CN105154126B

CN105154126B - Coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar method

Info

Publication number: CN105154126B
Application number: CN201510466235.4A
Authority: CN
Inventors: 范辉; 马英民; 崔晓曦; 王军亭; 王贵; 马国强; 张庆庚; 李晓; 时建敏; 王文婷
Original assignee: Sedin Engineering Co Ltd
Current assignee: Sedin Engineering Co Ltd
Priority date: 2015-07-31
Filing date: 2015-07-31
Publication date: 2017-05-31
Anticipated expiration: 2035-07-31
Also published as: CN105154126A

Abstract

A kind of coke-stove gas is that feed coal is converted into coke, tar and coke-stove gas through coke oven through the method for methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar, methanol-fueled CLC is carried out after coke-stove gas is purified, crude carbinol carries out the reaction that methyl alcohol converts gasoline processed, LPG and gasoline products are isolated to, hydrogenation of tar is refining to obtain LPG, diesel oil and heavy oil product.The present invention has the advantages that utilization rate high, process is simple, product structure are reasonable and environmental pollution is small.

Description

Coke-stove gas is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method

Technical field

The invention belongs to coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar method.

Technical background

China has rich coal, an energy resource structure of oil-poor and few gas, wherein oil and natural gas resource critical shortage, is 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.

Since the eighties in 20th century, China's economy is developed rapidly, and the coking industry of China achieves rapidly hair Exhibition, the technique and technical merit of coking are also improved constantly.But due to the unchecked construction of coke-oven plant of China, Coke Industry production capacity is serious Surplus, while being influenceed by steel industry, most of coal chemical enterprise faces the situation of loss.China's coke is produced within 2013 Amount is up to 4.8 hundred million tons, if distinguishing by-product 400m by 1 ton of coke of production³Coke-stove gas and 40 kilograms of tar calculate, only this year pair The coke-stove gas of product is just up to 192,000,000,000 m³, the tar of by-product is up to 19,200,000 tons, if the heat produced plus the dry distillation of coal and pyrolysis Vent one's spleen and tar, its yield will be bigger.If the so huge resource of quantity cannot get effective and clean utilization, it will cause The serious wasting of resources and environmental pollution.In recent years, as country is about encouragement comprehensive utilization of resources and the policy of environmental protection Regulation is promulgated, while the present situation of loss is faced in view of existing coking industry, the resource comprehensive such as coke-stove gas and coal tar profit With the exploitation of technology, as each enterprise and research unit's focus of attention.

The more ripe utilization technology of existing coke-stove gas includes coke-stove gas preparing natural gas and coke-stove gas methyl alcohol, but It should be noted that hydrogen-carbon ratio is general more than 6 in coke-stove gas, far above methanation and the theoretical hydrogen-carbon ratio of methanol-fueled CLC, lead Remaining substantial amounts of hydrogen is vented or returns coke-stove gas burning in the way of gas after causing reaction, in turn results in environmental pollution and money Source wastes.Simultaneously as coke-stove gas is using the diversification of technology, the actual cost price of coke-stove gas reaches 0.5 yuan/Nm³, The production capacity surplus of methyl alcohol so that the absolute profit of coke-stove gas methanol project is substantially reduced.And existing tar utilizes technology Tar production technology and the catalystic hydrogenation of coal tar technology of newer type that predominantly conventional physical is separate, the former is primarily to carry One-component or narrow component are taken, with long flow path, the big, problem that economic benefit is low and secondary pollution is serious is invested；And tar is urged Change hydrogen addition technology by hydrofinishing and be hydrocracked two steps, the fuel oil products of high-quality can be generated.At present, hydrogenation of tar institute The hydrogen for using typically is obtained by pressure-variable adsorption, but contains substantial amounts of CO and CH in its absorption tail gas₄It is straight Deng available gas Pick toward coke oven combustion, the serious wasting of resources for causing.It can be seen that, there is hydrogen excess using technology in single coke-stove gas, And individually there is CO and CH in pressure-variable adsorption tail gas in hydrogenation of tar₄The waste problem of resource, can not still realize coking by-productses All of.

It is comprehensive described, it is contemplated that domestic existing Energy Situation, coke-oven plant's deficiency in economic performance, methyl alcohol production capacity surplus and individually Coke-stove gas and the defect that exists using technology of tar, according to the yield and feature of coke chemicals, develop a kind of utilization rate it is high, The coking coke oven coal gas comprehensive utilization process that process is simple, product structure are reasonable and environmental pollution is small has great importance.

The content of the invention

It is an object of the invention to provide a kind of utilization rate is high, process is simple, Jiao that product structure is reasonable and environmental pollution is small Producer gas through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar method.

