CN105062592B

CN105062592B - Crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and the comprehensive utilization process for tar deep processing

Info

Publication number: CN105062592B
Application number: CN201510464232.7A
Authority: CN
Inventors: 范辉; 马英民; 崔晓曦; 王军亭; 王贵; 马国强; 张庆庚; 李晓; 史郭晓; 时建敏; 刘建卫; 王文婷
Original assignee: Sedin Engineering Co Ltd
Current assignee: Xinjiang Xinye Energy Chemical Co., Ltd.; Sedin Engineering Co Ltd
Priority date: 2015-07-31
Filing date: 2015-07-31
Publication date: 2017-09-26
Anticipated expiration: 2035-07-31
Also published as: CN105062592A

Abstract

A kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and comprehensive utilization process for tar deep processing are that crushed coal pressure gasifying synthesis gas first passes through conversion adjustment hydrogen-carbon ratio, again the sour gas such as removing carbon dioxide and hydrogen sulfide is eluted through low-temp methanol, and methane gas and by-product LNG are removed by methane cryogenic separation, then portion gas is removed into hydrogen through pressure-variable adsorption, and stripping gas and gas mixing without pressure-variable adsorption are through methanol synthesized gasoline, and hydrogen is used for the tar of crushed coal pressure gasifying by-product, the hydrogenation and cracking of heavy oil and naphtha, and prepare gasoline, diesel oil and heavy oil product.The present invention has the advantages that utilization rate is high, technique is simple, product structure is reasonable and environmental pollution is small.

Description

Crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and use In the comprehensive utilization process of tar deep processing

Technical field

It is the invention belongs to crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and deep for tar The comprehensive utilization process of processing.

Technical background

Energy resource structure of the China with rich coal, oil-poor and few gas, wherein oil and natural gas resource critical shortage, are far below World average level.In recent years, with the stable and rapid development of China's economy, domestic oil gas insufficiency of supply-demand increases year by year so that National energy security, economic security and social safety face big challenge.The successful exploitation of coal liquifaction and natural gas from coal technology And industrial applications, it is to realize the clean and effective conversion of coal resources, alleviate oil gas imbalance between supply and demand and ensure the weight of national security Want approach.

Coal gasification is to realize the key link of coal trans-utilization, and current industrial gas technology mainly includes fixed bed gas Three kinds of change, fluidized gasification and entrained flow gasification.Wherein because fixed bed crushed coal pressure gasifying technology includes drying, destructive distillation, gas Change and burning four steps, therefore coal after crushed coal pressure gasifying except produce the methane containing high concentration synthesis gas in addition to, go back by-product a large amount of The products such as tar, middle oil, naphtha and phenol, simultaneously because the gasification technology also has technology maturation, coal adaptability strong and energy Low advantage is consumed, there is extensive use in coal chemical industry.Although crushed coal pressure gasifying technology has many advantages, such as, existing coal Chemical project is only to carry out the synthesis of chemicals such as ammonia, methanol and natural gas, it is necessary to by synthesis gas individually with synthesis gas Methane be converted into CO and H₂, and largely the periodic off-gases containing available gas are directly discharged or burnt；Simultaneously in view of existing broken The utilization ratios such as tar, heavy oil and the naphtha of coal pressure gasification by-product are low, or even the producer having directly returns to gasification tar Gasification furnace burns, the serious environmental pollution and the wasting of resources caused.In recent years, comprehensive utilization of resources is encouraged as country is relevant Promulgated with the policies and regulations of environmental protection, at the same it is increasingly fierce in view of existing coal chemical industry market competition, develop a kind of broken coal and add Gasification synthesis gas comprehensive utilization technique is pressed, as each enterprise and research unit's focus of attention.

It is H that coal can produce composition after crushed coal pressure gasifying₂37~40%, CO 17%~20%, CO₂28~33%, CH₄8%~12%, N₂0.1~0.4% synthesis gas and mass yield is up to the pairs such as 3~8% tar, middle oil and naphtha Product.The tar of formation, middle oil and the oil product such as naphtha by hydrofinishing and can be hydrocracked and prepare petrol and diesel oil blender, and Hydrogen feed can be extracted from synthesis gas.But the H in crushed coal pressure gasifying synthesis gas₂/ CO is relatively low, if synthesis gas is carried out into first Alkanisation or ammonia synthesis, then need a large amount of even all of CO to carry out water-gas shift and carry hydrogen, cause a large amount of greenhouse gases CO₂Production It is raw, if the hydrogen needed for considering further that hydrogenation of tar, the yield of methane and ammonia can be had a strong impact on.Comparatively, methanol is closed Hydrogen carbon needed for is only 2, if by synthesis gas synthesizing methanol, and extract hydrogen partial and be used for tar production, then synthesis gas Utilization it is more reasonable.But methanol production capacity is seriously superfluous at present, if it is poor to be translated into methanol economic benefit, while burnt Oil is by being hydrogenated with and cracking is prepared has inferior quality and easily change, it is difficult to as fuel oil direct marketing, it is general by It is used as oil product conditioning agent, have impact on its economic benefit.

The successful exploitation of technique for preparing gasoline by methanol and industrial applications provide a technical strategies for oil replacement, If crushed coal pressure gasifying is converted into high-quality gasoline product through methanol, it is not only able to alleviate methanol surplus and oil shortage etc. Problem, and by-product tar by the oil product that is hydrogenated to, especially gasoline products can directly with MTG product mixes, make Sold for gasoline products, considerably increase the utilization ratio and economic benefit of crushed coal pressure gasifying synthesis gas.Based on above-mentioned analysis, Develop a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and the comprehensive utilization of tar deep processing Technique has great importance.

The content of the invention

It is an object of the invention to provide that a kind of utilization rate is high, technique is simple, product structure is reasonable and environmental pollution is small is broken Coal pressure gasification synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and the comprehensive utilization process for tar deep processing.

For up to above-mentioned purpose, inventor is real by substantial amounts of lab scale according to the characteristics of crushed coal pressure gasifying technology and product Test research, technical Analysis, processing simulation and many project design experiences and propose a kind of crushed coal pressure gasifying synthesis gas and first pass through Conversion adjustment hydrogen-carbon ratio, then the sour gas such as removing carbon dioxide and hydrogen sulfide is eluted through low-temp methanol, and pass through methane deep cooling point From removing methane gas and by-product LNG, portion gas is then removed into hydrogen through pressure-variable adsorption, and stripping gas and without pressure-variable adsorption Gas mixing through methanol synthesized gasoline, and hydrogen is used for the hydrogenation of the tar, heavy oil and naphtha of crushed coal pressure gasifying by-product And cracking, and prepare gasoline, diesel oil and heavy oil product.The technique is integrated by overall technology and material is matched, and is not only increased Plus the utilization ratio and economic value of crushed coal pressure gasifying synthesis gas, and and its major product all domestic LNG and oil in short supply Product, further alleviate the imbalance between supply and demand of the energy of the country, with important theory and realistic meaning.

A kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline disclosed by the invention, co-production of liquefied natural gas and it is used for The comprehensive utilization process of tar deep processing, its concrete technology is：

(1) feed coal is converted into synthesis gas and tar byproduct, a synthesis gas part for generation through crushed coal pressurized-gasification furnace The synthesis gas that transformed stove carries out walking side line with another part after water-gas shift is mixed into gas cooler, containing under condensation Oily waste water is sent in coal gas separator, and synthesis gas then enters in low temperature washing device for methanol, after synthesis gas is washed through low-temp methanol Remove H₂The materials such as S, naphtha and carbon dioxide, wherein the H removed₂S is sent to sulfur recovery system, and the naphtha of removing is sent to guarantor Protect in reactor, the carbon dioxide of removing is partly into synthesic gas compressor group, and another part is then as gasifying agent Be back in crushed coal pressurized-gasification furnace, and it is purified after synthesis gas enter methane cryogenic separator in；

(2) liquid phase methane (LNG) is isolated through methane cryogenic separator, and is sold as end product, after removing methane Synthesis gas from methane cryogenic separator discharge after be divided into two parts, Part I is sent to pressure swing adsorber, is obtained through pressure-variable adsorption To the hydrogen of volumetric concentration more than 99.9%, and the stripping gas of pressure-variable adsorption is closed with the Part II synthesis gas without pressure-variable adsorption And, and the circulating air of partial CO 2, methanol separator and the gas-liquid separator with being washed from low-temp methanol is mixed into conjunction Into in air compressor group, methyl alcohol synthetic reactor is sent to after supercharging；

(3) gas after supercharging enters from top carries out methanol-fueled CLC in methyl alcohol synthetic reactor, gaseous products are closed from methanol It is divided into two strands after into tower bottom discharge, wherein after first burst of gaseous products is condensed through methanol product condenser, into separating methanol In device, gas phase is back to synthesic gas compressor group after being discharged from the top of methanol separator, and by methanol, fusel, water and lower carbon number hydrocarbons Deng composition crude carbinol liquid phase from methanol separator bottom discharge after enter methanol purification device in purified, it is purified after it is thick After methanol solution is vaporized by crude carbinol vaporizer, synthesis oil reactor is mixed into second burst of gaseous products for walking side line In；

(4) gas phase crude carbinol carries out the reaction that methanol converts gasoline processed in synthesis oil reactor, and its product is produced through gasoline Enter after the condensation of product condenser in gas-liquid separator, the gas phase isolated is divided into two parts after being discharged from top, and Part I is returned It is back in synthesic gas compressor group, another part enters membrane separator, the hydrogen volume content more than 91% obtained through UF membrane Infiltration pneumatic transmission toward hydrogenation of tar, and fuel gas that stripping gas through UF membrane is isolated with oil product piece-rate system and stablize tower top Boiler combustion is sent to after the dry gas mixing of portion's discharge, the oil phase that gas-liquid separator separates go out enters oil product separation after being discharged from bottom In device, liquefied petroleum gas (LPG), gasoline products, fuel gas and C are obtained after being separated through oil product₁₀~C₁₂Heavy oil component, wherein The C isolated₁₀~C₁₂The heavy constituent of heavy oil component and refined products separator be mixed into cracker and carry out cracking Reaction；

(5) by the hydrogen of pressure-variable adsorption and the permeated hydrogen from membrane separator, refined products separator and crackate It is divided into four parts after the circulating hydrogen mixing of separator, Part I hydrogen enters protection reactor from top, and Part II hydrogen is certainly Top enters in cracker, and Part III hydrogen enters in hydrofining reactor from middle part, and Part IV hydrogen enters from middle part Enter in cracker,

(6) oily waste water from gas crushed coal pressurized-gasification furnace and from gas cooler enters in coal gas separator, The water isolated is sent to water treatment system, and the tar and middle oil ingredient isolated are purified rear into pre- with part outsourcing tar Cut in fractionating column, its pitch enters in delay coking stove after being discharged from fractionation column bottom, the pitch that delayed coking is obtained Jiaozhuo is production marketing, and obtained light component is then with the light component at the top of fractionating column out, from refined products separator Tail oil, a small amount of naphtha from low temperature washing device for methanol and step (5) Part I hydrogen be mixed into protection reactor in, Enter after the discharge of product self-shield reactor bottom in hydrofining reactor, hydrogenation products are arranged from hydrofining reactor bottom It is sent to after going out in refined products separator, wherein the light component isolated enters in stabilizer, the hydrogen isolated, which is back to, to be added Hydrogen system, and the heavy constituent part isolated returns to protection reactor as tail oil, and another part is separated with from oil product The C of device₁₀~C₁₂Heavy oil component be mixed into cracker and carry out cracking reaction, the cracking reactor bottom of its product Enter crackate separator after discharge, the hydrogen isolated returns to hydrogenation system, and the cracking oil product isolated is with coming from essence The light component of product separator processed is mixed into stabilizer, and dry gas self-stabilization top of tower is isolated after excluding with oil product separator Fuel gas mixing be sent to boiler combustion, and enter after the discharge of oil product self-stabilization tower bottom in tar production product separator, warp The gasoline mixing that isolated light aromatics is separated with oil product separator is sold as final gasoline products, and is obtained The LPG mixed sellings that LPG is also separated with oil product separator, while isolated diesel oil and heavy oil product.

The gasification temperature of crushed coal pressurized-gasification furnace as described above is 1000~1400 DEG C, and vapor pressure is 4~6MPa, gas Agent uses the polynary gasifying agent being made up of vapor, carbon dioxide and oxygen, and polynary gasifying agent is according to water vapour：Titanium dioxide Carbon：Oxygen=1~8kg：2~6m³：1m³Composition.

The synthesis gas volume composition that coal as described above is prepared through crushed coal pressure gasifying is H₂37~40%, CO 17%~ 20%th, CO₂28~33%, CH₄8%~12%, N₂0.1~0.4%.

The reaction condition of the water-gas shift of change furnace is as described above：150~460 DEG C of reaction temperature, reaction pressure be 2~ 6MPa, gas volume air speed is 2000~10000h^-1。

Water-gas shift catalyst as described above is sulfur-resistant transformation catalyst, including section of domestic Qilu Petrochemical research institute power QCS-04 types sulfur-resistant transformation catalyst, the QDB series catalysts of Qingdao Lian Xin chemical industry Co., Ltd production of work company production Agent or the K8-11 catalyst series of BASF productions.

Synthesis gas volume as described above through water-gas shift accounts for the 25 of the synthesis gas cumulative volume of crushed coal pressure gasifying generation ~35%, and remaining 65~75% synthesis gas is not transformed.

Low temperature washing device for methanol as described above is made up of desulfurizing tower and decarbonizing tower, and operation temperature is -20~-60 DEG C, behaviour Make 3~4.0MPa of pressure, the sulphur after being washed through low-temp methanol in gas is removed to below 0.1ppm, CO₂Be removed to 0.8Vol% with Under.

The carbon dioxide as described above removed through low-temp methanol elution is divided into two parts, wherein accounting for the two of cumulative volume 2~8% Carbonoxide goes synthesic gas compressor group, and remaining 92~98% carbon dioxide returns to crushed coal pressure gasifying as gasifying agent Stove.

It is as described above washed through low-temp methanol after synthesis gas be the step of carry out methane cryogenic separation：First by gas cooling After to -85~-70 DEG C, isolate ethane, propane, a small amount of carbon dioxide and sulfide in 3~4.0MPa and be sent to boiler combustion；So Gas phase is cooled further to -150~-175 DEG C afterwards, and the LNG productions of methane volumetric content >=97% are isolated in 3.0~4.0MPa Product.

Synthesis gas after methane cryogenic separator is divided into two parts as described above, wherein account for synthesis gas volume 20~ 30% Part I carries hydrogen into pressure swing adsorber, and remaining 70~80% Part II gas is through side line and and transformation The stripping gas of absorber is mixed into synthesic gas compressor group.

The adsorptive pressure of pressure-variable adsorption as described above is 3.0~4.0Mpa, and operation temperature is 30~40 DEG C, is inhaled through transformation Hydrogen volume ratio >=99.9% of attached extraction.

Circulating air sum from methanol separator and gas-liquid separator and the desorption from pressure-variable adsorption as described above The volume ratio of gas and the carbon dioxide sum washed from low-temp methanol is 3~5.

Methyl alcohol synthetic reactor as described above uses shell-and-tube isothermal reactor, and its reaction pressure is 5.7~6.5MPa, reaction Temperature is 240~260 DEG C, and gas space velocity is 15500~20000L/ (Kgh).

