CN104177227A - Method for preparing methanol and coproducing natural gas from coke oven gas and coal gas - Google Patents
Method for preparing methanol and coproducing natural gas from coke oven gas and coal gas Download PDFInfo
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- CN104177227A CN104177227A CN201410459956.8A CN201410459956A CN104177227A CN 104177227 A CN104177227 A CN 104177227A CN 201410459956 A CN201410459956 A CN 201410459956A CN 104177227 A CN104177227 A CN 104177227A
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- 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
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
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- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- 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
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/42—Fischer-Tropsch steps
-
- 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
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10L2290/548—Membrane- or permeation-treatment for separating fractions, components or impurities during preparation or upgrading of a fuel
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- 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)
- Industrial Gases (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing methanol and coproducing natural gas from coke oven gas and coal gas. The method comprises the following steps: coke oven gas is subjected to desulfurization and impurity removal and mixed with treated coal gas, and is compressed to methanol main synthesis pressure and mixed with circulation gas of a methanol main synthesis system; the gas mixture enters the main synthesis system to synthesize methanol; the methanol generated by the main synthesis system is separated by a separator, subjected to flash evaporation in a flash evaporation tank and sent to a methanol rectification system; most of the gas after separation methanol is sent to a main synthesis circulation compressor to be circulated, and the rest gas is discharged out of the main methanol synthesis system as purge gas; the discharged purge gas and small synthesis system circulation gas are mixed to enter a small synthesis system; and the methanol is prepared by a purge gas technique. The irrational hydrogen-carbon ratio in the coke oven gas in the methanol and natural gas coproduction process is regulated by utilizing the coal gas provided by the coal gas making plant, thereby achieving the optimal hydrogen and carbon utilization; and the rich hydrogen and carbon contained in the methanol purged gas are reutilized and subjected to methanation to obtain the natural gas product.
Description
Technical field
The invention belongs to chemical field, relate to chemical field coke(oven)gas and coal gas methyl alcohol processed and Sweet natural gas technology, be specially the method for coke(oven)gas and coal gas methanol with joint production Sweet natural gas processed.
background technology
Along with the economic form of coal chemical enterprise keeps falling, in order to extricate oneself from a predicament, most enterprises starts to consider the comprehensive coproduction Chemicals of coke-oven gas engineering project (such as combined production of methanol, production LNG, synthetic ammonia etc.), thereby realize enterprise transformation upgrading, breaking away from traditional coal chemical enterprise has " Jiao " (coke) to manage situation without the single excessive risk of " change " (Chemicals) product.
The technology that at present domestic large multiple enterprises adopts has synthesizing methanol from coke oven gas, off-gas emptying or use as fuel; After coke-oven gas methanation, produce LNG(or SNG, CNG etc.); After coke(oven)gas conversion, carry hydrogen synthetic ammonia etc.For the operational paths such as more reasonable, economic, effectively to adopt coal chemical enterprise by-product coke-oven gas combined production of methanol, Sweet natural gas, ammonia are still in constantly exploring.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides under a kind of just current economic form, the cost-effective method of utilizing coke-oven gas combined production of methanol and Sweet natural gas, the method recycles the hydrogen being rich in methanol purge gas, carbon, and after methanation, obtain gas product, mixture by coke-oven gas and coal gas can obtain more suitably hydrogen-carbon ratio, is conducive to adjust flexibly products scheme.
For solving the problems of the technologies described above, technical scheme of the present invention is:
The method of coke(oven)gas and coal gas methanol with joint production Sweet natural gas processed, the method has two kinds of modes, first method comprises the following steps: coke(oven)gas mixes with treated coal gas after desulfurization removing impurities matter, then by mixed gas through being compressed to methyl alcohol synthesis pressure and system for methanol synthesis circulation gas is mixed into synthesis system synthesizing methanol, the methyl alcohol that synthesis system generates separates through separator, then go to send methanol fractionation system after flash drum flash distillation, after separation of methanol, gas major part is gone synthesis cycle compressor cycle, small portion is discharged system for methanol synthesis as the venting of speeding, the not step-down of exitting of speeding of discharging directly enters methanation device, at methanation A reactor and second reactor, recycle compressor is set, after methanation device, speed venting in carbon monoxide and carbonic acid gas primitive reaction is complete, in speeding to exit, main component is methane, many carbon hydrocarbon, hydrogen, nitrogen, this speeds venting after dehydration, can obtain respectively natural gas liquids or compressed natural gas by deep cooling or membrane sepn.