Be up to above-mentioned purpose, inventor according to the characteristics of oven gas and coal tar, and by substantial amounts of pilot plant test study, Technical Analysis, processing simulation and working experience for many years propose a kind of coke-stove gas through methanol synthesized gasoline product, then will Gas carries out cryogenic separation and LNG is obtained, and residual gas through pressure-variable adsorption through being further obtained volume fraction more than 99.9% Hydrogen, and prepare the oil products such as gasoline and diesel oil for hydrogenation of tar.The technique is integrated by overall technology and material is matched, not only Greatly increase the utilization ratio and economic benefit of coke-stove gas and coal tar, and and all domestic LNG in short supply of its major product And oil product, the imbalance between supply and demand of the energy of the country is further alleviated, with important theory and realistic meaning.

A kind of coke-stove gas disclosed by the invention through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar side Method, its concrete technology is：

(1) feed coal is converted into coke, tar and coke-stove gas through coke oven, divides with from methyl alcohol after coke-stove gas is purified Circulating air from device is mixed into synthesic gas compressor group, after supercharging from top into methyl alcohol synthetic reactor in carry out methyl alcohol conjunction Into gaseous products are divided into two strands from after the discharge of methanol-fueled CLC tower bottom, wherein first burst of gaseous products is through methanol product condenser After condensation, into methanol separator, gas phase is sent to synthesic gas compressor group from after the discharge of methanol separator top, and by first The crude carbinol liquid phase of the compositions such as alcohol, fusel, water and lower carbon number hydrocarbons enters to enter in methanol purification device after being discharged from methanol separator bottom Row purification, it is purified after crude carbinol liquid phase by methanol gasifying device gasify after with methanol-fueled CLC tower bottom discharge second strand walk After the gaseous products mixing of side line, enter in synthesis oil reactor from top.

(2) gas phase crude carbinol carries out the reaction that methyl alcohol converts gasoline processed in oil reactor is synthesized, and its product is produced through gasoline Enter in gas-liquid separator after the condensation of product condenser, the gas phase isolated enters methane deep cooling from after the discharge of gas-liquid separator top Separator, and enter after the oil product isolated is discharged from gas-liquid separator bottom in oil product separator, it is isolated to liquefaction stone Oil gas (LPG) and gasoline products, the fuel gas isolated are back to coke oven combustion, and the C for isolating₁₀~C₁₂Heavy oil component Being mixed into cracker with the heavy constituent from refined products separator carries out cracking reaction；

(3) liquid phase methane (LNG) and C are isolated through methane cryogenic separator₂-C₄Lower carbon number hydrocarbons component, wherein liquid phase methane (LNG) sold as end product, and C₂-C₄Lower carbon number hydrocarbons be sent in gas-liquid separator, isolated in methane cryogenic separator Gas is sent to pressure-variable adsorption dehydrogenation, after the stripping gas of pressure-variable adsorption mixes with the dry gas of the fuel gas of gas-liquid separator and stabilizer Coke oven combustion is returned, and the hydrogen that the volume fraction for obtaining is 99.9% is separated with from 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 hydrogenation reactor from middle part, and it is anti-that Part IV hydrogen enters cracking from middle part In answering device；

(4) cut into prefractionator after the tar from coking system is purified with outsourcing tar, its pitch is certainly Enter in delayed coking after the discharge of prefractionator bottom of towe, the pitch coke that delayed coking is obtained is as production marketing, and the liquid for obtaining Light component, the tail oil from refined products separator and the hydrogen that phase is then cut with prefractionator are mixed into protection reactor In, entering in hydrofining reactor after the discharge of product autofining product separator bottom, hydrogenation products are from hydrofining reaction It is sent in refined products separator after the discharge of device bottom, the light component isolated enters in stabilizer, and the hydrogen isolated then does For circulating hydrogen is used, and isolate heavy constituent a part as tail oil return protection reactor in, and another part with come From the C of oil product separator₁₀~C₁₂Heavy oil component be mixed into cracker and carry out cracking reaction, its product is cracking anti- Device bottom is answered to enter crackate separator, isolated hydrogen and cracking oil product after discharging, cracking oil product is produced with autofining is carried out The light component of thing separator is mixed into stabilizer, and dry gas self-stabilization top of tower is back to coke oven combustion after excluding, and oil product Enter in tar production product separator after the discharge of self-stabilization tower bottom, the light aromatics being isolated to divides with oil product separator From gasoline mixing sold as final gasoline products, and LPG hybrid pins that the LPG for obtaining also with oil product separator separate Sell, while separable obtain diesel oil and heavy oil product.

The volume composition of coke-stove gas is H after purified and desulfurization as described above₂50~60%, CO 5%~8%, CO₂1.5~4%, CH₄23%~27%, N₂3~7%, C₂Above unsaturated hydrocarbons 2~4%.

In the as described above gas for entering synthesic gas compressor group, circulating air from methanol separator with come from coking The fresh coke-stove gas volume ratio of system is 3.0~5.0.

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 of Research Institute of Nanjing Chemical Industry Group exploitation, 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 75~90% of gas cumulative volume, and remaining 10~25% second burst of gaseous products.

The CT151 type acid-exchange resins of Piao Laite companies production are loaded 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 methyl alcohol as described above converts gasoline processed, and its synthesis oil reactor is anti-using heat-insulating fixed bed 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 methyl alcohol 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.