The catalyst of methanol-fueled CLC as described above is C306, C307 catalyst that Research Institute of Nanjing Chemical Industry Group is developed, Dalian Any one in the RK-5 catalyst of Rake Science and Technology Ltd. production or the C302 catalyst of southwestern chemical design institute exploitation.

The gaseous products of methyl alcohol synthetic reactor outlet as described above are divided into two strands, and first burst of gaseous products accounts for reactor outlet The 55~70% of gas cumulative volume, and remaining 30~45% are used as second burst of gaseous products.

The CT151 type acid-exchange resins of filling Piao Laite companies production in methanol purification device as described above, its Purpose is by the removing of the basic nitrogen compounds such as the amine in liquid phase crude carbinol, methylamine and dimethylamine, and by the alkali nitride in crude carbinol Thing content is controlled in below 20ppm.

It is one-step technology that methanol as described above, which converts gasoline processed, and it is anti-using heat-insulating fixed bed that it synthesizes oil reactor Device is answered, inlet gas temperature is 300~350 DEG C, reaction pressure is 1.5~2.5MPa, methanol quality air speed is 0.8~1.3h^-1。

The catalyst that methanol as described above converts gasoline processed is developed using Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences JX6201 types catalyst or rope company of Top exploitation GSK-10 type catalyst.

The gas phase as described above gone out through gas-liquid separator separates is divided into two parts, wherein accounting for the gas of cumulative volume 4~8% Into membrane separator, and remaining 92~96% gas phase is back to synthesic gas compressor group.

The prins using former Monsanto Chemicals' production of membrane separator as described aboveMembrane device or U.S. The membrane separator of national law liquid air company exploitation, 2.5~8.0MPa of separating pressure, 40~90 DEG C of separation temperature, after UF membrane Hydrogen volume yield is 90~92%, and hydrogen product volumetric concentration is 91~95%.

Tar, middle oil and the part outsourcing tar that coal gas separator as described above is isolated are purified rear into pre- point Tower is evaporated, 360~460 DEG C of distillate is isolated as hydrogenating materials, and remaining pitch enters in delay coking stove.

The reaction temperature of delay coking stove as described above is 490~570 DEG C, and reaction pressure is 0.1~0.5MPa.

The protection reaction condition of protection reactor is as described above：360~430 DEG C of temperature, 11~15MPa of reaction pressure, The volume ratio of hydrogen and oil is 500:1~2000:1, the volume space velocity of liquid is 0.1~2h^-1.

What the guard catalyst loaded in protection reactor as described above was developed for Sheng Bang Chemical Engineering Technologies Co., Ltd JEHT-11, JEHT-12 and JEHT-13 type protective agent or Sinopec Fushun Petrochemical Research Institute exploitation FZC-10, FZC10Q and FZC-100 catalyst series, protective agent is loaded by multi-layer classification.

Hydrofining reaction condition is as described above：300~430 DEG C of temperature, pressure is 10~17Pa, hydrogen to oil volume ratio For 1000:1~3000:1, liquid volume air speed is 0.1~1.5h^-1。

Hydrobon catalyst as described above is the JEHT-41 type hydrogenation catalysts that Sheng Bang Chemical Engineering Technologies Co., Ltd produces Agent, the serial hydrogenation catalysts of NUHC-40A/B/C/D of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation, Sinopec Fushun stone FH-5A types, FH-98 types hydrogenation catalyst or the DH3551 types hydrogenation of standard catalyst company production of oily chemical research institute's exploitation Catalyst for refining.

Hydrocracking reaction condition is as described above：360~470 DEG C of temperature, pressure is 10~17Pa, hydrogen and oil body Product is than being 800:1~2000:1, liquid volume air speed is 0.1~2h^-1。

Hydrocracking catalyst as described above is the NUHC-41A/B/C/ that Shanghai Xinyou Energy Technology Co., Ltd. develops D series hydrocracking catalysts or the Z3723 type hydrocracking catalysts of standard catalyst company production.

The present invention compared with prior art, is with substantive distinguishing features and marked improvement：

(1) the characteristics of inventor combines property and the by-product tar of crushed coal pressure gasifying synthesis gas, develops a kind of synthesis Gas comes out methane separation, is then converted into gasoline products through methanol, and hydrogen more than needed is refined and split for hydrogenation of tar Change, substantially increase the utilization ratio of crushed coal pressure gasifying synthesis gas.

(2) broken coal pressure synthesis gas of the present invention is through methanol synthesized gasoline, by substantial amounts of experiment, calculates and methanol for many years Gasoline design experiences processed, the crude carbinol only partially through gas-liquid separation is routed directly to synthesize oil reactor, methanol essence is reduced Equipment investment and the operating cost of unit are evaporated, refined methanol is used compared with the technology of raw material with existing preparing gasoline by methanol technique, its Equipment investment reduces more than 10%, and operating cost reduces nearly 5%, and its annual return improves nearly 20%.

(3) crushed coal pressure gasifying synthesis gas comprehensive utilization process disclosed by the invention, the vapour of its synthesis gas through methanol conversion The light aromatics that oil product can be generated with hydrogenation of tar can form the complementation of index, and the product of gasoline can be more improved after mediation Matter, can sell directly as gasoline products, it is to avoid gasoline products made from independent hydrogenation of tar are not up to standard and can not directly sell The problem of selling.

(4) crushed coal pressure gasifying synthesis gas comprehensive utilization process disclosed by the invention, pitch of prefractionator etc. is recombinated Divide the cracking and condensation reaction by delayed coking system, and by MTG heavy oil further by cracking reaction, further increase The product yield of tar conversion petrol and diesel oil.

(5) periodic off-gases of the invention by preparing gasoline by methanol are further by membrane separation technique hydrogen making, and are used for tar Hydrogenation, and the remaining stripping gas rich in carbon monoxide and carbon dioxide is back to synthesis gas compression and carries out methanol synthesis reaction, Reduce the discharge and environmental pollution of periodic off-gases.

(6) low-temp methanol is washed remaining CO by the present invention₂Gas is back to gasification furnace as gasifying agent and participates in gasification, not only The consumption of water vapour and the discharge capacity of carbon dioxide greenhouse gas are reduced, and adds methane and carbon monoxide etc. in coal gas The content of available gas composition.

(7) crushed coal pressure gasifying synthesis gas comprehensive utilization process disclosed by the invention, its major product be liquefied natural gas, The product such as gasoline and diesel oil, not only conforms to the adjustment direction of national energy structure, and can alleviate the country to the oil gas energy Demand contradictory, with important strategic importance and huge market prospects.

In summary, inventor is ground according to the product form and feature of crushed coal pressure gasifying technology by substantial amounts of experiment Study carefully, technology contrasts and simulated a large amount of performing creative labours such as calculating, and combines engineering experience for many years, numerous technologies are carried out Creative combination, and then develop that a kind of utilization rate is high, the broken coal that technique is simple, product structure is reasonable and environmental pollution is small adds Press the comprehensive utilization process of gasification synthesis gas, with potential industrial prospect, huge industrial prospect and realistic meaning.

Brief description of the drawings

Fig. 1 is process chart disclosed by the invention.

As shown in Figure 1,1 is crushed coal pressurized-gasification furnace, and 2 be change furnace, and 3 be gas cooler, and 4 be that low-temp methanol washes dress Put, 5 be methane cryogenic separator, and 6 be pressure swing adsorber, and 7 be synthesic gas compressor group, and 8 be methyl alcohol synthetic reactor, and 9 be methanol point From device, 10 be methanol purification device, and 11 be synthesis oil reactor, and 12 be gas-liquid separator, and 13 be oil product separator, and 14 be UF membrane Device, 15 be coal gas separator, and 16 be prefractionator, and 17 be delay coking stove, and 18 be protection reactor, and 19 be that hydrofinishing is anti- Device is answered, 20 be refined products piece-rate system, and 21 be cracker, and 22 be crackate piece-rate system, and 23 be stabilizer, and 24 are Tar production product separation system, 25 be methanol product condenser, and 26 be crude carbinol vaporizer, and 27 be gasoline products condenser.

