CN107032954A - The method that methanol and its derivative are produced using underground coal gasification(UCG) product gas - Google Patents
The method that methanol and its derivative are produced using underground coal gasification(UCG) product gas Download PDFInfo
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- CN107032954A CN107032954A CN201710304162.8A CN201710304162A CN107032954A CN 107032954 A CN107032954 A CN 107032954A CN 201710304162 A CN201710304162 A CN 201710304162A CN 107032954 A CN107032954 A CN 107032954A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
Abstract
The present invention relates to the method for a kind of utilization underground coal gasification(UCG) product gas production methanol and its derivative, step is as follows：（1）Underground coal gasification(UCG) produces the crude synthesis gas of appropriate economic scale；（2）Obtain dry synthesis gas；（3）Dry synthesis gas is delivered to acid Water gas shift/WGS and cooling unit, adjusts the desired C/Hratio of downstream methanol synthetic reaction；（4）Synthesis gas after cooling is delivered to acid gas removal unit desulfurization；（5）Synthesize gas decarbonization；（6）Synthesis gas carries out synthetic reaction by methanol synthesis unit and obtains final products methanol.Utilization underground coal gasification(UCG) product gas production methanol and its method for derivative that the present invention is provided, make full use of the principal by product in coal underground gasifying technology to extend downstream finished product scope, reduce the cost of post-production processing and discharge.
Description
Technical field
The present invention relates to the method for a kind of utilization underground coal gasification(UCG) product gas production methanol and its derivative, belong to coal
Underground gasification product gas technical field of comprehensive utilization.
Background technology
Underground coal gasification(UCG)（ISC）Be one by oxidant, burning and gasification reaction by subterranean coal are straight coal
Switch through the process for turning to product gas.Product gas is commonly known as synthesis gas, can be used as fuel production, Chemical Manufacture, generating etc.
The raw material of downstream process.The technical process set shaft building completion, underground coal mining and coal gasification process technology, with security
Well, the advantages of investing small, high efficiency, pollution less.
Coal gasification process is the process that coal is changed into synthesis gas by a series of chemical reaction.It is wherein main
Reaction includes：
C+H20 → H2+CO（Steam gasification reacts）
CO+H20 ↔ H2+CO2（Water gas shift reaction）
CO+3H2↔ CH4+H20 （Methanation reaction）
C+2H2 → CH4（Hydrogen gasification reaction）
C+½O2→ CO （Partial oxidation reaction）
C+O2 → CO2（Complete oxidation）
C+CO2→ 2CO（Carbon dioxide gasification reacts）
One drilling well for being used for oxidant injection is referred to as " injection well ", and another drilling well for being used to produce product gas is referred to as " production
Product well ".Directed drilling and vertical drilling can all be used as injection well or product well.Underground coal gasification(UCG)（ISC）May be in injection well
Also need to use one or more peupendicular holes between product well（For example：Functional well and service well）.
When having injection well, product well and horizontal channel to connect the two in coal seam, this construction is referred to as a coal
Charcoal underground gasification（ISC）Unit or well pair.ISC units include combustion zone, gasification zone and pyrolysis zone.Wherein, combustion zone is in coal seam
Near middle oxidant decanting point；Gasification zone is centered around around combustion zone with radial form or in combustion zone downstream, and coal exists
Gasification zone is gasified, part is oxidized, so as to generate product gas；Pyrolysis zone typically exists in gasification zone downstream, the pyrolytic reaction of coal
Here occur.The product gas of high temperature is finally transported to ground from gasification zone toward downstream flow from product well well head.In coal combustion
Or while gasification, it is big that the ISC burned out area in coal seam can grow change.
The product gas generated by underground coal gasification(UCG)（Crude synthesis gas）Usually contain synthesis gas（CO、CO2、H2、CH4And its
The mixture of his gas）And other compositions（Solid particle, water, coal tar, hydrocarbon vapours, other microcomponents include H2S、
NH4, COS etc.）.Its complicated component degree depends on many aspects：Oxidant used in underground coal gasification(UCG)（Air or other
Oxidant, such as oxygen, oxygen-enriched air or vapour mixture）, inherent water in coal seam or surrounding formations penetrate into coal seam water,
The operating parameter of ature of coal and coal underground gasifying technology, including temperature, pressure etc..
According to existing patent document, the comprehensive utilization of current underground coal gasification(UCG) product gas is still faced with many problems,
It is specific as follows：
A) small-scale air gasification synthesis gas power generating demonstration project is removed（Including the direct generation of electricity and mix burning generate electricity）Outside, lack extensive
Industrialize project implementation and operation.
