CN105037086B - A kind of Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal - Google Patents

A kind of Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal Download PDF

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CN105037086B
CN105037086B CN201510466032.5A CN201510466032A CN105037086B CN 105037086 B CN105037086 B CN 105037086B CN 201510466032 A CN201510466032 A CN 201510466032A CN 105037086 B CN105037086 B CN 105037086B
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low
coal
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synthesis
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CN105037086A (en
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赵焰飞
马英民
曹会博
王贵
王军亭
张永红
崔晓曦
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Sedin Engineering Co Ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
    • C07C273/08—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds from ammoniacal liquor
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Abstract

A kind of Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal includes coal gas unit, synthesis gas prepares clean unit, higher alcohols synthesis separates with separative element, gas liquor, refining of crude phenol unit and hydrogenation of tar unit.The present invention have technique it is simple, cost is low, can large-scale the advantages of.

Description

A kind of Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal
Technical field
The present invention relates to a kind of technique of preparing low-carbon mixed alcohol by synthetic gas, it is low through synthesis gas system to relate in particular to a kind of coal The Multi-class propagation technique of carbon mixed alcohol while a variety of chemical products of coproduction.
Background technology
Low carbon mixed alcohol refers to C1~C6 alcohol-based mixtures.For performance, low carbon mixed alcohol is a kind of good vapour Oil additive, it has high octane number and the blending performance good with gasoline, can added completely instead of MTBE as gasoline Add agent or clean fuel.By coal etc. through preparing low-carbon mixed alcohol by synthetic gas be the Chemical Engineering Technology of carbon one development key areas. Therefore, active development coal base synthesizing low-carbon mixed alcohol technology not only has great importance.Low carbon mixed alcohol is except as gasoline Outside additive, the low-carbon alcohols of various chemical industry purposes can also be isolated.
At present, China consumes 3 to 4 hundred million tons of oil every year, and thus the oil production rate in China causes at 1.8 hundred million tons or so China's oil importation dependence increases year by year, and crude oil price continue a high position hover, to a certain extent oil product into For China's economic development and national energy security an important factor for.And 6V:Q"p！S) D $ J coals are that a kind of relative abundance and price are low Honest and clean fossil fuel, particularly will be far richer compared with oil and natural gas in coal in China, and therefore, coal will take over oil Important energy source and industrial chemicals.Coal gasification is changed into synthesis gas, is then research by synthesis gas catalytic hydrogenation synthesis of low-carbon alcohol One of more problem, have broad prospects.
As at the beginning of synthesizing low-carbon alcohol from synthetic gas technology starts from last century, the oil crisis of the 1970s so that various countries Substantial amounts of research is done in terms of synthesizing low-carbon alcohol from synthetic gas, the process route for the higher alcohols synthesis developed mainly there are four kinds:
(1) Sygmol techniques.The technique is developed jointly by The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation, using isothermal reaction Device, vulcanize molybdenum series catalyst, low-carbon alcohols selectivity is high, and low-carbon alcohol content is high in product, and water content is low, catalyst anticaking carbon, resistance to Sulphur.
(2) IFP techniques.The technique carries out pilot scale research by France Petroleum Institute and Japan, mainly anti-using two-stage Device is answered, produces the low carbon mixed alcohol based on methanol.The process operating pressure and temperature are all relatively low, but poor selectivity, synthesis gas Utilization rate is low.
(3) Octamix techniques.The technique is developed by Lurgi, using shell and tube or anti-around tubular type isothermal reactor, carrying-off Answer the mode of heat to enter vapour for water to go out.Process form selectivity is high, but the easy heat inactivation of catalyst, low-carbon alcohol content in reaction product For 30%~50%, water content is less than 1%.
(4) MAS techniques.The technique is developed jointly by Italian Snam and Denmark Topse, by improving catalyst for methanol And process conditions, produce low-carbon alcohols while methanol is produced using existing methanol production line, product form be using methanol as Main alcohol-based mixtures.
Domestic Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences has also carried out the catalyst of synthesis gas hydrogenation synthesizing low carbon alcohol And the research of technique, the technique are similar to MAS techniques.
In above-mentioned technique, MAS techniques are most ripe, but more advanced at present is octamix techniques and Sygmol techniques, and this two Kind technological reaction mild condition, alcohol selectivity is high, and crude product water content is low.And the Auditory steady-state responses of Octamix techniques are significantly less than Sygmol techniques, this is favourable to improving process thermal efficiency.And Sygmol techniques use sulfur resistant catalyst, therefore it is expected to save Desulfurization process, the exploitation and popularization of the sulfur resistant catalyst, not only to mixed alcohol technique, and methanol industry may also be produced huge Big influence.Not only C2+ alcohol contents are high in Sygmol process products, and the content of ethanol and propyl alcohol accounts for 50%.Ethanol and Propyl alcohol is industrial chemicals in short supply at present, and expensive, therefore from the point of view of product structure, Sygmol techniques are more beneficial for industrial profit With.But all there is the problem of all not abundant enough to the components utilising of synthesis gas in these techniques.
