CN105062591B - A kind of technique of coke oven through methanol synthesized gasoline, coproduction natural gas and hydrogen - Google Patents
A kind of technique of coke oven through methanol synthesized gasoline, coproduction natural gas and hydrogen Download PDFInfo
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Abstract
A kind of coke oven is through methanol synthesized gasoline, the technique of coproduction natural gas and hydrogen is that coke-stove gas carries out low-temp methanol elution sulphur removal and carbon dioxide, remove the coke-stove gas after sulphur and carbon dioxide and enter deep cooling methane separation, the liquid phase methane product isolated is sent to LNG storage tank, and remaining coke-stove gas is divided into two parts, Part I, which is sent in pressure-variable adsorption, removes hydrogen, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas is mixed into the partial CO 2 gas washed after one-step desulfurization and from low-temp methanol with walking the Part II oven gas of side line, the part circulating air mixing of the circulating air and recycle gas compressor of methanol separator carries out synthesizing methanol, oil phase after artificial oil reaction is carried out again carries out the isolated fuel gas of oil product, liquefied petroleum gas, heavy oil and gasoline products.The present invention has the advantages that technological process is simple, equipment investment is few and energy consumption is low.
Description
Technical field
The invention belongs to a kind of technique of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen.
Technical background
China has rich coal, the energy resource structure of oil-poor and few gas, and the imbalance between supply and demand of especially oil is very prominent.2013
The external dependence degree of China's oil is up to 58.1%, it is contemplated that the external dependence degree of the year two thousand twenty China's oil is up to 65% so that
National energy security, economic security and social safety will face big challenge.Therefore, development substitute energy source for petroleum is to alleviate oil
Imbalance between supply and demand and the important channel for ensuring national security.
Methanol converts gasoline processed earliest by Mobil companies of the U.S. in the proposition in patent US3931349 in 1976, is specially
First by methanol in Cu/Al2O3Dehydration forms dimethyl ether on catalyst, is then converted into dimethyl ether under ZSM-5 catalytic action
High-octane gasoline products.A kind of technological process disclosed in Chinese patent ZL200610048298.9 is shorter and operates simpler
One-step method preparing gasoline by methanol technique, methanol is converted into gasoline products by the technology on modified zsm-5 zeolite.It is above-mentioned
The successful exploitation of two kinds of technique for preparing gasoline by methanol and industrial applications not only provide a technical strategies for oil replacement,
And compared with the oil replacement technology such as DCL/Direct coal liquefaction and coal indirect F-T liquefaction, preparing gasoline by methanol has that technique is simple, technology into
The advantages of ripe reliability and high yield of gasoline, the focus paid close attention to as recent year.
China is coke production, consumption and exported country maximum in the world.2012, China's coke output up to 4.43 hundred million t,
If producing 430m by one ton of coke of production3Coke-stove gas calculate, the coke-stove gas of only this year by-product is just up to 190,500,000,000 m3,
Wherein 70% or so coke-stove gas is used for coke oven heating and domestic gas, and remaining nearly 57,000,000,000 m3Coke-stove gas is not sharp
With causing the serious wasting of resources and environmental pollution.The successful exploitation of coke-stove gas methanol technology realizes coke-stove gas
Recycling, not only create certain economic benefit, and with good environmental benefit and social benefit.But with
Coke-stove gas utilizes the diversification of technology, the real price nearly 0.5 yuan/Nm of coke-stove gas3, while in view of methanol market
Production capacity is seriously superfluous, and methanol prices are decreased obviously, therefore the absolute profit of industrial coke-stove gas methanol project is seriously shunk, especially
Compared with coke-stove gas CNG and LNG, the relative profit of preparing methanol from coke oven gas is lower.
In view of the market status of domestic petroleum imbalance between supply and demand, the rise of coke-stove gas real price and methanol production capacity surplus,
If methanol prepared by coke-stove gas is further converted to gasoline products by technique for preparing gasoline by methanol, it is not only able to alleviate stone
The problem of oily shortage and superfluous methanol, and can further lift the economic benefit that coke-stove gas is utilized.But it is existing industrial
Preparing gasoline by methanol technique is both needed to use refined methanol (methanol concentration >=99.9%) as raw material so that the first prepared by coke-stove gas
Alcohol need to by refining methanol unit, and individually there is after-heat waste in coke-stove gas methanol technology, and methanol conversion is made
The contradiction of gasoline shortage of heat, causes final technology to have the shortcomings that complex process, equipment investment be big and high energy consumption, examines simultaneously
Consider production scale of the coke-stove gas through methanol-fueled CLC oil limited, it is extremely sensitive to above mentioned problem present in technique.Therefore, open
Integrated artistic of the coke-stove gas through methanol synthesized gasoline for sending out that technological process is simple, equipment investment is small and energy consumption is low a kind of has weight
The meaning wanted.
The content of the invention
It is an object of the invention to provide the coke-stove gas that a kind of technological process is simple, equipment investment is few and energy consumption is low through methanol
The technique of artificial oil, coproduction natural gas and hydrogen, the technique is not only able to alleviate domestic petroleum shortage and methanol production capacity surplus
Present situation, and can further increase the economic benefit of coke-stove gas.
For up to above-mentioned purpose, inventor impurity content, dopant species and follows first by lot of experiments in methanol
Ring gas is into influence of the grading factors to methanol synthesis catalyst activity, selectivity and stability；Then according to above-mentioned experimental data
Report, is further calculated and experience in design for many years, it is proposed that a kind of coke-stove gas is through low temperature first by substantial amounts of simulation
Alcohol is washed, deep cooling methane separation, pressure-variable adsorption dehydrogenation, methanol-fueled CLC, preparing gasoline by methanol and oil product separation integral process, the work
Skill not only enormously simplify technological process, and reduce equipment investment and overall energy by overall material and energy match
Consumption, further increases the economic benefit of coke-stove gas comprehensive utilization.
Technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen disclosed by the invention, its is specific
Processing step is as follows：
(1) during the coke-stove gas after removing dust and de-oiling is washed into low-temp methanol, sulphur and dioxy in removing coke-stove gas
Change carbon, wherein the sulphur removed is sent to sulfur recovery system, a carbon dioxide part for removing is sold as carbon dioxide product, and another
It is partly into synthesic gas compressor group, the coke-stove gas after removing sulphur and carbon dioxide enters deep cooling methane separation, separation
The liquid phase methane product gone out is sent to LNG storage tank, and remaining coke-stove gas is divided into two parts, and Part I is sent in pressure-variable adsorption
Hydrogen is removed, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas is mixed into walking the Part II oven gas of side line
In desulfurizer, after the further desulfurization of desulfurizer with wash from low-temp methanol partial CO 2 gas, methanol separator
The part circulating air of circulating air and recycle gas compressor is mixed into synthesic gas compressor group；
(2) mixed gas after the supercharging of synthesic gas compressor group goes out through methanol-fueled CLC air preheater with methanol-fueled CLC tower bottom
After implication heat exchange, enter from top and methanol synthesis reaction is carried out in methyl alcohol synthetic reactor, gaseous products are from after synthesis tower bottom discharge
It is divided into two strands, wherein first burst of gaseous products first exchanges heat through methanol-fueled CLC air preheater, then it is laggard through evaporative type cooler condensation
Enter in methanol separator, gas phase is back in synthesic gas compressor group after being discharged from the top of separator, and by methanol, fusel, water
Enter with the crude carbinol liquid phase of the composition such as lower carbon number hydrocarbons from after the discharge of methanol separator bottom and purified in methanol purification device, through net
Crude carbinol liquid phase after change is first preheated through methanol preheater, is arranged after then being gasified by methanol gasifying device with methanol-fueled CLC tower bottom
The second burst of gaseous products mixing gone out, most afterwards after methanol superheater further heating, enters in synthesis oil reactor from top；
(3) after gas phase crude carbinol is reacted in synthesis oil reactor, its product is first reclaimed through artificial oil waste heat boiler
Heat, then through methanol superheater and gas phase crude carbinol steam heat-exchanging, arranged finally by methanol preheater and methanol purification device bottom
Go out liquid phase crude carbinol heat exchange after enter air cooler in cool down, and further through oil product cooler cool down after enter oil and gas and water from
In device, gas phase is from after the discharge of separator top is pressurized through recycle gas compressor, and a part of gas is back to synthesis as circulating air
Air compressor group, another part is sent to coke oven combustion after being mixed as periodic off-gases with the fuel gas that oil product separator is isolated, cold
Solidifying process water is sent to water treatment system after being discharged from the bottom of oil gas water separator 12, and the water after processing is back to artificial oil and given up
Heat boiler produces middle pressure steam, and is sent to methanol gasifying device for methanol gasifying, and the oil phase isolated enters oil product separator
In, fuel gas, liquefied petroleum gas (LPG), heavy oil and gasoline products are obtained after separation.
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%.
Low-temp methanol as described above is washed to be made up of desulfurizing tower and decarbonizing tower, and operation temperature is -20~-60 DEG C, operation pressure
3~4.0MPa of power, the sulphur after being washed through low-temp methanol in gas is removed to 0.01~0.1ppm, CO2It is removed to 0.3~
0.8Vol%.
The carbon dioxide as described above removed through low-temp methanol elution is divided into two parts, wherein accounting for cumulative volume 30~45%
Carbon dioxide goes synthesic gas compressor group, and remaining carbon dioxide is used as product.
It is as described above washed through low-temp methanol after oven gas be the step of carry out deep cooling methane separation：First by coke-stove gas
It is cooled to after -85~-70 DEG C, ethane, propane and a small amount of CO is isolated in 3~4.0MPa2Lower carbon number hydrocarbons；Then gas phase is further
- 175~-150 DEG C are cooled to, the LNG product of methane content >=97%, remaining coke-stove gas are isolated in 3.0~4.0MPa
It is sent to subsequent cell.
Remaining coke-stove gas is divided into two parts after deep cooling methane separation as described above, wherein volume fraction be 70~
80% oven gas enters after pressure-variable adsorption dehydrogenation, and stripping gas enters desulfurizer, and the oven gas of residue 30~40% is without change
Pressure adsorption system is directly entered desulfurizer.
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
Attached volume fraction >=99.9% for extracting hydrogen.
It is as described above to enter in the gas of synthesic gas compressor group, following from methanol separator and oil gas water separator
The volume ratio for the carbon dioxide sum that ring gas sum is washed with gas and low-temp methanol from desulfurizer is 4.0~6.0.
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 that Research Institute of Nanjing Chemical Industry Group is developed, Dalian
Any one in the RK-5 catalyst of Rake Science and Technology Ltd. production or the C302 catalyst of southwestern chemical design institute exploitation.
It is overall that first burst of gaseous products in methyl alcohol synthetic reactor outlet as described above gaseous products account for outlet gaseous products
Long-pending 65~75%, and residue 25~35% is second burst of gaseous products.
The CT151 type acid-exchange resins of filling Piao Laite companies production in methanol filter as described above, its
Purpose is by the removing of the basic nitrogen compounds such as the amine in liquid phase crude carbinol, methylamine and dimethylamine, and by the alkali nitride in crude carbinol
Thing content is controlled in below 20ppm.
It is one-step technology that methanol as described above, which converts gasoline processed, and its reactor uses heat-insulating fixed bed reactors,
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 catalyst that methanol as described above converts gasoline processed is developed using Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences
JX6201 types catalyst or rope company of Top exploitation GSK-10 type catalyst.
After compression, wherein volume fraction is 70~80% to the gas of discharge at the top of oil gas water separator as described above
Gas is back to synthesic gas compressor group as circulating air, and remaining 20~30% gas is separated as periodic off-gases with oil product
As fuel gas after the fuel gas mixing that system is isolated.
The present invention compared with prior art, be with substantive distinguishing features and marked improvement：
(1) present invention proposes a kind of thinking of coke-stove gas through methanol synthesized gasoline, is not only the synthesis of coke-stove gas
Using there is provided a technical strategies, and the economic worth of coke-stove gas is further increased, be computed the present invention and open
The technology of hair is compared with single coke-stove gas methanol, and its annual return improves nearly 20%.
(2) coke-stove gas disclosed by the invention is according to coke-stove gas composition characteristic itself, first through the oily technique of methanol-fueled CLC
Alcohol is synthesized and methanol converts many-sided monoblock type technique developed such as gasoline processed, is turned with single coke-stove gas methanol and methanol
Change technique for preparing gasoline to compare, the present invention is routed directly to synthesize oil reactor by only by the crude carbinol of gas-liquid separation, reduces first
Alcohol rectification cell, its equipment investment reduces more than 10%, and operating cost reduces nearly 5%.