The method of coke(oven)gas and coal gas methanol with joint production Sweet natural gas processed, the second way of the method comprises the following steps: coke(oven)gas mixes with treated coal gas after desulfurization removing impurities matter, then mixed gas process is compressed to the main synthesis pressure of methyl alcohol, be mixed into and become owner of synthesis system synthesizing methanol with the main synthesis system circulation gas of methyl alcohol, the methyl alcohol that main synthesis system generates goes to send methanol fractionation system after flash drum flash distillation after separator separates, after separation of methanol, gas major part is gone main synthesis cycle compressor cycle, small portion is discharged main synthesizing methanol system as the venting of speeding, the venting of speeding of discharging is mixed into little synthesis system with little synthesis system circulation gas and produces methyl alcohol, can adopt the patent of speeding to exit (patent No. 201220101633.8) technology to produce methyl alcohol, little synthesis system flow process is identical with main synthesis system flow process, the not step-down of exitting of little speeding after synthetic directly enters methanation device, after methanation device, speed venting in carbon monoxide and carbonic acid gas primitive reaction is complete, in speeding to exit, main component is methane, many carbon hydrocarbon, hydrogen and nitrogen, this speeds venting after dehydration, can obtain respectively natural gas liquids or compressed natural gas by deep cooling or membrane sepn.
After above two kinds of modes are processed rear coke(oven)gas and processing, coal gas mixes rear hydrogen-carbon ratio size, except ensureing that methyl alcohol synthesizes the hydrogen-carbon ratio needing, and also will ensure to speed to exit methanation by carbon monoxide and the complete required amounts of hydrogen of carbon dioxide reaction.
In the time that little synthesis system is set, little synthesis cycle amount size is determined according to carbon monoxide and carbon dioxide content sum in the little synthetic venting of speeding, carbon monoxide and carbon dioxide content sum can ensure to speed to exit and directly enter methanation device and make not overtemperature of methanation reaction, and do not need to arrange methanation recycle compressor.
In the time little synthesis system not being set, the main synthetic venting of speeding enters methanation device, methanation one second order reaction need to arrange recycle compressor and ensure not overtemperature of methanation reaction, and methanation internal circulating load size is determined according to carbon monoxide and carbon dioxide content sum in the venting of speeding.
Above large synthesis system is only relative title with little synthesis system, does not relate to actual size relation.
Positively effect of the present invention is embodied in:
(1) coal gas that the unreasonable situation of ratio, according to the hydrogen-carbon ratio in coke-oven gas when combined production of methanol and the Sweet natural gas utilizes coal generating gas device to provide is allocated, and reaches optimum hydrogen carbon utilization.
(2), the hydrogen being rich in methanol purge gas, carbon are recycled, and after methanation, obtains gas product.
(3), can obtain more suitably hydrogen-carbon ratio by the mixture of coke-oven gas and coal gas, be conducive to adjust flexibly products scheme.
Brief description of the drawings
Fig. 1 is the process flow diagram that in the application, embodiment 1 records;
Fig. 2 is the process flow diagram that in the application, embodiment 2 records.
Wherein, the C1 in figure is methyl methanol syngas recycle compressor, and C2 is little synthesis cycle air compressor, and C3 is methanation recycle gas compressor.
Embodiment
Below the present invention is further detailed explanation for the embodiment by embodiment.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.Without departing from the idea case in the present invention described above, various replacements or the change made according to ordinary skill knowledge and customary means, include within the scope of the invention.
Embodiment 1:
The coke(oven)gas of the present embodiment and coal gas methanol with joint production Sweet natural gas processed techniqueflow is as follows:
Flow process as shown in Figure 1.The present embodiment is coke-oven gas pressure 1.6～2.3 MPa(G after desulfurization removing impurities matter), temperature normal temperature, flow is～25000 Nm
3/ h; Gas pressure 1.6～2.3 MPa(G after treatment), temperature normal temperature, flow～5000 Nm
3/ h(adopts fine coal gas making coal gas amount after treatment) coal gas; The two bursts of mixed hydrogen carbon of gas volume ratio～2.37, compressed to 5.8MPa(G) after and the main synthesis system circulation gas of methyl alcohol be mixed into and become owner of synthesis system synthesizing methanol, the methyl alcohol that main synthesis system generates send methanol fractionation system after separator divides the flash drum flash distillation of leaving away, after separation of methanol, gas major part is gone main synthesis cycle compressor C1 circulation, and small portion is got rid of main synthesizing methanol system as the venting of speeding.After methanol rectification, obtain methanol product～6.36t/h, off-gas tolerance～14330 Nm of eliminating
3/ h, wherein CO+CO
2～10.7%(V), H
2～45.0%(V); Methane～37.3%(V), pressure～5.5 MPa(G), temperature～36 DEG C.The not step-down of exitting of speeding of getting rid of directly enters methanation device, and methanation one second order reaction arranges recycle compressor C3, recycle ratio～1.5.The main component of exitting of speeding after methanation is methane～77.4%(V), many carbon hydrocarbon～5.3%(V), hydrogen～12.1%(V), nitrogen～5.0%(V), CO≤40ppm, CO
2≤ 50ppm; This speeds venting after the pre-treatment such as dehydration, obtains natural gas liquids～7195 Nm by low temperature separation process
3/ h(～5.65t/h), the hydrogen rich off gas in separation can be carried hydrogen or directly use tolerance～1210 Nm as fuel gas
3/ h, low heat value～2643 kcal/Nm
3.