A kind of methods by synthesis gas continuous production low-carbon alcohols of patent CN101805242A, disclose a kind of synthesis gas production The technique of low-carbon alcohols and alkene hydration generation correspondent alcohol, is a kind of continuous production processes, is in synthesis gas system the characteristics of the invention The reaction of alkene hydration generation correspondent alcohol, unreacted synthesis gas and light alkene closed cycle drop are added after low-carbon alcohols reaction Low energy consumption, improve the yield of synthesis gas utilization rate and alcohol.But the target product conversion ratio of this method is not high, exhaust gas component Complexity, and utilization is only synthesized again to the alkene in tail gas, it is seen that it is substantially relatively low to the utilization rate of tail gas, and this method Obtained fusel it is excessive, the selectivity of low-carbon alcohols is not high.
Patent CN202040470A is used for the method and a kind of synthesis gas of patent CN101891588A of low carbon alcohol by synthetic gas The method of synthesis of low-carbon alcohol, all disclose the method for preparing catalyst of a kind of synthesis of low-carbon alcohol and feasible on synthesis of low-carbon alcohol Property, industrialized application is not involved with completely.But also it is only to rest on laboratory bench scale, the amplification of its engineering also has very Big unpredictability, it is far away from industrial applications.
A kind of technologies of co-producing low-carbon alcohol and natural gas by coal synthesis gas of patent CN101735008A, disclosing one kind will be low The technology that carbon alcohol synthesis technique and methanation process are combined, including gas purification, synthesis collection, tail gas separation and the first of alcohol Several parts such as alkanisation, a tail gas part for synthesis of low-carbon alcohol are recycled back to higher alcohols synthesis device, another part synthesizing methane.Patent A kind of sulfur tolerant catalyzing process of preparing low carbon alcohol from synthesis gas and co-producing natural gas of CN101735009A, disclose a kind of by sulfur-resistant low-carbon Alcohol synthesis technique is combined technique with methanation in presence of sulfur production natural gas process, and synthesis gas can carry out low-carbon without fine de-sulfur Alcohol synthesis reaction, a tail gas part are recycled back to higher alcohols synthesis reactor, and another part enters methanation device synthesizing methane, real Show the Sulfur tolerance and Poly-generation of whole flow process, improve the economy of device to a certain extent.But both technologies are all deposited It is not high in low-carbon alcohols yield, and low-carbon alcohols do not separate, the shortcomings that high energy consumption.Its Patent CN101735009A works as synthesis gas Middle CH4>Elder generation's pressure-variable adsorption methane when 5%, then synthesis of low-carbon alcohol, as CH in synthesis gas4<Elder generation's synthesis of low-carbon alcohol when 5%, then transformation Adsorbed methane, synthesis of low-carbon alcohol.This method is difficult really to realize in the industrial production, it is therefore apparent that both techniques are present Flow is cumbersome, and operational management is complicated, is unsuitable for industrialization promotion.
The content of the invention
It is an object of the invention to provide a kind of technique is simple, cost is low, can synthesis of gas produced low-carbon caused by large-scale mix Close the Multi-class propagation technique of alcohol co-production LNG and coal tar deep processing.
The present invention is that by synthesis gas prepared by colm into low carbon mixed alcohol and each workshop section's unstripped gas is made full use of into coproduction Hydrogenated oil, phenol, the technique of liquefied natural gas, the multistage coproduction of coal being realized, classified utilization, energy-saving and water-saving, technological process is simple, Realize the clean utilization of coal.
This technique can be divided into by function：Coal gas unit, synthesis gas prepare clean unit, higher alcohols synthesis with separating list Member, the separation of coal tar deep processing unit, gas liquor and refining of crude phenol unit.