(3) coke-stove gas disclosed by the invention is calculated through the oily technique of methanol-fueled CLC and for many years by many experiments, simulation
Experience in design draws, material matching and Btu utilization are from overall technique consideration, it is to avoid single coke-stove gas system
Methanol heat residue wastes the contradiction that gasoline shortage of heat processed is converted with single methanol.
Brief description of the drawings
Fig. 1 is a kind of new entirety of the coke-stove gas disclosed by the invention through methanol-fueled CLC oil, coproduction natural gas and hydrogen
The flow chart of technique.
As shown in Figure 1,1 is that low-temp methanol is washed, and 2 be deep cooling methane separation, and 3 be pressure swing adsorption system, and 4 be synthesis gas compression
Unit, 5 be desulfurizer, and 6 be methyl alcohol synthetic reactor, and 7 be evaporative type cooler, and 8 be methanol separator, and 9 be methanol purification device, and 10 are
Oil reactor is synthesized, 11 be air cooler, and 12 be oil gas water separator, and 13 be oil product piece-rate system, and 14 be recycle gas compressor, 15
It is methanol-fueled CLC air preheater, 16 be methanol preheater, and 17 be methyl alcohol vaporizing device, and 18 be methanol superheater, and 19 be that artificial oil gives up
Heat boiler, 20 be oil product cooler.
Embodiment
The embodiment of the present invention is described in further detail below by specific embodiment, but should not be by
This is interpreted as the scope of the present invention and is only limitted to above-described embodiment.
Embodiment 1
(1) volume composition is H after removing dust and de-oiling260%th, CO 5.3%, CO22.7%th, CH423.7%th, N24.6%
And CnHm3.7% coke-stove gas enters in low-temp methanol system 1, temperature be -60 DEG C and pressure be under conditions of 4MPa it is de-
Except the sulphur and carbon dioxide in coke-stove gas, wherein the sulphur removed is sent to sulfur recovery system, and volume in the carbon dioxide removed
The 45% of fraction is mixed into synthesic gas compressor group 4 with the oven gas from desulfurizer 5, and the carbon dioxide of residue 55%
As production marketing, the coke-stove gas after removing sulphur and carbon dioxide enters deep cooling methane separation 2, first cools down coke-stove gas
After to -70 DEG C, coke oven combustion is sent in the 4.0MPa lower carbon number hydrocarbons containing ethane, propane and a small amount of carbon dioxide isolated, so
Gas phase is cooled further to -150 DEG C afterwards, and the LNG product of methane content >=97%, remaining coke-stove gas are isolated in 4.0MPa
It is divided into two parts, the gas of wherein volume fraction 70% is sent in pressure-variable adsorption 3, is 4.0Mpa, operation temperature in adsorptive pressure
To extract the hydrogen of volume composition >=99.9% under conditions of 30 DEG C, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas
It is mixed into 30% oven gas of walking side line in desulfurizer 5, with being washed from low-temp methanol after the further desulfurization of desulfurizer 5
The part circulating air of 1 partial CO 2 gas, the circulating air of methanol separator 8 and recycle gas compressor 14 is mixed into conjunction
Into in air compressor group 4, and the circulating air sum from methanol separator 8 and oil gas water separator 12 is controlled with coming from desulfurizer
The volume ratio that 5 synthesis gas and low-temp methanol washes 1 carbon dioxide sum is 6.0
(2) mixed gas after being pressurized through synthesic gas compressor group 4 is through methanol-fueled CLC air preheater 15 and methyl alcohol synthetic reactor 6
After the heat exchange of outlet at bottom gas, enter from top in the methyl alcohol synthetic reactor 6 for the C307 catalyst developed equipped with Research Institute of Nanjing Chemical Industry Group,
It is that 5.7MPa, reaction temperature are 240 DEG C and air speed is to carry out methanol-fueled CLC under conditions of 15500L/ (Kgh) in reaction pressure
Reaction, gaseous products are divided into two strands, wherein the first of volume fraction 75% burst gaseous products after being discharged from the bottom of methyl alcohol synthetic reactor 6
First exchanged heat through methanol-fueled CLC air preheater 15 and inlet gas, then enter methanol separator 8 after the condensation of evaporative type cooler 7
In, gas phase is back in synthesic gas compressor group 4 after being discharged from the top of methanol separator 8, and by methanol, fusel, water and low-carbon
The crude carbinol liquid phase of the compositions such as hydrocarbon enters after being discharged from the bottom of methanol separator 8 is filled with CT151 type acid-exchange resins
Methanol purification device 9 in purified, the basic nitrogen in crude carbinol is removed to below 20ppm, it is purified after crude carbinol liquid
Mutually first preheated through methanol preheater 16,25% is discharged with the bottom of methyl alcohol synthetic reactor 6 after then gasifying by methanol gasifying device 17
Second burst of gaseous products mixing, after being most further heated to 300 DEG C through methanol superheater 18 afterwards, enters from top and GSK-10 is housed
In the synthesis oil reactor 10 of type catalyst.
