CN105001900A - Technology of synthesizing gasoline by coke oven gas through methyl alcohol - Google Patents
Technology of synthesizing gasoline by coke oven gas through methyl alcohol Download PDFInfo
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- CN105001900A CN105001900A CN201510464178.6A CN201510464178A CN105001900A CN 105001900 A CN105001900 A CN 105001900A CN 201510464178 A CN201510464178 A CN 201510464178A CN 105001900 A CN105001900 A CN 105001900A
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Abstract
A technology of synthesizing gasoline by coke oven gas through methyl alcohol comprises the steps that supersaturated steam is added into the coke oven gas and oxygen, the mixture enters a coke oven gas reformer combustion chamber to conduct a combustion reaction and a transformation reaction, the transformed gas is compressed to conduct a methanol synthesis reaction, methanol separation is conducted on the reaction gas, one part of the gas which is exhausted from the top of a methanol separator returns to a synthesis gas compressor unit, the other part of the gas conducts a synthetic oil reaction, a crude methanol liquid phase conducts a methanol-to-synthesis oil reaction after being exhausted from the bottom of the methanol separator, oil-gas separation is conducted on a synthesis oil product, the separated oil phase enters an oil separator, and fuel gas, liquefied petroleum gas, heavy oil and gasoline products are obtained after separation. The technology of synthesizing the gasoline by the coke oven gas through the methyl alcohol has the advantages of being simple in technological process, less in equipment investment and low in energy consumption.
Description
Technical field
The invention belongs to a kind of coke-oven gas through methanol conversion is the technique of gasoline products.
Background technology
China has the energy structure of rich coal, oil-poor and weak breath, and especially the imbalance between supply and demand of oil is very outstanding.The external dependence degree of China's oil in 2013 reaches 58.1%, estimates that the external dependence degree of the year two thousand twenty China's oil will reach 65%, national energy security, economic security and social safety will be faced big challenge.Therefore, developing substitute energy source for petroleum is the important channel alleviated contradiction between oil supply and demand and guarantee national security.
Methanol conversion gasoline is proposed in 1976 by Mobil company of the U.S. the earliest in patent US3931349, be specially first by methyl alcohol at Cu/Al
2o
3on catalyzer, dehydration forms dme, then dme is converted into high-octane gasoline products under the katalysis of ZSM-5.A kind of technical process disclosed in Chinese patent ZL200610048298.9 is shorter and operate simpler single stage method preparing gasoline by methanol technique, and methyl alcohol is converted into gasoline products by this technology on modified zsm-5 zeolite.The successful exploitation of above-mentioned two kinds of technique for preparing gasoline by methanol and industrial applications are not only for oil replacement provides a technical strategies, and liquefy with the indirect F-T of DCL/Direct coal liquefaction and coal and wait oil replacement technology to compare, preparing gasoline by methanol has that technique is simple, technology maturation is reliable and yield of gasoline advantages of higher, becomes the focus that recent year is paid close attention to.
China is maximum in the world coke production, consumption and export State.2012, China's coke output reached 4.43 hundred million t, if produce 430m by production one ton of coke
3coke-oven gas calculate, only the coke-oven gas of this year by-product is just up to 1,905 hundred million m
3, wherein the coke-oven gas of about 70% is used for coke oven heating and domestic gas, and remaining nearly 57,000,000,000 m
3coke-oven gas is not utilized, and causes the serious wasting of resources and environmental pollution.The successful exploitation of coke-oven gas methyl alcohol technology achieves the recycling of coke-oven gas, not only creates certain economic benefit, and has good environmental benefit and social benefit.But along with coke-oven gas utilizes the diversification of technology, the real price 0.5 yuan/Nm nearly of coke-oven gas
3, consider that the production capacity of methanol market is seriously superfluous, methanol prices obviously declines simultaneously, therefore the absolute profit of industrial coke-oven gas methanol project is seriously shunk, and especially compares relative to coke-oven gas CNG with LNG, and the relative profit of preparing methanol from coke oven gas is lower.