It is as described above to be the step of carry out methane cryogenic separation from the gas isolated of gas-liquid separator：First by gas After being cooled to -85~-70 DEG C, C is isolated in 3~4.0MPa₂-C₄Hydro carbons；Then gas phase is cooled further to -150~-175 DEG C, the LNG product of methane content >=97% is isolated in 3.0~4.0MPa, the gas isolated is sent to the dehydrogenation of pressure-variable adsorption 10.

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.

It is as described above it is purified after tar enter prefractionator, isolate 360~460 DEG C of distillate as hydrogenation Raw material, and remaining pitch enters in delay coking stove.

The condition of delayed coking is as described above：Reaction temperature is 490-570 DEG C, and reaction pressure is 0.1- 0.5MPa。

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

The guard catalyst loaded in protection reactor as described above is the exploitation of 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 It is 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 of Sheng Bang Chemical Engineering Technologies Co., Ltd production Agent, the NUHC-40A/B/C/D series hydrogenation catalysts of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation, Sinopec Fushun stone FH-5A types, FH-98 types, FH-DS types hydrogenation catalyst or the production of standard catalyst company that oily chemical research institute develops DH3551 type Hydrobon catalysts.

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/ of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation D series hydrocracking catalysts or the Z3723 type hydrocracking catalysts of standard catalyst company production.

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

(1) coke chemicals comprehensive utilization process disclosed by the invention, coke-stove gas is added through methanol synthesized gasoline with tar Hydrogen is combined, overcome coke-stove gas and tar production individually with when the problem of resource waste that exists, make the profit of coking yield Greatly improved with rate.

(2) coke chemicals comprehensive utilization process disclosed by the invention, is not only Jiao by coke-stove gas through methanol synthesized gasoline Producer gas there is provided a technical strategies, only will be routed directly to synthesize oil reactor by the crude carbinol of gas-liquid separation, Methanol rectification unit is reduced, its equipment investment reduces more than 10%, and operating cost reduces nearly 5%, its annual return is carried High nearly 20%.

(3) coke chemicals comprehensive utilization process disclosed by the invention, its product is mainly liquefied natural gas (LNG), liquefaction Oil gas (LPG), gasoline, diesel oil, mink cell focus and pitch coke, the addition of MTG can form complementation with hydrogenation of tar, further increase The yield of gasoline products is added.

(4) heavy constituents such as coke chemicals comprehensive utilization process disclosed by the invention, the pitch of prefractionator pass through delay coke The cracking and condensation reaction of change system, increase the yield of light component oil, improve the value of low value-added pitch.

Brief description of the drawings

Fig. 1 is a kind of coke-stove gas disclosed by the invention through methanol-fueled CLC oil, coproduction natural gas and for tar deep processing Comprehensive utilization process flow chart.

As shown in Figure 1,1 is coke oven, and 2 is synthesic gas compressor group, and 3 is methyl alcohol synthetic reactor, and 4 is methanol separator, and 5 is first Alcohol clarifier, 6 is synthesis oil reactor, and 7 is gas-liquid separator, and 8 is oil product separator, and 9 is methane cryogenic separator, and 10 is to become Pressure absorption, 11 is prefractionator, and 12 is delayed coking, and 13 is protection reactor, and 14 is hydrofining reactor, and 15 is refined product Thing separator, 16 is cracker, and 17 is crackate separator, and 18 is stabilizer, and 19 is tar production product separator, 20 is methanol product condenser, and 21 is crude carbinol gasifier, and 22 is gasoline products condenser.

Subordinate list explanation

Table 1 is the tar property that is mixed to form by outsourcing tar and self-produced tar for raw tar.

Table 2 is the gasoline property that coke-stove gas is prepared through methyl alcohol.

Table 3 is the delayed coking of tar, hydrofinishing and product form and yield after being hydrocracked.

Specific embodiment

Specific embodiment of the 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) feed coal is converted into coke, tar and coke-stove gas through coke oven 1, is H by purified rear composition₂60%th, CO 5.3%th, CO₂2.7%th, CH₄25.4%th, N₂4.6% and C_nH_m2.0% coke-stove gas and following from methanol separator 4 Ring gas is mixed into synthesic gas compressor group 2, and the circulating air and fresh coke-stove gas volume ratio for controlling methanol separator 4 are 3.0, enter the methyl alcohol synthetic reactor 3 of the C306 catalyst developed equipped with Research Institute of Nanjing Chemical Industry Group from top through the synthesis gas after supercharging In, and be that 5.7MPa, reaction temperature are to enter under conditions of 240 DEG C and gas space velocity are 15500L/ (Kgh) in its reaction pressure Row methanol-fueled CLC, gaseous products are divided into two strands from after synthesizing tower bottom discharge, wherein accounting for the of total volume fraction 75% of working off one's feeling vent one's spleen After one gaseous products is condensed through methanol product condenser, into methanol separator 4, gas phase is sent from after the discharge of separator top Toward synthesic gas compressor group 2, and the crude carbinol liquid phase being made up of methyl alcohol, fusel, water and lower carbon number hydrocarbons etc. is from the bottom of methanol separator 4 Enter to be filled with CT151 type acid-exchange resin methanol purifications device 5 after portion's discharge and purified, basic nitrogen is removed to Below 20ppm, it is purified after crude carbinol liquid phase by methanol gasifying device 21 gasify after with methanol-fueled CLC tower bottom discharge account for out Implication total volume fraction 25% walk side line second burst of gaseous products be mixed and heated to 300 DEG C after, from top enter be equipped with In GSK-10 types catalyst synthesis oil reactor 6.

