CN104418703A - Serial methanol and methane synthesis process taking coke-oven gas as raw material - Google Patents
Serial methanol and methane synthesis process taking coke-oven gas as raw material Download PDFInfo
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- CN104418703A CN104418703A CN201310396839.7A CN201310396839A CN104418703A CN 104418703 A CN104418703 A CN 104418703A CN 201310396839 A CN201310396839 A CN 201310396839A CN 104418703 A CN104418703 A CN 104418703A
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 205
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 86
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002994 raw material Substances 0.000 title claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 104
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 10
- 238000005057 refrigeration Methods 0.000 claims abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000000571 coke Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229930195733 hydrocarbon Natural products 0.000 claims description 13
- 239000003345 natural gas Substances 0.000 claims description 13
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 239000011593 sulfur Substances 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003546 flue gas Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 230000023556 desulfurization Effects 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001741 organic sulfur group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- -1 carbon hydrocarbon Chemical class 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 claims 1
- 239000003949 liquefied natural gas Substances 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000003517 fume Substances 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 239000012263 liquid product Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002918 waste heat Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229940105296 zinc peroxide Drugs 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/1516—Multisteps
- C07C29/1518—Multisteps one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0485—Set-up of reactors or accessories; Multi-step processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a serial methanol and methane synthesis process taking coke-oven gas as a raw material. The serial methanol and methane synthesis process comprises the following steps: capturing CO2 from fume, adding into the coke-oven gas to adjust the hydrogen-carbon ratio; performing an NHD-process rough desulfuration and dry-process fine desulfuration, thereby obtaining a purified qualified synthesis gas; synthesizing methanol by using the synthesis gas in a methanol synthesis unit under the action of a methanol synthesis catalyst firstly, and performing heat exchange and cooling separation, thereby obtaining crude methanol; refining the crude methanol, thereby obtaining a fine methanol product; feeding the gas (generated after the crude methanol is separated) into a methane synthesis unit, completing methane synthesis reaction through three serially connected methane synthesis reactors, and performing cryogenic refrigeration on the generated gas, thereby obtaining liquefied natural gas of which the content of alkane is greater than 94%. According to the process, since the methanol synthesis unit is serially connected in front of the methane synthesis units, COX(CO+CO2) in the synthesis gas is reduced to be within 13%, the synthesis gas can be directly fed into the methane synthesis units without being diluted, and the whole synthesis process is simplified.
Description
Technical field
The invention belongs to new energy field, relating to a kind of take coke(oven)gas as series connection methyl alcohol, the process for synthesizing methane of raw material.
Background technology
Coke-oven gas is the byproduct in process of coking, its main component is hydrogen (55% ~ 60%) and methane (23% ~ 27%), in addition also containing a small amount of carbon monoxide (5% ~ 8%), more than C2 unsaturated hydrocarbons (2% ~ 4%), carbonic acid gas (1.5% ~ 3%), oxygen (0.3% ~ 0.8%), nitrogen (3% ~ 7%).Coke(oven)gas can be used as combustion gas, can also be used as the unstripped gas of Chemical Manufacture.
At present, the chemical utilization of coke(oven)gas is mainly used to methanol.According to incompletely statistics, current domestic coke(oven)gas methanol device has nearly 70 covers, and aggregated capacity is more than 9,000,000 t/a, and feature is that unit scale is relatively little, and majority is 100,000 t/a ~ 200,000 t/a.Under the serious superfluous background of China's methyl alcohol production capacity, methanol market is weak, and coke-oven gas methyl alcohol prospect allows of no optimist.And China's natural gas insufficiency of supply-demand is very large, in the long run, China's natural gas price will in progressively up-trend.