Subordinate list explanation

Table 1 is that raw tar is outsourcing tar and the mixed property of self-produced tar.

Table 2 is property oily in raw material.

Table 3 is the property of raw material naphtha.

The gasoline property that the coke-stove gas of table 4 is prepared through methanol.

The delayed coking of the tar of table 5, hydrofinishing and product form and yield after being hydrocracked.

Embodiment

The embodiment of the present invention is described in further detail below by specific embodiment, but should not be by This is interpreted as the scope of the present invention and is only limitted to above-described embodiment.

Embodiment 1

(1) raw material lignite is with water vapour：Carbon dioxide：Oxygen=8kg：2m³：1m³For gasifying agent, and at 1400 DEG C, gasification Pressure is that to be converted into composition through crushed coal pressure gasifying 1 under conditions of 4MPa be H₂37%th, CO 20%, CO₂33%th, CH₄ 9.9%, N₂Accounted in 0.1% synthesis gas and tar byproduct, the synthesis gas of generation 25% gas of synthesis gas cumulative volume in It is 460 DEG C, reaction pressure in reaction temperature in the QCS-04 sulphur-resistant conversions catalysis of Ke Li chemical companies of Qilu Petrochemical research institute production Power is 6MPa and gas space velocity is 10000h^-1Under conditions of carry out water gas shift reation after, with 75% walk side line synthesis gas mix Close and enter in gas cooling system 3, the oily waste water under condensation is sent in coal gas water separating system 15, and synthesis gas then enters low Warm methanol is washed in system 4, under conditions of operation temperature is -60 DEG C and operating pressure 4.0MPa, gas after being washed through low-temp methanol In sulphur be removed to 0.01~0.1ppm, CO₂0.3~0.8Vol% is removed to, wherein the H removed₂S is sent to sulfur recovery system, takes off The naphtha removed is sent in protection reactor 18, and the 8% of the carbon dioxide volume of removing enters synthesic gas compressor group 7 In, and remaining 92% is back in crushed coal pressurized-gasification furnace as gasifying agent, and it is purified after synthesis gas enter methane In cryogenic separation system 5.

(2) synthesis gas after low temperature methanol cleaning enters after methane cryogenic separation system 5, first cools down coke-stove gas After to -70 DEG C, isolate ethane, propane, a small amount of carbon dioxide and sulfide in 4.0MPa and be sent to boiler combustion；Then gas phase is entered One step is cooled to -150 DEG C, and the LNG product of methane content >=97% is isolated in 4.0MPa, and is sold as end product, takes off Except the synthesis gas after methane is divided into two parts from after the discharge of methane cryogenic separation system, wherein accounting for 30% gas of synthesis gas volume Body is sent to pressure swing adsorption system 6, and in adsorptive pressure be 4.0MPa and operation temperature is to carry out pressure-variable adsorption under conditions of 40 DEG C, is obtained The hydrogen of the volumetric concentration more than 99.9% arrived and the permeated hydrogen from film separation system 14, refined products piece-rate system 20 and It is used for hydrogenation of tar after the circulating hydrogen mixing of crackate piece-rate system 22, and the stripping gas of pressure-variable adsorption without transformation with inhaling The attached Part II synthesis gas for accounting for synthesis gas volume 70% merges, and with partial CO 2, the methanol washed from low-temp methanol The circulating air of separator 9 and gas-liquid separator 12 is mixed into synthesic gas compressor group 7, and control from methanol separator and The circulating air sum of gas-liquid separator 12 and the synthesis gas from pressure-variable adsorption and the partial CO 2 washed from low-temp methanol The volume ratio of sum is 3, and methyl alcohol synthetic reactor 8 is sent to after supercharging.

(3) synthesis gas after supercharging enters the methanol for the C306 catalyst developed equipped with Research Institute of Nanjing Chemical Industry Group from top In synthetic tower 8, and it is 6.5MPa, the bar that reaction temperature is 260 DEG C and gas space velocity is 20000L/ (Kgh) in reaction pressure Methanol-fueled CLC is carried out under part, gaseous products are divided into two strands from after synthesizing tower bottom discharge, wherein accounting for the first of volume fraction 55% After stock gaseous products are condensed through methanol product condenser 25, into methanol separator 9, gas phase is returned after being discharged from the top of separator It is back to synthesic gas compressor group 7, and the crude carbinol liquid phase being made up of methanol, fusel, water and lower carbon number hydrocarbons etc. is from the bottom of methanol separator 9 Enter to be filled with CT151 type acid-exchange resin methanol purifications device 10 after portion's discharge and purified, basic nitrogen is removed To below 20ppm, it is purified after crude carbinol liquid phase vaporized by crude carbinol vaporizer 26 after, second strand with remaining 45% The gaseous products for walking side line are mixed into the JX6201 type catalyst developed equipped with Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences Synthesis oil reactor 11 in.

(4) gas phase crude carbinol is in synthesis oil reactor 11, inlet gas temperature be 350 DEG C, reaction pressure be 2.5MPa It is 1.3h with methanol quality air speed^-1Under conditions of carry out the reaction that methanol converts gasoline processed, its product is through gasoline products condenser Enter after 27 condensations in gas-liquid separator 12, the gas phase isolated is divided into two parts after being discharged from top, accounts for volume of gas 92% Part I gas is back in synthesic gas compressor group 7, and 8% another part is given birth into Monsanto Chemicals The prins of productionFilm separation system, through UF membrane under conditions of separating pressure is 40 DEG C of 8.0MPa and separation temperature The infiltration gas of obtained hydrogen volume content more than 91%, and obtain hydrogen with pressure-variable adsorption and circulating hydrogen is mixed for tar Hydrogenation, and fuel gas and the dry gas of the top of stabilizer 23 discharge that the stripping gas through UF membrane is isolated with oil product piece-rate system are mixed Boiler combustion is sent to after conjunction, the fluid that gas-liquid separator 12 is isolated enters in oil product piece-rate system 13 after being discharged from bottom, Liquefied petroleum gas (LPG), gasoline products, fuel gas and C are obtained after being separated through oil product₁₀~C₁₂Heavy oil component, wherein isolating C₁₀~C₁₂The heavy constituent of heavy oil component and refined products piece-rate system 20 be mixed into cracker 21 and carry out cracking Reaction.