embodiment 2:
The coke(oven)gas of the present embodiment and coal gas methanol with joint production Sweet natural gas processed techniqueflow is as follows:
Flow process as shown in Figure 2.The present embodiment is coke-oven gas pressure 1.6～2.3 MPa(G after desulfurization removing impurities matter), temperature normal temperature, flow is～52300 Nm
3/ h; Gas pressure 1.6～2.3 MPa(G after treatment), temperature normal temperature, flow～9000 Nm
3/ h(adopts fine coal gas making coal gas amount after treatment) coal gas.Coal gas mixes with the pretreated coke-oven gas of process desulfurization removing impurities after treatment, hydrogen carbon volume ratio～2.4 after mixing, compressed to 5.8MPa(G) after and the main synthesis system circulation gas of methyl alcohol be mixed into and become owner of synthesis system synthesizing methanol, the methyl alcohol that main synthesis system generates send methanol fractionation system after separator divides the flash drum flash distillation of leaving away, after separation of methanol, gas major part is gone to main synthesis cycle compressor C1 circulation, main synthesis cycle compressor C1 recycle ratio～5.Small portion is got rid of main synthesizing methanol system as the venting of speeding.Blow off pressure～5.5 MPa(G speeds), temperature normal temperature, the venting of speeding of getting rid of is mixed into little synthesis system with little synthesis system circulation gas, adopts patent (patent No. 201220101633.8) technology of speeding to exit to produce methyl alcohol, and little synthesis system flow process is identical with main synthesis system flow process.Little synthesis cycle compressor C2 recycle ratio～5.The methyl alcohol that little synthesis system generates send in the lump methanol fractionation system with the main synthetic methyl alcohol obtaining after separating, and obtains product methyl alcohol～17.05t/h through rectifying; Little synthesis purge gas pressure～5.2 MPa(G), temperature normal temperature, tolerance～22080 Nm
3/ h, wherein CO+CO
2～4.4%(V), H
2～35.6%(V); Methane～48.9%(V).The little synthetic not step-down of speeding to exit directly enters methanation device, and methanation device does not need to establish methanation recycle compressor C3.The main component of exitting of speeding after methanation is methane～62.9%(V), many carbon hydrocarbon～5.0%(V), hydrogen～24.4%(V), nitrogen～7.4%(V), CO≤40ppm, CO
2≤ 50ppm; This speeds venting after the pre-treatment such as dehydration, obtains natural gas liquids～12500 Nm by low temperature separation process
3/ h(～9.96t/h), or obtain after SNG, SNG can continue to compress obtaining CNG by membrane sepn.
Claims (5)
1. the method for coke(oven)gas and coal gas methanol with joint production Sweet natural gas processed, it is characterized in that the method comprises the following steps: coke(oven)gas mixes with treated coal gas after desulfurization removing impurities matter, then by mixed gas through being compressed to methyl alcohol synthesis pressure and system for methanol synthesis circulation gas is mixed into synthesis system synthesizing methanol, the methyl alcohol that synthesis system generates separates through separator, then go to send methanol fractionation system after flash drum flash distillation, after separation of methanol, gas major part is gone synthesis cycle compressor cycle, and small portion is discharged system for methanol synthesis as the venting of speeding; The not step-down of exitting of speeding of discharging directly enters methanation device, at methanation A reactor and second reactor, recycle compressor is set, after methanation device, speed venting in carbon monoxide and carbonic acid gas primitive reaction is complete, in speeding to exit, main component is methane, many carbon hydrocarbon, hydrogen, nitrogen, this speeds venting after dehydration, can obtain respectively natural gas liquids or compressed natural gas by deep cooling or membrane sepn.