Coke(oven)gas is a kind of gas of rich hydrogen, (H wherein
2-CO
2/ CO+CO
2) reach 6 ~ 8, no matter still all there is H for the production of natural gas liquids for methanol
2excessive problem, in order to maximally utilise resource, needs to mend carbon to coke(oven)gas.Can to mix with coke(oven)gas with the gas compared with low hydrogen-carbon ratio and regulate (H
2-CO
2/ CO+CO
2) to 2.3 ~ 3.0.In process of coking, 45% ~ 50% of coke(oven)gas total amount will return pit kiln as heating gas, containing a large amount of CO in the flue gas of post combustion emission
2, can CO be trapped
2be supplemented in coke(oven)gas and regulate hydrogen-carbon ratio, reach the object increasing methyl alcohol and liquefied natural gas (LNG)-throughput.
Mend CO
2after synthetic gas in CO
xcontent reaches 17%, directly enters methane synthesis reactor and reaction bed temperature can be made to be raised to more than 900 DEG C, cause catalyst deactivation.
Summary of the invention
The object of this invention is to provide a kind of take coke(oven)gas as series connection methyl alcohol, the process for synthesizing methane of raw material.
The present invention take coke(oven)gas as series connection methyl alcohol, the process for synthesizing methane of raw material, and it is characterized in that mending the qualified coke(oven)gas of carbon after purification is raw material, adopts methyl alcohol, methane series connection synthesis technique combined production of methanol, natural gas liquids.
The qualified gas of described purification is first through methanol synthesis unit, and then through methane synthesis unit, all reactors are single pass reactors.
Described after methanol-fueled CLC, CO and CO in synthetic gas
2concentration sum <13%, directly enters the first methane synthesis reactor without dilution, within the scope that the temperature rise control of the first methane synthesis reactor allows at wide temperature methane synthesizing catalyst.
The temperature rise control of described first methane synthesis reactor is in 440 DEG C.
Described methane synthesis unit adopts three adiabatic methane synthesis reactors to connect, wherein, first methane synthesis reactor adopts the operation of wide temperature, reactor inlet temperature is 260 DEG C ~ 300 DEG C, temperature out 650 DEG C ~ 700 DEG C, second methane synthesis reactor temperature in is 260 DEG C ~ 300 DEG C, temperature out 500 DEG C ~ 600 DEG C, and leucoaurin synthesis reactor temperature in is 260 DEG C ~ 280 DEG C, temperature out 300 DEG C ~ 350 DEG C.
The coke(oven)gas that this technique mends carbon after purification qualified is raw material, adopts methyl alcohol, methane series connection synthesis technique combined production of methanol, natural gas liquids.Methanol synthesis unit is set before methane synthesis, first can consumes a part of CO by methanol-fueled CLC
x, make the CO entering methane synthesis unit
xcontrol within the range of permission, the first methane synthesis reactor just can adopt adiabatic reactor, and synthetic gas directly can enter without dilution, and beds temperature rise can control within 440 DEG C of scopes of wide temperature methane synthesizing catalyst permission.
A kind of typical technique of the present invention, comprises following unit process:
(1) synthetic gas prepares: coke(oven)gas carries out the process such as detar, naphthalene, benzene, ammonia, then adds the CO trapped from the flue gas of pit kiln discharge
2, (the H of adjustments of gas
2-CO
2/ CO+CO
2) to 2.3 ~ 3.0.Then compression boosts to 3.0 ~ 8.0MPa, then through the desulfurization of NHD method, Organic sulfur hydro-conversion, fine de-sulfur, total sulfur content is removed to below 0.1ppm.
(2) methanol synthesis unit: purify qualified unstripped gas one way by methyl alcohol synthetic reactor, carry out methanol-fueled CLC under the effect of efficient low pressure methanol synthesis catalyzer, reacted gas obtains crude carbinol by heat exchange refrigerated separation, then obtains refined methanol through rectifying.Gas after separation of methanol washes the remaining methyl alcohol of removing with water through washing tower.
(3) methane synthesis unit: through washing except the gas of methyl alcohol carries out methane building-up reactions through the adiabatic methane synthesis reactor of three series connection, CO content in gas is reduced to 50ppm, CO
2content is reduced to less than 1.5%.
