CN105037086A - Multistage utilization technology for preparing low-carbon mixed alcohol from coal through synthesis gas - Google Patents
Multistage utilization technology for preparing low-carbon mixed alcohol from coal through synthesis gas Download PDFInfo
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- 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
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- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
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Abstract
The invention relates to a multistage utilization technology for preparing low-carbon mixed alcohol from coal through synthesis gas. A coal gas unit, a synthesis gas preparing and purifying unit, a low-carbon alcohol synthesizing and separating unit, a coal, gas and water separating unit, a crude phenol refining unit and a tar hydrogenating unit are involved. The multistage utilization technology has the advantages of being simple, low in cost and capable of achieving large-scale production.
Description
Technical field
The present invention relates to a kind of technique of preparing low-carbon mixed alcohol by synthetic gas, relate in particular to the Multi-class propagation technique of a kind of coal through the multiple Chemicals of preparing low-carbon mixed alcohol by synthetic gas coproduction simultaneously.
Background technology
Mixture of lower alcohols refers to the alcohol-based mixtures of C1 ~ C6.Say from performance, mixture of lower alcohols is a kind of good gasoline dope, and it has high octane value and the blending performance good with gasoline, and MTBE can be replaced completely as gasoline dope or clean fuel.By coal etc. through preparing low-carbon mixed alcohol by synthetic gas be the key areas that carbon one Chemical Engineering Technology develops.Therefore, the coal-based synthesizing low-carbon mixed alcohol technology of active development not only has great importance.Mixture of lower alcohols, except being used as gasoline dope, also can isolate the low-carbon alcohol of various chemical industry purposes.
At present, China consumes 3 to 4 hundred million tons of oil every year, and the oil production rate of China is at about 1.8 hundred million tons, causes China's oil importation dependence to increase year by year thus, and crude oil price continues a high position and hovers, to a certain extent petroleum products become China's Economic development and
countrythe important factor of energy security.And 6V:Q " p
!s) D $ J coal is a kind of relative abundance and cheap mineral fuel, particularly coal in China comparatively oil and natural gas all to enrich many, therefore, coal will be important energy source and the industrial chemicals of taking over oil.Gasification is changed into synthetic gas, is then one of more problem of research by synthetic gas shortening synthesis of low-carbon alcohol, has broad prospects.
Start from the beginning of last century by synthesizing low-carbon alcohol from synthetic gas technology, the oil crisis of 20 century 70s, various countries are done in synthesizing low-carbon alcohol from synthetic gas large quantifier elimination, the operational path of the higher alcohols synthesis developed mainly contains four kinds:
(1) Sygmol technique.This technique is developed jointly by The Dow Chemical Co. (US) 2030 Dow Center, Abbott Road, Midland, Michigan 48640, and union carbide corporation, and adopt isothermal reactor, moly-sulfide series catalysts, low-carbon alcohol selectivity is high, and in product, low-carbon alcohol content is high, and water content is low, catalyzer anticaking carbon, resistant to sulfur.
(2) IFP technique.This technique by
franceoil institute and Japan carry out pilot scale research, mainly adopt two-stage reactor, produce the mixture of lower alcohols based on methyl alcohol.This process operating pressure and temperature are all lower, but poor selectivity, synthetic gas utilization ratio is low.
(3) Octamix technique.This technique is developed by Lurgi, adopts shell and tube or around tubular type isothermal reactor, the mode of carrying-off reaction heat is that water admission goes out.This process form selectivity is high, but the easy heat inactivation of catalyzer, in reaction product, low-carbon alcohol content is 30% ~ 50%, and water content is lower than 1%.
(4) MAS technique.This technique is developed jointly by Italian Snam and Denmark Topse, by improving catalyst for methanol and processing condition, utilizes existing methanol production line production low-carbon alcohol while methanol, and product composition is the alcohol-based mixtures based on methyl alcohol.
Domestic Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences has also carried out the catalyzer of synthetic gas hydrogenation synthesizing low carbon alcohol and the research of technique, and this technique is similar to MAS technique.
In above-mentioned technique, MAS technique is the most ripe, but at present more advanced be octamix technique and Sygmol technique, these two kinds of technological reaction mild conditions, alcohol selectivity is high, and thick product water content is low.And the Auditory steady-state responses of Octamix technique is significantly less than Sygmol technique, this is favourable to raising process thermal efficiency.And Sygmol technique adopts sulfur resistant catalyst, be therefore expected to save desulfurization process, the exploitation of this sulfur resistant catalyst and popularization, not only to alcohol mixture technique, and tremendous influence may be produced to methanol industry.In Sygmol process products, not only C2+ alcohol content is high, and the content of ethanol and propyl alcohol accounts for 50%.Ethanol and propyl alcohol are industrial chemicals in short supply at present, and expensive, therefore from product structure, Sygmol technique is more conducive to industrial utilization.But all there is the components utilising problem all not fully to synthetic gas in these techniques.
