus, more than can in the 24 given little stages, closing down gas turbine once.By during the stage of these off peak power demands, closing down at least one gas turbine, replacement is with mode operating turbine poor efficiency or uneconomic, can under constant rate of speed and maximum heat kinetics, operate gasifier effectively, and realize the economic worth of synthetic gas.

For example, comprise that the power-producing zone of two gas turbines can be in 90% or bigger down operation of full capacity.Along with the requirement of energy is reduced, (being the low price of energy) or low by thermodynamic efficiency for economic reasons can close down one or more gas turbines valuably.Thus, according to of the present invention abundant, be not continuation with one of mode operating turbine poor efficiency and/or uneconomic, but close down this turbine and the synthetic gas incoming flow changed into lead to chemical and produce the district to produce chemical.Thus, replaced using synthetic air produce chemical simultaneously turbine utilize that synthetic gas production can for example be sold on market or be used to compensate the chemical of the demand for fuel of gas turbine with the capacity coefficient operation of poor efficiency.This chemical produces the district can be used for producing any chemical that obtains from the synthetic gas charging effectively, for example methyl alcohol, alkyl formate, ammonia, dme, hydrogen, fischer-tropsch product, or one or more combination of these chemical.For example, in one embodiment of the invention, this chemical produces the district and produces the district for methyl alcohol.

This methyl alcohol produces the methyl alcohol synthesis device that the district can comprise any type, and these equipment are that those skilled in the art are well-known, and its majority is put into practice on commercial base widely.Most commercial methyl alcohol synthesis devices are operated under the pressure range of about 25～about 140bara, use various copper-based catalysts systems, depend on the technology that is adopted.The described technology in many different this areas is known for synthesizing methanol, for example ICI (Imperial Chemical Industries) technology, Lurgi technology and Mitsubishi technology.Liquid phase process also is well-known in the art.Thus, can comprise fixed bed or liquid silt oar phase methanol reactor according to methanol technics of the present invention.

Usually under the pressure of about 25～about 140bara, synthetic air is supplied to methanol reactor, depend on the method that is adopted.Subsequently synthetic gas is reacted on catalyzer to form methyl alcohol.This reaction is heat release, therefore, needs to reclaim heat usually.Subsequently rough or impure methyl alcohol is concentrated and can carry out purifying, comprise ethanol, propyl alcohol etc., perhaps the not purifying burning that just acts as a fuel to go out decon as higher alcohol.The unconcentrated gas phase that will comprise unreacted synthetic gas charging usually is recycled in the methanol technics charging.

Transition between energy generation and chemical produce is another aspect of the present invention.For example, when preparing methyl alcohol and during the stage that no methyl alcohol produces, can stop flowing to methanol reactor by gas-phase reaction.Reactor valves can be closed to contain other component within reactor, wherein reactive synthesis gas components will reach the balance limit that methyl alcohol produces apace.Can indefinitely reactor be remained on this stationary state.But, desirably keep temperature of reactor to make methanol production will begin opening wide again of synthetic air immediately and introduce, for example be higher than about 200 ℃.Find that surprisingly the thermal mass of catalyzer and reactor self will keep temperature to be higher than the scope several hours of expectation, be generally 4～10 hours, not add heat in addition.But, may must provide extra heat to be input in this immobilized reactor.This extra heat can be by cycling through reactor hot inert gas (for example nitrogen) or provide by heat exchange medium (for example hot water or steam) is contacted with the heat exchange surface of reactor, depend on reactor types as used herein.

For the slurries phase reactor, valuably when methanol reactor is in idle mode, during the stage of peak power requirement, keep catalyzer to be suspended in the liquid.With rare gas element for example nitrogen feed go into reactor surrogate response synthetic gas, speed and volume are enough to prevent the sedimentation of catalyzer.The method that is used to calculate the required flow rate of the suspension of guaranteeing catalyzer is well-known in the art.When methanol production will be recovered, when reducing flow of nitrogen gas, start synthetic gas and flow.When nitrogen amount reduces gradually, removing initially may be very high, in the reactor is reduced to normal level.

The thermal mass of slurry fluid, reactor vessel and catalyzer will keep this temperature the expectation scope on several hours, be generally 4～10 hours, do not add heat in addition.But, may must provide extra heat to be input in this immobilized reactor.This extra heat can be by cycling through reactor hot inert gas (for example nitrogen) or provide by heat exchange medium (for example hot water or steam) is contacted with the heat exchange surface of reactor.For example, in another embodiment of the present invention, the part of at least a synthetic air can be led to methyl alcohol and produce the district during the stage of peak power requirement, the production by small amount of methanol keeps methyl alcohol to produce the district at high temperature thus.During the stage of peak power requirement, whole methanol product can be produced the district as extra fuel from methyl alcohol subsequently and lead to power-producing zone.