B) all kinds of byproducts of underground coal gasification(UCG) production, such as hydrogen sulfide/sulphur, process water, carbon dioxide, coal tar
Oil etc. reduces or removed these byproducts without clear and definite and ripe industrialization method of comprehensive utilization or technique.
C) downstream syngas production methanol, gasoline blend component MTG and the diformazan for coal underground gasifying technology are lacked
Ether DME（Liquid fuel）Process scheme
D) conjunction that air gasification, three kinds of different process of oxygen-rich gasification and pure oxygen gasification in coal underground gasifying technology are produced
Distinguish larger into gas product quality, directly affect processing condition and method downstream, it is impossible to lump together.
E) downstream syngas is not considered and the beneficial byproduct coal bed gas in Optimum utilization coal seam in detail using technique.
The content of the invention
It is an object of the invention to solve the deficiencies in the prior art to produce using underground coal gasification(UCG) product gas there is provided one kind
The method of methanol and its derivative.Utilization underground coal gasification(UCG) product gas production methanol and its side of derivative that the present invention is provided
Method, makes full use of principal by product in coal underground gasifying technology to extend downstream finished product scope, not only reduces the later stage and adds
Work processing and the cost of discharge, also add Project Product yield and income from sales.
The technical solution adopted for the present invention to solve the technical problems is：
The method that methanol and its derivative are produced using underground coal gasification(UCG) product gas, methods described is comprised the following steps：
（1）The crude synthesis gas that multiple underground gasification furnace or gasification furnace groups pass through the appropriate economic scale of pure oxygen gasification technique productions；
（2）Crude synthesis gas is delivered to ground by product well, and enters crude synthesis gas cooling, washing and separative element, is done
Synthesis gas, the dry synthesis gas includes H2、CO、CO2、CH4、H2S, COS and HCN composition；
（3）Dry synthesis gas is delivered to CO excessive in acid Water gas shift/WGS and cooling unit, dry synthesis gas and carried out with water vapour
Catalytic reaction, generates H2And CO2, adjust the desired C/Hratio of downstream methanol synthetic reaction；
（4）Synthesis gas after cooling is delivered to acid gas removal unit, and the porch of the acid gas removal unit is provided with
Mercury removal reactor, using counter-current gas absorption process, the sour gas in synthesis gas is absorbed in absorption tower using renewable solvent
Body H2S and CO2, obtain and meet downstream synthesis technique requirement H2S contents<1ppmv synthesis gas；
（5）Unnecessary carbon dioxide is further removed by acid gas removal unit in synthesis gas, further to verify methanol
H in the synthesis gas of synthetic reaction requirement2:CO2Stoichiometric proportion is 3 or H2:CO stoichiometric proportions are 2；
（6）Synthesis gas carries out synthetic reaction by methanol synthesis unit and obtains final products methanol, and the methanol synthesis unit enters
Mouth is provided with the protection reactor of cobalt molybdenum zinc oxide catalyst, it is ensured that the sulphur of any residual in removing synthesis gas.
It is preferred that, step（2）The direct cooling technique that the middle step of use cooling water washing one is carried out, or use cooling water washing two
Walk the indirect cooling technique carried out.
It is preferred that, step（6）Middle methanol synthesis reaction uses fixed bed reactors, fixed bed reactors are by multistage reaction
Device is constituted, and methanol and unreacted syngas mixture are cooled down by heat-exchange apparatus, is separated by condensation, recovery with synthesis gas
The wet methanol of liquid intermediate, purity≤96% of methanol are obtained afterwards.
It is preferred that, the wet methanol of liquid intermediate obtains the high-purity first of purity 99.9% by methanol distillation unit
Alcohol.
It is preferred that, in addition to step（7）：Step（6）The methanol of acquisition enters preparing gasoline by methanol unit, and methanol is urged in zeolite
Reacted in agent, generation raw gasoline is delivered to gasoline refinery unit, further production liquefied petroleum gas and gasoline blend component.
It is preferred that, in addition to step（7）：Step（6）The methanol of acquisition is introduced into dimethyl ether production unit, by methanol oxidation
The thick product dimethyl ether of dehydration production, thick dimethyl ether enters dimethyl ether refined unit, final products dimethyl ether is obtained after distillation.