Patent CN101805242A mono-kind is by the method for synthetic gas continuous seepage low-carbon alcohol, disclose the technique that a kind of synthetic gas production low-carbon alcohol and olefin hydration generate correspondent alcohol, it is a kind of continuous production processes, this characteristic feature of an invention adds the reaction that olefin hydration generates correspondent alcohol after low carbon alcohol by synthetic gas reaction, unreacted synthetic gas and light alkene closed cycle reduce energy consumption, improve the productive rate of synthetic gas utilization ratio and alcohol.But the target product transformation efficiency of the method is not high, exhaust gas component is complicated, and only carries out resynthesis utilization to the alkene in tail gas, obviously on the low side to the utilization ratio of tail gas as seen, and the obtained fusel of the method is too much, and the selectivity of low-carbon alcohol is not high.
The method of patent CN202040470A for the synthesis of gas low-carbon alcohol and the method for a patent CN101891588A synthesizing low-carbon alcohol from synthetic gas, all disclose a kind of method for preparing catalyst of synthesis of low-carbon alcohol and the feasibility on synthesis of low-carbon alcohol, do not relate to industrialized application completely.But be only also rest on laboratory bench scale, its engineering amplifies unpredictability very large in addition, far away from industrial applications.
The technology of a patent CN101735008A co-producing low-carbon alcohol and natural gas by coal synthesis gas, disclose a kind of technology of higher alcohols synthesis technique and methanation process being carried out combine, comprise gas purification, the synthesis collection of alcohol, a few part such as tail gas separation and methanation, a tail gas part for synthesis of low-carbon alcohol loops back higher alcohols synthesis device, another part synthesizing methane.The sulfur tolerant catalyzing process of a patent CN101735009A preparing low carbon alcohol from synthesis gas and co-producing natural gas, disclose and a kind of sulfur-resistant low-carbon alcohol synthesis technique and methanation in presence of sulfur are produced natural gas process carry out combined process, synthetic gas just can carry out higher alcohols synthesis reaction without the need to fine de-sulfur, a tail gas part loops back higher alcohols synthesis reactor, another part enters methanation device synthesizing methane, achieve Sulfur tolerance and the Poly-generation of whole flow process, improve the economy of device to a certain extent.But it is not high all to there is low-carbon alcohol productive rate in these two kinds of technology, and low-carbon alcohol is not separated, the shortcoming that energy consumption is high.Its Patent CN101735009A is as CH in synthetic gas
4first pressure-variable adsorption methane during >5%, resynthesis low-carbon alcohol, as CH in synthetic gas
4first synthesis of low-carbon alcohol during <5%, then pressure-variable adsorption methane, synthesis of low-carbon alcohol.This method is difficult to real realization in the industrial production, and obviously, it is loaded down with trivial details that these two kinds of techniques exist flow process, and operational management is complicated, is unsuitable for industrialization promotion.
Summary of the invention
The object of this invention is to provide a kind of technique simple, cost is low, can the preparing low-carbon mixed alcohol by synthetic gas co-production LNG of large-scale generation and the Multi-class propagation technique of coal tar deep processing.
The present invention is technique low grade coal prepared mixture of lower alcohols by synthetic gas and each workshop section unstripped gas is made full use of coproduction hydrogenated oil, phenol, natural gas liquids, achieve the multistage coproduction of coal, classified utilization, energy-saving and water-saving, technical process is simple, achieves the clean utilization of coal.
This technique can be divided into by function: gas maked coal unit, synthetic gas prepare clean unit, higher alcohols synthesis is separated and refining of crude phenol unit with separating unit, coal tar deep processing unit, gas liquor.
The Multi-class propagation technique of a kind of low carbon alcohol by synthetic gas provided by the invention comprises the following steps:
(1) raw coal, oxygen and water vapour obtain raw gas through gas maked coal unit style, and raw gas is the obtained pure synthetic gas meeting higher alcohols synthesis after sulfur-resisting transformation, low-temperature rectisol and methane separation; Isolated H
2s concentrated gas desulfuration reclaims, and isolated methane makes LNG product;
(2) synthetic gas after purification obtains low-carbon alcohol mix products through higher alcohols synthesis catalyzer, and low-carbon alcohol mix products obtains methyl alcohol, ethanol, propyl alcohol and butanols product after being separated;
(3) off-gas of higher alcohols synthesis is through membrane sepn (PSA), isolated H
2be separated the tar come with gas liquor and carry out hydrogenation of tar together, other gases such as isolated CO return low-temperature rectisol;
(4) by the gas liquor of gas maked coal by-product through gas liquor separating unit, the H that the tar of separation is separated through PSA with low-carbon alcohol off-gas
2enter hydrogenation of tar unit and make hydrogenated oil, hydrogenated oil obtains 1# hydrogenated gasoline mixed oil, 2# hydrogenation aviation kerosene mixed oil, 3# hydrogenated diesel oil mixed oil and 4# hydro-treated lube base oil mixed oil respectively through refining;
(5) gas liquor isolating tar enters phenol recovery ammonia unit, phenol recovery ammonia isolates liquefied ammonia and crude phenols, the liquefied ammonia be wherein separated is sent outside as product, and the crude phenols of separation carry out refining of crude phenol and obtain phenol, xylenol, face a cresols and paracresol product.