Alternatively, can desirably during transitory stage, synthetic air be transferred to methanol reactor from gas turbine gradually, avoid thus any heat or the physical impact of catalyzer or any excessive synthetic gas of avoiding glittering from the peak power requirement to off peak power demand.Thus, method of the present invention further comprises: before closing down gas turbine, forward whole synthetic airs to methyl alcohol from least one gas turbine gradually and produce the district, simultaneously to be enough to the keeping speed of gas turbine under at least 50% maximum capacity that methyl alcohol is co-fed to gas turbine.Gas is being forwarded to or producing employed " gradually " or " little by little " in the content that produces the district from methyl alcohol, its implication is that the transfer of synthetic air for example took place within 5 minutes～several hours in for some time, on the contrary, shifting synthetic air may take place moment, for example controlling by valve.The synthetic gas that will be fed into gas turbine gradually forwards in the methanol process, and simultaneously co-fed enough methyl alcohol is to keep gas turbine within the valid function form of its full capacity of at least 50%.For example, turbine can be remained under its full capacity of at least 60%, at least 70%, at least 80% or at least 90%.Produce the district in case synthetic air is all introduced methyl alcohol, just can close down gas turbine by cutting off methanol feeding.

Similarly,, all or part of synthetic air can be produced the district from methyl alcohol or chemical and forward at least one gas turbine gradually to during the transitory stage of peak power requirement in off peak power demand.Thus, method of the present invention further comprises: at least a synthetic air of 100 volume % produces the district from methyl alcohol and forwards at least one gas turbine gradually at the most during the transitory stage from off peak power demand to the peak power requirement, simultaneously methyl alcohol is co-fed to gas turbine, consumption is enough to keep this gas turbine under at least 50% maximum capacity.For example, turbine can be remained at least 60%, at least 70%, at least 80% or at least 90% time of its full capacity.Can start turbine by charging methyl alcohol only.When with synthetic gas when methyl alcohol produces the district and forwards gas turbine to, methyl alcohol is co-fed to gas turbine to keep this turbine under its full operation capacity of at least 50%.When having obtained enough synthetic gas, methanol feeding is suitably reduced and final the cut-out.

Transition from no methyl alcohol to full methanol production for gas phase or Liquid-phase reactor can less than 1 hour, take place in more typically less than 30 minutes.Variation in the flowing of any methyl alcohol purification devices downstream of methanol reactor can be enough to continue relay storage low by the stage or that do not have a crude methanol of methanol production and alleviates by providing.By this way, the downstream purification device can be operated with the speed of substantially constant, and only handles the average day throughput rate of methyl alcohol pari passu but not the peak value generating rate.

Often, in desulfurization zone, remove the sulfocompound that exists in the synthetic gas desirably synthetic gas being led to chemical generation district or power-producing zone with before preventing that chemical from producing the poisoning or the sulphur emissions of reduction to environment of used any catalyzer in the district.This desulfurization zone can comprise well known in the art being used for from any of the several different methods of gaseous stream desulfurization.Can sulphur compound be removed from the gaseous feed of desulfurization zone by the chemisorption method, for example use caustic soda, salt of wormwood or other mineral alkali or alkanolamine.The example that is applicable to alkanolamine of the present invention comprise contain altogether 10 carbon atoms at the most and have primary and secondary amine alcohol less than about 250 ℃ normal boiling point.Specific examples comprises that primary amine alcohol is as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), the amino fourth of 1--2-alcohol, the amino fourth of 2--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 and secondary amine alcohol are as diethanolamine (DEA), 2-(ethyl base)-ethanol (EAE), 2-(methylamino)-ethanol (MAE), 2-(propyl group amino)-ethanol, 2-(sec.-propyl amino)-ethanol, 2-(butyl amino)-ethanol, 1-(ethylamino)-ethanol, 1-(methylamino)-ethanol, 1-(propyl group amino)-ethanol, 1-(sec.-propyl amino)-ethanol, and 1-(butyl amino)-ethanol.