(4) deep refrigeration unit: by deep refrigeration, the methane gas, the liquefaction of many carbon hydrocarbon are separated from methane synthesis reactor gas out, obtain the natural gas liquids of hydrocarbon content more than 94%, be rich in hydrogen in remaining gas phase.
The present invention take coke(oven)gas as raw material methanol and natural gas liquids simultaneously, compared with traditional preparing methanol from coke oven gas technique, flow process simplifies greatly, eliminate air separation facility, pure oxygen catalytic partial oxidation converter and methanol synthesis loop compression system etc., greatly reduce plant investment, reduce working cost.
Mend the qualified synthetic gas of carbon after purification can directly to connect methanol and natural gas liquids, methanol-fueled CLC wherein and methane synthesis are one way reaction, and methanol sythesis reactor and the first methane synthesis reactor all do not need to be equipped with gas-circulating system, simplify flow process.
Accompanying drawing explanation
Fig. 1 is that the benefit carbon of the embodiment of the present invention prepares synthesis gas process general flow chart, and Fig. 2 is series connection methyl alcohol, the process for synthesizing methane general flow chart of the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in detail.
The technological process of embodiment as shown in figure 1 and 2.
Embodiment 1
Coke(oven)gas supplements CO
2regulate (H
2-CO
2/ CO+CO
2) to 2.3 ~ 3.0, compressedly boost to 8.4MPa, then wet method crude desulfurization, fine desulfurization process by dry to below total sulfur content 0.1ppm, be purified qualified synthetic gas.
When synthetic gas enters methyl alcohol synthetic reactor, pressure is 8.1MPa, temperature is 220 DEG C, methanol-fueled CLC reaction is carried out under the effect of low pressure methanol synthesis catalyzer, the liquid product that reacted gas is obtained by heat exchange refrigerated separation is crude carbinol, then obtains refined methanol through rectifying.Be separated (H in the gas after liquid product
2-CO
2/ CO+CO
2) be about 3, CO
xcontent <11%, enters washing tower and washes remaining methyl alcohol with water, then enter methane synthesis unit.
Methane synthesis unit is made up of two adiabatic methane synthesis reactors of connecting, and gas is warmed up to 250 DEG C through heat exchange and enters the first methane synthesis reactor, and methane synthesis liberated heat makes gas temperature rise to 600 DEG C; Reclaim its reaction heat by heat exchanger, waste heat boiler, by-product ultra-high voltage superheated vapour (11MPa) from the first methane synthesis reactor gas out, after heat exchange, synthetic gas temperature is down to about 250 DEG C.Enter second stage methane synthesis reactor again, after reaction, gas temperature rises to 450 DEG C, and in gas, CO content is reduced to 100ppm, CO
2content is reduced to 1.5%, obtains the gas-phase product of hydrocarbon content 88% after the water that refrigerated separation generates
.
By gas-phase product deep refrigeration to-165 DEG C, the CH in gas
4be separated with more than C2 hydro carbons and obtain the natural gas liquids of hydrocarbon content more than 94%.
Embodiment 2
The flue gas discharged pit kiln combustion chamber introduces CO
2capture unit, adopts pressure swing absorption process to obtain the CO of purity 99%
2; Coke(oven)gas after the pre-treatment such as detar, de-benzene, de-naphthalene with the CO trapped from flue gas
2mixing, compressedly boosts to 5.4MPa, then through the desulfurization of NHD method, is then warmed up to 220 DEG C, enters hydrocracking stove and the organic sulfur conversion in coke(oven)gas is become inorganic sulfur, then through zinc peroxide fine de-sulfur, total sulfur is removed to below 0.1ppm, obtain consisting of H
253%%, C
2h
62%, CH
428%, CO 6%, CO
210%, N
2the synthetic gas of 1%.