Consider domestic petroleum imbalance between supply and demand, coke-oven gas real price goes up and the market status of methyl alcohol production capacity surplus, if the methyl alcohol prepared by coke-oven gas is further converted to gasoline products by technique for preparing gasoline by methanol, not only can alleviate the problem of oil shortage and methyl alcohol surplus, and the economic benefit of coke-oven gas utilization can be promoted further.But existing industrial preparing gasoline by methanol technique all needs to use refined methanol (methanol concentration >=99.9%) as raw material, make the methyl alcohol prepared by coke-oven gas need by refining methanol unit, and there is surplus heat waste in independent coke-oven gas methyl alcohol, and the contradiction of methanol conversion gasoline shortage of heat, final technology is caused to there is complex process, facility investment is large and energy consumption is high shortcoming, consider that coke-oven gas is limited through the industrial scale of methanol-fueled CLC oil simultaneously, extremely responsive to the problems referred to above existed in technique.Therefore, develop the coke-oven gas that a kind of technical process is simple, facility investment is little and energy consumption is low to have great importance through the monoblock type technique of methanol-fueled CLC oil.
Summary of the invention
The object of the invention is to develop a kind of technical process is simple, facility investment is few and energy consumption the is low coke-oven gas integrated artistic through methanol synthesized gasoline.
For reaching above-mentioned purpose, contriver first by lot of experiments foreign matter content in methyl alcohol, dopant species to become with circulation gas that grading factors is active on methanol synthesis catalyst, the impact of selectivity and stability; Then report according to above-mentioned experimental data, further by a large amount of analog calculations and experience in design for many years, propose the integral process that a kind of coke-oven gas is separated with oil product through conversion, synthetic gas compression, methanol-fueled CLC, preparing gasoline by methanol, this technique is by overall material and energy match, not only enormously simplify technical process, and decrease facility investment and overall energy consumption, further increase the economic benefit that coke-oven gas utilizes.
A kind of coke-oven gas of the present invention, through the integrated artistic of methanol-fueled CLC oil, comprises the steps:
(1) coke-oven gas after purification first allocates supersaturated vapor into, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater and coke oven gas converter again, enter in coke oven gas converter after heating further finally by burning preheating oven, after allocating supersaturated vapor into from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber and first carry out combustion reactions with coke-oven gas, then the gas mixture after burning enters from top to bottom in converting coke oven gas furnace catalyst layer and carries out conversion reaction, after transforming, gas first reclaims heat through converter waste heat boiler after bottom is discharged, again through coke-oven gas preheater and coke-oven gas heat exchange, then by entering in gas-liquid separator after the cooling of reforming gas water cooler, be separated the process water that obtains discharge bottom gas-liquid separator and be sent to converter waste heat boiler by-product middle pressure steam after mixing with the process water from oil gas water separator, a part of middle pressure steam of by-product enters after burning preheating oven heated rear formation supersaturated vapor, respectively with purification after coke-oven gas and enter the top of coke oven gas converter from the oxygen mix in space division system, another part middle pressure steam provides vaporization heat for methyl alcohol vaporizing device, be separated the gas phase obtained to discharge from gas-liquid separator, and be mixed in synthesic gas compressor group with circulation gas after the further desulfurization of desulfurizer and carry out supercharging,
(2) after the reactant gases heat exchange of the mixed gas after supercharging through discharging bottom synthesis air preheater and methanol reactor, enter from top in methanol sythesis reactor and carry out methanol-fueled CLC reaction, reactant gases is discharged bottom methanol sythesis reactor, first through the heat exchange of synthesis air preheater, enter in methanol separator after evaporative type cooler condensation again, gas phase is discharged from methanol separator top and is back to synthesic gas compressor group with the gas and vapor permeation rear portion gas from flash drum, another part gas first after synthesis oil reactor inlet gas preheater preheats with gasification after crude carbinol be mixed in synthetic oil reactor, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer after discharging bottom methanol separator, after acidic ion exchange resin filters, enter flash drum carry out flash separation, a small amount of gas phase is discharged from flash drum top and is mixed with methanol separator overhead gas, and crude carbinol liquid phase is discharged from flash drum bottom,
(3) first through methanol preheater preheating from the crude carbinol that flash drum is next, gasified by methyl alcohol vaporizing device again, after overheated finally by methyl alcohol superheater, enter in synthetic oil reactor with the gas and vapor permeation from synthetic oil Reactor inlet air preheater and carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, wherein first strand of material enters in oil product air cooler after synthesis oil inlet gas interchanger with the gas converting heat come from methanol separator, and second strand of material first reclaims heat through synthetic oil waste heat boiler, again through methyl alcohol superheater and crude carbinol steam heat-exchanging, finally by methanol preheater with merge with first strand of material from after the liquid phase crude carbinol heat exchange of strainer, synthetic oil product after merging is further by entering in separator after oil product air cooler and the cooling of oil product water cooler, gas phase from oil gas water separator top discharge and after recycle gas compressor supercharging, part gas is back to synthesic gas compressor group as circulation gas, another part mixes to be sent in the preheating oven that burns with the isolated fuel gas of oil product separator and burns, the process water that condensation is got off is discharged and is sent to byproduct steam in converter waste heat boiler after mixing with the process water from gas-liquid separator bottom oil gas water separator, and isolated oil phase enters in oil product separator, fuel gas is obtained after separation, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
After purification and desulfurization, the volume of coke-oven gas consists of H as above
250 ~ 60%, CO 5% ~ 8%, CO
21.5 ~ 4%, CH
423% ~ 27%, N
23 ~ 7%, C
2above unsaturated hydrocarbons 2 ~ 4%.