(2) gas phase crude carbinol is 1.5MPa in reaction pressure and methanol quality air speed is 1.3h^-1Under conditions of carry out methyl alcohol Conversion gasoline reaction processed, enters in gas-liquid separator 7 after its product is condensed, and the gas phase isolated enters first after being discharged from top In alkane cryogenic separation system 9, and enter after the oil product isolated is discharged from the bottom of gas-liquid separator 7 in oil product separator 8, through oil Product obtain liquefied petroleum gas (LPG) and gasoline products after separating, and the fuel gas isolated is back to coke oven 1 and burns, and isolates C₁₀~C₁₂Heavy constituent and the heavy constituent from refined products piece-rate system 15 be mixed into cracker 16 in carry out cracking Reaction.

(3) gas phase that gas-liquid separator 7 is isolated enters from after the discharge of top carries out deep cooling point in methane cryogenic separator 9 From after coke-stove gas first is cooled into -70 DEG C, C being isolated in 4.0MPa₂-C₄Lower carbon number hydrocarbons be sent to gas-liquid separator 7, Ran Houqi - 150 DEG C are mutually cooled further to, the LNG for isolating methane content >=97% in 4.0MPa sells as end product, methane depth The gas that cold separator 9 is isolated is sent to the dehydrogenation of pressure-variable adsorption 10, and in adsorptive pressure be 4.0Mpa and operation temperature is 40 DEG C Under the conditions of carry out pressure-variable adsorption, fuel gas and the top of stabilizer 18 that Utilization of PSA Relief Gas is isolated with oil product piece-rate system 8 Coke oven 1 is returned to after the dry gas mixing of discharge to burn, and the hydrogen that the volume fraction for obtaining is 99.9% divides with from refined products It is divided into two parts after the circulating hydrogen mixing of system 15 and crackate piece-rate system 16, Part I mixes with imported raw material Enter in protection reactor 13 and cracker 16 from top afterwards, and another part enters hydrogenation instead as cold shock gas from middle part Answer participation reaction in device 14 and cracker 16.

(4) cut into prefractionator 11 after the tar from coking system is purified with outsourcing tar, its pitch Enter from after bottom of towe discharge in delayed coking 12 Deng mixture, it is the bar of 0.5MPa with reaction pressure to be 570 DEG C in reaction temperature Delayed coking is carried out under part, the pitch coke for obtaining is as production marketing, and 360 that the liquid phase for obtaining then cuts out with prefractionator Light component below DEG C, the tail oil from refined products piece-rate system 15 and hydrogen are mixed into and be filled with from top to bottom victory side chemical industry In the protectant protection reactor 13 of JEHT-11, JEHT-12 and JEHT-13 type of Technology Co., Ltd.'s exploitation, in temperature 350 DEG C, reaction pressure 15MPa, hydrogen with oil volume ratio be 500:1 and liquid volume space velocity be 0.1h^-1Under conditions of protected Shield reaction, product enters the JEHT-41 type hydrogenation catalysts equipped with the production of Sheng Bang Chemical Engineering Technologies Co., Ltd after being discharged from bottom Hydrofining reactor 14 in, 300 DEG C of temperature, pressure be 17Pa, hydrogen to oil volume ratio be 1000:1 and liquid volume air speed It is 0.1h^-1Under conditions of carry out hydrogenation reaction, hydrogenation products are sent in refined products piece-rate system 15 after being discharged from bottom, wherein The light component isolated is mixed into stabilizer 18 with crackate, and the vapor phase hydrogen isolated is returned as circulating air and reacted Device, and isolate heavy constituent a part as tail oil return protection reactor 13, and another part with come from oil product separator 8 C₁₀~C₁₂Heavy oil component be mixed into the Z3723 type hydrocracking catalysts equipped with the production of standard catalyst company and split In change reactor, and it is that 17Pa, hydrogen and oil volume ratio are 800 in 360 DEG C of temperature, pressure:1 and liquid volume air speed be 0.1h^-1Cracking reaction is carried out, crackate piece-rate system 17, the hydrogen isolated are entered after the discharge of its product autoreactor bottom With the hydrogen mixing Returning reactor from refined products piece-rate system 15, and the cracking oil product isolated with come from refined products The light component of piece-rate system 15 is mixed into stabilizer 18, and dry gas stabilizer top is back to coke oven combustion after excluding, and oily Enter in tar production product separation system 19 after the discharge of product self-stabilization tower bottom, the light aromatics being isolated to divides with oil product The gasoline mixing for from device 8 separate is sold as final gasoline products, and the LPG that the LPG for obtaining also with oil product separator 8 separate Mixed selling, while separable obtain diesel oil and heavy oil product.