A kind of Multi-class propagation technique of low carbon alcohol by synthetic gas provided by the invention comprises the following steps：
(1) raw coal, oxygen and vapor obtain raw gas through coal gas unit style, and raw gas is through sulphur-resistant conversion, low-temp methanol Wash and the obtained pure synthesis gas for meeting higher alcohols synthesis after methane separation；The H isolated2S concentrated gas goes sulfur recovery, isolates Methane LNG product is made；
(2) low-carbon alcohols mix products, low-carbon alcohols mix products are made through higher alcohols synthesis catalyst in the synthesis gas after purifying Methanol, ethanol, propyl alcohol and butanol product are obtained after separation；
(3) off-gas of higher alcohols synthesis is through UF membrane (PSA), the H isolated2Together with the tar come being separated with gas liquor Other gases return low-temp methanol such as hydrogenation of tar, the CO isolated is carried out to wash；
(4) gas liquor of coal gas by-product is passed through into gas liquor separative element, tar and the low-carbon alcohols off-gas of separation pass through The H of PSA separation2Hydrogenated oil is made into hydrogenation of tar unit, 1# hydrogasoline ready-mixed oils are made by refined in hydrogenated oil respectively, 2# is hydrogenated with aviation kerosine ready-mixed oil, 3# hydrogenated diesel oils ready-mixed oil and 4# hydro-treated lube base oil ready-mixed oils；
(5) gas liquor for isolating tar enters phenol ammonia recovery unit, and phenol recovery ammonia isolates liquefied ammonia and crude phenols, wherein dividing From liquefied ammonia sent outside as product, the crude phenols of separation carry out refining of crude phenol and phenol, xylenol are made, faces a cresols and paracresol Product.
Coal gas unit as described above uses the bituminous coal broken coal suitable for low-quality lignite (water content 20%-30%) Pressurized-gasification furnace or slack coal slag gasifier (BGL), gasification temperature is at 1000-1450 DEG C, vapor pressure 4.0-6.0MPa.
The remarkable advantage of the gasification technology is：
(1) it is adapted to the low-quality coal gasification that water content is big, ash is high, about 8-12% methane is rich in raw gas,
(2) rate of gasification is high, and the intensity of gasification is big, and crushed coal pressure gasifying technology vapor pressure is big, and gasification temperature is high, therefore gasifies Reaction speed is high, and the intensity of gasification greatly improves, and compared with other gasification technologies, the cold gas efficiency of crushed coal pressure gasifying reaches 90%, efficiency of carbon con version>99.5%, more than 93% energy be converted into can trans-utilization fuel, and water-coal-slurry under the same terms For 78% or so, shell gasification furnace is 82% or so.
(3) oxygen consumption is low, and for vapour/oxygen than low, steam consumption is low：
(4) technology maturation, stable, crushed coal pressure gasifying technology has domesticized and in Datang gram flag and Xinjiang celebrating China Successful application more than 70 covers, the design for gasification furnace, and manufacture and the operational control country all have wide experience, and generally speaking broken coal adds Calming the anger furnace technology is simple, and auxiliary equipment is few, and reliability is high, stable, flexible adjustment.
Sulphur-resistant conversion as described above uses the Co-Mo sulfur-resistant transformation catalyst medium temperature sulphur-resistant conversions with high hydrolysis function Technique, conversion pressure are 2.5-4.4MPa, and transformation temperature is 220-450 DEG C, water/gas mol ratio between 0.25-0.40, with It is 3000-5000h that dry gas, which calculates volume space velocity,-1。
The Co-Mo sulfur-resistant transformation catalysts with high hydrolysis function mainly include following several as described above：
World Catalyst：The SSK type catalyst of Top of Denmark rope, the K8-11 type catalyst of BASF Corp. of Germany, Japan are emerging The C113 type catalyst of Co., Ltd. is produced, the C25-2-02 catalyst of UCI companies of the U.S., above-mentioned four kinds of catalyst are all once in state Applied in interior industry, it is especially the most successful with the K8-11 catalyst of BASF AG, but in recent years, with the progress of domestic technique, Multiple serial sulfur-resistant transformation catalysts have successfully been developed, and its various performance has been fully achieved or better than World Catalyst.
Domestic catalyst：The QDB series sulfur-resistant transformation catalysts of Qingdao Lian Xin chemical industry Co., Ltd production, wherein especially Using QDB-04 types catalyst to be best, it not only has higher activity and stability, and can be with a certain degree of suppression first The side reactions such as alkanisation.The QCS series sulfur-resistant transformation catalysts of Ke Li chemical companies of Qilu Petrochemical research institute production, have intensity Height, low temperature active with great difficulty regenerate the advantages that, representative is QCS-04 type catalyst；The exploitation of Hubei chemical research institute The sulfur-resistant transformation catalyst of EB series, the good catalyst activity, long lifespan, easily regeneration, it is widely used.