Coke oven gas converter as above is fixed bed adiabatic reactor, its reaction pressure is 2.0 ~ 2.5MPa, coke-oven gas inlet temperature is 600 ~ 700 DEG C, converter is divided into combustion chamber, top and bottom conversion chamber, the upper and lower two-layer catalyzer of lower floor's conversion chamber filling, upper strata is Z205 type conversion catalyst, and its admission space accounts for 15 ~ 25Vol% of beds cumulative volume; Lower floor is Z204 type conversion catalyst, and admission space accounts for 75 ~ 85Vol% of beds cumulative volume, and two kinds of catalyzer are produced by Sichuan Tianyi Science & Technology Co., Ltd;
The volume ratio of the coke-oven gas and oxygen that enter coke oven gas converter is as above 4.5 ~ 5.5, in the middle pressure steam that converter waste heat boiler produces, a part enters burning preheating oven and produces supersaturated vapor, supersaturated vapor is back in converter respectively by allocating coke-oven gas into the mode allocating oxygen into, the volume ratio wherein controlling supersaturated vapor and coke-oven gas is 0.15 ~ 0.25, the volume ratio controlling supersaturated vapor and oxygen is 3.0 ~ 3.5, and remaining another part middle pressure steam is sent to methyl alcohol vaporizing device for methanol gasifying.
Methanol sythesis reactor as above adopts shell-and-tube isothermal reactor, and its reaction pressure is 5.7 ~ 6.5MPa, and temperature of reaction is 240 ~ 260 DEG C, and gas space velocity is 15500 ~ 20000L/ (Kgh).
The catalyzer of methanol-fueled CLC as above is C306, C307 catalyzer of Research Institute of Nanjing Chemical Industry Group exploitation, the one in the C302 catalyzer of the RK-5 catalyzer that Dalian Reak Science and Technology Co., Ltd. produces or the exploitation of southwestern chemical design institute.
The circulation gas sum from methanol separator and oil gas water separator entered as above in synthesic gas compressor group is 5.0 ~ 6.0 with the volume ratio from desulfurizer gas phase.
Be two portions after methanol separator the top as above gas phase of discharging and the gas phase of discharging from flash drum merge, the gas being wherein back to synthesic gas compressor group is 2.5 ~ 3.0 with the gas volume ratio entering methanol sythesis reactor.
Load the CT151 type acidic ion exchange resin that Piao Laite company produces in methyl alcohol strainer as above, the basic nitrogen overall controls such as the methylamine contained in crude carbinol after filtration, dimethylamine are at below 20ppm.
Methanol conversion gasoline as above is one-step technology, and its reactor adopts heat-insulating fixed-bed reactor, and inlet gas temperature is 300 ~ 350 DEG C, and reaction pressure is 1.5 ~ 2.5MPa, and methanol quality air speed is 0.8 ~ 1.3h
-1.
The catalyzer of methanol conversion gasoline as above adopts the JX6201 type catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation or the GSK-10 type catalyzer of rope company of Top exploitation.
Be 4.4 ~ 7.8 from the gas of methanol separator and the volume ratio of gas phase crude carbinol in the inlet gas of synthetic oil reactor described above.
The mass ratio of first strand of material as above and second strand of material is 1.5 ~ 2.5, for methanol gasifying after the middle pressure steam wherein produced by synthetic oil waste heat boiler is mixed with the part middle pressure steam that converter waste heat boiler produces.
After compression, wherein the gas of volume fraction 3 ~ 5% is sent in the preheating oven that burns after mixing with the isolated fuel gas of oil product separator and burns oil gas water separator top as above expellant gas, and remaining gas is back to synthesic gas compressor group.