The raw tar property used in the present embodiment for details see attached table 1, the gasoline property that it is synthesized by MTG for details see attached table 2, The gasoline products property of hydrogenation of tar for details see attached table 3.

Embodiment 2

Coke-stove gas after the present embodiment purification constitutes and is：H₂59.6%th, CO 5.0%, CO₂1.5%th, CH₄27%th, N₂3.0% and C_nH_m3.9%；The circulating air and fresh coke-stove gas volume ratio for controlling methanol separator 4 are 3.5；Using southization The C307 catalyst of research institute of group exploitation, and be that 5.9MPa, reaction temperature are that 245 DEG C and gas space velocity are in reaction pressure Nearly row methanol-fueled CLC under conditions of 17000L/ (Kgh)；Methanol reactor outlet gas in it is condensed, separate and gasification First burst of gaseous products of the total volume 78%, and remaining 22% gas phase then walks side line；MTG reactor inlet temperatures are 310 DEG C, with GSK-10 type catalyst, in reaction pressure be 1.7MPa and methanol quality air speed is 1.2h^-1Under conditions of synthesize anti- Should；The step of methane cryogenic separation, is first by gas cooling to after -74 DEG C, C to be isolated in 3.8MPa₂-C₄Lower carbon number hydrocarbons be sent to gas Liquid/gas separator 7, then gas phase be cooled further to -155 DEG C, isolate the LNG of methane content >=97% as end in 3.8MPa End production marketing；The gas discharged in methane cryogenic separator 6 is sent to pressure-variable adsorption dehydrogenation, is 3.8Mpa and behaviour in adsorptive pressure Make temperature to carry out pressure-variable adsorption under conditions of 37 DEG C；Prefractionator carries out cutting temperature for 380 DEG C；Pitch of prefractionator etc. Component carries out delayed coking under conditions of 510 DEG C and 0.2MPa；With Sheng Bang Chemical Engineering Technologies Co., Ltd develop JEHT-11, JEHT-12 and JEHT-13 types protective agent is catalyst, and in 370 DEG C of temperature, reaction pressure 14MPa, hydrogen and oily volume ratio It is 1000:1 and liquid volume space velocity be 0.5h^-1Under conditions of carry out protection reaction；The limited public affairs of energy science and technology are newly helped in Shanghai Take charge of production NUHC-40 type hydrogenation catalysts, and 320 DEG C of temperature, pressure be 15Pa, hydrogen to oil volume ratio be 1500:1 and liquid Volume space velocity is 0.5h^-1Under conditions of carry out hydrofining reaction；It is hydrocracked in the Z3723 types of standard catalyst company production Catalyst, and be that 15Pa, hydrogen and oil volume ratio are 1200 in 390 DEG C of temperature, pressure:1 and liquid volume air speed be 0.5h^-1Enter Row cracking reaction.Remaining step is same as Example 1.

Embodiment 3

Coke-stove gas after the present embodiment purification constitutes and is：H₂57.8%th, CO 5.7%, CO₂3.8%th, CH₄23%th, N₂5.8% and C_nH_m3.9%；The circulating air and fresh coke-stove gas volume ratio for controlling methanol separator 4 are 4.0；Using southization The C307 catalyst of research institute of group exploitation, and be that 6.1MPa, reaction temperature are that 250 DEG C and gas space velocity are in reaction pressure Nearly row methanol-fueled CLC under conditions of 18000L/ (Kgh)；Methanol reactor outlet gas in it is condensed, separate and gasification First burst of gaseous products of the total volume 81%, and remaining 19% gas phase then walks side line；MTG reactor inlet temperatures are 330 DEG C, with GSK-10 type catalyst, in reaction pressure be 2.0MPa and methanol quality air speed is 1.1h^-1Under conditions of synthesize anti- Should；The step of methane cryogenic separation, is first by gas cooling to after -79 DEG C, C to be isolated in 3.6MPa₂-C₄Lower carbon number hydrocarbons be sent to gas Liquid/gas separator 7, then gas phase be cooled further to -160 DEG C, isolate the LNG of methane content >=97% as end in 3.6MPa End production marketing；The gas discharged in methane cryogenic separator 6 is sent to pressure-variable adsorption dehydrogenation system, is 3.6Mpa in adsorptive pressure With operation temperature be 35 DEG C under conditions of carry out pressure-variable adsorption；Prefractionator carries out cutting temperature for 400 DEG C；The drip of prefractionator The components such as green grass or young crops carry out delayed coking under conditions of 530 DEG C and 0.3MPa；With the FZC- that Sheng Bang Chemical Engineering Technologies Co., Ltd develops The agent of 10 and FZC-100 type hybrid protections is catalyst, and in 390 DEG C of temperature, reaction pressure 13MPa, hydrogen and oily volume ratio It is 1500:1 and liquid volume space velocity be 1.0h^-1Under conditions of carry out protection reaction；In Sinopec Fushun, petrochemical industry is ground Study carefully institute exploitation FH-5A type mixed hydrogenation catalyst, and 370 DEG C of temperature, pressure be 13Pa, hydrogen to oil volume ratio be 2000:1 He Liquid volume air speed is 1.0h^-1Under conditions of carry out hydrofining reaction；In the Z3723 types hydrogenation of standard catalyst company production Cracking catalyst, and be that 13Pa, hydrogen and oil volume ratio are 1500 in 410 DEG C of temperature, pressure:1 and liquid volume air speed be 1.0h^-1Carry out cracking reaction.Remaining step is same as Example 1.