(3) gas phase crude carbinol enters in synthesis oil reactor 10, and in reaction pressure be 2.5MPa and methanol quality air speed is
0.8h-1Under conditions of reacted, its product first reclaims heat through artificial oil waste heat boiler 19, then through methanol superheater 18 and gas
Phase crude carbinol steam heat-exchanging, after the liquid phase crude carbinol heat exchange discharged finally by methanol preheater 16 and the bottom of methanol purification device 9
Into in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and is further cooled down through oil product cooler 20 laggard
Enter in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of oil gas water separator 12, wherein
80% gas is back to synthesic gas compressor group 4 as circulating air, and remaining 20% gas is used as periodic off-gases and oil product
Coke oven combustion is sent to after the fuel gas mixing that separator 13 is isolated, the process water of condensation is discharged from the bottom of oil gas water separator 12
After be sent to water treatment system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gas
Changing device 17 is used for methanol gasifying, and the oil phase isolated enters in oil product separator 13, and fuel gas, liquefaction stone are obtained after separation
Oil gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 2
(1) volume composition is H after removing dust and de-oiling259.6%th, CO 5.0%, CO23.0%th, CH425.8%th,
N23.0% and CnHm3.6% coke-stove gas enters in low-temp methanol system 1, and it is 3.8MPa's with pressure to be -50 DEG C in temperature
Under the conditions of sulphur and carbon dioxide in removing coke-stove gas, wherein the sulphur removed is sent to sulfur recovery system, and the titanium dioxide removed
The 38% of volume fraction is mixed into synthesic gas compressor group 4 with carrying out the oven gas of bin cure protector in carbon, and residue 62%
Carbon dioxide as production marketing, the coke-stove gas after removing sulphur and carbon dioxide enters deep cooling methane separation 2, first by coke oven
Coal gas is cooled to after -74 DEG C, is isolated the lower carbon number hydrocarbons containing ethane, propane and a small amount of carbon dioxide in 3.8MPa and is sent to coke oven combustion
Burn, then gas phase is cooled further to -155 DEG C, and the LNG product of methane content >=97%, remaining Jiao are isolated in 3.8MPa
Producer gas is divided into two parts, and the gas of wherein volume fraction 72% is sent in pressure swing adsorption system 3, is in adsorptive pressure
3.8Mpa, operation temperature is the hydrogen of extraction volume composition >=99.9% under conditions of 32 DEG C, and hydrogen removes gas holder as product, and
Utilization of PSA Relief Gas is mixed into sulphur protector 5 with walking 28% oven gas of side line, through the further desulfurization of sulphur protector
Afterwards with the partial CO 2 gas from rectisol system, the circulating air of methanol separator 8 and recycle gas compressor 14
Part circulating air be mixed into synthesic gas compressor group 4, and control following from methanol separator and oil gas water separator
Ring gas sum is 5.6 with carrying out the volume ratio for the carbon dioxide sum that the synthesis gas and low-temp methanol of bin cure protector are washed, through supercharging
After be sent to methyl alcohol synthetic reactor carry out methanol-fueled CLC.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, enter from top in the methyl alcohol synthetic reactor 6 for the C306 catalyst developed equipped with Research Institute of Nanjing Chemical Industry Group, anti-
It is that 5.8MPa, reaction temperature are 244 DEG C and air speed is to carry out methanol synthesis reaction under conditions of 16000L/ (Kgh) to answer pressure,
Gaseous products are divided into two strands from after synthesizing tower bottom discharge, and wherein the first of volume fraction 73% burst gaseous products are first closed through methanol
Exchange heat, then enter after the condensation of evaporative type cooler 7 in methanol separator 8 into air preheater 15 and import synthesis gas, gas phase is certainly
It is back to after being discharged at the top of separator in synthesic gas compressor group 4, and the thick first being made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Alcohol liquid phase enters after being discharged from the bottom of methanol separator 8 to be filled with the methanol purification device 9 of CT151 type acid-exchange resins
Purified, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first through methanol preheater
16 preheatings, second burst of gaseous products after then being gasified by methanol gasifying device 17 with methanol-fueled CLC tower bottom discharge 27% are mixed
Close, after being most further heated to 310 DEG C through methanol superheater 18 afterwards, enter the artificial oil equipped with GSK-10 type catalyst from top
In reactor 10.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 2.3MPa and methanol quality air speed is
0.9h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 78%
Gas is back to synthesic gas compressor group as circulating air, and remaining 22% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 3
(1) volume composition is H after removing dust and de-oiling257.8%th, CO 5.7%, CO22.6%th, CH424.2%th,
N25.8% and CnHm3.9% coke-stove gas enters in low-temp methanol system 1, and it is 3.6MPa's with pressure to be -40 DEG C in temperature
Under the conditions of sulphur and carbon dioxide in removing coke-stove gas, wherein the sulphur removed is sent to sulfur recovery system, and the titanium dioxide removed
The 36% of volume fraction is mixed into synthesic gas compressor group 4 with carrying out the oven gas of bin cure protector in carbon, and remaining dioxy
Change carbon as production marketing, remove the coke-stove gas after sulphur and carbon dioxide and enter deep cooling methane separation 2, first by coke-oven coal air cooling
But to after -76 DEG C, coke oven combustion, Ran Houqi are sent in the 3.6MPa lower carbon number hydrocarbons for isolating ethane, propane and a small amount of carbon dioxide
- 160 DEG C are mutually cooled further to, the LNG product of methane content >=97% is isolated in 3.6MPa, remaining coke-stove gas is divided into
Two parts, the gas of wherein volume fraction 74% is sent in pressure swing adsorption system 3, is 3.6Mpa, operation temperature in adsorptive pressure
To extract the hydrogen of volume composition >=99.9% under conditions of 34 DEG C, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas
Be mixed into 26% oven gas of walking side line in sulphur protector 5, after the further desulfurization of sulphur protector with from low temperature first
The part circulating air that alcohol washes the partial CO 2 gas, the circulating air of methanol separator 8 and recycle gas compressor 14 of system is mixed
Close and enter in synthesic gas compressor group 4, and control the circulating air sum from methanol separator and oil gas water separator with coming from
The volume ratio for the carbon dioxide sum that the synthesis gas and low-temp methanol of sulphur protector are washed is 5.2, and methanol-fueled CLC is sent to after supercharging
Tower carries out methanol-fueled CLC.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, enter from top in the methyl alcohol synthetic reactor 6 for the C307 catalyst developed equipped with Research Institute of Nanjing Chemical Industry Group, anti-