The present invention compared with prior art, has substantive distinguishing features and marked improvement is:
(1) the present invention proposes the thinking of coke-oven gas through methanol-fueled CLC oil first, not only for the comprehensive utilization of coke-oven gas provides a technical strategies, and further increase the economic worth of coke-oven gas, as calculated the present invention exploitation technology and independent coke-oven gas methanol phase ratio, its annual return raising nearly 20%.
(2) coke-oven gas disclosed by the invention is according to many-sided monoblock type technique developed such as the composition characteristic of coke-oven gas own, methanol-fueled CLC and methanol conversion gasoline through methanol-fueled CLC oil technique, compare with methanol conversion technique for preparing gasoline with independent coke-oven gas methyl alcohol, crude carbinol by means of only gas-liquid separation is directly sent to synthetic oil reactor by the present invention, decrease methanol rectification unit, its facility investment decreases more than 10%, and running cost reduces nearly 5%.
(3) coke-oven gas disclosed by the invention is drawn by great many of experiments, analog calculation and experience in design for many years through methanol-fueled CLC oil technique, material coupling and Btu utilization are all considered from the technique of entirety, avoid independent coke-oven gas methyl alcohol heat residue waste and the contradiction of independent methanol conversion gasoline shortage of heat.
Accompanying drawing explanation
Fig. 1 is the schema of a kind of coke-oven gas disclosed by the invention through methanol-fueled CLC oil integrated artistic
As shown in the figure, 1 is burning preheating oven, 2 is coke oven gas converters, 3 is gas-liquid separators, 4 is desulfurizers, 5 is synthesic gas compressor groups, 6 is methanol sythesis reactors, 7 is evaporative type coolers, 8 is methanol separators, 9 is methyl alcohol strainers, 10 is flash drums, 11 is synthetic oil reactors, 12 is oil product air coolers, 13 is oil gas water separators, 14 is oil product separators, 15 is recycle gas compressors, 16 is converter waste heat boilers, 17 is coke(oven)gas preheaters, 18 is reforming gas water coolers, 19 is methanol-fueled CLC air preheaters, 20 is synthetic oil waste heat boilers, 21 is methyl alcohol superheaters, 22 is methanol preheater, 23 methyl alcohol vaporizing devices, 24 is oil product water coolers, 25 is synthetic oil Reactor inlet air preheaters.
Embodiment
Below by specific embodiment, the specific embodiment of the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to above-described embodiment.
Embodiment 1
(1) volume after purification consists of H
260%, CO 5.3%, CO
22.7%, CH
423.7%, N
24.6% and C
nh
mthe coke-oven gas of 3.7% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling supersaturated vapor and coke-oven gas is 0.25, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 600 DEG C further finally by burning preheating oven 1, 3 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 4.5, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.5MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 15%, the volume fraction of lower floor Z204 catalyzer is 85%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C307 catalyzer that Research Institute of Nanjing Chemical Industry Group exploitation is housed, be 5.7MPa in reaction pressure, temperature of reaction is 240 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 15500L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 71.4% be back to synthesic gas compressor group 5, the gas of 28.6% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:4.4 is mixed in the synthetic oil reactor 11 that GSK-10 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 300 DEG C, and be 2.5MPa and methanol quality air speed in reaction pressure is 0.8h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 60wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 40wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 97% is back to synthesic gas compressor group 5 as circulation gas, and the gas remaining 3% mixes with the isolated fuel gas of oil product separator 14 to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, and isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 2
(1) volume after purification consists of H
259.6%, CO 5.0%, CO
23.0%, CH
425.8%, N
23.0% and C
nh
mthe coke-oven gas of 3.6% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling supersaturated vapor and coke-oven gas is 0.23, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 620 DEG C further finally by burning preheating oven 1, 3.1 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 4.7, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.6, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.4MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 18%, the volume fraction of lower floor Z204 catalyzer is 82%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5.2, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C306 catalyzer that Research Institute of Nanjing Chemical Industry Group exploitation is housed, be 5.8MPa in reaction pressure, temperature of reaction is 245 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 16000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 72% be back to synthesic gas compressor group 5, the gas of 28% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:5 is mixed in the synthetic oil reactor 11 that GSK-10 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 310 DEG C, and be 2.2MPa and methanol quality air speed in reaction pressure is 0.9h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 62wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 38wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 96% is back to synthesic gas compressor group 5 as circulation gas, and the gas remaining 4% mixes with the isolated fuel gas of oil product separator 14 to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 3
(1) volume after purification consists of H
257.8%, CO 5.7%, CO
22.6%, CH
424.2%, N
25.8% and C
nh