The tar property used in the present embodiment for details see attached table 1, the gasoline property that it is synthesized by MTG for details see attached table 2, tar The gasoline products property of hydrogenation for details see attached table 3.

Embodiment 4

Coke-stove gas after the present embodiment purification constitutes and is：H₂54.7%th, CO 6.9%, CO₂3.5%th, CH₄ 25.6%th, N₂6.1% and C_nH_m3.2%；The circulating air and fresh coke-stove gas volume ratio for controlling methanol separator 4 are 4.5； Using Dalian Reak Science and Technology Co., Ltd. develop RK-5 catalyst, and reaction pressure be 6.3MPa, reaction temperature be 255 DEG C It is nearly row methanol-fueled CLC under conditions of 19000L/ (Kgh) with gas space velocity；Condensed in the gas of methanol reactor outlet, The first burst of gaseous products of the total volume 86% for separating and gasifying, and remaining 14% gas phase then walks side line；MTG reactors enter Mouth temperature is 340 DEG C, and with JX6201 type catalyst, in reaction pressure be 2.3MPa and methanol quality air speed is 0.9h^-1Condition Under carry out synthetic reaction；The step of methane cryogenic separation, is first by gas cooling to after -82 DEG C, C to be isolated in 3.2MPa₂-C₄'s Lower carbon number hydrocarbons is sent to gas-liquid separator 7, and then gas phase is cooled further to -165 DEG C, and methane content >=97% is isolated in 3.2MPa LNG as end product sell；The gas discharged in methane cryogenic separator 6 is sent to pressure-variable adsorption dehydrogenation, in adsorptive pressure For 3.2Mpa and operation temperature are to carry out pressure-variable adsorption under conditions of 32 DEG C；Prefractionator carries out cutting temperature for 430 DEG C；Pre- point Evaporate the components such as the pitch of tower carries out delayed coking under conditions of 550 DEG C and 0.4MPa；Ground with Sinopec Fushun petrochemical industry FZC-10 the and FZC-100 type hybrid protections agent for studying carefully institute's exploitation is catalyst, and in 410 DEG C of temperature, reaction pressure 12MPa, hydrogen Gas is 2000 with the volume ratio of oil:1 and liquid volume space velocity be 1.5h^-1Under conditions of carry out protection reaction；In Sinopec The FH-DS type hydrogenation catalysts of Fushun Petrochemical Research Institute's exploitation, and be 12Pa, hydrogen to oil volume ratio in 400 DEG C of temperature, pressure It is 2500:1 and liquid volume air speed be 1.5h^-1Under conditions of carry out hydrofining reaction；It is limited energy science and technology newly to be helped in Shanghai The NUHC-41 type hydrocracking catalysts of company's production, and in 440 DEG C of temperature, pressure for 11MPa, hydrogen and oil volume ratio are 1800:1 and liquid volume air speed be 1.5h^-1Carry out cracking reaction.Remaining step is same as Example 1.

Embodiment 5

Coke-stove gas after the present embodiment purification constitutes and is：H₂50%th, CO 8%, CO₂4%th, CH₄27%th, N₂7% And C_nH_m4%；The circulating air and fresh coke-stove gas volume ratio for controlling methanol separator 4 are 5；Opened using southwestern chemical design institute The C302 catalyst of hair, and be that 6.5MPa, reaction temperature are that 260 DEG C and gas space velocity are 20000L/ (Kgh) in reaction pressure Under conditions of carry out methanol-fueled CLC；First burst of gaseous products that be condensed in the gas of methanol reactor outlet, separating and gasify Of the total volume 90%, and remaining 10% gas phase then walks side line；MTG reactor inlet temperatures are 350 DEG C, are urged with JX6201 types Agent, in reaction pressure be 2.5MPa and methanol quality air speed is 0.8h^-1Under conditions of carry out synthetic reaction；Methane cryogenic separation The step of first by gas cooling to after -85 DEG C, C to be isolated in 3.0MPa₂-C₄Lower carbon number hydrocarbons be sent to gas-liquid separator 7, then Gas phase is cooled further to -170 DEG C, and the LNG for isolating methane content >=97% in 3.0MPa sells as end product；Methane The gas discharged in cryogenic separator 6 is sent to pressure-variable adsorption dehydrogenation system, and in adsorptive pressure be 3.0Mpa and operation temperature is 30 Pressure-variable adsorption is carried out under conditions of DEG C；Prefractionator carries out cutting temperature for 460 DEG C；The components such as the pitch of prefractionator are 570 DEG C and 0.5MPa under conditions of carry out delayed coking；With FZC-10 and FZC- that Sinopec Fushun Petrochemical Research Institute develops 100 type hybrid protection agent are catalyst, and are 1500 in 430 DEG C of temperature, reaction pressure 11MPa, hydrogen and the volume ratio of oil:1 It is 2.0h with the volume space velocity of liquid^-1Under conditions of carry out protection reaction；Add in the DH3551 types of standard catalyst company production Hydrogen catalyst, and 430 DEG C of temperature, pressure be 10Pa, hydrogen to oil volume ratio be 3000:1 and liquid volume air speed be 1.5h^-1Bar Hydrofining reaction is carried out under part；In the NUHC-41 type hydrocracking catalysts of Shanghai Xinyou Energy Technology Co., Ltd.'s production, And in 470 DEG C of temperature, pressure for 10MPa, hydrogen and oil volume ratio are 2000:1 and liquid volume air speed be 1.5h^-1Carry out cracking Reaction.Remaining step is same as Example 1.