It is that 5.9MPa, reaction temperature are 248 DEG C and air speed is to carry out methanol synthesis reaction under conditions of 17000L/ (Kgh) to answer pressure,
Gaseous products are divided into two strands from after synthesizing tower bottom discharge, and wherein the first of volume fraction 71% burst gaseous products are first closed through methanol
Exchange heat, then enter after the condensation of evaporative type cooler 7 in methanol separator 8 into air preheater 15 and import synthesis gas, gas phase is certainly
It is back to after being discharged at the top of separator in synthesic gas compressor group 4, and the thick first being made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Alcohol liquid phase enters after being discharged from the bottom of methanol separator 8 to be filled with the methanol purification device 9 of CT151 type acid-exchange resins
Purified, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first through methanol preheater
16 preheatings, second burst of gaseous products after then being gasified by methanol gasifying device 17 with methanol-fueled CLC tower bottom discharge 29% are mixed
Close, after being most further heated to 320 DEG C through methanol superheater 18 afterwards, enter the artificial oil equipped with GSK-10 type catalyst from top
In reactor 10.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 2.1MPa and methanol quality air speed is
1.0h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 76%
Gas is back to synthesic gas compressor group as circulating air, and remaining 24% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 4
(1) volume composition is H after removing dust and de-oiling254.7%th, CO 6.9%, CO23.5%th, CH425.6%th,
N26.1% and CnHm3.2% coke-stove gas enters in low-temp methanol system 1, and it is 3.4MPa's with pressure to be -30 DEG C in temperature
Under the conditions of sulphur and carbon dioxide in removing coke-stove gas, wherein the sulphur removed is sent to sulfur recovery system, and the titanium dioxide removed
The 34% of volume fraction is mixed into synthesic gas compressor group 4 with carrying out the oven gas of bin cure protector in carbon, and remaining dioxy
Change carbon as production marketing, remove the coke-stove gas after sulphur and carbon dioxide and enter deep cooling methane separation 2, first by coke-oven coal air cooling
But to after -79 DEG C, coke oven combustion is sent in the 3.4MPa lower carbon number hydrocarbons containing ethane, propane and a small amount of carbon dioxide isolated,
Then gas phase is cooled further to -165 DEG C, and the LNG product of methane content >=97%, remaining coke-oven coal are isolated in 3.4MPa
Qi leel is two parts, and the gas of wherein volume fraction 76% is sent in pressure swing adsorption system 3, is 3.4Mpa, behaviour in adsorptive pressure
Make temperature to extract the hydrogen of volume composition >=99.9% under conditions of 36 DEG C, hydrogen removes gas holder as product, and pressure-variable adsorption
Stripping gas is mixed into sulphur protector 5 with walking 24% oven gas of side line, with coming from after the further desulfurization of sulphur protector
The part of the partial CO 2 gas of rectisol system, the circulating air of methanol separator 8 and recycle gas compressor 14 is followed
Ring gas is mixed into synthesic gas compressor group 4, and controls the circulating air sum from methanol separator and oil gas water separator
It is 4.9 with carrying out the volume ratio for the carbon dioxide sum that the synthesis gas and low-temp methanol of bin cure protector are washed, first is sent to after supercharging
Alcohol synthetic tower carries out methanol-fueled CLC.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, enter from top in the methyl alcohol synthetic reactor 6 of the C302 catalyst equipped with southwestern chemical design institute's exploitation, anti-
It is that 6.1MPa, reaction temperature are 252 DEG C and air speed is to carry out methanol synthesis reaction under conditions of 18000L/ (Kgh) to answer pressure,
Gaseous products are divided into two strands from after synthesizing tower bottom discharge, and wherein the first of volume fraction 68% burst gaseous products are first closed through methanol
Exchange heat, then enter after the condensation of evaporative type cooler 7 in methanol separator 8 into air preheater 15 and import synthesis gas, gas phase is certainly
It is back to after being discharged at the top of separator in synthesic gas compressor group 4, and the thick first being made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Alcohol liquid phase enters after being discharged from the bottom of methanol separator 8 to be filled with the methanol purification device 9 of CT151 type acid-exchange resins
Purified, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first through methanol preheater
16 preheatings, second burst of gaseous products after then being gasified by methanol gasifying device 17 with methanol-fueled CLC tower bottom discharge 32% are mixed
Close, after being most further heated to 330 DEG C through methanol superheater 18 afterwards, enter the artificial oil equipped with JX6201 type catalyst from top
In reactor 10.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 1.9MPa and methanol quality air speed is
1.1h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 74%
Gas is back to synthesic gas compressor group as circulating air, and remaining 26% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 5
(1) volume composition is H after removing dust and de-oiling250%th, CO 8%, CO24%th, CH427%th, N27% and CnHm4%
Coke-stove gas enter in low-temp methanol system 1, it is to remove coke-stove gas under conditions of 3.2MPa with pressure be -25 DEG C in temperature
In sulphur and carbon dioxide, wherein the sulphur removed is sent to sulfur recovery system, and in the carbon dioxide removed volume fraction 32%
It is mixed into carrying out the oven gas of bin cure protector in synthesic gas compressor group 4, and residual carbon dioxide takes off as production marketing
Coke-stove gas after sulphur removal and carbon dioxide enters deep cooling methane separation 2, and first coke-stove gas is cooled to after -82 DEG C, in
The lower carbon number hydrocarbons containing ethane, propane and a small amount of carbon dioxide that 3.2MPa is isolated is sent to coke oven combustion, and then gas phase is further
- 170 DEG C are cooled to, the LNG product of methane content >=97% is isolated in 3.2MPa, remaining coke-stove gas is divided into two parts,
The gas of wherein volume fraction 78% is sent in pressure swing adsorption system 3, is 3.2Mpa in adsorptive pressure, operation temperature is 38 DEG C
Under the conditions of extract the hydrogen of volume composition >=99.9%, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas and walks side line
22% oven gas be mixed into sulphur protector 5, after the further desulfurization of sulphur protector with from rectisol system
Partial CO 2 gas, the part circulating air of the circulating air of methanol separator 8 and recycle gas compressor 14 be mixed into conjunction
Into in air compressor group 4, and the circulating air sum from methanol separator and oil gas water separator is controlled with carrying out bin cure protector
Synthesis gas and the volume ratio of carbon dioxide sum washed of low-temp methanol be 4.6, methyl alcohol synthetic reactor is sent to after supercharging and carries out first
Alcohol is synthesized.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, enter from top in the methyl alcohol synthetic reactor 6 of the C302 catalyst equipped with southwestern chemical design institute's exploitation, anti-