When synthetic gas enters methyl alcohol synthetic reactor, pressure is 5.3MPa, temperature is 220 DEG C, methanol-fueled CLC reaction is carried out under the effect of low pressure methanol synthesis catalyzer, the liquid product that reacted gas is obtained by heat exchange refrigerated separation is crude carbinol, then obtains refined methanol through rectifying.Be separated (H in the gas after liquid product
2-CO
2/ CO+CO
2) be about 3, CO
xcontent <13%, enters washing tower and washes remaining methyl alcohol with water, then enter methane synthesis unit.
Methane synthesis unit is made up of three adiabatic methane synthesis reactors of connecting, and gas is warmed up to 250 DEG C through heat exchange and enters the first methane synthesis reactor, and methane synthesis liberated heat makes gas temperature rise to 680 DEG C; Reclaim its reaction heat by heat exchanger, waste heat boiler, by-product ultra-high voltage superheated vapour (11MPa) from the first methane synthesis reactor gas out, after heat exchange, synthetic gas temperature is down to about 250 DEG C.Enter second stage methane synthesis reactor again, after reaction, gas temperature rises to 600 DEG C, is cooled to 260 DEG C enters leucoaurin synthesis reactor by heat exchange, and after reaction, gas temperature is 360 DEG C, and in gas, CO content is reduced to 50ppm, CO
2content is reduced to 1%, obtains the gas-phase product of hydrocarbon content 90% after the water that refrigerated separation generates
.
By gas-phase product deep refrigeration to-165 DEG C, the CH in gas
4be separated with more than C2 hydro carbons and obtain the natural gas liquids of hydrocarbon content more than 94%.
Embodiment 3
The flue gas discharged pit kiln combustion chamber introduces CO
2capture unit, adopts membrane separating method to obtain the CO of purity 99%
2; Coke(oven)gas after the pre-treatment such as detar, de-benzene, de-naphthalene with the CO trapped from flue gas
2mixing, compressedly boosts to 6.4MPa, then through the desulfurization of NHD method, is then warmed up to 220 DEG C, enters hydrocracking stove and the organic sulfur conversion in coke(oven)gas is become inorganic sulfur, then through zinc peroxide fine de-sulfur, total sulfur is removed to below 0.1ppm, obtain consisting of H
253%%, C
2h
62%, CH
428%, CO 6%, CO
210%, N
2the synthetic gas of 1%.
When synthetic gas enters methyl alcohol synthetic reactor, pressure is 6.3MPa, temperature is 220 DEG C, methanol-fueled CLC reaction is carried out under the effect of low pressure methanol synthesis catalyzer, the liquid product that reacted gas is obtained by heat exchange refrigerated separation is crude carbinol, then obtains refined methanol through rectifying.Be separated (H in the gas after liquid product
2-CO
2/ CO+CO
2) be about 3, CO
xcontent <12%, enters washing tower and washes remaining methyl alcohol with water and make gas carry the moisture of 20%, then enter methane synthesis unit.
Methane synthesis unit is made up of three adiabatic methane synthesis reactors of connecting, and gas is warmed up to 250 DEG C through heat exchange and enters the first methane synthesis reactor, and methane synthesis liberated heat makes gas temperature rise to 650 DEG C; Reclaim its reaction heat by heat exchanger, waste heat boiler, by-product ultra-high voltage superheated vapour (11MPa) from the first methane synthesis reactor gas out, after heat exchange, synthetic gas temperature is down to about 250 DEG C.Enter second stage methane synthesis reactor again, after reaction, gas temperature rises to 560 DEG C, is cooled to 260 DEG C enters leucoaurin synthesis reactor by heat exchange, and after reaction, gas temperature is 370 DEG C, and in gas, CO content is reduced to 80ppm, CO
2content is reduced to 1.2%, obtains the gas-phase product of hydrocarbon content 90% after the water that refrigerated separation generates
.
By gas-phase product deep refrigeration to-165 DEG C, the CH in gas
4be separated with more than C2 hydro carbons and obtain the natural gas liquids of hydrocarbon content more than 94%.