Alternatively, can the sulphur in the gaseous feed of desulfurization zone be removed by the physical adsorption method.The example of suitable physical absorbent is methyl alcohol and other alkanol, propylene carbonate and other alkyl carbonate, and (generally well-known trade mark is Selexol to the dimethyl ether of the polyoxyethylene glycol of 2～12 diol units with its mixture ^TMSolvent), just-methyl-pyrrolidone, and tetramethylene sulfone.Can adopt physics and chemisorption method, for example Sulfinol simultaneously ^TMTechnology uses tetramethylene sulfone and alkanol as sorbent material, perhaps Amisol ^TMTechnology uses monoethanolamine and methanol mixture as sorbent material.

Can sulfocompound be removed from the gaseous feed of desulfurization zone by the solid absorption method, use that solid is fixed, fluidisation or moving-bed, for example zinc titanate, zinc ferrite, stannic oxide, zinc oxide, ferric oxide, cupric oxide, cerium oxide or its mixture.When the specific desulfurization technology that this utilized needs, can add in desulfurizer that one or more gas cooling steps are to reduce the temperature of rough synthetic gas.Can the enthalpy energy in the synthetic gas be generated by the steam in the cooling row by mode well known in the art and reclaim.If necessity for chemosynthesis needs can increase extra final sulfur method after chemistry or physical adsorption process or solid absorption process.The example of this final sulfur removal technology is for to adsorb on zinc oxide, cupric oxide or ferric oxide.

Usually, can in desulfurization zone, remove 90mol% at least, more typically 95mol% and even whole sulfocompounds in the synthetic gas of 99mol% at least more typically at least.Usually, chemical produces the district needs severeer desulfurization, i.e. the desulfurization of 99.5mol% at least prevents the inactivation of chemical synthetic catalyst thus, and more typically the eluting gas in the desulfurization zone contains the sulphur less than 5ppm (volume).If desired, the desulfurization before the power-producing zone and chemical can be produced district's group is incorporated in the same apparatus and realizes.

Method of the present invention may further include removes or is reduced by at least a carbonic acid gas in the synthetic air.For example, can before synthetic gas being led to chemical generation district, remove a part of carbonic acid gas.Removing or reducing of carbonic acid gas can comprise in the several different methods well known in the art any.Can remove carbonic acid gas in the gaseous feed by the chemisorption method, for example use caustic soda, salt of wormwood or other mineral alkali or alkanolamine.The example that is applicable to alkanolamine of the present invention comprise contain altogether 10 carbon atoms at the most and have primary and secondary amine alcohol less than about 250 ℃ normal boiling point.Specific examples comprises that primary amine alcohol is as monoethanolamine (MEA), 2-amino-2-methyl-1-propanol (AMP), the amino fourth of 1--2-alcohol, the amino fourth of 2--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 and secondary amine alcohol are as diethanolamine (DEA), 2-(ethylamino)-ethanol (EAE), 2-(methylamino)-ethanol (MAE), 2-(propyl group amino)-ethanol, 2-(sec.-propyl amino)-ethanol, 2-(butyl amino)-ethanol, 1-(ethylamino)-ethanol, 1-(methylamino)-ethanol, 1-(propyl group amino)-ethanol, 1-(sec.-propyl amino)-ethanol, and 1-(butyl amino)-ethanol.

Alternatively, can the carbonic acid gas in the gaseous feed be removed by the physical adsorption method.The example of suitable physical absorbent is methyl alcohol and other alkanol, propylene carbonate and other alkyl carbonate, and (generally well-known trade mark is Selexol to the dimethyl ether of the polyoxyethylene glycol of 2～12 diol units with its mixture ^TMSolvent), just-methyl-pyrrolidone, and tetramethylene sulfone.Can adopt physics and chemisorption method, for example Sulfino simultaneously ^TMTechnology uses tetramethylene sulfone and alkanol as sorbent material, perhaps Amisol ^TMTechnology uses monoethanolamine and methanol mixture as sorbent material.

When at this utilized specific decarbonation Technology Need, can add in the decarbonation device that one or more gas cooling steps are to reduce the temperature of rough synthetic gas.Can the enthalpy energy in the synthetic gas be generated by the steam in the cooling row by mode well known in the art and reclaim.If necessity for chemosynthesis needs can increase extra final decarbonation method after chemistry or physical adsorption process or solid absorption process.The example of this final decarbonation technology is pressure or temperature-swing absorbing process.

When for chemical is synthetic must the time, typically in the decarbonation district, remove the carbonic acid gas at least 60%, more typically at least 80% the feeding gas.For example, method of the present invention may further include: before synthetic gas being led to methyl alcohol generation district, carbonic acid gas at least one synthetic air is removed to obtain the gas concentration lwevel of 0.5～10mol%, based on the gas total mole number in this synthetic air.In another embodiment, the carbonic acid gas at least one synthetic air can be removed the concentration that goes to 2～5mol%.Many desulfurization and decarbonation technology can be removed desulfuration and carbonic acid gas simultaneously.Thus, desulfurization zone and decarbonation district can be integrated to remove desulfuration and carbonic acid gas simultaneously, selectively (promptly in independently product flows basically) or non-selectively (promptly as a product of mixing stream).