It is preferred that, step（6）It is replaced by as follows：Synthesis gas carries out inertia under 250 DEG C of moderate temperatures and 69barg pressure
Fluid is combined to reaction, and methanol and dimethyl ether are directly catalyzed and synthesized using dual catalytic agent Cu/ZnO/Al2O3 and gama-alumina.
It is preferred that, step（2）The coal tar of acquisition, into coal tar processing unit, is divided into coal by distilling by coal tar
Tar naphtha and coal tar distillate, then by removing the sulphur of residual to coal tar naphtha hydrotreating, after desulfurization
Coal tar naphtha be delivered to pre-reforming unit, gas stream of the production rich in methane is simultaneously delivered to self-heating recapitalization unit, from
In thermal reforming unit, the gas stream rich in methane is reformed using carbon dioxide or steam and oxygen, self-heating recapitalization unit
Synthesis gas enters acid water gas conversion after being mixed with dry synthesis gas with suitable proportion and cooling unit carries out subsequent treatment.
It is preferred that, H in steam autothermal reforming reaction, steam self-heating recapitalization product gas is selected in self-heating recapitalization unit2:COization
Metering is learned than being 2.5:1, the H in carbon dioxide self-heating recapitalization product gas2:CO stoichiometric proportions are 1:1.
It is preferred that, step（3）Dry synthesis gas, is firstly transferred to acid gas removal cell processing, and the sour gas takes off
Except the porch of unit includes COS hydrolysis units, in the porch of self-heating recapitalization unit, dry synthesis gas is protected by a catalyst
Reactor is protected, residual impurity is removed, to protect ATR catalyst and downstream methanol synthetic catalyst, then synthesis gas enters self-heating
Reformer unit, the high methane content of the oxygen produced with air-separating plant, the steam of boiler for producing and pre-reforming unit production
Product solid/liquid/gas reactions, produce self-heating recapitalization unit ATR synthesis gas, afterwards, ATR synthesis gas enters back into Water gas shift/WGS and cooling is single
Member, the H needed for adjustment methanol synthesis unit2:CO stoichiometric proportions.
It is preferred that, the process water of self-heating recapitalization unit generation is delivered to recycling after process water processing unit processes,
Excessive carbon dioxide is removed by decarburization unit, the decarbonization process used include chemisorbed, physical absorption, adsorbent bed,
Absorption regeneration method, low temperature processing or membrane separation process.
The beneficial effects of the invention are as follows：Utilization underground coal gasification(UCG) product gas production methanol and its derivative that the present invention is provided
The method of thing, makes full use of the principal by product in coal underground gasifying technology to extend downstream finished product scope, not only reduces
Post-production processing and the cost of discharge, also add Project Product yield and income from sales.
Brief description of the drawings
Retouched to more clearly describe the accompanying drawing used required in the technology flow of the present invention, specific embodiment
State as follows.It should be evident that drawings in the following description are only some embodiments of the present invention, for the common skill in this area
For art personnel, on the premise of not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is the square process chart that underground coal gasification(UCG) pure oxygen gasification product gas produces methanol, scheme one；
Fig. 2 is underground coal gasification(UCG) pure oxygen gasification product gas production methanol and gasoline blend component（MTG）Square technological process
Figure, scheme one；
Fig. 3 is underground coal gasification(UCG) pure oxygen gasification product gas production methanol and dimethyl ether（DME）Square process chart, scheme
One；
Fig. 4 is the square process chart that underground coal gasification(UCG) pure oxygen gasification product gas produces methanol, scheme two；
Fig. 5 is the square process chart that underground coal gasification(UCG) pure oxygen gasification product gas produces methanol, scheme three.
In the accompanying drawings, identical reference refers to same parts.
1st, air-separating plant（ASU）；2nd, oxygen；3rd, nitrogen；4th, ISC underground gasification furnaces；5th, crude synthesis gas；6th, thick synthesis
Air cooling, washing and separative element；7th, dry synthesis gas；8th, process water；9th, technique unit for treating water；10th, raw water；11st, Waste
Material；12nd, the process water of processing；13rd, gasify unit for treating water；14th, gasified water；15th, coal tar；16th, coal tar processing unit；
17th, the coal tar of processing；17a, coal tar naphtha；17b, coal tar distillate；18th, acid Water gas shift/WGS（SWGS）/ water
Gas conversion（WGS）And cooling unit；19th, sour water stripping (SWS)（SWS）Unit；20th, sour gas；21st, acid gas removal（AGR）
Unit；22nd, carbon dioxide；23rd, sulfur cream unit；24th, sulphur；25th, pre-reforming unit；26th, self-heating recapitalization unit（ATR）；
27th, ATR synthesis gas；28th, boiler；29th, steam；340th, flammable boiler exhaust gas；31st, decarburization unit；；32nd, methanol synthesis unit；
33rd, rich in Methane offgas（For fuel, generate electricity or sale）；34th, methanol distillation unit；35th, methanol；36th, preparing gasoline by methanol
（MTG）Unit；37th, raw gasoline；38th, gasoline refining unit；39th, gasoline blend component；40th, liquefied petroleum gas（LPG）；41st, two
Methyl ether（DME）Production unit；42nd, dimethyl ether（DME）Refined unit；43rd, dimethyl ether（DME）；44th, methanol is reclaimed；45th, flammable tail
Gas（For generating electricity or selling）.