mthe coke-oven gas of 3.9% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling supersaturated vapor and coke-oven gas is 0.22, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 630 DEG C further finally by burning preheating oven 1, 3.2 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 4.9, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.7, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.3MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 20%, the volume fraction of lower floor Z204 catalyzer is 80%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5.3, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C307 catalyzer that Research Institute of Nanjing Chemical Industry Group exploitation is housed, be 6.0MPa in reaction pressure, temperature of reaction is 248 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 17000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 73% be back to synthesic gas compressor group 5, the gas of 27% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:5.5 is mixed in the synthetic oil reactor 11 that GSK-10 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 320 DEG C, and be 2.0MPa and methanol quality air speed in reaction pressure is 1.0h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 64wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 36wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 95% is back to synthesic gas compressor group 5 as circulation gas, and the gas remaining 5% mixes with the isolated fuel gas of oil product separator 14 to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 4
(1) volume after purification consists of H
254.7%, CO 6.9%, CO
23.5%, CH
425.6%, N
26.1% and C
nh
mthe coke-oven gas of 3.2% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling supersaturated vapor and coke-oven gas is 0.20, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 650 DEG C further finally by burning preheating oven 1, 3.3 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 5.0, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.8, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.2MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 22%, the volume fraction of lower floor Z204 catalyzer is 78%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5.5, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C302 catalyzer that the exploitation of southwestern chemical design institute is housed, be 6.2MPa in reaction pressure, temperature of reaction is 250 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 18000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 74% be back to synthesic gas compressor group 5, the gas of 26% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:6.0 is mixed in the synthetic oil reactor 11 that JX6201 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 330 DEG C, and be 1.8MPa and methanol quality air speed in reaction pressure is 1.1h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 66wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 34wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 95% is back to synthesic gas compressor group as circulation gas, and the gas remaining 5% mixes with the isolated fuel gas of oil product separator to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, and isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 5
(1) volume after purification consists of H
250%, CO 8%, CO
24%, CH
427%, N
27% and C
nh
mthe coke-oven gas of 4% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling supersaturated vapor and coke-oven gas is 0.19, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 670 DEG C further finally by burning preheating oven 1, 3.4 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 5.2, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.9, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.1MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 23%, the volume fraction of lower floor Z204 catalyzer is 77%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5.7, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C302 catalyzer that the exploitation of southwestern chemical design institute is housed, be 6.3MPa in reaction pressure, temperature of reaction is 253 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 19000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 75% be back to synthesic gas compressor group 5, the gas of 25% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:6.5 is mixed in the synthetic oil reactor 11 that JX6201 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 340 DEG C, and be 1.7MPa and methanol quality air speed in reaction pressure is 1.2h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 68wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 32wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 96% is back to synthesic gas compressor group as circulation gas, and the gas remaining 4% mixes with the isolated fuel gas of oil product separator to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, and isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 6
(1) volume after purification consists of H
256.2%, CO 6.4%, CO
23.4%, CH
425.1%, N
25.7% and C
nh
mthe coke-oven gas of 3.2% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling saturation steam and coke-oven gas is 0.17, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 680 DEG C further finally by burning preheating oven 1, 3.5 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 5.3, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.8, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.0MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 24%, the volume fraction of lower floor Z204 catalyzer is 76%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 5.8, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the C302 catalyzer that the exploitation of southwestern chemical design institute is housed, be 6.4MPa in reaction pressure, temperature of reaction is 256 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 20000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 74% be back to synthesic gas compressor group 5, the gas of 26% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:7.0 is mixed in the synthetic oil reactor 11 that JX6201 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 345 DEG C, and be 1.6MPa and methanol quality air speed in reaction pressure is 1.3h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 70wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 30wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 96% is back to synthesic gas compressor group as circulation gas, and the gas remaining 4% mixes with the isolated fuel gas of oil product separator 14 to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
The synthetic oil product composition for details see attached table 1 prepared under the technique and reaction conditions of the present embodiment.