Gas maked coal unit as above adopts the bituminous coal crushed coal pressurized-gasification furnace or the slack coal slag gasifier (BGL) that are applicable to low-quality brown coal (water content is 20%-30%), gasification temperature is at 1000-1450 DEG C, and vapor pressure is 4.0-6.0MPa.
The remarkable advantage of this gasification technology is:
(1) be applicable to the inferior coal gasification that water content is large, ash is high, in raw gas, be rich in the methane of about 8-12%,
(2) vaporization rate is high, gasification intensity is large, and crushed coal pressure gasifying technology vapor pressure is large, and gasification temperature is high, therefore gasification reaction speed is high, gasification intensity improves greatly, and compared with other gasification technologies, the cold gas efficiency of crushed coal pressure gasifying reaches 90%, efficiency of carbon conversion >99.5%, the Conversion of energy of more than 93% is can the fuel of trans-utilization, and under the same terms, coal water slurry is about 78%, and shell vapourizing furnace is about 82%.
(3) oxygen consumption is low, and vapour/oxygen is than low, and steam consumption is low:
(4) technology maturation, stable, crushed coal pressure gasifying technology domesticized and at Datang gram flag and
xinjiangcelebrate magnificent successful Application more than 70 cover, for the design of vapourizing furnace, to manufacture and operation controls domesticly all to have wide experience, generally speaking crushed coal pressurized-gasification furnace technique is simple, and utility appliance is few, and reliability is high, stable, flexible adjustment.
Sulfur-resisting transformation as above adopts has warm sulfur resistant conversion process in the Co-Mo sulfur-resistant transformation catalyst of high hydrolysis function, conversion pressure is 2.5-4.4MPa, transformation temperature is 220-450 DEG C, and water/gas mol ratio, between 0.25-0.40, calculates volume space velocity for 3000-5000h with dry gas
-1.
The Co-Mo sulfur-resistant transformation catalyst as above with high hydrolysis function mainly comprises following several:
World Catalyst: the SSK type catalyzer of Top of Denmark rope, the K8-11 type catalyzer of BASF Corp. of Germany, the C113 type catalyzer of Xing Chan Co., Ltd. of Japan, the C25-2-02 catalyzer of UCI company of the U.S., above-mentioned four kinds of catalyzer were all once applied in industry at home, especially successful with the K8-11 catalyzer of BASF AG, but in recent years, along with the progress of domestic technique, successfully develop the sulfur-resistant transformation catalyst of multiple series, its various performance reaches completely or is better than World Catalyst.
State's inner catalyst: the QDB series sulfur-resistant transformation catalyst that Qingdao Lian Xin chemical industry company limited produces, be wherein best with QDB-04 type catalyzer especially, it not only has higher activity and stability, and can the side reaction such as suppression methanation to a certain degree.The QCS series sulfur-resistant transformation catalyst that Ke Li chemical company of Qilu Petrochemical research institute produces, has intensity high, and low temperature active is the advantage such as regeneration with great difficulty, and representative is QCS-04 type catalyzer; The sulfur-resistant transformation catalyst of the EB series of Hubei chemical research institute exploitation, this good catalyst activity, the life-span is long, easily regenerates, and is widely used.
Low-temperature rectisol as above is the low-temp methanol washing process being provided with prewashing and regeneration system rapidly, and service temperature is-35 to-55 DEG C, working pressure 2.0-6.0MPa's, H in the synthetic gas after low-temperature rectisol
2s<0.1ppm, CO
2<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 gaseous fraction comprises CO, H
2, CO
2, CH
4, H
2s, organosulfur, C
2h
4, C
2h
6, C
3h
8, C
4h
10, HCN, N
2, Ar and tar, lipid acid, single phenol, multiple phenol, petroleum naphtha, wet goods.Except CO, H in these components
2active principle and CH
4, N
2, Ar and hydro carbons belong to outside rare gas element, all the other all components comprise CO
2all need the detrimental impurity that removes with sulfide, the arduousness of its purification task as seen.Make a general survey of current various gas purifying technique, this person with heavy responsibilities's non-cryogenic methanol wash column can be taken on and do not belong to.This is because only have low-temperature rectisol to purify just all can remove various objectionable constituent neatly, such as CO in same device
2, H
2s, COS, C
4h
4s, HCN, NH
3, H
2o, C
2above hydro carbons (comprising light oil, aromatic hydrocarbon, petroleum naphtha, alkene and colloid etc.) and other carbonyl compound etc., and other any purification process all cannot be accomplished.Slag gasified raw material atmospheric pressure is higher in addition, CO in gas
2, H
2s dividing potential drop is relatively high, so be inherently conducive to the characteristic playing low-temperature rectisol physical absorption.In addition, low-temp methanol washing process also has following various significant advantage compared with other purification process:
(1) receptivity is strong, and solution circulated amount is little
(2) gas purification degree is high
(3) methanol solvate is cheap and easy to get, and regeneration energy consumption is low
(4) thermostability and chemical stability good, solvent is not degraded, non-foaming, and pure methyl alcohol does not corrode equipment
(5) soltion viscosity is little, is conducive to saving power
(6) first alcohol and water can dissolve each other by arbitrary proportion, utilizes this characteristic can with its dried feed gas, and
(7) mutual solubility of itself and water is utilized methyl alcohol can be extracted from petroleum naphtha
Low-temperature rectisol achieves removing of plurality of impurities in the same apparatus, and for the multiple purification process combination of other purifying methods, operation is relatively single, reasonable, and convenient operation manages.