It is that 6.3MPa, reaction temperature are 256 DEG C and air speed is to carry out methanol synthesis reaction under conditions of 19000L/ (Kgh) to answer pressure,
Gaseous products are divided into two strands from after synthesizing tower bottom discharge, and wherein the first of volume fraction 66% burst gaseous products are first closed through methanol
Exchange heat, then enter after the condensation of evaporative type cooler 7 in methanol separator 8 into air preheater 15 and import synthesis gas, gas phase is certainly
It is back to after being discharged at the top of separator in synthesic gas compressor group 4, and the thick first being made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Alcohol liquid phase enters after being discharged from the bottom of methanol separator 8 to be filled with the methanol purification device 9 of CT151 type acid-exchange resins
Purified, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first through methanol preheater
16 preheatings, second burst of gaseous products after then being gasified by methanol gasifying device 17 with methanol-fueled CLC tower bottom discharge 34% are mixed
Close, after being most further heated to 340 DEG C through methanol superheater 18 afterwards, enter the artificial oil equipped with JX6201 type catalyst from top
In reactor 10.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 1.7MPa and methanol quality air speed is
1.2h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 72%
Gas is back to synthesic gas compressor group as circulating air, and remaining 28% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 6
(1) volume composition is H after removing dust and de-oiling256.2%th, CO 6.4%, CO23.4%th, CH425.1%th,
N25.7% and CnHm3.2% coke-stove gas enters in low-temp methanol system 1, and it is 3.0MPa's with pressure to be -20 DEG C in temperature
Under the conditions of sulphur and carbon dioxide in removing coke-stove gas, wherein the sulphur removed is sent to sulfur recovery system, and the titanium dioxide removed
The 30% of volume fraction is mixed into synthesic gas compressor group 4 with carrying out the oven gas of bin cure protector in carbon, and remaining dioxy
Change carbon as production marketing, remove the coke-stove gas after sulphur and carbon dioxide and enter deep cooling methane separation 2, first by coke-oven coal air cooling
But to after -85 DEG C, coke oven combustion, Ran Houqi are sent in the 3.0MPa lower carbon number hydrocarbons for isolating ethane, propane and a small amount of carbon dioxide
- 170 DEG C are mutually cooled further to, the LNG product of methane content >=97% is isolated in 3.0MPa, remaining coke-stove gas is divided into
Two parts, the gas of wherein volume fraction 80% is sent in pressure swing adsorption system 3, is 3.0Mpa, operation temperature in adsorptive pressure
To extract the hydrogen of volume composition >=99.9% under conditions of 40 DEG C, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas
Be mixed into 20% oven gas of walking side line in sulphur protector 5, after the further desulfurization of sulphur protector with from low temperature first
The part circulating air that alcohol washes the partial CO 2 gas, the circulating air of methanol separator 8 and recycle gas compressor 14 of system is mixed
Close and enter in synthesic gas compressor group 4, and control the circulating air sum from methanol separator and oil gas water separator with coming from
The volume ratio for the carbon dioxide sum that the synthesis gas and low-temp methanol of sulphur protector are washed is 4.3, and methanol-fueled CLC is sent to after supercharging
Tower carries out methanol-fueled CLC.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, enter from top in the methyl alcohol synthetic reactor 6 of the C302 catalyst equipped with southwestern chemical design institute's exploitation, anti-
It is that 6.4MPa, reaction temperature are 258 DEG C and air speed is to carry out methanol synthesis reaction under conditions of 19500L/ (Kgh) to answer pressure,
Gaseous products are divided into two strands from after synthesizing tower bottom discharge, and wherein the first of volume fraction 65% burst gaseous products are first closed through methanol
Exchange heat, then enter after the condensation of evaporative type cooler 7 in methanol separator 8 into air preheater 15 and import synthesis gas, gas phase is certainly
It is back to after being discharged at the top of separator in synthesic gas compressor group 4, and the thick first being made up of methanol, fusel, water and lower carbon number hydrocarbons etc.
Alcohol liquid phase enters after being discharged from the bottom of methanol separator 8 to be filled with the methanol purification device 9 of CT151 type acid-exchange resins
Purified, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first through methanol preheater
16 preheatings, second burst of gaseous products after then being gasified by methanol gasifying device 17 with methanol-fueled CLC tower bottom discharge 35% are mixed
Close, after being most further heated to 350 DEG C through methanol superheater 18 afterwards, enter the artificial oil equipped with JX6201 type catalyst from top
In reactor 10.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 1.6MPa and methanol quality air speed is
1.3h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 70%
Gas is back to synthesic gas compressor group as circulating air, and remaining 30% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Embodiment 7
(1) volume composition is H after removing dust and de-oiling260%th, CO 6.0%, CO21.5%th, CH423.3%th, N26.6%
And CnHm2.6% coke-stove gas enters in low-temp methanol system 1, temperature be -50 DEG C be 3.0MPa with pressure under conditions of
The sulphur and carbon dioxide in coke-stove gas are removed, wherein the sulphur removed is sent to sulfur recovery system, and body in the carbon dioxide removed
The 35% of fraction is mixed into synthesic gas compressor group 4 with carrying out the oven gas of bin cure protector, and residual carbon dioxide is made
For production marketing, the coke-stove gas after removing sulphur and carbon dioxide enters deep cooling methane separation 2, be first cooled to coke-stove gas-
After 80 DEG C, coke oven combustion, Ran Houqi are sent in the 3.0MPa lower carbon number hydrocarbons containing ethane, propane and a small amount of carbon dioxide isolated
- 170 DEG C are mutually cooled further to, the LNG product of methane content >=97% is isolated in 3.0MPa, remaining coke-stove gas is divided into
Two parts, the gas of wherein volume fraction 80% is sent in pressure swing adsorption system 3, is 3.0Mpa, operation temperature in adsorptive pressure
To extract the hydrogen of volume composition >=99.9% under conditions of 40 DEG C, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas
Be mixed into 20% oven gas of walking side line in sulphur protector 5, after the further desulfurization of sulphur protector with from low temperature first
The part circulating air that alcohol washes the partial CO 2 gas, the circulating air of methanol separator 8 and recycle gas compressor 14 of system is mixed
Close and enter in synthesic gas compressor group 4, and control the circulating air sum from methanol separator and oil gas water separator with coming from
The volume ratio for the carbon dioxide sum that the synthesis gas and low-temp methanol of sulphur protector are washed is 4.0, and methanol-fueled CLC is sent to after supercharging
Tower carries out methanol-fueled CLC.