Can use hydrogen/carbon monoxide ratio that water-gas shift reaction changes synthetic gas.The present invention may further include thus: one or more synthetic airs of 100 volume % lead to energy or water-gas shift reaction district before, chemical generation district at the most, wherein at least a portion carbon monoxide and water are reacted to produce hydrogen and carbonic acid gas:

CO+H ₂OCO ₂+H ₂

Usually realize this water-gas shift reaction with the catalysis pattern by means commonly known in the art.When this water-gas shift reaction district was before desulfurization zone, the water-gas shift catalyzer was anti-sulphur valuably so.For example, the catalyzer of the anti-sulphur of this meeting comprises but is not to be defined in the cobalt-molybdenum catalyzer.Service temperature is generally 250 ℃～500 ℃.Alternatively, can after removing, a large amount of sulphur use high or low temperature transfer catalyst to realize this water-gas shift reaction.High temperature shift catalysts is for example with chromium or the promoted ferric oxide of copper, 300 ℃～500 ℃ operations down.Low-temperature shift catalyst, for example copper-zinc-Al catalysts is 200 ℃～300 ℃ operations down.Alternatively, when being higher than about 900 ℃, gas temperature can not realize this water-gas shift reaction by catalyzer.Because the high exothermic character of this water-gas shift reaction can produce steam by the heat in the exit gas of recycle-water gas shift reactor.Can realize this water-gas shift reaction with any reaction pattern that the heat that is used to control thermopositive reaction well known in the art discharges.The example of suitable reactor pattern comprises the single-stage insulation fix bed reactor; Multistage insulation fix bed reactor has interstage cooling, steam generation or cold-shotting; Tubular fixed bed reactor has steam generation or cooling; Or fluidized-bed.

Water-gas shift reaction district and chemical can be produced the integrated and combination in district, itself or can produce district's physical separation with chemical.For example,, chemical comprises when producing the fischer-tropsch reaction of hydrocarbon, valuably Fischer-Tropsch synthesis device and water-gas shift reaction while and in same reactor, operating with ferrum-based catalyst when producing the district.Comprise by other example of the suitable chemical of one or more deutero-in hydrogen, carbon monoxide or the carbonic acid gas but be not to be defined in methyl alcohol, dme, methyl-formiate, hydrogen, ammonia and its derivative, and fischer-tropsch product.

Another embodiment of the present invention is a kind of method that is used for producing off and on electric energy and chemical, and it comprises:

(d) during transitory stage from the peak power requirement to off peak power demand gradually all at least one synthetic air transfer to methyl alcohol from least one gas turbine and produce the district, simultaneously methyl alcohol is co-fed to this gas turbine to be enough to keep this at least one gas turbine in the speed of at least 50% maximum capacity;

(e) during the stage of off peak power demand, close down at least one gas turbine;

(f) during the stage of off peak power demand, at least one synthetic air is led to methyl alcohol produce the district, produce methyl alcohol thus; With

(g) gradually will be at the most during transitory stage from off peak power demand to the peak power requirement at least one synthetic air of 100 volume % produce the district from methyl alcohol and transfer at least one gas turbine, simultaneously methyl alcohol is co-fed at least one gas turbine to be enough to keep this gas turbine in the speed of at least 50% maximum capacity.

Should be understood that aforesaid method comprises the various embodiments of aforesaid gasifier, synthetic air, oxidant stream, carbonaceous material, power-producing zone, desulfurization and decarbonation.

Such as pointed out in this article, our novel method is used in the thermodynamic efficiency and the maximization of economic rank value of the synthetic air of energy generation.Thus, another embodiment of the present invention is a kind of maximized method of value of money that is used for making the synthetic air of gasification, and it comprises:

(a) oxidant stream that will comprise at least 95 volume % oxygen is fed in the gasifier continuously;

(b) oxidant stream and carbonaceous material are reacted in gasifier, produce synthetic air thus;

(c) during the stage of peak power requirement, synthetic air is led to comprise the power-producing zone of at least one gas turbine;

(d) during the stage of off peak power demand, make synthetic air lead to methyl alcohol and produce the district; With

Should be understood that this method comprises the various embodiments of aforesaid gasifier, synthetic air, oxidant stream, carbonaceous material, power-producing zone, desulfurization and decarbonation.For example, can use gasifier that carbonaceous material such as coke or petroleum coke are oxidized to synthetic gas, and the maximum capacity demand for fuel of at least 90% power-producing zone can be provided according to size.The purity of oxidant stream is generally at least 90 volume % oxygen, and can comprise the oxygen of at least 95 volume %, perhaps the oxygen of at least 98 volume % in another embodiment.This methyl alcohol generation is distinguished as previously mentioned and can be comprised, for example, and fixed bed or liquid slurry phase methanol reactor.