So in view of the raw gas complicated component of crushed coal pressure gasifying and low-temp methanol washing process disposablely can remove the unique advantage of various impurity, raw gas carries out the most suitable technique that purifies beyond doubt.
Methane separation as above adopts low temperature separation process, adopt the azeotrope patented technology of the U.S. safe this and the neat company of Bock Lightware, temperature-150 DEG C to-170 DEG C, preferably-155 DEG C to-165 DEG C, pressure 3-8Mpa, preferred 4.0-5.5Mpa, isolated methane is compressed to be sent outside as product, and the synthetic gas of separation of methane carries out higher alcohols synthesis reaction.
Higher alcohols synthesis processing condition as above are: reaction pressure 3-8MPa, and temperature of reaction is 260-350 DEG C, and H:Cmoleratio is H
2/ CO=2.0-5.0, be preferably 2.3-4.2, volume space velocity is 5000-50000h
-1the synthesis of low-carbon alcohol is carried out under condition.
The catalyzer of higher alcohols synthesis as above adopts the MoS of DOW chemical company of the U.S.
2one in the Zn-Cr-K catalyzer of-M-K catalyzer or Italian Snam company or the modification Cu-Zn-Al series catalysts of German Lurgi company
Low-carbon alcohol as above is separated and just adopts normal pressure or vacuum rectification tower, and operational condition is: temperature 80-150 DEG C, and pressure is normal pressure or decompression, and after being separated, the mol ratio of alcohol is methyl alcohol 30%-65%, ethanol 5-25%, propyl alcohol 8-20%, butanols 5-20%.
Hydrogenation of tar as above adopts fixed bed hydrogenation at reaction pressure 5-15MPa, and temperature of reaction 250-380 DEG C, hydrogen to oil volume ratio is 800:1-2500:1, and liquid air speed is 0.5-3.0h
-1carry out hydrogenation of tar reaction under condition, obtained hydrogenated oil obtains 1# hydrogenated oil, 2# hydrogenated oil, 3# hydrogenated oil, 4# hydrogenated oil product through being separated.
It is the graduate FZC catalyst series in Fushun that hydrogenation of tar as above reacts the catalyzer adopted, as FZC-11Q, FZC-12Q, FZC-13Q, FZC-25, FZC-40 catalyzer.
Hydrogenated oil as above is separated and adopts atmospheric distillation tower, operational condition is: temperature 80-150 DEG C, pressure is normal pressure or decompression, the mol ratio being separated back end hydrogenation oil is the 1# hydrogenated gasoline mixed oil of 30%-50%, the 2# hydrogenation aviation kerosene mixed oil of 20-35%, the 3# hydrogenated diesel oil mixed oil of 15-25%, the 4# hydro-treated lube base oil mixed oil of 10-20%.
Phenol recovery ammonia unit described above comprises depickling deammoniation tower and dephenolize tower, depickling deammoniation tower adopts tray column, and tower top working pressure is 350-500kpa, and temperature is 130-160 DEG C, isolated ammonia is sent outside as product after cooling concentration, and the gas liquor after deamination enters dephenolize tower
Dephenolize technology as above adopts the patented technology (CN101870529A) of SaiDing Engineering Co., Ltd, dephenolize tower adopts turntable extracting tower, extraction agent is Di Iso Propyl Ether, counter current contact extracts, extraction temperature is 35-50 DEG C, pressure position normal pressure, the volume ratio of extraction agent and phenolic wastewater is: extraction agent/phenolic wastewater volume ratio is 1:7-12, and the crude phenols that dephenolize tower is separated obtain phenol, xylenol through refining spearation, face a cresols and paracresol product
The present invention compared with prior art, has the following advantages
(1) compare with existing low carbon alcohol by synthetic gas technology, this patent takes full advantage of the high feature of synthetic gas methane content, can production low-carbon alcohol, can also coproduction Sweet natural gas, the diversification of the product processed of synthetic gas can be realized, expanded the technological line of coal-based clean derived energy chemical.