It is low-temp methanol washing process there is provided prewashing and regenerative system that low-temp methanol as described above, which is washed, operation temperature For -35 to -55 DEG C, operating pressure 2.0-6.0MPa's, H in the synthesis gas after low-temp methanol is washed2S<0.1ppm,CO2< 20pp。
Due to low-quality coal complicated component, the coal gas tapping temperature through crushed coal pressure gasifying is low, raw gas complicated component.Its Gas component includes CO, H2、CO2、CH4、H2S, organic sulfur, C2H4、C2H6、C3H8、C4H10、 HCN、N2, Ar and tar, fat Sour, single phenol, multiple phenol, naphtha, oil etc..CO, H are removed in these components2Active principle and CH4、N2, Ar and hydro carbons category inertia Outside gas, remaining all components includes CO2All it is the objectionable impurities for needing to remove with sulfide, it is seen that it purifies the difficult of task It is huge.Current various gas purifying techniques are made a general survey of, this person with heavy responsibilities's non-cryogenic methanol can be taken on washes and do not belong to.Because only low temperature first Alcohol cleanization just all can neatly remove various harmful components, such as CO in same device2、H2S、COS、C4H4S、 HCN、NH3、H2O、C2Above hydro carbons (including light oil, aromatic hydrocarbon, naphtha, alkene and colloid etc.) and other carbonyl compounds Thing etc., and other any purification techniques can not all accomplish.Other slag gasified raw material atmospheric pressure is higher, CO in gas2、H2S partial pressures It is of a relatively high, so being advantageous for playing the characteristic that low-temp methanol washes Physical Absorption in itself.In addition, low-temp methanol washing process Also there is the advantages of following various notable compared with other purification techniques：
(1) absorbability is strong, and solution internal circulating load is small
(2) gas purification degree is high
(3) methanol solvate is cheap and easy to get, and regeneration energy consumption is low
(4) heat endurance and chemical stability are good, and solvent is non-degradable, non-foaming, and pure methanol does not corrode to equipment
(5) solution viscosity is small, is advantageous to save power
(6) first alcohol and water can be dissolved each other with arbitrary proportion, and its dry feedstock gas can be used using this characteristic, and
(7) methanol can be extracted from naphtha using the intersolubility of itself and water
Low-temp methanol washes the removing for realizing plurality of impurities in the same apparatus, relative to a variety of net of other purification methods For changing process combination, process is relatively single, reasonable, management easy to operation.
So in view of the raw gas complicated component and low-temp methanol washing process of crushed coal pressure gasifying can be removed disposably The unique advantage of various impurity, the most suitable technique that undoubtedly raw gas is purified.
Methane separation as described above use cryogenic separation, and using the U.S., safe this is cold with the mixing of the neat company of Bock Lightware Agent patented technology, -150 DEG C to -170 DEG C of temperature, preferably -155 DEG C Dao -165 DEG C, preferably pressure 3-8Mpa, 4.0-5.5Mpa, point The compressed conduct product of methane separated out is sent outside, and the synthesis gas of separation of methane carries out higher alcohols synthesis reaction.
Higher alcohols synthesis process conditions are as described above：Reaction pressure 3-8MPa, reaction temperature are 260-350 DEG C, hydrogen Carbon mol ratio is H2/ CO=2.0-5.0, preferably 2.3-4.2, volume space velocity 5000-50000h-1Under the conditions of carry out low-carbon alcohols Synthesis.
The catalyst of higher alcohols synthesis as described above uses the MoS of DOW chemical companies of the U.S.2- M-K catalyst or meaning are big One kind in the Zn-Cr-K catalyst of sharp Snam companies or the modification Cu-Zn-Al series catalysts of German Lurgi companies
Low-carbon alcohols separation as described above just uses normal pressure or vacuum rectification tower, and operating condition is：80-150 DEG C of temperature, pressure Power is normal pressure or decompression, and the mol ratio of alcohol is methanol 30%-65%, ethanol 5-25%, propyl alcohol 8-20%, butanol 5- after separation 20%.
Hydrogenation of tar as described above using fixed bed hydrogenation in reaction pressure 5-15MPa, 250-380 DEG C of reaction temperature, Hydrogen to oil volume ratio is 800:1-2500:1, liquid air speed is 0.5-3.0h-1Under the conditions of carry out hydrogenation of tar reaction, it is obtained plus Hydrogen oil obtains 1# hydrogenated oils, 2# hydrogenated oils, 3# hydrogenated oils, 4# through separation and is hydrogenated with oil product.
Catalyst is the graduate FZC catalyst series in Fushun used by hydrogenation of tar reaction as described above, Such as FZC-11Q, FZC-12Q, FZC-13Q, FZC-25, FZC-40 catalyst.
Hydrogenated oil separation as described above uses atmospheric distillation tower, and operating condition is：80-150 DEG C of temperature, pressure are normal pressure Or decompression, the 1# hydrogasoline ready-mixed oils that the oily mol ratio of separation back end hydrogenation is 30%-50%, 20-35% 2# hydrogenation aviations Kerosene ready-mixed oil, 15-25% 3# hydrogenated diesel oil ready-mixed oils, 10-20% 4# hydro-treated lube base oil ready-mixed oils.