Table 1

Density (g/cm³)

1.180

Distillation (DEG C)
		IBP	126
10m%	181
		20m%	250
30m%	279
		40m%	305
50m%	351
		60m%	380
70m%	410
		80m%	459
90m%	534
		95m%	556
FBP (99m%)	630
		Condensation point/DEG C	5
S/%	0.54
		N/%	0.82
C/%	89.45
		H/%	5.31
Carbon residue/%	22.20

Table 2

Table 3

Claims

1. a kind of coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar method, it is characterised in that bag Include following steps：

(1) feed coal is converted into coke, tar and coke-stove gas through coke oven, after coke-stove gas is purified and from methanol separator Circulating air be mixed into synthesic gas compressor group, after supercharging from top into methyl alcohol synthetic reactor in carry out methanol-fueled CLC, Gaseous products are divided into two strands from after the discharge of methanol-fueled CLC tower bottom, wherein first burst of gaseous products is condensed through methanol product condenser Afterwards, into methanol separator, gas phase is sent to synthesic gas compressor group from after the discharge of methanol separator top, and by methyl alcohol, miscellaneous Alcohol, water and lower carbon number hydrocarbons composition crude carbinol liquid phase from methanol separator bottom discharge after enter methanol purification device in purified, Crude carbinol liquid phase after purified walks side line by second strand after the gasification of methanol gasifying device with the discharge of methanol-fueled CLC tower bottom After gaseous products mixing, enter in synthesis oil reactor from top；

(2) gas phase crude carbinol carries out the reaction that methyl alcohol converts gasoline processed in oil reactor is synthesized, and its product is cold through gasoline products Enter in gas-liquid separator after condenser condensation, the gas phase isolated enters methane cryogenic separation from after the discharge of gas-liquid separator top Device, and enter after the oil product isolated is discharged from gas-liquid separator bottom in oil product separator, it is isolated to LPG and gasoline is produced Product, the fuel gas isolated is back to coke oven combustion, and the C for isolating₁₀~C₁₂Heavy oil component separated with from refined products The heavy constituent of device carries out cracking reaction in being mixed into cracker；

(3) liquid phase methane and C are isolated through methane cryogenic separator₂-C₄Lower carbon number hydrocarbons component, wherein liquid phase methane is used as terminal Production marketing, and C₂-C₄Lower carbon number hydrocarbons be sent in gas-liquid separator, the gas isolated in methane cryogenic separator is sent to transformation Absorption dehydrogenation, the stripping gas of pressure-variable adsorption returns to coke oven combustion after mixing with the dry gas of the fuel gas of gas-liquid separator and stabilizer Burn, and the volume fraction for obtaining is 99.9% hydrogen and the recycle hydrogen from refined products separator and crackate separator It is divided into four parts after gas mixing, Part I hydrogen enters protection reactor from top, and it is anti-that Part II hydrogen enters cracking from top Answer in device, Part III hydrogen enters in hydrogenation reactor from middle part, Part IV hydrogen enters in cracker from middle part；

(4) cut into prefractionator after the tar from coking system is purified with outsourcing tar, its pitch is from pre- point Enter in delayed coking after evaporating the discharge of tower bottom of towe, the pitch coke that delayed coking is obtained is as production marketing, and the liquid phase for obtaining is then Light component, the tail oil from refined products separator and the hydrogen cut with prefractionator are mixed into protection reactor, are produced Enter in hydrofining reactor after the discharge of thing autofining product separator bottom, hydrogenation products are from hydrofining reactor bottom It is sent to after discharge in refined products separator, the light component isolated enters in stabilizer, and the hydrogen isolated is then as circulation Hydrogen is used, and isolate heavy constituent a part as tail oil return protection reactor in, and another part with come from oil product The C of separator₁₀~C₁₂Heavy oil component be mixed into cracker and carry out cracking reaction, the cracking reactor bottom of its product Enter crackate separator, isolated hydrogen and cracking oil product after portion's discharge, cracking oil product is separated with from refined products The light component of device is mixed into stabilizer, and dry gas self-stabilization top of tower is back to coke oven combustion after excluding, and oil product self-stabilization Enter in tar production product separator after tower bottom discharge, the vapour that the light aromatics being isolated to oil product separator separate Oil mixing is sold as final gasoline products, and the LPG mixed sellings that the LPG for obtaining also with oil product separator separate, while It is separable to obtain diesel oil and heavy oil product.

2. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the volume composition of coke-stove gas is H after described purified and desulfurization₂50~60%, CO 5%~ 8%th, CO₂1.5~4%, CH₄23%~27%, N₂3~7%, C₂Above unsaturated hydrocarbons 2~4%.

3. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that in the gas of described entrance synthesic gas compressor group, circulating air from methanol separator with come from The fresh coke-stove gas volume ratio of coking system is 3.0~5.0.

4. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described methyl alcohol synthetic reactor uses shell-and-tube isothermal reactor, its reaction pressure is 5.7~6.5MPa, Reaction temperature is 240~260 DEG C, and gas space velocity is 15500~20000L/Kgh.

5. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the catalyst of described methanol-fueled CLC is C306, C307 catalyst of Research Institute of Nanjing Chemical Industry Group exploitation, or One kind in the C302 catalyst of southwestern chemical design institute's exploitation.

6. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the gaseous products of described methyl alcohol synthetic reactor outlet are divided into two strands, and first burst of gaseous products accounts for reactor Work off one's feeling vent one's spleen the 75~90% of cumulative volume, and remaining 10~25% second burst of gaseous products.

7. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the CT151 type acid-exchange resins of Piao Laite companies production are loaded in described methanol purification device, It is simultaneously controlled in below 20ppm the basic nitrogen compound content in crude carbinol.

8. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that it is one-step technology that described methyl alcohol converts gasoline processed, its synthesis oil reactor is fixed using heat-insulating Bed reactor, inlet gas temperature be 300~350 DEG C, reaction pressure be 1.5~2.5MPa, methanol quality air speed be 0.8~ 1.3h^-1。

9. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described methyl alcohol converts the catalyst of gasoline processed using the GSK-10 types catalysis of rope company of Top exploitation Agent.

10. a kind of coke-stove gas as claimed in claim 1 is through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described is the step of carrying out methane cryogenic separation from the gas isolated of gas-liquid separator：First will After extremely -85~-70 DEG C of gas cooling, C is isolated in 3~4.0MPa₂-C₄Hydro carbons；Then gas phase be cooled further to -150~- 175 DEG C, the LNG product of methane content >=97% is isolated in 3.0~4.0MPa, the gas isolated is sent to pressure-variable adsorption 10 and takes off Hydrogen.

A kind of 11. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the adsorptive pressure of described pressure-variable adsorption is 3.0~4.0MPa, and operation temperature is 30~40 DEG C, through becoming Press hydrogen volume ratio >=99.9% of adsorbing and extracting.

A kind of 12. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that it is described it is purified after tar enter prefractionator, isolate 360~460 DEG C of distillate conduct Hydrogenating materials, and remaining pitch enters in delay coking stove.

A kind of 13. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the condition of described delayed coking is：Reaction temperature is 490-570 DEG C, and reaction pressure is 0.1- 0.5MPa。

A kind of 14. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that protection reaction condition is in described protection reactor：360~430 DEG C of temperature, reaction pressure 11~ The volume ratio of 15MPa, hydrogen and oil is 500:1~2000:1, the volume space velocity of liquid is 0.1~2h^-1。

A kind of 15. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that the guard catalyst loaded in described protection reactor is Sinopec Fushun Petrochemical Research Institute FZC-10, FZC10Q and FZC-100 catalyst series of exploitation.

A kind of 16. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described hydrofining reaction condition is：300~430 DEG C of temperature, pressure is 10~17Pa, hydrogen oil body Product is than being 1000:1~3000:1, liquid volume air speed is 0.1~1.5h^-1。

A kind of 17. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described Hydrobon catalyst is the JEHT-41 types hydrogenation of Sheng Bang Chemical Engineering Technologies Co., Ltd production Catalyst, the NUHC-40A/B/C/D series hydrogenation catalysts or Sinopec of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation are comforted Along FH-5A types, FH-98 types, the FH-DS type hydrogenation catalysts of Petroleum Chemical Engineering Institute's exploitation.

A kind of 18. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described hydrocracking reaction condition is：360~470 DEG C of temperature, pressure be 10~17Pa, hydrogen and Oil volume ratio is 800:1~2000:1, liquid volume air speed is 0.1~2h^-1。

A kind of 19. coke-stove gas as claimed in claim 1 are through methanol synthesized gasoline, co-production of liquefied natural gas and hydrogenation of tar Method, it is characterised in that described hydrocracking catalyst is the NUHC-41A/ of Shanghai Xinyou Energy Technology Co., Ltd.'s exploitation B/C/D series hydrocracking catalysts or the Z3723 type hydrocracking catalysts of standard catalyst company production.