Embodiment
Below by specific embodiment, and with reference to accompanying drawing, technical scheme is described in further detail.
In one embodiment, methanol is produced using underground coal gasification(UCG) product gas（Fig. 1）, air-separating plant
（ASU）1 is used to produce the liquid oxygen that concentration is higher than 90mole%（LOX）2 are used for underground coal gasification(UCG) pure oxygen gasification.Meanwhile, air
Separator（ASU）1 also produces nitrogen 3, can be used as the public work of whole technique, such as ISC underground gasification furnaces 4 are purged, pipeline
With equipment purging, project driving and parking purging etc..When needing the nitrogen of higher pressure, using booster compressor to provide
The supply pressure needed.High concentration liquid oxygen（LOX）2 also pass through booster pump, increase oxygen supply pressure.Then by evaporator, to
The injection well of ISC underground gasification furnaces 4 provides gaseous state oxygen（GOX）2.For ISC pure oxygen gasifications, air compressor is only used for downstream
Debugging, startup and shutoff operation during process disruption, and can be shared between multiple ISC underground gasification furnaces 4.Therefore, Fig. 1 is being just
Unlisted air compressor in normal operation process flow.Single air-separating plant（ASU）1 with can providing multiple ISC simultaneously
Lower gasification furnace 4, is specifically dependent upon single air-separating plant（ASU）The oxygen demand of 1 production capacity and single ISC underground gasification furnaces 4.
High concentration gaseous state oxygen（GOX）Reacted after 2 injection ISC underground gasification furnaces 4 with coal seam, produce the extremely low thick conjunction of nitrogen content
Into gas 5, high pressure and the pyrolytic conversion application in downstream are relatively more suitable for.Crude synthesis gas 5 is delivered to ground by product well, and enters
Crude synthesis gas cooling, washing and separative element 6.Crude synthesis gas 5 passes through direct cooling technique（Liquid or gas cooling, venturi
Device, cooling tower etc.）Or indirect cooling technique（Blade fan, heat exchanger etc.）It is quickly cooled to<150oC.Wherein, it is directly cold
But technique contains the step of crude synthesis gas is washed, and cooling technique then needs at least one scrubbing tower by crude synthesis gas indirectly
Trace contaminant（Particulate matter, chloride, mercury, ammonia etc.）Removed from crude synthesis gas.Synthesis gas after washing subsequently into
The free fluid remained in gas-liquid separator, removing synthesis gas, generates temperature<100oC dry synthesis gas 7.It is gentle from scrubbing tower
The process water 8 that liquid/gas separator is isolated is delivered to technique unit for treating water 9.Pass through Mechanical Method（Gravitational settling, oil skimmer, filtering,
Counter-infiltration）, chemical method（Such as coagulating agent, antisludging agent, corrosion inhibiter, pH nertralizers）And bioanalysis（Aerobic bacteria, anaerobic bacteria,
Activated sludge process, cyclic activated sludge process, the fixed film activity sludge of integration, membrane bioreactor etc.）Handled.Raw water
10, as the supplement water of whole technological process, also handled in the lump into technique unit for treating water 9.Process residue 11, including
Solid waste, sludge and strong brine by garbage loading embeading, burning or third party's facility, it is necessary to be carried out at specialty extraction
Reason.The process water 12 of processing can be used for all downstream applications or be directly entered gasification unit for treating water 13, with producing for ISC
The gasified water 14 of lower gasification furnace 4.Coal tar 15 is delivered in coal tar processing unit 16 and is processed further, and removes in coal tar 15
All remaining moisture（Process water 8）, such as handled by demulsification, precipitation and water-oil separating etc..Dry coal tar 15 is through sieving
Divide and be filtered to remove after the solid particle of its residual and obtain byproduct coal tar 17 available for boiler and generating set（For example it is reciprocal
Formula engine, turbine etc.）Fuel or direct marketing.The dry main component of synthesis gas 7 is H2, CO, CO2And CH4, contain simultaneously
H2S, COS and HCN trace impurity.