(5) gasification waste water from gas crushed coal pressure gasifying system 1 and from gas cooling system is separated into gas liquor In system 15, the water isolated is sent to water treatment system, and the tar and middle oil ingredient isolated and part outsourcing tar warp are net Enter after change and cut in prefractionator 16, cutting temperature is 460 DEG C, 460 DEG C of its ＞ pitch enters from after bottom of towe discharge In delayed coking system 17, it is 570 DEG C in reaction temperature and reaction pressure is to carry out delayed coking under conditions of 0.1MPa, obtain Pitch coke as production marketing, and obtained light component is then cut with fractionating column≤460 DEG C of light component, carry out autofining production The tail oil of thing piece-rate system 20, a small amount of naphtha and hydrogen washed from low-temp methanol are mixed into is filled with victory side from top to bottom In the protectant protection reactor 18 of JEHT-11, JEHT-12 and JEHT-13 type of Chemical Engineering Technology Co., Ltd exploitation, in temperature 430 DEG C, reaction pressure 15MPa, hydrogen and oily volume ratio are 2000:1 and liquid volume space velocity be 0.1h^-1Under conditions of enter Row protection reaction, product enters the JEHT-41 types hydrogenation produced equipped with Sheng Bang Chemical Engineering Technologies Co., Ltd and urged after being discharged from bottom It is that 17Pa, hydrogen to oil volume ratio are 3000 in 430 DEG C of temperature, pressure in the hydrofining reactor 19 of agent:1 and liquid volume Air speed is 0.1h^-1Under conditions of carry out hydrogenation reaction, its hydrogenation products from bottom discharge after be sent to refined products piece-rate system 20 In, wherein the light component isolated enters in stabilizer 18, the hydrogen isolated then is mixed with the hydrogen of crackate piece-rate system Cooperate to be back to hydrogenation system for circulating air, and the heavy constituent part isolated returns to protection reactor 18 as tail oil, and Another part and the C from oil product piece-rate system 13₁₀~C₁₂Heavy oil component be mixed into and energy science and technology is newly helped equipped with Shanghai have In the cracker 21 of the serial hydrocracking catalysts of NUHC-41A/B/C/D of limit company exploitation, in 470 DEG C of temperature, pressure It is 2000 for 17Pa, hydrogen and oil volume ratio:1 and liquid volume air speed be 0.1 under conditions of carry out cracking reaction, its product from Reactor bottom discharge after enter crackate piece-rate system 22, the hydrogen isolated with from refined products piece-rate system 15 Hydrogen, the hydrogen of pressure swing adsorption system 6 and from film separation system 14 permeated hydrogen mixing after be divided into two parts, first Enter after point mix with imported raw material from top and protect in reactor and cracker, and another part is as cold shock gas in oneself Portion enters hydrogenation reactor and cracker, and the cracking oil product isolated and light group from refined products piece-rate system 15 Divide and be mixed into stabilizer 18, the fuel gas isolated after the discharge of dry gas self-stabilization top of tower with oil product piece-rate system, which is mixed, to be sent Toward boiler combustion, and enter after the discharge of oil product self-stabilization tower bottom in tar production product separation system 19, be isolated to The mixing of gasoline that light aromatics is separated with oil product piece-rate system 13 is sold as final gasoline products, and obtained LPG also with The LPG mixed sellings that oil product piece-rate system 13 is separated, while separable obtain diesel oil and heavy oil product.

The raw tar property used in the present embodiment for details see attached table 1, medium oil matter for details see attached table 2, naphtha property is detailed 3 are seen attached list, its gasoline property synthesized by MTG for details see attached table 4, the gasoline products property of hydrogenation of tar for details see attached table 5.

Embodiment 2

The present embodiment is using jet coal as raw material, and polynary gasifying agent composition is water vapour：Carbon dioxide：Oxygen=6kg：3m³： 1m³, at 1300 DEG C, vapor pressure is carries out crushed coal pressure gasifying under conditions of 4.5MPa, synthesis gas composition is H₂40%th, CO 17%th, CO₂33%th, CH₄9.6%, N₂0.4%；28% gas of synthesis gas cumulative volume is accounted in the synthesis gas of generation in neat It is 400 DEG C, reaction pressure in reaction temperature in the QCS-04 sulphur-resistant conversions catalysis of Shandong Ke Li chemical companies of petrochemical industry research institute production It is 8000h for 5MPa and gas space velocity^-1Under conditions of carry out water gas shift reation after, and 72% without transformationreation；Low temperature It is -50 DEG C of temperature and operating pressure 3.8MPa that methanol, which washes condition,；The 6% of the carbon dioxide volume of removing enters synthesis air pressure In contracting unit 7, and remaining 94% is back in crushed coal pressurized-gasification furnace as gasifying agent；The step of deep cooling methane separation For：First coke-stove gas is cooled to after -74 DEG C, ethane, propane, a small amount of carbon dioxide and sulfide is isolated in 3.8MPa and is sent to Boiler combustion, then gas phase be cooled further to -155 DEG C, isolate the LNG product of methane content >=97% in 3.8MPa；It is deep 28% gas is 3.8MPa in adsorptive pressure in cold methane separation system and operation temperature is to carry out transformation under conditions of 38 DEG C Absorption, 72% gas is directly entered synthesic gas compressor group 7 without pressure-variable adsorption；The C307 developed using Research Institute of Nanjing Chemical Industry Group Catalyst, and be under conditions of 6.3MPa, reaction temperature are 255 DEG C and gas space velocity is 19000L/ (Kgh) in reaction pressure Carry out methanol synthesis reaction；First burst of gaseous products of condensed, separation and gasification are accounted for always in the gas of methanol reactor outlet The 60% of volume, and the gas phase of residue 40% then walks side line；Developed using Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences JX6201 type catalyst, inlet gas temperature be 340 DEG C, reaction pressure is 2.3MPa and methanol quality air speed is 1.1h^-1Bar The reaction that methanol converts gasoline processed is carried out under part；93% gas that gas-liquid separator separates go out is back to synthesis gas compression, and 7% gas is sent to the prins of Monsanto Chemicals' productionFilm separation system, is 6.0MPa in separating pressure With carry out UF membrane under conditions of 50 DEG C of separation temperature；The cutting temperature of prefractionator is 420 DEG C；The reaction condition of delayed coking For：550 DEG C of reaction temperature and reaction pressure 0.2MPa；JEHT-11, the JEHT- developed using Sheng Bang Chemical Engineering Technologies Co., Ltd 12 and JEHT-13 type protective agents, and be 1900 in the volume ratio in 410 DEG C of temperature, reaction pressure 14MPa, hydrogen and oil:1 He The volume space velocity of liquid is 0.5h^-1Under conditions of carry out protection reaction；Developed using Shanghai Xinyou Energy Technology Co., Ltd. NUHC-40A/B/C/D series hydrogenation catalysts, are that 15Pa, hydrogen to oil volume ratio are 2500 in 400 DEG C of temperature, pressure:1 and liquid Volume space velocity is 0.5h^-1Under conditions of carry out hydrogenation reaction；The NUHC- developed using Shanghai Xinyou Energy Technology Co., Ltd. 41A/B/C/D series hydrocracking catalysts, and be that 15Pa, hydrogen and oil volume ratio are 1700 in 420 DEG C of temperature, pressure:1 He Liquid volume air speed be 0.5 under conditions of carry out cracking reaction.Remaining step is same as Example 1.

The tar property used in the present embodiment for details see attached table 1, medium oil matter for details see attached table 2, naphtha property refers to attached Table 3, its gasoline property synthesized by MTG for details see attached table 4, the gasoline products property of hydrogenation of tar for details see attached table 5.