(2) well-known, no matter be crushed coal pressure gasifying or slag pressurized gasification, coal gasification course all will produce unmanageable containing phenol oily(waste)water in a large number, huge pollution may be caused as dealt with improperly, this patent takes full advantage of the high feature of gas liquor phenol ammonia oil content, be separated and coal tar hydrogenating through gas liquor, obtained liquefied ammonia, polyphenol and hydrogenation wet goods product, follow-up sewage treatment load can be reduced, more unmanageable gas liquor can be turned waste into wealth, create larger benefit, achieve resource multi and utilize.
(3) in this patent energy gas maked coal, each component is made the best use of everything, energy-conservation, water saving, investment reduction, and technical process is simple, and operation is stablized, and achieves the coordinated development of economy, environment, the energy.
Accompanying drawing explanation
fig. 1technical process of the present invention
figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but be interpreted as, and these embodiments are only for specifically describing the present invention more in detail, and the scope that should not be construed as the above-mentioned theme of the present invention is only limitted to the restriction of following embodiment.
Embodiment 1
(1) pure synthetic gas preparation purification
With water content be 25% brown coal for raw material, pass into oxygen and water vapour through the obtained raw gas of crushed coal pressure gasifying (vapor pressure 4.5MPa, gasification temperature 1150 DEG C), raw gas by volume the consisting of of per-cent: CO:49.85, H
2: 24.73, CO
2: 10.21, CH
4: 14.82, H
2s:0.39;
Raw gas, at 250 DEG C, carries out through sulfur-resisting transformation under 3.0MPa, Qilu Petrochemical QCS-04 type catalyzer, calculates volume space velocity for 3800h with dry gas
-1, after conversion, water/gas mol ratio is 0.30;
Raw gas after conversion is separated H with low-carbon alcohol off-gas through PSA
2after gas enter low-temperature rectisol together, temperature-40 DEG C, through low-temperature rectisol under pressure 4.0MPa, make H
2s reduces to 0.1ppm, CO
2<20ppm, through the H of low-temperature rectisol
2s concentrated gas sends to sulfur recovery;
Raw gas after low-temperature rectisol enters methane low temperature separation process, adopt the azeotrope of the U.S. safe this and the neat company of Bock Lightware, temperature-160 DEG C, under pressure 4.0Mpa, methane separation in raw gas is obtained LNG (natural gas liquids) product (methane volumetric mark >=98%, sulphur content≤0.1ppm, carbonic acid gas volume fraction≤1.0%), namely raw gas obtains the pure synthetic gas meeting higher alcohols synthesis after low temperature separation process methane.
(2) higher alcohols synthesis and separation
Pure synthetic gas after low temperature separation process enters higher alcohols synthesis device, adopts the modification Cu-Zn-Al series catalysts of German Lurgi company, and at reaction pressure 4.0MPa, reaction pressure 290 DEG C, H:Cmoleratio is H
2/ CO=2.5, volume space velocity is 20000h
-1the synthesis of low-carbon alcohol is carried out under condition;
Off-gas H after PSA is separated of synthesis of low-carbon alcohol
2tar removing hydrogenation unit, other gas circulation return low-temperature rectisol,
Mixing low-carbon alcohol through the synthesis of higher alcohols synthesis device enters normal pressure low-carbon alcohol rectifying separation device, tower top temperature temperature 80 DEG C, column bottom temperature 175 DEG C, pressure is normal pressure, reflux ratio is runoff detachment under 2.2 conditions, separation after the mol ratio of alcohol be methyl alcohol 51%, ethanol 22%, propyl alcohol 17%, butanols 10%.
(3) coal tar deep processing
Through the H that the coal tar of gas liquor separation is separated through PSA with synthesis of low-carbon alcohol off-gas
2enter coal tar hydrogenating reactor together, use the graduate FZC-11Q catalyzer in Fushun, reaction pressure 8.0MPa, temperature of reaction 310 DEG C, hydrogen to oil volume ratio is 1500:1, liquid air speed 1.2h
-1the 1# hydrogenated gasoline mixed oil that the obtained mol ratio of hydrogenation of tar reaction is 40% is carried out, the 2# hydrogenation aviation kerosene mixed oil of 25%, the 3# hydrogenated diesel oil mixed oil of 20%, the 4# hydro-treated lube base oil mixed oil of 15% under condition.