For example, as mentioned above, this method may further include: before closing down gas turbine, forward whole synthetic airs to methyl alcohol gradually from one or more gas turbines and produce the district, simultaneously be enough to keep gas turbine maximum capacity at least 50% under speed methyl alcohol is co-fed to gas turbine.Also can during the stage of peak power requirement the part of at least a synthetic air be led to methyl alcohol and produce the district, the production by small amount of methanol keeps the methanol production district at high temperature thus.Can during the stage of peak power requirement, whole methanol product be produced the district from methyl alcohol subsequently and lead to power-producing zone.Before energy or chemical produce the district, can be further with the synthetic gas purifying to remove the whole sulfocompounds that exist of 95mol% at least, perhaps in another embodiment, can remove the sulphur compound of 99mol% at least.Also can remove carbonic acid gas as described herein like that or reduce its concentration.

The better understanding of one embodiment of the present invention is provided in particular with reference to the method flow diagram described in Fig. 1.In the embodiment shown in Fig. 1, supply with the synthetic gas that the gasification of reformation by the hydrocarbon material or carbonaceous material obtains by conduit 18 with the speed of substantially constant, wherein this synthetic gas is enough to supply with the maximum capacity demand for fuel of 100% power-producing zone.By flow control method well known in the art being flowing between

conduit

20 and 26 of synthetic gas separated, wherein the proportion of flow of two streams depends on instant energy assignment loading coefficient.The mark of introducing the gas of conduit 26 can flowing for 0～100% conduit 18.When the stream 18 when 100% was introduced into conduit 40, beta maximum energy production took place.When the stream 18 when 100% was introduced into conduit 48, maximum methanol production took place.

Energy assignment loading coefficient is depended in further describing of this embodiment of this method.During the peak power requirement, 100% stream 18 is introduced desulfurization zone 34 and power-producing zone 36 by conduit 26.In desulfurization zone 34, the sulfocompound of rough synthetic gas is removed for example hydrogen sulfide, carbonyl sulfide, and other trace impurity such as ammonia, hydrogenchloride, prussic acid and trace-metal such as mercury, arsenic etc.Can before sweetener, provide one or more gas cooling steps, thus as reduce the temperature of rough synthetic gas desired at the specific desulfurization technology of this utilization.Can the enthalpy energy in the synthetic gas be generated by the steam in the cooling row by mode well known in the art and reclaim.Can consequent steam be exported from first desulfurization zone by conduit 28.

Sulfur material for example elementary sulfur, sulfuric acid leaves desulfurization zone by conduit 30.Usually the sulphur content that limits the synthetic gas of cleaning for the environmental legislation of sour gas discharging in the power station is that per 1,000,000 volumes are less than 100 parts.Can in desulfurization zone 34, produce elementary sulfur by means commonly known in the art, for example Claus reaction.Alternatively, can mix with the sulphur oxidation and with water to produce sulfuric acid by method well-known in the art.

The synthetic gas of cleaning leaves desulfurization zone by pipeline 32, and all forwards power-producing zone 36 to by pipeline 40, wherein with synthetic gas and air or another suitable oxygen containing gaseous combustion.In preferred energy production units, the combustion gases of heat are expanded to drive at least one internal combustion turbine to produce electric energy, export by conduit 38.Preferably will be still the turbine exhaust gas of heat be fed in the heat recovery steam producer producing steam, can be with this steam output with other district (by conduit 41) of being used for this method or drive one or more steam turbine formula generators to produce extra electric power.Cleaning, waste gas cooled leaves by the conduit 42 that wherein it can be discharged in the atmosphere, but some residual heats can be recovered and think other unit that is used for this method valuably.Certainly, expection this layout disclosed herein can be improved greatly according to principle of the present invention.