Embodiment 7
(1) volume after purification consists of H
260%, CO 6.0%, CO
21.5%, CH
423.3%, N
26.6% and C
nh
mthe coke-oven gas of 2.6% first allocates a certain amount of supersaturated vapor into, the volume ratio controlling saturation steam and coke-oven gas is 0.15, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater 17 and coke oven gas converter 2 again, enter in coke oven gas converter 2 after being heated to 700 DEG C further finally by burning preheating oven 1, 3.5 times are allocated into after the supersaturated vapor of oxygen volume from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber, the volume ratio controlling coke-oven gas and oxygen is 5.5, and the volume ratio controlling middle pressure steam and coke-oven gas and the oxygen allocated into is 0.9, oxygen first carries out combustion reactions with coke-oven gas, then gas mixture enters catalyst layer from top to bottom carry out conversion reaction under pressure is 2.3MPa, catalyst layer at the middle and upper levels Z205 catalyst volume fraction is 25%, the volume fraction of lower floor Z204 catalyzer is 75%, after transforming, gas first reclaims heat through converter waste heat boiler 16 after bottom is discharged, again through coke-oven gas preheater 17 and coke-oven gas heat exchange, then enter in gas-liquid separator 3 after being cooled by reforming gas water cooler 18, discharge bottom process water self-separation device and after mixing with the process water from oil gas water separator, be sent to converter waste heat boiler 16 by-product middle pressure steam, and gas phase is discharged from top and after sulphur protector 4 further desulfurization, doubly synthesic gas compressor group 5 is mixed into the circulation gas of inverting oven coke furnace gas with volume 6.0, enter after supercharging in methanol sythesis reactor 6.
(2) synthetic gas after supercharging and circulation gas mixed gas are worked off one's feeling vent one's spleen after heat exchange through synthesizing air preheater 19 and methanol reactor, enter from top in the methanol sythesis reactor of the RK-5 type catalyzer that Dalian Reak Science and Technology Co., Ltd.'s exploitation is housed, be 6.5MPa in reaction pressure, temperature of reaction is 260 DEG C and air speed is carry out methanol-fueled CLC reaction under the condition of 18000L/ (Kgh), first through synthesis air preheater 19 and the heat exchange of import synthetic gas after getting rid of bottom reactant gases autoreactor, enter in methanol separator 8 after evaporative type cooler 7 condensation again, gas phase self-separation device top discharge and with the gas and vapor permeation from flash drum 10 after the gas of volume fraction 75% be back to synthesic gas compressor group 5, the gas of 25% first after the preheating of synthesis oil reactor inlet gas preheater 25 with gasification after crude carbinol be mixed in synthetic oil reactor 11, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer 9 after discharging bottom methanol separator 8, through be filled with CT151 type acidic ion exchange resin filter and after the fatty amine in crude carbinol is removed to below 0.5ppm, enter flash drum 10 and carry out flash separation, a small amount of gas phase is discharged from flash drum 10 top and is mixed with methanol separator 8 overhead gas, and crude carbinol liquid phase enters synthetic oil system after discharging bottom flash drum 10.
(3) first through methanol preheater 22 preheating from the crude carbinol of flash drum 10, gasified by methyl alcohol vaporizing device 23 again, after overheated finally by methyl alcohol superheater 21, be that 1:7.1 is mixed in the synthetic oil reactor 11 that JX6201 type catalyzer is housed with the gas come from methanol separator 8 top with volume ratio, controlling inlet gas temperature is 350 DEG C, and be 1.5MPa and methanol quality air speed in reaction pressure is 1.2h
-1condition under carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, the first strand of material wherein accounting for the 70wt% of synthetic oil product population enters in oil product air cooler 12 after synthesis oil inlet gas interchanger 25 with the gas converting heat from methanol separator 8, and second of 30wt% strand of material first reclaims heat through synthetic oil waste heat boiler 20, again through methyl alcohol superheater 21 and crude carbinol steam heat-exchanging, finally by methanol preheater 22 with enter in oil product air cooler 12 from after the liquid phase crude carbinol heat exchange of strainer 10 with first burst of merging, synthetic oil product after merging enters in oil gas water separator 13 after cooling further by oil product air cooler 12 and oil product water cooler 24, gas phase self-separation device 13 top discharge and after recycle gas compressor 15 supercharging, the gas of volume fraction 96% is back to synthesic gas compressor group as circulation gas, and the gas remaining 4% mixes with the isolated fuel gas of oil product separator to be sent in the preheating oven 1 that burns and burns, the process water of condensation from bottom discharge and with mix from gas-liquid separator 8 process water after be sent to byproduct steam in converter waste heat boiler 16, and isolated oil phase enters in oil product separator 14, fuel gas is obtained after stage trapping, liquefied petroleum gas (LPG) (LPG), heavy oil and gasoline products.