Phenol ammonia recovery unit as described above includes depickling deammoniation tower and dephenolize tower, and depickling deammoniation tower uses plate column, tower top Operating pressure is 350-500kpa, and temperature is 130-160 DEG C, and the ammonia isolated is sent outside after cooling concentration as product, deamination Gas liquor afterwards enters dephenolize tower
Dephenolize technology as described above uses the patented technology (CN101870529A) of SaiDing Engineering Co., Ltd, dephenolize tower Using turntable extracting tower, extractant is Di Iso Propyl Ether, and counter current contacting extraction, extraction temperature is 35-50 DEG C, pressure position normal pressure, The volume ratio of extractant and phenol wastewater is：Extractant/phenol wastewater volume ratio is 1：7-12, the crude phenols of dephenolize tower separation are through essence System separation is made phenol, xylenol, faces a cresols and paracresol product
The present invention compared with prior art, has advantages below
(1) compared with existing low carbon alcohol by synthetic gas technology, it is high that this patent takes full advantage of synthesis gas methane content Feature, low-carbon alcohols can be produced, moreover it is possible to coproduction natural gas, the diversification of the product processed of synthesis gas can be achieved, it is clear to have expanded coal base The technology path of clean derived energy chemical.
(2) it is well known that whether crushed coal pressure gasifying or slag pressurized gasification, coal gasification course will all produce a large amount of Intractable oily waste water containing phenol, huge pollution may be caused by such as dealing with improperly, and this patent takes full advantage of gas liquor phenol ammonia oil The characteristics of content is high, by gas liquor separation and coal tar hydrogenating, the products such as liquefied ammonia, polyphenol and hydrogenated oil is made, can reduce Follow-up sewage treatment load, intractable gas liquor can more be turned waste into wealth, create bigger benefit, realize resource multi profit With.
(3) each component is made the best use of everything in this patent energy coal gas, and energy-conservation, water saving, investment reduction, technological process is simple, fortune Row stable operation, realize the coordinated development of economy, environment, the energy.
Brief description of the drawings
The process chart of Fig. 1 present invention.
Embodiment
With reference to specific embodiment, the present invention is described in detail, it is to be understood that these embodiments are only used for more The present invention is specifically described in detail, and the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the limitation of following embodiments.
Embodiment 1
(1) pure synthesis gas prepares purification
Using water content be 25% lignite as raw material, be passed through oxygen and vapor pass through crushed coal pressure gasifying (vapor pressure 4.5MPa, 1150 DEG C of gasification temperature) raw gas is made, raw gas is by the composition of percent by volume：CO：49.85 H2： 24.73 CO2：10.21 CH4：14.82 H2S：0.39；
Raw gas enters sulphur-resistant conversion of passing through under 250 DEG C, 3.0MPa, Qilu Petrochemical QCS-04 type catalyst, in terms of dry gas Calculation volume space velocity is 3800h-1, water/gas mol ratio is 0.30 after conversion；
Raw gas after conversion separates H with low-carbon alcohols off-gas through PSA2Gas afterwards is washed into low-temp methanol together, - 40 DEG C of temperature, washed by low-temp methanol under pressure 4.0MPa, make H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware Azeotrope, at -160 DEG C of temperature, pressure 4.0Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas) Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane.
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the modification Cu- of German Lurgi companies Zn-Al series catalysts, in reaction pressure 4.0MPa, 290 DEG C of reaction pressure, H:Cmoleratio H2/ CO=2.5, volume space velocity For 20000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The off-gas of synthesis of low-carbon alcohol H after PSA is separated2Tar removing hydrogenation unit, other gas circulations return low-temp methanol Wash,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature 80 DEG C, 175 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.2, separation after the mol ratio of alcohol be Methanol 51%, ethanol 22%, propyl alcohol 17%, butanol 10%.
(3) coal tar deep processing
The H that the coal tar separated through gas liquor separates with synthesis of low-carbon alcohol off-gas through PSA2Enter coal tar hydrogenating together Reactor, use the graduate FZC-11Q catalyst in Fushun, reaction pressure 8.0MPa, 310 DEG C of reaction temperature, hydrogen oil body Product is than being 1500:1, liquid air speed 1.2h-1Under the conditions of carry out hydrogenation of tar reaction be made mol ratio be 40% 1# hydrogasolines Ready-mixed oil, 25% 2# hydrogenation aviation kerosine ready-mixed oils, 20% 3# hydrogenated diesel oil ready-mixed oils, 15% 4# hydro-treated lube base oils are adjusted And oil.