(4) gas liquor is separated and refining of crude phenol
The waste water that crushed coal pressurized-gasification furnace produces enters gas liquor separating unit, after oily water separation, by the gas liquor of oil removing through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolate liquefied ammonia and crude phenols, depickling deammoniation tower tower top working pressure is 420kpa, service temperature 140 DEG C, rotating disk extracting and dephenolizing tower extraction temperature 35 DEG C, pressure normal pressure, the volume ratio of extraction agent and phenolic wastewater is: extraction agent/phenolic wastewater volume ratio is 1:10.Isolated liquefied ammonia delivers to reactor for synthesis of urea urea synthesis, and isolated crude phenols obtain phenol, xylenol through refining spearation, face a product such as cresols and paracresol
Embodiment 2
(1) pure synthetic gas preparation purification
With water content be 28% brown coal for raw material, pass into oxygen and water vapour through the obtained raw gas of broken coal slag gasification (vapor pressure 5.0MPa, gasification temperature 1250 DEG C), raw gas by volume the consisting of of per-cent: CO:47.67, H
2: 24.96, CO
2: 12.01, CH
4: 15.02, H
2s:0.34;
Raw gas is at 290 DEG C, and 3.5MPa, carries out through sulfur-resisting transformation under the EB type catalyzer of Hubei chemical research institute, calculates volume space velocity for 4500h with dry gas
-1, after conversion, water/gas mol ratio is 0.36;
Raw gas after conversion is separated H with low-carbon alcohol off-gas through PSA
2after gas enter low-temperature rectisol together, temperature-45 DEG C, through low-temperature rectisol under pressure 5.0MPa, make H
2s reduces to 0.1ppm, CO
2<20ppm, through the H of low-temperature rectisol
2s concentrated gas sends to sulfur recovery;
Raw gas after low-temperature rectisol enters methane low temperature separation process, adopt the azeotrope of the U.S. safe this and the neat company of Bock Lightware, temperature-162 DEG C, under pressure 4.3Mpa, methane separation in raw gas is obtained LNG (natural gas liquids) product (methane volumetric mark >=98%, sulphur content≤0.1ppm, carbonic acid gas volume fraction≤1.0%), namely raw gas obtains the pure synthetic gas meeting higher alcohols synthesis after low temperature separation process methane
(2) higher alcohols synthesis and separation
Pure synthetic gas after low temperature separation process enters higher alcohols synthesis device, adopts the MoS of DOW chemical company of the U.S.
2-M-K catalyzer, at reaction pressure 5.0MPa, reaction pressure 310 DEG C, H:Cmoleratio is H
2/ CO=3.2, volume space velocity is 30000h
-1the synthesis of low-carbon alcohol is carried out under condition;
Off-gas H after PSA is separated of synthesis of low-carbon alcohol
2tar removing hydrogenation unit, other gas circulation return low-temperature rectisol,
Mixing low-carbon alcohol through the synthesis of higher alcohols synthesis device enters normal pressure low-carbon alcohol rectifying separation device, tower top temperature temperature 85 DEG C, column bottom temperature 180 DEG C, pressure is normal pressure, reflux ratio is runoff detachment under 2.3 conditions, separation after the mol ratio of alcohol be methyl alcohol 53%, ethanol 23%, propyl alcohol 14%, butanols 10%
(3) coal tar deep processing
Through the H that the coal tar of gas liquor separation is separated through PSA with synthesis of low-carbon alcohol off-gas
2enter coal tar hydrogenating reactor together, use the graduate FZC-15 catalyzer in Fushun, reaction pressure 10.0MPa, temperature of reaction 360 DEG C, hydrogen to oil volume ratio is 1800:1, liquid air speed 1.6h
-1the 1# hydrogenated gasoline mixed oil that the obtained mol ratio of hydrogenation of tar reaction is 45% is carried out, the 2# hydrogenation aviation kerosene mixed oil of 23%, the 3# hydrogenated diesel oil mixed oil of 18%, the 4# hydro-treated lube base oil mixed oil of 14% under condition.
(4) gas liquor is separated and refining of crude phenol
The waste water that crushed coal pressurized-gasification furnace produces enters gas liquor separating unit, after oily water separation, by the gas liquor of oil removing through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolate liquefied ammonia and crude phenols, depickling deammoniation tower tower top working pressure is 450kpa, service temperature 150 DEG C, rotating disk extracting and dephenolizing tower extraction temperature 40 DEG C, pressure normal pressure, the volume ratio of extraction agent and phenolic wastewater is: extraction agent/phenolic wastewater volume ratio is 1:11.Isolated liquefied ammonia delivers to reactor for synthesis of urea urea synthesis, and isolated crude phenols obtain phenol, xylenol through refining spearation, face a cresols and paracresol product.