Embodiment 3

The present embodiment is using jet coal as raw material, and polynary gasifying agent composition is water vapour：Carbon dioxide：Oxygen=4kg：4m³： 1m³, at 1200 DEG C, vapor pressure is carries out crushed coal pressure gasifying under conditions of 5MPa, synthesis gas composition is H₂40%th, CO 19.9%th, CO₂28%th, CH₄12%, N₂0.1%；30% gas of synthesis gas cumulative volume is accounted in the synthesis gas of generation in green grass or young crops In the QDB-03 sulphur-resistant conversions catalysis of Dao Lianxin chemical industry Co., Ltd production, reaction temperature be 300 DEG C, reaction pressure be 4MPa and gas space velocity are 6000h^-1Under conditions of carry out water gas shift reation after, and 70% without transformationreation；Low temperature first It is -40 DEG C of temperature and operating pressure 3.5MPa that alcohol, which washes condition,；The 5% of the carbon dioxide volume of removing enters synthesis gas and compressed In unit 7, and remaining 95% is back in crushed coal pressurized-gasification furnace as gasifying agent；The step of deep cooling methane separation is： First coke-stove gas is cooled to after -78 DEG C, ethane, propane, a small amount of carbon dioxide and sulfide is isolated in 3.5MPa and is sent to pot Stove burns, and then gas phase is cooled further to -160 DEG C, and the LNG product of methane content >=97% is isolated in 3.5MPa；Deep cooling 25% gas is 3.5MPa in adsorptive pressure in methane separation system and operation temperature is that transformation suction is carried out under conditions of 35 DEG C Attached, 75% gas is directly entered synthesic gas compressor group without pressure-variable adsorption；Developed using Dalian Reak Science and Technology Co., Ltd. RK-5 catalyst, and be 6.0MPa, the bar that reaction temperature is 250 DEG C and gas space velocity is 17000L/ (Kgh) in reaction pressure Methanol synthesis reaction is carried out under part；First burst of gaseous products of condensed, separation and gasification in the gas of methanol reactor outlet Of the total volume 65%, and the gas phase of residue 35% then walks side line；Developed using Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences JX6201 type catalyst, inlet gas temperature be 320 DEG C, reaction pressure is 2.0MPa and methanol quality air speed is 1.0h^-1's Under the conditions of carry out the reaction that methanol converts gasoline processed；94% gas that gas-liquid separator separates go out is back to synthesis gas compression, And 6% gas is sent to the prins of Monsanto Chemicals' productionFilm separation system, be in separating pressure UF membrane is carried out under conditions of 70 DEG C of 5.0MPa and separation temperature；The cutting temperature of prefractionator is 400 DEG C；Delayed coking it is anti- The condition is answered to be：530 DEG C of reaction temperature and reaction pressure 0.3MPa；Using Sheng Bang Chemical Engineering Technologies Co., Ltd develop JEHT-11, JEHT-12 and JEHT-13 type protective agents, and be 1400 in the volume ratio of 390 DEG C of temperature, reaction pressure 13MPa, hydrogen and oil:1 Volume space velocity with liquid is 1h^-1Under conditions of carry out protection reaction；Using Sinopec, Fushun Petrochemical Research Institute develops FH-5A hydrogenation catalysts, be that 13Pa, hydrogen to oil volume ratio are 2000 in 380 DEG C of temperature, pressure:1 and liquid volume air speed be 0.9h^-1Under conditions of carry out hydrogenation reaction；The NUHC-41A/B/C/D systems developed using Shanghai Xinyou Energy Technology Co., Ltd. Row hydrocracking catalyst, and be that 13Pa, hydrogen and oil volume ratio are 1300 in 390 DEG C of temperature, pressure:1 and liquid volume it is empty Speed be 0.9 under conditions of carry out cracking reaction.Remaining step is same as Example 1.

Embodiment 4

The present embodiment is using jet coal as raw material, and polynary gasifying agent composition is water vapour：Carbon dioxide：Oxygen=2kg：5m³： 1m³, at 1100 DEG C, vapor pressure is carries out crushed coal pressure gasifying under conditions of 5.5MPa, synthesis gas composition is H₂38.5%th, CO 20%th, CO₂33%th, CH₄8%, N₂0.5%；32% gas of synthesis gas cumulative volume is accounted in the synthesis gas of generation in Qingdao In the QDB-03 sulphur-resistant conversions catalysis of Lian Xin chemical industry Co., Ltd production, reaction temperature be 250 DEG C, reaction pressure be 3MPa and gas space velocity are 4000h^-1Under conditions of carry out water gas shift reation after, and 68% without transformationreation；Low temperature first It is -30 DEG C of temperature and operating pressure 3.2MPa that alcohol, which washes condition,；The 4% of the carbon dioxide volume of removing enters synthesis gas and compressed In unit 7, and remaining 96% is back in crushed coal pressurized-gasification furnace as gasifying agent；The step of deep cooling methane separation is： First coke-stove gas is cooled to after -81 DEG C, ethane, propane, a small amount of carbon dioxide and sulfide is isolated in 3.2MPa and is sent to pot Stove burns, and then gas phase is cooled further to -165 DEG C, and the LNG product of methane content >=97% is isolated in 3.2MPa；Deep cooling 23% gas is 3.2MPa in adsorptive pressure in methane separation system and operation temperature is that transformation suction is carried out under conditions of 32 DEG C Attached, 77% gas is directly entered synthesic gas compressor group without pressure-variable adsorption；The C302 developed using southwestern chemical design institute is urged Agent, and be that 5.9MPa, reaction temperature are 245 DEG C and gas space velocity is to enter under conditions of 16000L/ (Kgh) in reaction pressure Row methanol synthesis reaction；First burst of gaseous products of condensed, separation and gasification account for totality in the gas of methanol reactor outlet Long-pending 70%, and the gas phase of residue 30% then walks side line；The GSK-10 type catalyst developed using rope company of Top, in inlet gas Temperature is 310 DEG C, reaction pressure is 1.8MPa and methanol quality air speed is 1.1h^-1Under conditions of carry out methanol and convert gasoline processed Reaction；95% gas that gas-liquid separator separates go out is back to synthesis gas compression, and to be sent to U.S. Meng Shan all public for 5% gas Take charge of the prins of productionFilm separation system, is carried out under conditions of separating pressure is 80 DEG C of 4.0MPa and separation temperature UF membrane；The cutting temperature of prefractionator is 380 DEG C；The reaction condition of delayed coking is：510 DEG C of reaction temperature and reaction pressure 0.4MPa；FZC-10, FZC-10Q and the FZC-100 developed using Fushun Petrochemical Research Institute, and in 370 DEG C of temperature, reaction The volume ratio of pressure 12MPa, hydrogen and oil is 1000:1 and liquid volume space velocity be 1.5h^-1Under conditions of carry out protecting anti- Should；The FH-98 hydrogenation catalysts developed using Sinopec Fushun Petrochemical Research Institute, be in 340 DEG C of temperature, pressure 11Pa, hydrogen to oil volume ratio are 1500:1 and liquid volume air speed be 1.2h^-1Under conditions of carry out hydrogenation reaction；Use standard catalyst The Z3723 hydrocracking catalysts of agent company exploitation, and be that 12Pa, hydrogen and oil volume ratio are in 380 DEG C of temperature, pressure 1000:1 and liquid volume air speed be 1.5 under conditions of carry out cracking reaction.Remaining step is same as Example 1.

Embodiment 5

The present embodiment is using jet coal as raw material, and polynary gasifying agent composition is water vapour：Carbon dioxide：Oxygen=1kg：6m³： 1m³, at 1000 DEG C, vapor pressure is carries out crushed coal pressure gasifying under conditions of 6MPa, synthesis gas composition is H₂39%th, CO 19%th, CO₂31%th, CH₄10.7%, N₂0.3%；Accounted in the synthesis gas of generation 35% gas of synthesis gas cumulative volume in In the K8-11 sulphur-resistant conversions catalysis of BASF AG's production, reaction temperature be 150 DEG C, reaction pressure be 2MPa and gas space velocity For 2000h^-1Under conditions of carry out water gas shift reation after, and 65% without transformationreation；Low-temp methanol wash condition for temperature- 20 DEG C and operating pressure 3.0MPa；The 2% of the carbon dioxide volume of removing enters in synthesic gas compressor group 7, and remaining 98% be back to as gasifying agent in crushed coal pressurized-gasification furnace；The step of deep cooling methane separation is：First by coke-oven coal air cooling But to after -85 DEG C, ethane, propane, a small amount of carbon dioxide and sulfide is isolated in 3.0MPa and is sent to boiler combustion, then gas phase - 175 DEG C are cooled further to, the LNG product of methane content >=97% is isolated in 3.0MPa；In deep cooling methane separation system 20% gas is 3.0MPa in adsorptive pressure and operation temperature is that pressure-variable adsorption is carried out under conditions of 30 DEG C, 80% gas without Pressure-variable adsorption is directly entered synthesic gas compressor group；The C302 catalyst developed using southwestern chemical design institute, and in reaction pressure Power is that 5.7MPa, reaction temperature are 240 DEG C and gas space velocity is to carry out methanol synthesis reaction under conditions of 15500L/ (Kgh)； First burst of gaseous products of the total volume 70% of condensed, separation and gasification in the gas of methanol reactor outlet, and it is remaining 30% gas phase then walks side line；The GSK-10 type catalyst developed using rope company of Top, is 300 DEG C, instead in inlet gas temperature Answer that pressure is 1.5MPa and methanol quality air speed is 1.3h^-1Under conditions of carry out the reaction that methanol converts gasoline processed；Gas-liquid separation 96% gas that device is isolated is back to synthesis gas compression, and 4% gas is sent to the Puli of Monsanto Chemicals' production It is gloomyFilm separation system, UF membrane is carried out under conditions of separating pressure is 90 DEG C of 2.5MPa and separation temperature；Pre- point The cutting temperature for evaporating tower is 360 DEG C；The reaction condition of delayed coking is：490 DEG C of reaction temperature and reaction pressure 0.5MPa；Use Fushun Petrochemical Research Institute exploitation FZC-10, FZC-10Q and FZC-100, and 360 DEG C of temperature, reaction pressure 11MPa, The volume ratio of hydrogen and oil is 500:1 and liquid volume space velocity be 2h^-1Under conditions of carry out protection reaction；Use standard catalyst The DH3551 hydrogenation catalysts of agent company exploitation, are that 10Pa, hydrogen to oil volume ratio are 1000 in 300 DEG C of temperature, pressure:1 and liquid Volume space velocity is 1.5h^-1Under conditions of carry out hydrogenation reaction；The Z3723 hydrocracking catalysts developed using standard catalyst company Agent, and be that 10Pa, hydrogen and oil volume ratio are 800 in 360 DEG C of temperature, pressure:1 and liquid volume air speed be 2.0 under conditions of Carry out cracking reaction.Remaining step is same as Example 1.