(4) gas liquor separation and refining of crude phenol
Waste water caused by crushed coal pressurized-gasification furnace enters gas liquor separative element, after water-oil separating, by the coal gas of oil removing Water passes through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolates liquefied ammonia and crude phenols, and depickling deamination column overhead operating pressure is The body of 420kpa, 140 DEG C of operation temperature, 35 DEG C of rotating disk extracting and dephenolizing tower extraction temperature, pressure normal pressure, extractant and phenol wastewater Accumulating ratio is：Extractant/phenol wastewater volume ratio is 1：10.The liquefied ammonia isolated is sent to reactor for synthesis of urea urea synthesis, point The crude phenols separated out are made phenol, xylenol through refining spearation, face the products such as a cresols and paracresol
Embodiment 2
(1) pure synthesis gas prepares purification
Using water content be 28% lignite as raw material, be passed through oxygen and vapor by broken coal slag gasification (vapor pressure 5.0MPa, 1250 DEG C of gasification temperature) raw gas is made, raw gas is by the composition of percent by volume：CO：47.67 H2： 24.96 CO2：12.01 CH4：15.02 H2S：0.34；
Raw gas enters sulphur-resistant conversion of passing through under 290 DEG C, 3.5MPa, the EB type catalyst of Hubei chemical research institute, with dry It is 4500h that gas, which calculates volume space velocity,-1, water/gas mol ratio is 0.36 after conversion；
Raw gas after conversion separates H with low-carbon alcohols off-gas through PSA2Gas afterwards is washed into low-temp methanol together, - 45 DEG C of temperature, washed by low-temp methanol under pressure 5.0MPa, make H2S is reduced to 0.1ppm, CO2<20ppm, washed through low-temp methanol H2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, using the U.S. safe this and the neat company of Bock Lightware Azeotrope, at -162 DEG C of temperature, pressure 4.3Mpa, the methane separation in raw gas is obtained into LNG (liquefied natural gas) Product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through deep cooling The pure synthesis gas for meeting higher alcohols synthesis is made after separation of methane
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the MoS of DOW chemical companies of the U.S.2- M-K catalyst, in reaction pressure 5.0MPa, 310 DEG C of reaction pressure, H:Cmoleratio H2/ CO=3.2, volume space velocity are 30000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The off-gas of synthesis of low-carbon alcohol H after PSA is separated2Tar removing hydrogenation unit, other gas circulations return low-temp methanol Wash,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature 85 DEG C, 180 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.3, separation after the mol ratio of alcohol be Methanol 53%, ethanol 23%, propyl alcohol 14%, butanol 10%
(3) coal tar deep processing
The H that the coal tar separated through gas liquor separates with synthesis of low-carbon alcohol off-gas through PSA2Enter coal tar hydrogenating together Reactor, use the graduate FZC-15 catalyst in Fushun, reaction pressure 10.0MPa, 360 DEG C of reaction temperature, hydrogen oil body Product is than being 1800:1, liquid air speed 1.6h-1Under the conditions of carry out hydrogenation of tar reaction be made mol ratio be 45% 1# hydrogasolines Ready-mixed oil, 23% 2# hydrogenation aviation kerosine ready-mixed oils, 18% 3# hydrogenated diesel oil ready-mixed oils, 14% 4# hydro-treated lube base oils are adjusted And oil.
(4) gas liquor separation and refining of crude phenol
Waste water caused by crushed coal pressurized-gasification furnace enters gas liquor separative element, after water-oil separating, by the coal gas of oil removing Water passes through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolates liquefied ammonia and crude phenols, and depickling deamination column overhead operating pressure is The body of 450kpa, 150 DEG C of operation temperature, 40 DEG C of rotating disk extracting and dephenolizing tower extraction temperature, pressure normal pressure, extractant and phenol wastewater Accumulating ratio is：Extractant/phenol wastewater volume ratio is 1：11.The liquefied ammonia isolated is sent to reactor for synthesis of urea urea synthesis, point The crude phenols separated out are made phenol, xylenol through refining spearation, face a cresols and paracresol product.