Embodiment 3
(1) pure synthetic gas preparation purification
Be raw material with bituminous coal, pass into oxygen and water vapour through the obtained raw gas of crushed coal pressure gasifying (vapor pressure 5.5MPa, gasification temperature 1200 DEG C), raw gas by volume the consisting of of per-cent: CO:48.29, H
2: 23.83, CO
2: 13.73, CH
4: 13.94, H
2s:0.21;
Raw gas is at 250 DEG C, and 3.0MPa, carries out through sulfur-resisting transformation under the connection letter QDB-04 type catalyzer of Qingdao, calculate volume space velocity for 4300h with dry gas
-1, after conversion, water/gas mol ratio is 0.35;
Raw gas after conversion is separated H with low-carbon alcohol off-gas through PSA
2after gas enter low-temperature rectisol together, temperature-45 DEG C, under pressure 4.3MPa, make H through low-temperature rectisol (interpolation operational condition)
2s reduces to 0.1ppm, CO
2<20ppm, through the H of low-temperature rectisol
2s concentrated gas sends to sulfur recovery;
Raw gas after low-temperature rectisol enters methane low temperature separation process, adopt the azeotrope of the U.S. safe this and the neat company of Bock Lightware, temperature-165 DEG C, under pressure 5.1Mpa, methane separation in raw gas is obtained LNG (natural gas liquids) product (methane volumetric mark >=98%, sulphur content≤0.1ppm, carbonic acid gas volume fraction≤1.0%), namely raw gas obtains the pure synthetic gas meeting higher alcohols synthesis after low temperature separation process methane.
(2) higher alcohols synthesis and separation
Pure synthetic gas after low temperature separation process enters higher alcohols synthesis device, adopts the Zn-Cr-K catalyzer of Italian Snam company, and at reaction pressure 6.0MPa, reaction pressure 320 DEG C, H:Cmoleratio is H
2/ CO=4.2, volume space velocity is 40000h
-1the synthesis of low-carbon alcohol is carried out under condition;
Off-gas H after PSA is separated of synthesis of low-carbon alcohol
2tar removing hydrogenation unit, other gas circulation return low-temperature rectisol,
Mixing low-carbon alcohol through the synthesis of higher alcohols synthesis device enters normal pressure low-carbon alcohol rectifying separation device, at tower top temperature temperature 70 C, and column bottom temperature 175 DEG C, pressure is normal pressure, and reflux ratio is runoff detachment under 2.1 conditions, separation after the mol ratio of alcohol be methyl alcohol 56%, ethanol 23%, propyl alcohol 13%, butanols 8%
(3) coal tar deep processing
Through the H that the coal tar of gas liquor separation is separated through PSA with synthesis of low-carbon alcohol off-gas
2enter coal tar hydrogenating reactor together, use the graduate FZC-13Q catalyzer in Fushun, reaction pressure 11.0MPa, temperature of reaction 330 DEG C, hydrogen to oil volume ratio is 1800:1, liquid air speed 2.0h
-1carrying out hydrogenation of tar reaction mol ratio processed under condition is: the 1# hydrogenated gasoline mixed oil of 35%, the 2# hydrogenation aviation kerosene mixed oil of 30%, the 3# hydrogenated diesel oil mixed oil of 20%, the 4# hydro-treated lube base oil mixed oil of 15%.
(4) gas liquor is separated and refining of crude phenol
The waste water that crushed coal pressurized-gasification furnace produces enters gas liquor separating unit, after oily water separation, by the gas liquor of oil removing through depickling deammoniation tower and rotating disk extracting and dephenolizing tower, isolate liquefied ammonia and crude phenols, depickling deammoniation tower tower top working pressure is 460kpa, service temperature 150 DEG C, rotating disk extracting and dephenolizing tower extraction temperature 45 DEG C, pressure normal pressure, the volume ratio of extraction agent and phenolic wastewater is 1:9.Isolated liquefied ammonia delivers to reactor for synthesis of urea urea synthesis, and isolated crude phenols obtain phenol, xylenol through refining spearation, face a cresols and paracresol product.
Claims (19)
1.
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that comprising the steps:
(1) raw coal, oxygen and water vapour obtain raw gas through gas maked coal unit style, and raw gas is the obtained pure synthetic gas meeting higher alcohols synthesis after sulfur-resisting transformation, low-temperature rectisol and methane separation; The isolated H of low-temperature rectisol
2s concentrated gas desulfuration reclaims, CO
2remove urea synthesis, the methane that methane separation obtains makes LNG product;
(2) synthetic gas after purification obtains low-carbon alcohol mix products through higher alcohols synthesis catalyzer, and low-carbon alcohol mix products obtains methyl alcohol, ethanol, propyl alcohol and butanols product after being separated;
(3) off-gas of higher alcohols synthesis is through membrane sepn, isolated H
2be separated the tar come with gas liquor and carry out hydrogenation of tar together, other gases such as isolated CO return low-temperature rectisol;
(4) by the gas liquor of gas maked coal by-product through gas liquor separating unit, the H that the tar of separation is separated through PSA with low-carbon alcohol off-gas
2enter hydrogenation of tar unit and make hydrogenated oil, hydrogenated oil obtains 1# hydrogenated gasoline mixed oil, 2# hydrogenation aviation kerosene mixed oil, 3# hydrogenated diesel oil mixed oil and 4# hydro-treated lube base oil mixed oil respectively through refining;
(5) gas liquor isolating tar enters phenol recovery ammonia unit, phenol recovery ammonia isolates liquefied ammonia and crude phenols, the liquefied ammonia be wherein separated is sent outside as product, and the crude phenols of separation carry out refining of crude phenol and obtain phenol, xylenol, face a cresols and paracresol product.