(2) mixed gas from synthesic gas compressor group is through methanol-fueled CLC air preheater 15 and the bottom of methyl alcohol synthetic reactor 6
Work off one's feeling vent one's spleen after heat exchange, the methyl alcohol synthetic reactor of the RK-5 type catalyst produced equipped with Dalian Reak Science and Technology Co., Ltd. is entered from top
It is that 6.5MPa, reaction temperature are 260 DEG C and air speed is to carry out methanol under conditions of 20000L/ (Kgh) in reaction pressure in 6
Synthetic reaction, gaseous products are divided into two strands, wherein the first of volume fraction 70% burst gaseous products from after synthesizing tower bottom discharge
First exchanged heat through methanol-fueled CLC air preheater 15 and import synthesis gas, then enter methanol separator 8 after the condensation of evaporative type cooler 7
In, gas phase is back in synthesic gas compressor group 4 after being discharged from the top of separator, and by groups such as methanol, fusel, water and lower carbon number hydrocarbons
Into crude carbinol liquid phase discharged from the bottom of methanol separator 8 after enter and be filled with the methanol of CT151 type acid-exchange resins
Purified in clarifier 9, the basic nitrogen in crude carbinol be removed to below 20ppm, it is purified after crude carbinol liquid phase first pass through
Methanol preheater 16 is preheated, with second strand of gas of methanol-fueled CLC tower bottom discharge 30% after then being gasified by methanol gasifying device 17
Phase product mix, after being most further heated to 350 DEG C through methanol superheater 18 afterwards, enters from top and JX6201 type catalyst is housed
Synthesis oil reactor 10 in.
(3) gas phase crude carbinol is in synthesis oil reactor 10, and in reaction pressure be 1.5MPa and methanol quality air speed is
1.2h-1Under conditions of reacted after, its product first through artificial oil waste heat boiler 19 reclaim heat, then through methanol superheater 18 with
Gas phase crude carbinol steam heat-exchanging, the liquid phase crude carbinol discharged finally by methanol preheater 16 and the bottom of methanol purification device 9 exchanges heat
Enter afterwards in air cooler 11, synthesis oil product is cooled down by oil product air cooler 11, and further after the cooling of oil product cooler 20
Into in oil gas water separator 12, gas phase is discharged after the supercharging of recycle gas compressor 14 from the top of separator 12, wherein 70%
Gas is back to synthesic gas compressor group as circulating air, and remaining 30% gas is used as periodic off-gases and oil product piece-rate system
Coke oven combustion is sent to after the fuel gas mixing isolated, the process water of condensation is sent to water from after the discharge of the bottom of oil gas water separator 12
Processing system, the water after processing is back to artificial oil waste heat boiler 19 and produces middle pressure steam, and is sent to methanol gasifying device 17 and uses
In methanol gasifying, and the oil phase isolated enters in oil product piece-rate system 14, and fuel gas, liquefied petroleum are obtained after multi-stage separation
Gas (LPG), heavy oil and gasoline products.
The artificial oil product form prepared under the technique and reaction condition of the present embodiment for details see attached table 1.
Table 1
Claims (15)
1. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen, it is characterised in that including following step
Suddenly：
(1) during the coke-stove gas after removing dust and de-oiling is washed into low-temp methanol, sulphur and carbon dioxide in removing coke-stove gas,
The sulphur wherein removed is sent to sulfur recovery system, and a carbon dioxide part for removing is sold as carbon dioxide product, and another portion
Divide and enter in synthesic gas compressor group, the coke-stove gas after removing sulphur and carbon dioxide enters deep cooling methane separation, isolates
Liquid phase methane product is sent to LNG storage tank, and remaining coke-stove gas is divided into two parts, and Part I is sent in pressure-variable adsorption and removed
Hydrogen, hydrogen removes gas holder as product, and Utilization of PSA Relief Gas is mixed into desulfurization with walking the Part II oven gas of side line
In groove, with the circulation of the partial CO 2 gas, methanol separator washed from low-temp methanol after the further desulfurization of desulfurizer
The part circulating air of gas and recycle gas compressor is mixed into synthesic gas compressor group；
(2) mixed gas after the supercharging of synthesic gas compressor group is through methanol-fueled CLC air preheater and methyl alcohol synthetic reactor outlet at bottom gas
After heat exchange, enter from top and methanol synthesis reaction is carried out in methyl alcohol synthetic reactor, gaseous products are divided into from after synthesizing tower bottom discharge
Two strands, wherein first burst of gaseous products first exchanges heat through methanol-fueled CLC air preheater, then enter first after being condensed through evaporative type cooler
In alcohol separator, gas phase is back in synthesic gas compressor group after discharging at the top of the separator, and by methanol, fusel, water and low
Carbon hydrocarbon composition crude carbinol liquid phase from methanol separator bottom discharge after enter methanol purification device in is purified, it is purified after
Crude carbinol liquid phase is first preheated through methanol preheater, the discharged after then being gasified by methanol gasifying device with methanol-fueled CLC tower bottom
Two bursts of gaseous products mixing, most afterwards after methanol superheater further heating, enter in synthesis oil reactor from top；
(3) after gas phase crude carbinol is reacted in synthesis oil reactor, its product first reclaims heat through artificial oil waste heat boiler,
Again through methanol superheater and gas phase crude carbinol steam heat-exchanging, the liquid discharged finally by methanol preheater and methanol purification device bottom
Enter after the heat exchange of phase crude carbinol in air cooler and cool down, and further enter after the cooling of oil product cooler in oil gas water separator,
Gas phase is from after the discharge of separator top is pressurized through recycle gas compressor, and a part of gas is back to synthesis gas as circulating air and compressed
Unit, another part is sent to coke oven combustion, the work of condensation after being mixed as periodic off-gases with the fuel gas that oil product separator is isolated
Skill water is sent to water treatment system after being discharged from oil gas water separator bottom, and the water after processing is back to the production of artificial oil waste heat boiler
Raw middle pressure steam, and methanol gasifying device is sent to for methanol gasifying, and the oil phase isolated enters in oil product separator, through separation
After obtain fuel gas, liquefied petroleum gas, heavy oil and gasoline products.
2. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
The volume composition for levying coke-stove gas after the purified and desulfurization described in being is H250~60%, CO 5%~8%, CO2 1.5
~4%, CH423%~27%, N23~7%, C2Above unsaturated hydrocarbons 2~4%.
3. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
It is that described low-temp methanol is washed and is made up of desulfurizing tower and decarbonizing tower to levy, and operation temperature is -20~-60 DEG C, operating pressure 3~
4.0MPa, the sulphur after being washed through low-temp methanol in gas is removed to 0.01~0.1ppm, CO2It is removed to 0.3~0.8Vol%.
4. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
It is that the described carbon dioxide removed through low-temp methanol elution is divided into two parts to levy, wherein accounting for the titanium dioxide of cumulative volume 30~45%
Carbon goes synthesic gas compressor group, and remaining carbon dioxide is used as product.
5. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
Levy be it is described washed through low-temp methanol after oven gas be the step of carry out deep cooling methane separation：First coke-stove gas is cooled down
After to -85~-70 DEG C, ethane, propane and a small amount of CO are isolated in 3~4.0MPa2Lower carbon number hydrocarbons；Then gas phase is further cooled down
To -175~-150 DEG C, the LNG product of methane content >=97% is isolated in 3.0~4.0MPa, remaining coke-stove gas is sent to
Subsequent cell.
6. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
Levy remaining coke-stove gas after the deep cooling methane separation described in being and be divided into two parts, wherein volume fraction is 70~80% Jiao
Furnace gas enters after pressure-variable adsorption dehydrogenation, and stripping gas enters desulfurizer, and the oven gas of residue 30~40% is without pressure-variable adsorption system
System is directly entered desulfurizer.
7. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
It is that the adsorptive pressure of described pressure-variable adsorption is 3.0~4.0MPa to levy, and operation temperature is 30~40 DEG C, is extracted through pressure-variable adsorption
Volume fraction >=99.9% of hydrogen.
8. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
Levy be described entrance synthesic gas compressor group gas in, the circulating air from methanol separator and oil gas water separator it
Volume ratio with the carbon dioxide sum washed with gas and low-temp methanol from desulfurizer is 4.0~6.0.
9. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, it is special
It is that described methyl alcohol synthetic reactor uses shell-and-tube isothermal reactor to levy, and its reaction pressure is 5.7~6.5MPa, and reaction temperature is
240~260 DEG C, gas space velocity is 15500~20000L/Kgh.
10. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
C306, C307 catalyst or southwest that the catalyst that methanol-fueled CLC described in being characterised by is used is developed for Research Institute of Nanjing Chemical Industry Group
One kind in the C302 catalyst of chemical design institute's exploitation.
11. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
First burst of gaseous products being characterised by described methyl alcohol synthetic reactor outlet gaseous products account for outlet gaseous products cumulative volume
65~75%, and residue 25~35% is second burst of gaseous products.
12. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
The CT151 type acid-exchange resins of filling Piao Laite companies production in described methanol filter are characterised by, and will be thick
Basic nitrogen compound content in methanol is controlled in below 20ppm.
13. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
It is characterised by that it is one-step technology that reaction is carried out in described synthesis oil reactor, its reactor uses heat-insulating fixed bed reaction
Device, 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。
14. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
It is characterised by the GSK-10 types catalysis that the catalyst reacted in described synthesis oil reactor is developed using rope company of Top
Agent.
15. technique of a kind of coke-stove gas through methanol synthesized gasoline, coproduction natural gas and hydrogen as claimed in claim 1, its
It is characterised by the gas discharged at the top of described oil gas water separator after compression, wherein volume fraction is 70~80% gas
Synthesic gas compressor group is back to as circulating air, and remaining 20~30% gas is used as periodic off-gases and oil product piece-rate system
As fuel gas after the fuel gas mixing isolated.
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| CN106831326A (en) * | 2016-12-22 | 2017-06-13 | 赛鼎工程有限公司 | A kind of comprehensive utilization process of coke-stove gas synthesizing methanol co-production liquefied natural gas |
| CN106631693A (en) * | 2016-12-22 | 2017-05-10 | 赛鼎工程有限公司 | Process for efficiently synthesizing methanol and co-producing liquefied natural gas by coke oven gas |
| CN109795986B (en) * | 2019-01-03 | 2020-10-27 | 青海盐湖工业股份有限公司 | Coke oven gas recycling system |
| CN109553508B (en) * | 2019-01-17 | 2024-03-29 | 河北科技大学 | Device and method for producing methanol by directly reforming raw coke oven gas with water vapor |
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| CN101538483A (en) * | 2009-04-03 | 2009-09-23 | 中国科学院山西煤炭化学研究所 | Poly-generation technique for using coal gas and coke oven gas as raw materials |
| CN103275757A (en) * | 2013-05-23 | 2013-09-04 | 陕西煤业化工技术研究院有限责任公司 | Oil-gas coupling poly-generation method in coal chemical engineering industry |
| WO2014063758A1 (en) * | 2012-10-23 | 2014-05-01 | Haldor Topsøe A/S | Process for the preparation of hydrocarbons |
| CN103865599A (en) * | 2012-12-10 | 2014-06-18 | 中冶焦耐工程技术有限公司 | Preparation method of liquefied natural gas (LNG) |
| CN103980093A (en) * | 2014-05-29 | 2014-08-13 | 王天双 | Method for preparing methanol from coke oven gas |
| CN204211706U (en) * | 2014-11-05 | 2015-03-18 | 新奥能源贸易有限公司 | Cog joint is utilized to produce the production equipment of Sweet natural gas and hydrogen |
-
2015
- 2015-07-31 CN CN201510464146.6A patent/CN105062591B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538483A (en) * | 2009-04-03 | 2009-09-23 | 中国科学院山西煤炭化学研究所 | Poly-generation technique for using coal gas and coke oven gas as raw materials |
| WO2014063758A1 (en) * | 2012-10-23 | 2014-05-01 | Haldor Topsøe A/S | Process for the preparation of hydrocarbons |
| CN103865599A (en) * | 2012-12-10 | 2014-06-18 | 中冶焦耐工程技术有限公司 | Preparation method of liquefied natural gas (LNG) |
| CN103275757A (en) * | 2013-05-23 | 2013-09-04 | 陕西煤业化工技术研究院有限责任公司 | Oil-gas coupling poly-generation method in coal chemical engineering industry |
| CN103980093A (en) * | 2014-05-29 | 2014-08-13 | 王天双 | Method for preparing methanol from coke oven gas |
| CN204211706U (en) * | 2014-11-05 | 2015-03-18 | 新奥能源贸易有限公司 | Cog joint is utilized to produce the production equipment of Sweet natural gas and hydrogen |
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