2. the method for coke(oven)gas according to claim 1 and coal gas methanol with joint production Sweet natural gas processed, it is characterized in that the method comprises the following steps: coke(oven)gas mixes with treated coal gas after desulfurization removing impurities matter, then mixed gas process is compressed to the main synthesis pressure of methyl alcohol, be mixed into and become owner of synthesis system synthesizing methanol with the main synthesis system circulation gas of methyl alcohol, the methyl alcohol that main synthesis system generates goes to send methanol fractionation system after flash drum flash distillation after separator separates, after separation of methanol, gas major part is gone main synthesis cycle compressor cycle, small portion is discharged main synthesizing methanol system as the venting of speeding, the venting of speeding of discharging is mixed into little synthesis system with little synthesis system circulation gas and produces methyl alcohol, little synthesis system flow process is identical with main synthesis system flow process, the not step-down of exitting of little speeding after synthetic directly enters methanation device, after methanation device, speed venting in carbon monoxide and carbonic acid gas primitive reaction is complete, in speeding to exit, main component is methane, many carbon hydrocarbon, hydrogen and nitrogen, this speeds venting after dehydration, can obtain respectively natural gas liquids or compressed natural gas by deep cooling or membrane sepn.
3. according to the method for claim 1 or coke(oven)gas claimed in claim 2 and coal gas methanol with joint production Sweet natural gas processed, it is characterized in that: after processing, coke(oven)gas mixes rear hydrogen-carbon ratio size with coal gas after processing, except ensureing the synthetic hydrogen-carbon ratio needing of methyl alcohol, also to ensure to speed to exit methanation by carbon monoxide and the complete required amounts of hydrogen of carbon dioxide reaction.
4. the method for coke(oven)gas according to claim 2 and coal gas methanol with joint production Sweet natural gas processed, it is characterized in that: in the time that little synthesis system is set, little synthesis cycle amount size is determined according to carbon monoxide and carbon dioxide content sum in the little synthetic venting of speeding, carbon monoxide and carbon dioxide content sum can ensure to speed to exit and directly enter methanation device and make not overtemperature of methanation reaction, and do not need to arrange methanation recycle compressor.
5. the method for coke(oven)gas according to claim 1 and coal gas methanol with joint production Sweet natural gas processed, it is characterized in that: in the time little synthesis system not being set, the main synthetic venting of speeding enters methanation device, methanation one second order reaction need to arrange recycle compressor and ensure not overtemperature of methanation reaction, and methanation internal circulating load size is determined according to carbon monoxide and carbon dioxide content sum in the venting of speeding.
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| CN201410459956.8A CN104177227B (en) | 2014-09-11 | 2014-09-11 | The method of coke(oven)gas and coal gas methanol with joint production Sweet natural gas |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745257A (en) * | 2015-03-10 | 2015-07-01 | 华南理工大学 | System and process for producing natural gas through combined supply of coal and coke-oven gas |
| CN105062590A (en) * | 2015-07-31 | 2015-11-18 | 赛鼎工程有限公司 | Comprehensive utilization technology used for production of gasoline and liquefied natural gas through methanol synthesis of coke coal gas and used for deep processing of tar |
| CN106520240A (en) * | 2015-09-15 | 2017-03-22 | 上海华西化工科技有限公司 | Process for synthesis of LNG by methanol purge gas methanation |
| 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 |
| CN106699508A (en) * | 2016-12-22 | 2017-05-24 | 赛鼎工程有限公司 | Process for high-efficiency and environment-friendly synthesis of methanol by coke oven gas |
| 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 |
| CN107118818A (en) * | 2016-02-25 | 2017-09-01 | 中国石油化工股份有限公司 | The technique that a kind of utilization methanol purge gas synthesizes LNG |
| CN108265145A (en) * | 2018-01-26 | 2018-07-10 | 中国科学院上海高等研究院 | A kind of utilization method and system of carbon dioxide enriched blast furnace gas |
| CN110002953A (en) * | 2019-04-30 | 2019-07-12 | 华南理工大学 | A kind of process and device of static bed coal gasification synthesis of methanol with joint production LNG |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104745257A (en) * | 2015-03-10 | 2015-07-01 | 华南理工大学 | System and process for producing natural gas through combined supply of coal and coke-oven gas |
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| CN105062590B (en) * | 2015-07-31 | 2017-07-11 | 赛鼎工程有限公司 | A kind of comprehensive utilization process of coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and tar deep processing |
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| 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 |
| CN106699508A (en) * | 2016-12-22 | 2017-05-24 | 赛鼎工程有限公司 | Process for high-efficiency and environment-friendly synthesis of methanol by coke oven gas |
| 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 |
| CN108265145A (en) * | 2018-01-26 | 2018-07-10 | 中国科学院上海高等研究院 | A kind of utilization method and system of carbon dioxide enriched blast furnace gas |
| CN110002953A (en) * | 2019-04-30 | 2019-07-12 | 华南理工大学 | A kind of process and device of static bed coal gasification synthesis of methanol with joint production LNG |
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