During the stage of off peak power demand, at least one gas turbine in the power-producing zone is closed down, and forward corresponding synthetic air to chemical generation district, be described as the production of methyl alcohol in this embodiment.By conduit 20 synthetic air 18 is introduced the chemical that comprises water-gas shift reaction district 22, desulfurization zone 34, decarbonation district 52 and methanol reaction zone 54 and produce the district.A part of gas is introduced water-gas shift reaction district 22 by conduit 21, and remainder is passed through conduit 23 from branch road.On the cobalt-molybdenum catalyzer, carry out the water-gas shift reaction of equilibrium-limited by that part of gas of conduit 21 introducings.The steam that heat by exothermic shift reaction generates is by conduit 24 leaving water coal gas transition zones.

Usually for maximum methanol production, adjusting is by the mark of pipeline 23 22 streams 20 of walking around on every side in the water-gas shift district, make the mole ratio of components R of live gas stream 48 of methanol reaction zone between 1.8～2.5, more preferably the numerical value of R is about 1.9～2.1.This ratio of components R is defined as:

R=(mole H ₂-mole CO ₂)/(mole CO+ mole CO ₂)

By conduit 25 gas delivery of changing is arrived above-mentioned desulfurization zone 34, wherein remove the sulfocompound of rough synthetic gas, for example hydrogen sulfide, carbonyl sulfide, and other trace impurity such as ammonia, hydrogenchloride, prussic acid and trace-metal such as mercury, arsenic etc.Can before sweetener, provide one or more gas cooling steps, thus as reduce the temperature of rough synthetic gas desired at the specific desulfurization technology of this utilization.Can the enthalpy energy in the synthetic gas be generated by the steam in the cooling row by mode well known in the art and reclaim.Can consequent steam be exported from first desulfurization zone by conduit 28.

Sulfur material for example elementary sulfur, sulfuric acid leaves desulfurization zone by conduit 30.Proper handling in order to ensure catalyst for methanol, usually by only being used to preserve the sulphur purifying method of the capacity of purifying method, the sulphur content of cleaning synthetic gas is dropped to 1 part of per 100 ten thousand volume from the required level of generating electricity (usually less than the 100ppm volume) in the methanol production manipulate.The example of sulphur purification techniques is for to adsorb on zinc oxide, cupric oxide or ferric oxide.Alternatively, if from the expectation of discharging viewpoint, can produce this purifying method of manipulate at energy and chemical simultaneously.

The synthetic gas of essentially no sulphur is introduced in the conduit 48 in decarbonation district 52 by conduit 32, wherein in the decarbonation district, removed the carbonic acid gas in the feeding gas more than 90%.Carbonic acid gas leaves district 52 by conduit 50, and by conduit 56 fresh synthetic gas is transported to methanol reaction zone 54, wherein on suitable catalyzer feeding gas is converted into methyl alcohol.The example of suitable catalyzer is the copper base supported catalyst.

Because the high exothermic character of methyl alcohol building-up reactions can retrieve to generate steam by conduit 62 from methanol reaction zone.Can realize this methyl alcohol building-up reactions with any reactor pattern that the heat that is used to control thermopositive reaction known in this field discharges.The example of suitable reactor pattern comprises the single-stage insulation fix bed reactor; Multistage insulation fix bed reactor has interstage cooling, steam generation or cold-shotting; Tubular fixed bed reactor has steam generation or cooling; Fluidized-bed, or slurry bed reactor.This methyl alcohol building-up reactions can realize in gas phase or liquid phase.Methanol product is left district 54 by conduit 58.

Usually, under the reaction conditions that is adopted, i.e. 150～260 ℃ of temperature and about 25～97bara, the reaction that is used to form the synthesis gas components of methyl alcohol is halfway, and is generally 20～70% inlet gas.Thus, methanol reaction zone must comprise the equipment that is used for unreacted gas circulation is concentrated to comprising, the cooling and the reactor of pressure exerting device.By this way, can be with the carbon monoxide and the hydrogen that pass through conduit 56 introducing methanol reaction zone 54 of 100mol% are converted into methyl alcohol at the most.

From reaction zone 54, remove the accumulation of tail gas by conduit 60 with inert substance (for example nitrogen, argon gas and methane) in the control methanol reaction zone.Usually, this is removed and to be the stream less than 5% conduit 56.The pipeline igniting that this tail gas can be used in gas turbine or be used for mixed cycle district 36 HRSG is with generating or with the fuel of the independent oil-firing boiler that acts on the generation of steam or energy.In our another embodiment of novel method, can forward a part of synthetic gas to methanol reactor from power-producing zone, guarantee that especially reactor is at high temperature during the stage of peak power requirement.The methyl alcohol that is generated by this synthetic gas can be led to power-producing zone.