The synthetic oil product composition prepared under the technique and reaction conditions of the present embodiment refers to table 1.
Table 1
Claims (15)
1. coke-oven gas is through a technique for methanol synthesized gasoline, it is characterized in that comprising the steps:
(1) coke-oven gas after purification first allocates supersaturated vapor into, to be worked off one's feeling vent one's spleen heat exchange by coke(oven)gas preheater and coke oven gas converter again, enter in coke oven gas converter after heating further finally by burning preheating oven, after allocating supersaturated vapor into from the oxygen in space division system, enter from top in converting coke oven gas stove combustion chamber and first carry out combustion reactions with coke-oven gas, then the gas mixture after burning enters from top to bottom in converting coke oven gas furnace catalyst layer and carries out conversion reaction, after transforming, gas first reclaims heat through converter waste heat boiler after bottom is discharged, again through coke-oven gas preheater and coke-oven gas heat exchange, then by entering in gas-liquid separator after the cooling of reforming gas water cooler, be separated the process water that obtains discharge bottom gas-liquid separator and be sent to converter waste heat boiler by-product middle pressure steam after mixing with the process water from oil gas water separator, a part of middle pressure steam of by-product enters after burning preheating oven heated rear formation supersaturated vapor, respectively with purification after coke-oven gas and enter the top of coke oven gas converter from the oxygen mix in space division system, another part middle pressure steam provides vaporization heat for methyl alcohol vaporizing device, be separated the gas phase obtained to discharge from gas-liquid separator, and be mixed in synthesic gas compressor group with circulation gas after the further desulfurization of desulfurizer and carry out supercharging,
(2) after the reactant gases heat exchange of the mixed gas after supercharging through discharging bottom synthesis air preheater and methanol reactor, enter from top in methanol sythesis reactor and carry out methanol-fueled CLC reaction, reactant gases is discharged bottom methanol sythesis reactor, first through the heat exchange of synthesis air preheater, enter in methanol separator after evaporative type cooler condensation again, gas phase is discharged from methanol separator top and is back to synthesic gas compressor group with the gas and vapor permeation rear portion gas from flash drum, another part gas first after synthesis oil reactor inlet gas preheater preheats with gasification after crude carbinol be mixed in synthetic oil reactor, and by methyl alcohol, fusel, the crude carbinol liquid phase that water and lower carbon number hydrocarbons etc. form enters in methyl alcohol strainer after discharging bottom methanol separator, after acidic ion exchange resin filters, enter flash drum carry out flash separation, a small amount of gas phase is discharged from flash drum top and is mixed with methanol separator overhead gas, and crude carbinol liquid phase is discharged from flash drum bottom,
(3) first through methanol preheater preheating from the crude carbinol that flash drum is next, gasified by methyl alcohol vaporizing device again, after overheated finally by methyl alcohol superheater, enter in synthetic oil reactor with the gas and vapor permeation from synthetic oil Reactor inlet air preheater and carry out synthetic oil reaction, synthetic oil product is divided into two strands of materials, wherein first strand of material enters in oil product air cooler after synthesis oil inlet gas interchanger with the gas converting heat come from methanol separator, and second strand of material first reclaims heat through synthetic oil waste heat boiler, again through methyl alcohol superheater and crude carbinol steam heat-exchanging, finally by methanol preheater with merge with first strand of material from after the liquid phase crude carbinol heat exchange of strainer, synthetic oil product after merging is further by entering in separator after oil product air cooler and the cooling of oil product water cooler, gas phase from oil gas water separator top discharge and after recycle gas compressor supercharging, part gas is back to synthesic gas compressor group as circulation gas, another part mixes to be sent in the preheating oven that burns with the isolated fuel gas of oil product separator and burns, the process water that condensation is got off is discharged and is sent to byproduct steam in converter waste heat boiler after mixing with the process water from gas-liquid separator bottom oil gas water separator, and isolated oil phase enters in oil product separator, fuel gas is obtained after separation, liquefied petroleum gas (LPG), heavy oil and gasoline products.
2. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the volume of coke-oven gas after purification and desulfurization consists of H
250 ~ 60%, CO 5% ~ 8%, CO
21.5 ~ 4%, CH
423% ~ 27%, N
23 ~ 7%, C
2above unsaturated hydrocarbons 2 ~ 4%.
3. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that coke oven gas converter is fixed bed adiabatic reactor, its reaction pressure is 2.0 ~ 2.5MPa, coke-oven gas inlet temperature is 600 ~ 700 DEG C, converter is divided into combustion chamber, top and bottom conversion chamber, the upper and lower two-layer catalyzer of lower floor's conversion chamber filling, upper strata is Z205 type conversion catalyst, and its admission space accounts for 15 ~ 25Vol% of beds cumulative volume; Lower floor is Z204 type conversion catalyst, and admission space accounts for 75 ~ 85Vol% of beds cumulative volume.
4. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the volume ratio of the coke-oven gas and oxygen entering coke oven gas converter is 4.5 ~ 5.5.
5. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that in the middle pressure steam that converter waste heat boiler produces, a part enters burning preheating oven generation supersaturated vapor, supersaturated vapor is back in converter respectively by allocating coke-oven gas into the mode allocating oxygen into, the volume ratio wherein controlling supersaturated vapor and coke-oven gas is 0.15 ~ 0.25, the volume ratio controlling supersaturated vapor and oxygen is 3.0 ~ 3.5, and remaining another part middle pressure steam is sent to methyl alcohol vaporizing device for methanol gasifying.
6. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that described methanol sythesis reactor adopts shell-and-tube isothermal reactor, its reaction pressure is 5.7 ~ 6.5MPa, and temperature of reaction is 240 ~ 260 DEG C, and gas space velocity is 15500 ~ 20000L/Kgh.
7. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the catalyzer of described methanol-fueled CLC is C306, C307 catalyzer of Research Institute of Nanjing Chemical Industry Group exploitation, the one in the C302 catalyzer of the RK-5 catalyzer that Dalian Reak Science and Technology Co., Ltd. produces or the exploitation of southwestern chemical design institute.
8. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the described circulation gas sum from methanol separator and oil gas water separator entered in synthesic gas compressor group is 5.0 ~ 6.0 with the volume ratio from desulfurizer gas phase.
9. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the gas phase of discharging at described methanol separator top and the gas phase of discharging from flash drum are two portions after merging, the gas being wherein back to synthesic gas compressor group is 2.5 ~ 3.0 with the gas volume ratio entering methanol sythesis reactor.
10. a kind of coke-oven gas as claimed in claim 1 is through the technique of methanol synthesized gasoline, it is characterized in that the CT151 type acidic ion exchange resin loading the production of Piao Laite company in described methyl alcohol strainer, the basic nitrogen overall controls such as the methylamine contained in crude carbinol after filtering, dimethylamine are at below 20ppm.
11. a kind of coke-oven gas as claimed in claim 1 are through the technique of methanol synthesized gasoline, it is characterized in that described methanol conversion gasoline is one-step technology, its reactor adopts heat-insulating fixed-bed reactor, inlet gas temperature is 300 ~ 350 DEG C, reaction pressure is 1.5 ~ 2.5MPa, and methanol quality air speed is 0.8 ~ 1.3h
-1.
12. a kind of coke-oven gas as claimed in claim 1, through the technique of methanol synthesized gasoline, is characterized in that the catalyzer of described methanol conversion gasoline adopts the JX6201 type catalyzer of Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences's exploitation or the GSK-10 type catalyzer of rope company of Top exploitation.
13. a kind of coke-oven gas as claimed in claim 1, through the technique of methanol synthesized gasoline, to is characterized in that in the inlet gas of described synthetic oil reactor from the gas of methanol separator and the volume ratio of gas phase crude carbinol being 4.4 ~ 7.8.
14. a kind of coke-oven gas as claimed in claim 1 are through the technique of methanol synthesized gasoline, the mass ratio that it is characterized in that first strand of described material and second strand of material is 1.5 ~ 2.5, for methanol gasifying after the middle pressure steam wherein produced by synthetic oil waste heat boiler is mixed with the part middle pressure steam that converter waste heat boiler produces.
15. a kind of coke-oven gas as claimed in claim 1 are through the technique of methanol synthesized gasoline, it is characterized in that described oil gas water separator top expellant gas after compression, wherein the gas of volume fraction 3 ~ 5% is sent in the preheating oven that burns after mixing with the isolated fuel gas of oil product separator and burns, and remaining gas is back to synthesic gas compressor group.
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| CN107964416A (en) * | 2016-10-19 | 2018-04-27 | 深圳市新路田科技有限公司 | A kind of method and system of coupling between methanol light naphtha gasoline |
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| CN108854167B (en) * | 2018-09-17 | 2023-12-05 | 陕西黑猫焦化股份有限公司 | Recycling system of condensate after methane steam conversion in coke oven gas |
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