2.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described gas maked coal unit adopts bituminous coal crushed coal pressurized-gasification furnace or slack coal slag gasifier, gasification temperature is at 1000-1450 DEG C, and vapor pressure is 4.0-6.0MPa.
3.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gasit is characterized in that described sulfur-resisting transformation employing has warm sulfur resistant conversion process in the Co-Mo sulfur-resistant transformation catalyst of high hydrolysis function, conversion pressure is 2.5-4.4MPa, transformation temperature is 220-450 DEG C, water/gas mol ratio, between 0.25-0.40, calculates volume space velocity for 3000-5000h with dry gas
-1.
4.
as claimdescribed in 3
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gasit is characterized in that the described Co-Mo sulfur-resistant transformation catalyst with high hydrolysis function is: the SSK type catalyzer of Top of Denmark rope, the K8-11 type catalyzer of BASF Corp. of Germany, the C113 type catalyzer of Xing Chan Co., Ltd. of Japan, the C25-2-02 catalyzer of UCI company of the U.S., the QDB series sulfur-resistant transformation catalyst that Qingdao Lian Xin chemical industry company limited produces, the sulfur-resistant transformation catalyst of the EB series of Hubei chemical research institute.
5.
as claimdescribed in 4
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that the QDB series sulfur-resistant transformation catalyst that Qingdao Lian Xin chemical industry company limited produces is QDB-04 type catalyzer.
6.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described low-temperature rectisol is the low-temp methanol washing process being provided with prewashing and regeneration system rapidly, service temperature is-35 to-55 DEG C, working pressure 2.0-6.0MPa's, H in the synthetic gas after low-temperature rectisol
2s<0.1ppm, CO
2<20pp.
7.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described methane separation adopts low temperature separation process, adopt the azeotrope technology of the U.S. safe this and the neat company of Bock Lightware, separation temperature-150 DEG C to-170 DEG C, pressure 3-8Mpa.
8.
as claimdescribed in 7
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described separation temperature is-155 DEG C to-165 DEG C, pressure is 4.0-5.5Mpa.
9.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described higher alcohols synthesis processing condition are: reaction pressure 3-8MPa, temperature of reaction is 260-350 DEG C, and H:Cmoleratio is H
2/ CO=2.0-5.0, volume space velocity is 5000-50000h
-1the synthesis of low-carbon alcohol is carried out under condition.
10.
as claimdescribed in 9
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described H:Cmoleratio is H
2/ CO=2.3-4.2.
11.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that the catalyzer of described higher alcohols synthesis adopts the MoS of DOW chemical company of the U.S.
2one in the Zn-Cr-K catalyzer of-M-K catalyzer, Italian Snam company or the modification Cu-Zn-Al series catalysts of German Lurgi company.
12.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described low-carbon alcohol is separated and adopt normal pressure or vacuum rectification tower, operational condition is: temperature 80-150 DEG C, and pressure is normal pressure or decompression.
13.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described hydrogenation of tar adopts fixed bed hydrogenation at reaction pressure 5-15MPa, temperature of reaction 250-380 DEG C, hydrogen to oil volume ratio is 800:1-2500:1, and liquid air speed is 0.5-3.0h
-1hydrogenation of tar reaction is carried out under condition.
14.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described hydrogenation of tar reacts the catalyzer adopted is Fushun graduate FZC catalyst series or the graduate RHT catalyst series of petroleum science.
15.
as claimdescribed in 14
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that the graduate FZC catalyst series in described Fushun is FZC-11Q, FZC-12Q, FZC-13Q, FZC-25 or FZC-40 catalyzer.
16.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described hydrogenated oil is separated and adopt atmospheric distillation tower, operational condition is: temperature 80-150 DEG C, and pressure is normal pressure or decompression.
17.
as claimdescribed in 1
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described phenol recovery ammonia unit comprises depickling deammoniation tower and dephenolize tower.
18.
as claimdescribed in 17
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described depickling deammoniation tower adopts tray column, tower top working pressure is 350-500kpa, and temperature is 130-160 DEG C.
19.
as claimdescribed in 17
a kind of by the Multi-class propagation technique of coal through preparing low-carbon mixed alcohol by synthetic gas, it is characterized in that described dephenolize tower adopts turntable extracting tower, extraction agent is Di Iso Propyl Ether, and counter current contact extracts, and extraction temperature is 35-50 DEG C, pressure position normal pressure, and the volume ratio of extraction agent and phenolic wastewater is: extraction agent/phenolic wastewater volume ratio is 1:7-12.
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