Claims (9)
1. one kind take coke(oven)gas as series connection methyl alcohol, the process for synthesizing methane of raw material, comprise following unit step: synthetic gas prepares, methanol synthesis unit, methane synthesis unit, deep refrigeration unit, it is characterized in that mending the qualified coke(oven)gas of carbon after purification is raw material, adopts methyl alcohol, methane series connection synthesis technique combined production of methanol, natural gas liquids.
2. technique as claimed in claim 1, it is characterized in that purifying qualified gas first through methanol synthesis unit, then through methane synthesis unit, all reactors are single pass reactors.
3. method as claimed in claim 2, is characterized in that after methanol-fueled CLC, CO and CO in synthetic gas
2concentration sum <13%, directly enters the first methane synthesis reactor without dilution, within the scope that the temperature rise control of the first methane synthesis reactor allows at wide temperature methane synthesizing catalyst.
4. method as claimed in claim 3, is characterized in that the temperature rise control of the first methane synthesis reactor is in 440 DEG C.
5. method as claimed in claim 2, it is characterized in that methane synthesis unit adopts three adiabatic methane synthesis reactors to connect, wherein, first methane synthesis reactor adopts the operation of wide temperature, reactor inlet temperature is 260 DEG C ~ 300 DEG C, temperature out 650 DEG C ~ 700 DEG C, second methane synthesis reactor temperature in is 260 DEG C ~ 300 DEG C, temperature out 500 DEG C ~ 600 DEG C, and leucoaurin synthesis reactor temperature in is 260 DEG C ~ 280 DEG C, temperature out 300 DEG C ~ 350 DEG C.
6. technique as claimed in claim 1, is characterized in that described synthetic gas is prepared as: coke(oven)gas carries out detar, naphthalene, benzene, ammonia treatment, then adds the CO trapped from the flue gas of pit kiln discharge
2, (the H of adjustments of gas
2-CO
2/ CO+CO
2) to 2.3 ~ 3.0, then compression boosts to 3.0 ~ 8.0MPa, then through the desulfurization of NHD method, Organic sulfur hydro-conversion, fine de-sulfur, total sulfur content is removed to below 0.1ppm.
7. technique as claimed in claim 1, it is characterized in that described methanol synthesis unit is: purify qualified unstripped gas one way and pass through methyl alcohol synthetic reactor, methanol-fueled CLC is carried out under the effect of efficient low pressure methanol synthesis catalyzer, reacted gas obtains crude carbinol by heat exchange refrigerated separation, obtain refined methanol through rectifying again, the gas after separation of methanol washes the remaining methyl alcohol of removing with water through washing tower.
8. technique as claimed in claim 1, is characterized in that described methane synthesis unit is: through the gas of washing except methyl alcohol, the adiabatic methane synthesis reactor through three series connection carries out methane building-up reactions, and CO content in gas is reduced to 50ppm, CO
2content is reduced to less than 1.5%.
9. technique as claimed in claim 1, it is characterized in that described deep refrigeration unit is: the methane gas, the liquefaction of many carbon hydrocarbon are separated from methane synthesis reactor gas out by deep refrigeration, the liquid-phase product obtained is the natural gas liquids of hydrocarbon content more than 94%, is rich in hydrogen in gas phase.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105294394A (en) * | 2015-05-08 | 2016-02-03 | 徐州伟天化工有限公司 | Methanol co-production recycling system |
| CN114082287A (en) * | 2021-11-25 | 2022-02-25 | 中化学科学技术研究有限公司 | Method and system for directly hydrogenating flue gas |
| CN114349602A (en) * | 2020-10-12 | 2022-04-15 | 中石化南京化工研究院有限公司 | Process for synthesizing low-carbon mixed alcohol with coal-to-synthesis gas as raw material and tandem methanation |
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| CN114082287A (en) * | 2021-11-25 | 2022-02-25 | 中化学科学技术研究有限公司 | Method and system for directly hydrogenating flue gas |
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