In another embodiment of the present invention, in chemical generation district, produce ammonia, wherein make the rough synthetic gas of all guiding chemical generation district into forward the water-gas shift reaction district to, make the maximization of hydrogen and carbon dioxide production thus.Usually carbon monoxide is converted into the transformation efficiency of hydrogen and carbonic acid gas greater than 95%.This decarbonation district can comprise that above-mentioned routine absorbs or adsorption technology, and purification step subsequently.For example, pressure oscillating absorption, wherein the oxide content with hydrogen is reduced to the volume less than 2ppm.Can produce in the district at chemical by Haber-Bosch technology by mode well known in the art and generate ammonia, for example as LeBlance etc. at " Ammonia ", Kirk-Othmer Encylcopedia of Chemical Technology rolls up 2,3 ^RdVersion, such described in 1978, the 494-500 pages or leaves.

In another embodiment of the present invention, can produce in the district production charges tropsch products for example hydrocarbon and alcohol at chemical by fischer-tropsch reaction, for example as US 5,621,155 and 6,682, such described in 711.Usually, can in fixed bed, slurry bed or fluidized-bed reactor, carry out fischer-tropsch reaction.This fischer-tropsch reaction condition can comprise the temperature of reaction between using 190 ℃～340 ℃, and wherein the real reaction temperature is mainly determined by reactor layout.For example, when using fluidized-bed reactor, temperature of reaction is preferably 300 ℃～340 ℃; When using fixed-bed reactor, temperature of reaction is preferably 200 ℃～250 ℃; And when using slurry bed reactor, temperature of reaction is preferably 190 ℃～270 ℃.

The inlet synthetic gas pressure of operable fischer-tropsch reactor is 1～50bar, is preferably 15～50bar.H in the synthetic gas fresh feed ₂: the CO mol ratio can be 1.5: 1～2.5: 1, is preferably 1.8: 1～2.2: 1.This synthetic gas comprises the sulphur of 0.1wppm or still less usually.Can randomly gas circulation be used for step of reaction, and the ratio of gas circulation rate and fresh synthesis gas feeding rate, based on mole number, can be 1: 1～3: 1 so, be preferably 1.5: 1～2.5: 1.The air speed that step of reaction is used is 1～20, be preferably 8～12m ³(kg catalyzer) ^-1Hr ^-1

In principle, can use iron-based, cobalt-based or iron/cobalt-Ji fischer-tropsch catalysts in fischer-tropsch reaction stage, adopt high chain growth probability (be that the α value is 0.8 or bigger, be preferably 0.9 or bigger, more preferably 0.925 or bigger) to come the operational cost fischer-tropsch catalyst but common is.Preferably the selective reaction condition so that the formation of methane and ethane minimize.Tend to like this provide and mainly comprise wax and heavy product, promptly be mainly aliphatics C ₂₀The product stream of+linear hydrocarbons.

The iron-base fischer-tropsch catalyzer can comprise precipitated or interfused iron and/or ferric oxide.But, the iron and/or the ferric oxide that also can use on appropriate carrier sintering, joint or inject.Before Fischer-Tropsch is synthetic, iron should be reduced to metallic iron.This ferrum-based catalyst can contain the promotor of multiple level, its effect can be change final activity of such catalysts, stability and optionally one or more.Common promotor being influences those (" structural promotor ") of the surface-area of reduced iron, and these promotor comprise oxide compound or metal or its combination of Mn, Ti, Mg, Cr, Ca, Si, Al or Cu.

Product in the fischer-tropsch reaction often comprises gaseous reaction products and liquid reacting product.For example, gaseous reaction products generally includes boiling point and is lower than the about 343 ℃ hydrocarbon tail gas of middle distillment (for example by).Liquid reacting product (condensation portion) comprises that boiling point is higher than the alcohol of also 343 ℃ the hydrocarbon vacuum tail gas of pyroparaffine (for example by) and different chain length.

