CN104119975A - Method of combined production of methanol and liquefied natural gas in coking plant - Google Patents

Method of combined production of methanol and liquefied natural gas in coking plant Download PDF

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CN104119975A
CN104119975A CN201410313760.8A CN201410313760A CN104119975A CN 104119975 A CN104119975 A CN 104119975A CN 201410313760 A CN201410313760 A CN 201410313760A CN 104119975 A CN104119975 A CN 104119975A
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gas
coke
methanol
oven
natural gas
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CN201410313760.8A
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CN104119975B (en
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王洪记
褚宏春
李存宝
梁道广
吕运江
朱本启
张志伟
郭宝贵
李存涛
石柏洲
亓栋
宋淑群
王伟
赵忠萍
金俊杰
王艾青
邢涛
李仕超
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兖矿集团有限公司煤化分公司
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Abstract

The invention belongs to the technical field of comprehensive coke-oven gas utilization, and particularly relates to a method of combined production of methanol and liquefied natural gas (LNG) in a coking plant. Coke-oven gas is subjected to temperature swing adsorption (TSA), desulphurization, vacuum pressure swing adsorption (VPSA), and other purifying treatment, and is subjected to cryogenic liquidation separation to obtain a liquefied natural gas (LNG) product. The main component of the non-liquefied part is (CO+H2), and is adopted as methanol synthesis gas used for producing methanol, wherein the insufficient carbon component based on the H2is supplied by continuous oxygen-rich gas production from chopped coke having a size of 7-24 mm by a normal-pressure gasifier. The method achieves direct utilization of CH4 that is one of the main components of the coke-oven gas, the (CO+H2) are directly used for methanol synthesis, and the insufficient carbon source is supplied by a normal-pressure gasifier adopting the chopped coke produced by the coking plant as a gas production raw material, and therefore intermolecular conversion and other main energy-consumption sections and high-investment devices are reduced, the whole process is simplified, the comprehensive energy consumption for producing the methanol and the liquefied natural gas (LNG) is low, the whole economic benefit of coking enterprises is increased, and the investment is saved.