Embodiment 3
(1) pure synthesis gas prepares purification
Using bituminous coal as raw material, it is passed through oxygen and vapor passes through crushed coal pressure gasifying (vapor pressure 5.5MPa, gasification temperature 1200 DEG C) raw gas is made, raw gas is by the composition of percent by volume：CO：48.29 H2：23.83 CO2：13.73 CH4： 13.94 H2S：0.21；
Raw gas enters sulphur-resistant conversion of passing through under 250 DEG C, 3.0MPa, Qingdao connection letter QDB-04 type catalyst, in terms of dry gas Calculation volume space velocity is 4300h-1, water/gas mol ratio is 0.35 after conversion；
Raw gas after conversion separates H with low-carbon alcohols off-gas through PSA2Gas afterwards is washed into low-temp methanol together, - 45 DEG C of temperature, washing (addition operating condition) by low-temp methanol under pressure 4.3MPa makes H2S is reduced to 0.1ppm, CO2<20ppm, warp The H that low-temp methanol is washed2S concentrated gas sends to sulfur recovery；
Raw gas after low-temp methanol is washed enters methane cryogenic separation, public together using the U.S. safe this and Bock Lightware The azeotrope of department, at -165 DEG C of temperature, pressure 5.1Mpa, the methane separation in raw gas is obtained into LNG, and (liquefaction is natural Gas) product (methane volumetric fraction >=98%, sulfur content≤0.1ppm, carbon dioxide volume fraction≤1.0%), raw gas is through depth The pure synthesis gas for meeting higher alcohols synthesis is made after cold separation of methane.
(2) higher alcohols synthesis and separation
Pure synthesis gas after cryogenic separation enters higher alcohols synthesis device, using the Zn-Cr-K of Italian Snam companies Catalyst, in reaction pressure 6.0MPa, 320 DEG C of reaction pressure, H:Cmoleratio H2/ CO=4.2, volume space velocity 40000h-1Under the conditions of carry out low-carbon alcohols synthesis；
The off-gas of synthesis of low-carbon alcohol H after PSA is separated2Tar removing hydrogenation unit, other gas circulations return low-temp methanol Wash,
The mixing low-carbon alcohols synthesized through higher alcohols synthesis device enter normal pressure low-carbon alcohols rectifying separator, in tower top temperature temperature 70 DEG C, 175 DEG C of column bottom temperature, pressure is normal pressure, and reflux ratio is runoff detachment under the conditions of 2.1, separation after the mol ratio of alcohol be Methanol 56%, ethanol 23%, propyl alcohol 13%, butanol 8%
(3) coal tar deep processing
The H that the coal tar separated through gas liquor separates with synthesis of low-carbon alcohol off-gas through PSA2Enter coal tar hydrogenating together Reactor, use the graduate FZC-13Q catalyst in Fushun, reaction pressure 11.0MPa, 330 DEG C of reaction temperature, hydrogen oil body Product is than being 1800:1, liquid air speed 2.0h-1Under the conditions of carry out hydrogenation of tar and react mol ratio processed be：35% 1# hydrogasolines are adjusted And oil, 30% 2# hydrogenation aviation kerosine ready-mixed oils, 20% 3# hydrogenated diesel oil ready-mixed oils, 15% 4# hydro-treated lube base oils reconcile Oil.
(4) gas liquor separation and refining of crude phenol
Waste water caused by crushed coal pressurized-gasification furnace enters gas liquor separative element, after water-oil separating, by the coal gas of oil removing Water passes through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolates liquefied ammonia and crude phenols, and depickling deamination column overhead operating pressure is The body of 460kpa, 150 DEG C of operation temperature, 45 DEG C of rotating disk extracting and dephenolizing tower extraction temperature, pressure normal pressure, extractant and phenol wastewater Product is than being 1：9.The liquefied ammonia isolated is sent to reactor for synthesis of urea urea synthesis, and benzene is made through refining spearation in the crude phenols isolated Phenol, xylenol, face a cresols and paracresol product.