Dry synthesis gas 7 is firstly transferred to acid Water gas shift/WGS（SWGS）With cooling unit 18.It is excessive in dry synthesis gas 7
CO carries out catalytic reaction with water vapour（Such as cobalt-molybdenum catalyst or other suitable catalyst）, generate H2And CO2, with realization
The desired C/Hratio of methanol synthesis reaction is swum, for methanol synthesizing process, required H2:CO stoichiometric proportions are 2:1 or H2:CO2
Stoichiometric proportion 3:1（Methanol-fueled CLC exothermic reaction：CO + 2H2 ↔ CH3OH, H298K, 50bar= -90.7 kJ/mol；CO2
+ 3H2 ↔ CH3OH + H2O, H298K, 50bar= -40.9 kJ/mol；CO + H2O ↔ CO2 + H2, H298K, 50bar
= -49.8 kJ/mol）.Gas concentration lwevel is between 4-12mole% in synthesis gas, and methanol synthesis reaction total conversion is most
It is high.If CO contents are limited in synthesis gas, need to improve CO in methanol synthesizer synthesis gas2Content is to convert wherein all H2,
Its cost is that the conversion ratio of single reaction is lower slightly.Therefore, if CO in synthesis gas2Content is higher, then needs to carry out many secondary responses
H in complete transformation of synthetic gas2.In course of reaction, CO2Conversion ratio it is higher, moisture is higher in intermediate wet methanol.With tradition
Water-gas changes after desulfurization（WGS）Technique is compared, using acid Water gas shift/WGS（SWGS）Technique can be by nitric sulfid（COS）With
Other organic sulfur conversions are hydrogen sulfide（H2S）, be conducive to downstream sulfur removal technology, it is not necessary to extra nitric sulfid（COS）At hydrolysis
Reason.In addition, acid Water gas shift/WGS（SWGS）The optimum position of unit 18 is cooling down positioned at crude synthesis gas, washed and separative element 6
Afterwards, water content higher in synthesis gas is conducive to improving the conversion ratio of Water gas shift/WGS and reduces reaction water steam consumption
Amount.Wherein, the CO contents such as in dried fruit synthesis gas 7 are relatively low, without converting more CO with the H needed for realizing2:CO stoichiometries
Than then can select acid Water gas shift/WGS（SWGS）Unit branch road skips the processing procedure（Fig. 1 is not marked）.
For 200-600 meters of ub-bituminous coal-bituminous coal of buried depth, the synthesis gas H of underground coal gasification(UCG) ISC productions2:CO chemistry meters
Amount is than usually 2:1-3:1, H2:CO2Stoichiometric proportion is usually 1:1.2-1:2.5.If underground combustion and the water burst of gasification zone
Amount is higher and when still keeping optimal gasification condition, then the H of synthesis gas2And CO2Content increase, while CO contents are reduced（Similar water coal
Gas converter unit 18）.If likewise, implementing underground coal gasification(UCG) in the deeper coal seam of buried depth, due to methanation reaction tendency
In higher operating pressure condition, so the H of synthesis gas2Reduced with CO contents, while CH4And CO2Content increase.
Synthesis gas after conversion is after supercooling, and the liquids recovery of condensation is simultaneously delivered at sour water stripping (SWS) unit 19
Reason.The waste heat of cooling procedure can be used for production low-pressure steam or preboiler feedwater.By directly or indirectly heating sour water stripping (SWS)
The reactor of unit 19 simultaneously adds the sour gas 20 that caustic soda will be condensed in acidic liquid simultaneously（H2S, a small amount of CO2And NH3）Point
From.Then sour gas 20 is delivered to sulfur cream unit 23（Such as claus sulphur recovery units）, by H2S changes into sulphur
24.Synthesis gas after cooling is delivered to acid gas removal unit（AGR）21, wherein there is mercury removal in the porch of the unit
Reactor（Fig. 1 is not marked）.The unit uses counter-current gas absorption process, and synthesis gas is absorbed using renewable solvent in absorption tower
In sour gas（H2S and CO2）, obtain and meet downstream synthesis technique requirement H2S contents<1ppmv synthesis gas, preferably H2S contains
Amount<0.1ppmv.The technology that the unit is used is that low-temp methanol washes physical solvent adsorption technology with SELEXOL techniques.Leave
The solvent rich in sour gas for absorbing tower bottom is sent in regeneration reactor, and stripping desolvation by low-pressure steam absorbs
H2S, then converts it into sulphur 24.Handled by multi-step pressure reduction and nitrogen stripping, can by with H2S together absorbed two
Carbonoxide 22 is removed from solvent.Unnecessary carbon dioxide 22 passes through acid gas removal（AGR）After unit 21 is removed, it can be used for
Fertilizer production, carbon dioxide drive（EOR）Or further sale after purification.