In another embodiment, this chemical produces the district and can be used for producing hydrogen by synthetic gas as mentioned above by water-gas shift reaction.In still another embodiment of the present invention, in chemical generation district, produce for example methyl-formiate of alkyl formate.Exist several being used for to synthesize for example currently known methods of methyl-formiate of alkyl formate at present by synthetic gas and alkyl alcohol charging.Except US 3,716, outside 619, they comprise US 3,816,513, wherein, carbon monoxide and methyl alcohol are reacted with the formation methyl-formiate in liquid phase or gas phase at basic catalyst and be enough to stop carbon monoxide to be converted in the presence of the hydrogen of methyl alcohol; With US 4,216,339, wherein use the liquid reaction mixture stream that contains methyl alcohol and basic metal or alkaline-earth metal methylate catalyzer, carbon monoxide is reacted under high temperature and high pressure to generate methyl-formiate.But, in the most wide in range embodiment of the present invention, any effective commercially available method that is used for being formed by charging that comprises corresponding alkyl alcohol and the synthetic gas that makes that sufficiently is rich in carbon monoxide alkyl formate also is within the scope of the present invention.Selected accurate catalyzer or multiple catalyzer, and concentration, duration of contact etc. can vary widely, it also is known to those skilled in the art.Preferably use US 4,216, disclosed catalyzer in 339 well known to a person skilled in the art multiple other catalyzer but also can use.

Claims

1, a kind of method that is used for producing off and on electric energy and chemical, it comprises:

(b) described oxidant stream and carbonaceous material are reacted in described one or more gasifiers, produce one or more synthetic airs that comprise carbon monoxide, hydrogen, carbonic acid gas and sulfocompound thus;

(c) during the stage of peak power requirement, make at least one described synthetic air lead to the power-producing zone that comprises at least one gas turbine, produce electric energy thus;

(d) during the stage of off peak power demand, make at least one described synthetic air lead to chemical and produce the district, produce chemical thus; With

(e) during the stage of described off peak power demand, close down described at least one gas turbine.

2, according to the process of claim 1 wherein that described chemical produces the district and produces methyl alcohol, alkyl formate ester, dme, ammonia, hydrogen, fischer-tropsch product or its combination.

3, according to the method for claim 2, wherein said chemical produces the district and produces the district for methyl alcohol.

4, according to the method for claim 3, wherein step (e) further comprises: gradually all described at least one synthetic airs are transferred to described methyl alcohol from described at least one gas turbine and produce the district during the transitory stage from the peak power requirement to off peak power demand, before closing down described at least one gas turbine methyl alcohol is co-fed to described at least one gas turbine to be enough to keep described at least one gas turbine at least 50% speed of maximum capacity simultaneously.

5, according to the method for claim 3, it further comprises: (f) gradually will be at the most during transitory stage from off peak power demand to the peak power requirement described at least one synthetic air of 100 volume % produce the district from described methyl alcohol and transfer to described at least one gas turbine, simultaneously methyl alcohol is co-fed to described at least one gas turbine to be enough to keep described at least one gas turbine at least 50% speed of maximum capacity.

6, according to the method for claim 3, it further comprises:

(f) during the stage of described peak power requirement, at least one described synthetic air of a part is led to described methyl alcohol produce the district, keep described methyl alcohol to produce the district at high temperature thus; With

(g) during the stage of described peak power requirement, all products that described methyl alcohol is produced in the district lead to described power-producing zone.

7, according to the process of claim 1 wherein that described methyl alcohol produces the district and comprises fixed-bed reactor or slurries phase reactor.

8, according to the process of claim 1 wherein that described oxidant stream comprises the oxygen of at least 95 volume %.

9, according to the method for claim 1, it further comprises: in step (c) or (d) before, remove the 95mol% at least of the whole sulfocompounds that exist in the described synthetic air in the sulphur removal district.

10, according to the method for claim 3, it further comprises: before the described methyl alcohol of leading to of step (d) produces the district, from described at least one synthetic air, remove described carbonic acid gas to obtain the gas concentration lwevel of 0.5～10mol%, based on the gas total mole number in described at least one synthetic air.

11, according to the method for claim 10, wherein said gas concentration lwevel is 2～5mol%.

12, according to the method for claim 1, it further comprises: in step (c) or (d) before, described at least one synthetic air of 100 volume % is at the most led to the water gas shift reaction district, wherein with the described carbon monoxide of at least a portion and water reaction to produce hydrogen and carbonic acid gas.

13, according to the process of claim 1 wherein that described carbonaceous material is coal or refinery coke, described power-producing zone comprises the circulating system of combination, and during step (c) described gas turbine at least 70% time operation of its maximum capacity.

14, according to the process of claim 1 wherein that the size of determining described one or more gasifiers is with at least 90% of maximum capacity fuel requirement that described power-producing zone is provided.

15, a kind of maximized method of value of money that is used for making the gasifying process synthetic air, it comprises:

(b) described oxidant stream and carbonaceous material are reacted in described gasifier, produce synthetic air thus;

(c) during the stage of peak power requirement, make described synthetic air lead to the power-producing zone that comprises at least one gas turbine;

(d) during the stage of off peak power demand, make described synthetic air lead to methyl alcohol and produce the district; With