Table 1

Density (g/cm³)	1.032
		Viscosity (cp)	35.96
Distill (DEG C)
		IBP~10%	~196.6
20%~30%	223.4~257.6
		40%~50%	290.6~322.6
60%~70%	363.4~415.0
		80%~90%	489.2~605.4
S/%	0.54
		N/%	1.04
C/%	81.5
		H/%	8.0
O/%	8.92
		Carbon residue/%	3.16
Moisture/%	--
		Ash content/%	0.03

Table 2

Density (g/cm³)	1.002
		Viscosity (cp)	12.72
Distill (DEG C)
		IBP~10%	~183.6
20%~30%	204.2~223.8
		40%~50%	249.8~284.4
60%~70%	321.6~375.8
		80%~90%	448.8~750.0
S/%	0.62
		N/%	0.85
C/%	82.4
		H/%	8.17
O/%	7.92
		Carbon residue/%	1.82
Moisture/%	--
		Ash content/%	0.02

Table 3

Density (g/cm³)	0.826
		Distill (DEG C)
IBP~10%	40~60
		20%~30%	70~78
40%~50%	83~88
		60%~70%	91~98
80%~90%	107~120
		95%~FBP	150~
S/%	1.82
		N/%	0.03
C/%	85.7
		H/%	13.4
O/%	0.69
		Carbon residue/%	0.15
Moisture/%	~
		Ash content/%	0.03

Table 4

Table 5

Claims

1. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline, co-production of liquefied natural gas and for the comprehensive of tar deep processing Conjunction utilizes technique, it is characterised in that comprise the following steps：

(1) feed coal is converted into synthesis gas and tar byproduct through crushed coal pressurized-gasification furnace, and a synthesis gas part for generation is through becoming Change the synthesis gas for walking side line with another part after stove progress water-gas shift to be mixed into gas cooler, the oily waste water under condensation Water is sent in coal gas separator, and synthesis gas then enters in low temperature washing device for methanol, and synthesis gas is removed after being washed through low-temp methanol H₂S, naphtha and carbon dioxide material, wherein the H removed₂S is sent to sulfur recovery system, and the naphtha of removing is sent to protection reaction In device, the carbon dioxide of removing is partly into synthesic gas compressor group, and another part is then back to as gasifying agent In crushed coal pressurized-gasification furnace, and it is purified after synthesis gas enter methane cryogenic separator in；

(2) liquid phase methane is isolated through methane cryogenic separator, and is sold as end product, the synthesis gas after removing methane is certainly It is divided into two parts after the discharge of methane cryogenic separator, Part I is sent to pressure swing adsorber, and volumetric concentration is obtained through pressure-variable adsorption More than 99.9% hydrogen, and the stripping gas of pressure-variable adsorption merges with the Part II synthesis gas without pressure-variable adsorption, and with coming The circulating air of partial CO 2, methanol separator and the gas-liquid separator washed from low-temp methanol is mixed into synthesic gas compressor In group, methyl alcohol synthetic reactor is sent to after supercharging；

(3) gas after supercharging enters in methyl alcohol synthetic reactor from top carries out methanol-fueled CLC, and gaseous products are from methyl alcohol synthetic reactor It is divided into two strands after the discharge of bottom, wherein after first burst of gaseous products is condensed through methanol product condenser, into methanol separator, Gas phase is back to synthesic gas compressor group after discharging at the top of the methanol separator, and be made up of methanol, fusel, water and lower carbon number hydrocarbons Crude carbinol liquid phase from methanol separator bottom discharge after enter methanol purification device in is purified, it is purified after crude carbinol liquid phase After being vaporized by crude carbinol vaporizer, it is mixed into second burst of gaseous products for walking side line in synthesis oil reactor；

(4) gas phase crude carbinol carries out the reaction that methanol converts gasoline processed in synthesis oil reactor, and its product is cold through gasoline products Enter after condenser condensation in gas-liquid separator, the gas phase isolated is divided into two parts after being discharged from top, and Part I is back to In synthesic gas compressor group, another part enters membrane separator, and the hydrogen volume content more than 91% that is obtained through UF membrane is oozed It is ventilative to be sent to hydrogenation of tar, and arranged at the top of the fuel gas and stabilizer that the stripping gas through UF membrane is isolated with oil product piece-rate system Boiler combustion is sent to after the dry gas mixing gone out, the oil phase that gas-liquid separator separates go out enters oil product separator after being discharged from bottom In, LPG, gasoline products, fuel gas and C are obtained after being separated through oil product₁₀~C₁₂Heavy oil component, wherein the C isolated₁₀~C₁₂ The heavy constituent of heavy oil component and refined products separator be mixed into cracker and carry out cracking reaction；

(5) hydrogen of pressure-variable adsorption is separated with the permeated hydrogen from membrane separator, refined products separator and crackate It is divided into four parts after the circulating hydrogen mixing of device, Part I hydrogen enters protection reactor from top, Part II hydrogen is from top Into in cracker, Part III hydrogen enters in hydrofining reactor from middle part, and Part IV hydrogen enters from middle part to be split Change in reactor,

(6) oily waste water from gas crushed coal pressurized-gasification furnace and from gas cooler enters in coal gas separator, separation The water gone out is sent to water treatment system, and the tar and middle oil ingredient isolated and part outsourcing tar it is purified after enter prefractionation Cut in tower, its pitch enters in delay coking stove after being discharged from fractionation column bottom, pitch Jiaozhuo that delayed coking is obtained For production marketing, and obtained light component then with the light component at the top of fractionating column out, the tail from refined products separator Oil, a small amount of naphtha from low temperature washing device for methanol and step (5) Part I hydrogen are mixed into protection reactor, product Enter after the discharge of self-shield reactor bottom in hydrofining reactor, after hydrogenation products are discharged from hydrofining reactor bottom It is sent in refined products separator, wherein the light component isolated enters in stabilizer, the hydrogen isolated is back to hydrogenation system System, and isolate heavy constituent a part as tail oil return protection reactor, and another part with from oil product separator C₁₀~C₁₂Heavy oil component be mixed into cracker and carry out cracking reaction, the cracking reactor bottom discharge of its product Enter crackate separator afterwards, the hydrogen isolated returns to hydrogenation system, and the cracking oil product isolated is with carrying out autofining production The light component of thing separator is mixed into stabilizer, the combustion that dry gas self-stabilization top of tower is isolated after excluding with oil product separator Boiler combustion is sent in material gas mixing, and is entered after the discharge of oil product self-stabilization tower bottom in tar production product separator, through separation The gasoline mixing that obtained light aromatics is separated with oil product separator is sold as final gasoline products, and obtained LPG The LPG mixed sellings separated with oil product separator, while isolated diesel oil and heavy oil product.

2. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the gasification temperature of described crushed coal pressurized-gasification furnace be 1000~ 1400 DEG C, vapor pressure is 4~6MPa, and gasifying agent uses the polynary gasifying agent being made up of vapor, carbon dioxide and oxygen, many First gasifying agent is according to water vapour：Carbon dioxide：Oxygen=1~8kg：2~6m³：1m³Composition.

3. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the synthesis gas volume that described coal is prepared through crushed coal pressure gasifying Constitute as H₂37~40%, CO 17%~20%, CO₂28~33%, CH₄8%~12%, N₂0.1~0.4%.

4. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the reaction condition of the water-gas shift of the change furnace is：Reaction 150~460 DEG C of temperature, reaction pressure is 2~6MPa, and gas volume air speed is 2000~10000h^-1。

5. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described water-gas shift catalyst is sulfur-resistant transformation catalyst, QCS-04 types sulfur-resistant transformation catalyst, the Qingdao connection produced including domestic Ke Li chemical companies of Qilu Petrochemical research institute believes chemical work The QDB catalyst series of industry Co., Ltd production or the K8-11 catalyst series of BASF productions.

6. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the synthesis gas volume through water-gas shift accounts for broken coal pressurization The 25~35% of the synthesis gas totality that gasification is produced, and remaining 65~75% synthesis gas is not transformed.

7. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described low temperature washing device for methanol is by desulfurizing tower and decarbonizing tower group Into operation temperature is -20~-60 DEG C, and 3~4.0MPa of operating pressure, the sulphur after being washed through low-temp methanol in gas is removed to Below 0.1ppm, CO₂It is removed to below 0.8Vol%.

8. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the carbon dioxide removed through low-temp methanol elution is divided into two Part, wherein the carbon dioxide for accounting for cumulative volume 2~8% goes synthesic gas compressor group, and remaining 92~98% carbon dioxide Crushed coal pressurized-gasification furnace is returned as gasifying agent.

9. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that it is described washed through low-temp methanol after synthesis gas to carry out methane deep The step of cold separation is：First by after extremely -85~-70 DEG C of gas cooling, ethane, propane, a small amount of dioxy are isolated in 3~4.0MPa Change carbon and sulfide is sent to boiler combustion；Then gas phase is cooled further to -150~-175 DEG C, is isolated in 3.0~4.0MPa The LNG product of methane volumetric content >=97%.

10. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the synthesis gas after the cryogenic separator through methane is divided into two Part, wherein account for the Part I of synthesis gas volume 20~30% carries hydrogen into pressure swing adsorber, and remaining 70~80% Part II gas through side line and is mixed into synthesic gas compressor group with the stripping gas of pressure swing adsorber.

11. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the adsorptive pressure of described pressure-variable adsorption is 3.0~4.0Mpa, Operation temperature is 30~40 DEG C, hydrogen volume ratio >=99.9% extracted through pressure-variable adsorption.

12. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the circulation from methanol separator and gas-liquid separator Gas sum is 3~5 with stripping gas and the volume ratio for the carbon dioxide sum washed from low-temp methanol from pressure-variable adsorption.

13. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described methyl alcohol synthetic reactor uses shell-and-tube isothermal reactor, Its reaction pressure is 5.7~6.5MPa, and reaction temperature is 240~260 DEG C, and gas space velocity is 15500~20000L/Kgh.

14. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the catalyst of described methanol-fueled CLC is Research Institute of Nanjing Chemical Industry Group C306, C307 catalyst of exploitation, the RK-5 catalyst of Dalian Reak Science and Technology Co., Ltd.'s production or southwestern chemical design institute are opened Any one in the C302 catalyst of hair.

15. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the gaseous products of described methyl alcohol synthetic reactor outlet are divided into two Stock, first burst of gaseous products accounts for the 55~70% of reactor outlet gas cumulative volume, and remaining 30~45% are used as second strand of gas Phase product.

16. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the production of Piao Laite companies is loaded in described methanol purification device CT151 type acid-exchange resins, and the basic nitrogen compound content in crude carbinol is controlled in below 20ppm.

17. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that it is one-step technology that described methanol, which converts gasoline processed, it is closed Into oil reactor use heat-insulating fixed bed reactors, inlet gas temperature be 300~350 DEG C, reaction pressure be 1.5~ 2.5MPa, methanol quality air speed is 0.8~1.3h^-1。

18. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described methanol converts the catalyst of gasoline processed using Chinese section The JX6201 types catalyst of institute's Shanxi coal chemistry institute exploitation or the GSK-10 type catalyst of rope company of Top exploitation.

19. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the gas phase gone out through gas-liquid separator separates is divided into two Point, wherein the gas for accounting for cumulative volume 4~8% enters membrane separator, and remaining 92~96% gas phase is back to synthesis air pressure Contracting unit.

20. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the former Monsanto Chemicals' life of use of described membrane separator The prins of productionMembrane device or the membrane separator of U.S. law liquid air company exploitation, 2.5~8.0MPa of separating pressure, separation 40~90 DEG C of temperature, the hydrogen volume yield after UF membrane is 90~92%, and hydrogen product volumetric concentration is 91~95%.

21. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that tar that described coal gas separator is isolated, middle oil and Enter prefractionator after part outsourcing tar is purified, isolate 360~460 DEG C of distillate as hydrogenating materials, and it is remaining Pitch enter delay coking stove in.

22. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the reaction temperature of described delay coking stove is 490~570 DEG C, reaction pressure is 0.1~0.5MPa.

23. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the protection reaction condition of the protection reactor is：Temperature 360 ~430 DEG C, 11~15MPa of reaction pressure, hydrogen and oily volume ratio are 500:1~2000:1, the volume space velocity of liquid is 0.1 ~2h^-1。

24. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that the guard catalyst loaded in described protection reactor is victory Help JEHT-11, JEHT-12 and JEHT-13 type protective agent or Sinopec Fushun oil of Chemical Engineering Technology Co., Ltd exploitation FZC-10, FZC10Q and FZC-100 catalyst series of work research institute exploitation.

25. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described hydrofining reaction condition is：Temperature 300~430 DEG C, pressure is 10~17Pa, and hydrogen to oil volume ratio is 1000:1~3000:1, liquid volume air speed is 0.1~1.5h^-1。

26. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described Hydrobon catalyst is limited for victory side Chemical Engineering Technology The JEHT-41 type hydrogenation catalysts of company's production, the NUHC-40A/B/C/D systems of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation Row hydrogenation catalyst, FH-5A types, FH-98 types hydrogenation catalyst or the standard of the exploitation of Sinopec Fushun Petrochemical Research Institute The DH3551 type Hydrobon catalysts of catalyst Co. production.

27. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described hydrocracking reaction condition is：Temperature 360~470 DEG C, pressure is 10~17Pa, and hydrogen and oil volume ratio are 800:1~2000:1, liquid volume air speed is 0.1~2h^-1。

28. a kind of crushed coal pressure gasifying synthesis gas through methanol synthetic gasoline as claimed in claim 1, co-production of liquefied natural gas and Comprehensive utilization process for tar deep processing, it is characterised in that described hydrocracking catalyst is that energy science and technology is newly helped in Shanghai The serial hydrocracking catalysts of NUHC-41A/B/C/D of Co., Ltd's exploitation or the Z3723 types of standard catalyst company production add Hydrogen Cracking catalyst.