Because sulphur can cause the poisoning of methanol synthesizing process catalyst（Such as Cu/ZnO/Al2O3）, in methanol synthesis unit 32
Porch need to generally install the protection reactor for being loaded with cobalt molybdenum zinc oxide catalyst, it is ensured that the sulphur of any residual in removing synthesis gas
（<0.1ppmv）.The typical entrance operating pressure of methanol synthesis reactor is 50barg, it is necessary to be lifted by synthesic gas compressor
Synthesize atmospheric pressure.Synthesis gas after purification and impurity removal is converted into methanol in fixed bed reactors, and fixed bed reactors can be by more
Rank reactor is constituted.Methanol and unreacted syngas mixture pass through heat-exchange apparatus（Such as classification cooling）Cooling.Pass through
Condensation, recovery obtain the wet methanol of liquid intermediate after being separated with synthesis gas, and now the purity of methanol can reach 96%（Other are water
The CO dissolved on a small quantity2）.For one way reaction system, unreacted synthesis gas is as rich in Methane offgas 33（Fuel gas,
CH4>70mole%）The unit 32 is discharged, can be used as fuel, generate electricity or sell.For the multi-way circulatory system, most of unreacted
Synthesis gas be recirculated to methanol synthesis reactor（Fig. 1 is not marked）Entrance, the discharge of which part tail gas is to prevent inertia
Gas（Mainly CH4）Accumulation.The methanol of high-purity can be produced by methanol distillation unit 34（99.9mole%）Product.
In another embodiment, Fig. 2 is shown the wet methanol production gasoline blend component 39 of intermediate, rather than will
It distills production high purity methanol product 35.Preparing gasoline by methanol（MTG）In unit 36, methanol reacts on zeolite catalyst（Behaviour
Make pressure about 14barg）.For fluidized-bed reactor, catalyst burns some carbon distributions by part and cyclic regeneration is circulated, no
Need extra reactant.For fixed bed reactors, then multiple reactors are needed, so that reactor periodically stops to urging
Agent carries out regeneration cycle or fresh makeup catalyst.The raw gasoline 37 of generation is delivered to gasoline refinery unit 38, production liquefaction
Oil gas（LPG）40 and gasoline blend component 39.Final products gasoline blend component 39 can reconcile with typical refiner product to be made
For Fuel Petroleum.
In another embodiment, Fig. 3, which is shown, converts methanol into dimethyl ether（DME）Technological process.The technique
Using two step method, the generation crude carbinol of methanol synthesis unit 32 is first passed through, then by dimethyl ether production unit 41 by methanol oxidation
Dehydration（Gama-alumina）To produce thick product dimethyl ether（2CH3OH ↔CH3OCH3 + H2O）.Thick dimethyl ether enters dimethyl ether
（DME）Final products dimethyl ether is obtained after refined unit 42, distillation（DME）43, it can sell or former as chemical synthesis
Material.Methanol 44 is reclaimed also to be cycled back in the charging of dimethyl ether production unit 41.Meanwhile, in dimethyl ether（DME）Refined unit
42 outlet recovery process water 8 and flammable tail gas 45（For generating electricity or selling）.Also dimethyl ether can directly be produced using one-step method
（DME）, synthesis gas is in moderate temperature and pressure（250 DEG C, 69barg）Under liquid phase（Inert oil）Synthetic reaction, is urged using dual
Agent（Cu/ZnO/Al2O3And gama-alumina）Directly produce methanol and dimethyl ether.