Claims (8)

1. a kind of Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal, it is characterised in that comprise the following steps：
(1) raw coal, oxygen and vapor obtain raw gas through coal gas unit style, raw gas washed through sulphur-resistant conversion, low-temp methanol and The pure synthesis gas for meeting higher alcohols synthesis is made after methane separation；Low-temp methanol washes the H isolated2S concentrated gas goes sulfur recovery, CO2Urea synthesizing is removed, LNG product is made in the methane that methane separation obtains；
(2) low-carbon alcohols mix products are made through higher alcohols synthesis catalyst in the synthesis gas after purifying, and low-carbon alcohols mix products are through dividing Methanol, ethanol, propyl alcohol and butanol product are obtained from after；
(3) off-gas of higher alcohols synthesis is through UF membrane, the H isolated2Tar is carried out together with separating the tar come with gas liquor to add Other gases such as hydrogen, the CO isolated return to low-temp methanol and washed；
(4) gas liquor of coal gas by-product is passed through into gas liquor separative element, the tar of separation divides with low-carbon alcohols off-gas through PSA From H2Hydrogenated oil is made into hydrogenation of tar unit, 1# hydrogasoline ready-mixed oils are made by refined in hydrogenated oil respectively, and 2# adds Hydrogen aviation kerosine ready-mixed oil, 3# hydrogenated diesel oils ready-mixed oil and 4# hydro-treated lube base oil ready-mixed oils；
(5) gas liquor for isolating tar enters phenol ammonia recovery unit, and phenol recovery ammonia isolates liquefied ammonia and crude phenols, wherein separate Liquefied ammonia is sent outside as product, and the crude phenols of separation carry out refining of crude phenol obtained phenol, xylenol, face a cresols and paracresol production Thing；
Described coal gas unit uses bituminous coal crushed coal pressurized-gasification furnace or slack coal slag gasifier, and gasification temperature is in 1000- 1450 DEG C, vapor pressure 4.0-6.0MPa；
Described sulphur-resistant conversion uses the Co-Mo sulfur-resistant transformation catalyst medium temperature sulfur resistant conversion process with high hydrolysis function, becomes It is 2.5-4.4MPa to change pressure, and transformation temperature is 220-450 DEG C, and water/gas mol ratio is between 0.25-0.40, in terms of dry gas Calculation volume space velocity is 3000-5000h-1；
The described Co-Mo sulfur-resistant transformation catalysts with high hydrolysis function are：The SSK type catalyst of Top of Denmark rope, Germany The K8-11 type catalyst of BASF AG, the C113 type catalyst of Japanese Xing Chan Co., Ltd., the C25-2-02 of UCI companies of the U.S. Property catalyst, Qingdao Lian Xin chemical industry Co., Ltd production QDB series sulfur-resistant transformation catalysts, Hubei chemical research institute The sulfur-resistant transformation catalyst of EB series；
It is the low-temp methanol washing process for being provided with prewashing and regenerative system that described low-temp methanol, which is washed, and operation temperature is -35 to -55 DEG C, operating pressure 2.0-6.0MPa's, H in the synthesis gas after low-temp methanol is washed2S<0.1ppm,CO2<20ppm；
Described methane separation uses cryogenic separation, using the azeotrope technology of the U.S. safe this and the neat company of Bock Lightware, - 150 DEG C to -170 DEG C of separation temperature, pressure 3-8MPa；
Described low-carbon alcohols separation uses normal pressure or vacuum rectification tower, and operating condition is：80-150 DEG C of temperature, pressure be normal pressure or Decompression；
Described hydrogenation of tar is using fixed bed hydrogenation in reaction pressure 5-15MPa, 250-380 DEG C of reaction temperature, hydrogen oil volume Than for 800:1-2500:1, liquid air speed is 0.5-3.0h-1Under the conditions of carry out hydrogenation of tar reaction；
Catalyst is the graduate FZC catalyst series in Fushun or naphthology used by described hydrogenation of tar reaction Graduate RHT catalyst series；
The phenol ammonia recovery unit includes depickling deammoniation tower and dephenolize tower；
The depickling deammoniation tower uses plate column, and tower top operating pressure is 350-500kpa, and temperature is 130-160 DEG C；
The dephenolize tower uses turntable extracting tower, and extractant is Di Iso Propyl Ether, and counter current contacting extracts, extraction temperature 35-50 DEG C, pressure is normal pressure, and the volume ratio of extractant and phenol wastewater is：Extractant/phenol wastewater volume ratio is 1：7-12.
A kind of 2. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that The QDB series sulfur-resistant transformation catalyst of Qingdao Lian Xin chemical industry Co., Ltd production is QDB-04 type catalyst.
A kind of 3. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that Described higher alcohols synthesis process conditions are：Reaction pressure 3-8MPa, reaction temperature are 260-350 DEG C, H:Cmoleratio H2/ CO=2.0-5.0, volume space velocity 5000-50000h-1Under the conditions of carry out low-carbon alcohols synthesis.
A kind of 4. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 3, it is characterised in that Described H:Cmoleratio is H2/ CO=2.3-4.2.
A kind of 5. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that The catalyst of described higher alcohols synthesis uses the MoS of DOW chemical companies of the U.S.2- M-K catalyst, Italian Snam companies One kind in Zn-Cr-K catalyst or the modification Cu-Zn-Al series catalysts of German Lurgi companies.
A kind of 6. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that Described separation temperature is -155 DEG C to -165 DEG C, pressure 4.0-5.5MPa.
A kind of 7. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that The graduate FZC catalyst series in described Fushun are that FZC-11Q, FZC-12Q, FZC-13Q, FZC-25 or FZC-40 are urged Agent.
A kind of 8. Multi-class propagation technique through preparing low-carbon mixed alcohol by synthetic gas by coal as claimed in claim 1, it is characterised in that Described hydrogenated oil separation uses atmospheric distillation tower, and operating condition is：80-150 DEG C of temperature, pressure are normal pressure or decompression.
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