In another embodiment, technological process as shown in Figure 4, improves and utilizes the production of underground coal gasification(UCG) product gas
The by-product utilization rate of methanol.Coal tar naphtha 17a after desulfurization is generated into the gas rich in methane by pre-reforming unit 25
Unreacted synthesis gas in body stream and methanol synthesis unit 32（Rich in Methane offgas 33）It is delivered to self-heating recapitalization unit（ATR）26
Produce ATR synthesis gas 27.The synthesis gas is fed as the supplement of the dry synthesis gas 7 of underground coal gasification(UCG) ISC, is delivered to acid water coal
Gas is converted（SWGS）With cooling unit 18 and subsequent technique.Self-heating recapitalization unit（ATR）Steam 29 needed for 26 is by boiler 28
Production is provided, and its fuel can select coal tar fraction 17b, synthetic natural gas（SNG）Product or other fuel oil.Required boiler
Feedwater is provided by gasification unit for treating water 13.
In another embodiment, Fig. 5 is shown with high methane content（>15mole%）Underground coal gasification(UCG) production
Product gas produces the technological process of methanol.Dry synthesis gas 7 is delivered to acid gas removal（AGR）Unit 21 is handled.The flow will be
The porch of acid gas removal unit 21 includes COS hydrolysis units（Fig. 5 is not marked）.Carbon dioxide removal 22 and sulphur 24
Afterwards, synthesis gas enters self-heating recapitalization unit（ATR）26.In self-heating recapitalization unit（ATR）26 porch, synthesis gas passes through one
Catalyst protection reactor（Fig. 5 is not marked）, remove the mercury of residual, other heavy metals, sulphur, the impurity such as chlorine, to protect ATR to be catalyzed
Agent and downstream methanol synthetic catalyst.Then synthesis gas enters self-heating recapitalization unit（ATR）26, with air-separating plant（ASU）1
The product solid/liquid/gas reactions for the high methane content that the steam 29 and pre-reforming unit 25 that oxygen 2, the boiler 28 of production are produced are produced, production
ATR synthesis gas 27.Afterwards, ATR synthesis gas 27 enters Water gas shift/WGS（WGS）With cooling unit 18（Fig. 5 does not mark branch road）, adjust
H needed for whole methanol synthesis unit 322:CO stoichiometric proportions.Self-heating recapitalization unit（ATR）The process water 8 of 26 generations simultaneously, it is defeated
Deliver to recycling after technique unit for treating water 9 is handled.Unnecessary carbon dioxide 22 is removed by decarburization unit 31.Used
Decarbonization process include chemisorbed（Methylethanolamine, Benfield etc.）, physical absorption（Low-temp methanol is washed, SELEXOL techniques）、
Adsorbent bed（Aluminum oxide, zeolite, activated carbon）, absorption regeneration method（Transformation, alternating temperature, washing）, low temperature processing or membrane separation process.Root
Factually border operational circumstances, choose wherein most easy integration, the method with Optimum Economic benefit.Finally, the synthesis gas after decarburization is defeated
Deliver to methanol synthesis unit 32 and subsequent technique., can if being not enough to the charging for pre-reforming unit 25 rich in Methane offgas 33
The desulfurization and decarburization synthesis gas of the outlet of addition acid gas removal unit 21 is used as supplement.
For producing methanol and its derivative using underground coal gasification(UCG) product gas, air gasification or oxygen-rich gasification are all uncomfortable
Close large-scale commercial project.Because the N in oxidant feed2To be present in all the time in whole technological process, be ultimately present in
In methanol-fueled CLC tail gas and downstream refining fractionation unit.According to air gasification, the Lower heat value of tail gas is ultimately resulted in（LHV）Compared with
It is low（About 4.0 MJ/Nm3）, combustion gas is not suitable as, and need to be using the N in expensive cryogenic separation technology removing tail gas2。
Meanwhile, the process equipment in all downstreams requires larger size to adapt to substantial amounts of inert gas N2, greatly increase project
Input, and to the yield of methanol and its derivative without contribution.
Embodiment described above is a kind of preferably scheme of the present invention, not makees any formal to the present invention
Limitation, also has other variants and remodeling on the premise of without departing from the technical scheme described in claim.
Claims (10)
1. utilize the method for underground coal gasification(UCG) product gas production methanol and its derivative, it is characterised in that：Methods described includes
Following steps：
（1）The crude synthesis gas that multiple underground gasification furnace or gasification furnace groups pass through the appropriate economic scale of pure oxygen gasification technique productions；
（2）Crude synthesis gas is delivered to ground by product well, and enters crude synthesis gas cooling, washing and separative element, is done
Synthesis gas, the dry synthesis gas includes H2、CO、CO2、CH4、H2S, COS and HCN composition；
（3）Dry synthesis gas is delivered to CO excessive in acid Water gas shift/WGS and cooling unit, dry synthesis gas and carried out with water vapour
Catalytic reaction, generates H2And CO2, adjust the desired C/Hratio of downstream methanol synthetic reaction；
（4）Synthesis gas after cooling is delivered to acid gas removal unit, and the porch of the acid gas removal unit is provided with
Mercury removal reactor, using counter-current gas absorption process, the sour gas in synthesis gas is absorbed in absorption tower using renewable solvent
Body H2S and CO2, obtain and meet downstream synthesis technique requirement H2S contents<1ppmv synthesis gas；
（5）Unnecessary carbon dioxide is further removed by acid gas removal unit in synthesis gas, further to verify methanol
H in the synthesis gas of synthetic reaction requirement2:CO2Stoichiometric proportion is 3 or H2:CO stoichiometric proportions are 2；
（6）Synthesis gas carries out synthetic reaction by methanol synthesis unit and obtains final products methanol, and the methanol synthesis unit enters
Mouth is provided with the protection reactor of cobalt molybdenum zinc oxide catalyst, it is ensured that the sulphur of any residual in removing synthesis gas.
2. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：Step（2）The direct cooling technique that the middle step of use cooling water washing one is carried out, or carried out using the step of cooling water washing two
Indirect cooling technique.
3. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：Step（6）Middle methanol synthesis reaction uses fixed bed reactors, and fixed bed reactors are made up of multistage reactor, first
Alcohol and unreacted syngas mixture are cooled down by heat-exchange apparatus, and liquid is obtained after being separated by condensation, recovery with synthesis gas
The wet methanol of body intermediate, purity≤96% of methanol.
4. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 3 and its derivative, it is special
Levy and be：The wet methanol of liquid intermediate obtains the high purity methanol of purity 99.9% by methanol distillation unit.
5. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：
Also include step（7）：Step（6）The methanol of acquisition enters preparing gasoline by methanol unit, and methanol reacts on zeolite catalyst,
Generation raw gasoline is delivered to gasoline refinery unit, further production liquefied petroleum gas and gasoline blend component.
6. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：
Also include step（7）：Step（6）The methanol of acquisition is introduced into dimethyl ether production unit, and Catalytic dehydration of methanol is produced into thick
Product dimethyl ether, thick dimethyl ether enters dimethyl ether refined unit, and final products dimethyl ether is obtained after distillation.
7. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：
Step（6）It is replaced by as follows：It is anti-that synthesis gas carries out inert oil liquid phase synthesis under 250 DEG C of moderate temperatures and 69barg pressure
Should, utilize dual catalytic agent Cu/ZnO/Al2O3Methanol and dimethyl ether are directly catalyzed and synthesized with gama-alumina.
8. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：Step（2）The coal tar of acquisition, into coal tar processing unit, is divided into coal tar oilstone brain by distilling by coal tar
Oil and coal tar distillate, then by removing the sulphur of residual to coal tar naphtha hydrotreating, the coal tar after desulfurization
Naphtha is delivered to pre-reforming unit, and gas stream of the production rich in methane is simultaneously delivered to self-heating recapitalization unit, in self-heating recapitalization list
In member, the gas stream rich in methane is reformed using carbon dioxide or steam and oxygen, self-heating recapitalization unit synthesis gas with
Dry synthesis gas enters acid water gas conversion after being mixed with suitable proportion and cooling unit carries out subsequent treatment.
9. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 5 and its derivative, it is special
Levy and be：H in steam self-heating recapitalization product gas2:CO stoichiometric proportions are 2.5:1, in carbon dioxide self-heating recapitalization product gas
H2:CO stoichiometric proportions are 1:1.
10. the method for utilization underground coal gasification(UCG) product gas production methanol according to claim 1 and its derivative, it is special
Levy and be：Step（3）Dry synthesis gas, is firstly transferred to acid gas removal cell processing, the acid gas removal unit
Porch includes COS hydrolysis units, and in the porch of self-heating recapitalization unit, dry synthesis gas is reacted by a catalyst protection
Device, removes residual impurity, to protect self-heating recapitalization unit catalyst and downstream methanol synthetic catalyst, and then synthesis gas enters certainly
Thermal reforming unit, the high methane of the oxygen produced with air-separating plant, the steam of boiler for producing and pre-reforming unit production contains
The product solid/liquid/gas reactions of amount, produce self-heating recapitalization unit synthesis gas, afterwards, self-heating recapitalization unit synthesis gas enters back into Water gas shift/WGS
And cooling unit, the H needed for adjustment methanol synthesis unit2:CO stoichiometric proportions.
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