Description

The method of coke-oven plant's combined production of methanol and natural gas liquids
Technical field
The invention belongs to coke(oven)gas comprehensive utilization technique field, be specially the method for coke-oven plant's combined production of methanol and natural gas liquids (LNG).
Background technology
China is coke production big country, a large amount of coke(oven)gas of by-product in coke production, and especially independent coke-oven plant of large-scale coke-oven plant must the feasible effective coke(oven)gas comprehensive utilization device of auxiliary construction.Coke(oven)gas comparison of ingredients is complicated and unstable, and generally, the coke(oven)gas low heat value after purifying is 17580～18420kJ/m 3, density is 0.45～0.48kg/m 3, it is few that the principal feature of component shows as the many carbon of hydrogen, according to volume fraction meter, and CH in coke(oven)gas 4nearly 25%, CO, CO 2, CH 4, CnHm adds up to approximately 40%, H 2can be up to 60%.
According to the component feature of coke(oven)gas, the at present main approach that utilizes, the one, be directly used in city domestic gas, this approach is limited by the factors such as region, civilian tolerance, combustion cleaning, is progressively being replaced by Sweet natural gas; The 2nd, for gas turbine power generation, this utilizes the economic benefit of approach to be limited by networking electricity price; The 3rd, through transforming, carry the chemical such as the different courses of processing such as hydrogen, synthesizing methanol, synthetic ammonia; The 4th, through courses of processing such as methanations, the clean fuels such as production synthetic natural gas (SNG), compressed natural gas (CNG) or natural gas liquids (LNG).Because the chemical such as methyl alcohol, synthetic ammonia is basic chemical industry raw material, of many uses; Sweet natural gas is the cleanest domestic gas and industrial raw material, is also the best substitute of motor vehicle gasoline, has the features such as calorific value is high, good environmental protection, cheapness, and therefore latter two approach is the main direction of coke(oven)gas comprehensive utilization.
The prior art processes flow process of coke(oven)gas LNG processed is illustrated as shown in Figure 1.
The method of existing coke(oven)gas preparing liquefied natural gas (LNG), for improving methane production, its core reaction is CO, CO 2the methanation reaction of hydrogenation.CO, CO after coke(oven)gas purifies 2content is mostly 7%～11%, and pressurization enters methanation device, CO and CO 2generate methane with H-H reaction, simultaneously a small amount of oxygen also generates water with hydrogen reaction.After refrigerated separation is fallen water, enter pressure-variable adsorption (PSA) tripping device, obtain containing CH 490% gas product (being synthetic natural gas SNG), compressed, decarburization, dry, cryogenic liquefying obtain natural gas liquids (LNG), and the isolated hydrogen rich off gas of PSA needs comprehensive utilization.
Because methanation reaction is all strong exothermal reactions, temperature rise ratio is larger, and the thermal insulation warming of every conversion 1%CO is about 63 DEG C, every conversion 1%CO 2thermal insulation warming be about 50.5 DEG C, along with temperature raise, CO and CO 2equilibrium conversion reduce.Because CO content in coke(oven)gas is high, directly carry out methanation reaction with coke(oven)gas, temperature out is up to more than 650 DEG C, and this is unfavorable to methanation reaction, CO and CO 2transformation efficiency lower.For fear of reaction outlet excess Temperature, take multistage reaction, in the middle of reaction, heat exchange is cooling, walks heat with vapor zone, and to control temperature rise, or the gas circulation of having taked part methanation goes back to dilute raw coke oven gas, thereby reduces import CO concentration.
There is obvious shortcoming in above-mentioned technical process, although methanation reaction can increase gas production, it is that to sacrifice total energy be cost.Because methanation is by CO, CO in coke(oven)gas 2(accounting for 10% left and right) hydrogenation becomes CH 4, methanation is actually coke(oven)gas component readjusts the process of combination, to CH 4, CO, CO 2, H 2four kinds of effective gas composition restructuring, by effective gas CO, the CO of methanol 2, H 2be converted into CH by methanation 4, not the direct utilization to effective gas composition, do not possess " molecule economy ", and methanation power loss is huge, although the energy of loss reclaims major part with the form that produces steam, but still lose more than gain.
At present, the existing technical process of coke(oven)gas methanol is illustrated as shown in Figure 2.
The CH that contains 25% left and right due to coke(oven)gas 4, be rich in H 2, must be converted into and mainly contain CO, CO through conversion section for the production of methyl alcohol 2and H 2the synthetic gas that is 2.10～2.15 Deng composition, hydrogen-carbon ratio.Therefore, conversion section is the core workshop section of this technique, conventionally adopts the Technology of " heat exchange type coke(oven)gas pressurized catalysis partial oxidation process producing synthesis gas ", and invert point maintains 1000 DEG C of left and right substantially.In order to improve CH 4equilibrium conversion, and prevent from analysing on catalyzer charcoal reaction, cause catalyst deactivation, need to add a large amount of steam.At conversion section, the coke(oven)gas after purification enters process furnace preheating after saturator is adjusted vapour coke ratio, then enters converter and under the effect of catalyzer, carries out partial oxidation reaction with the pure oxygen dividing from sky and transform.Pyrolytic conversion gas is through the useless pot of high pressure and the useless pot difference by-product middle pressure steam of low pressure and a low-pressure saturated steam, and reforming gas send compression section synthesic gas compressor again after boiler water-suppling heater, de-salted water well heater, water cooler are cooling afterwards.CO, CO in synthetic gas 2with H 2synthesizing methanol under the effect of catalyzer is emitted large calorimetric by-product middle pressure steam simultaneously.
The problem that this technique exists is: in order to improve methanol output, coke(oven)gas major part need be converted into methyl methanol syngas, the one, coke(oven)gas need to be converted into methyl methanol syngas by conversion section, conversion process energy consumption is high, safety operation degree requires high, does not possess " molecule economy "; The 2nd, conversion section needs pure oxygen, needs auxiliary construction large-scale space division device, and investment increases greatly, and for 200,000 t/a preparing methanol from coke oven gas devices, conversion and supporting Kong Fen workshop section investment account for 1/3 of whole investment in fixed assets.
Summary of the invention
The present invention is directed to coke(oven)gas component feature, good in conjunction with the self-produced 7～24mm chopped cooked entrails of sheep of coal chemical enterprise coke inner quality, price is low, the practical situation of sales difficulty, integrated by process optimization, the method for coke-oven plant's combined production of methanol and natural gas liquids (LNG) is provided.Coke(oven)gas, through purifying treatment such as Temp .-changing adsorption (TSA), desulfurization, Vacuum Pressure Swing Adsorption (VPSA), separates and obtains natural gas liquids (LNG) product through cryogenic liquefying, and the part main component of liquefaction is not (CO+H 2), as methyl methanol syngas, for the production of methyl alcohol, not enough carbon component is with H 2for benchmark, supplemented by the burnt oxygen enrichment atmospheric gasification stove gas processed continuously of 7～24mm chopped cooked entrails of sheep.The present invention realizes one of coke(oven)gas main ingredient CH 4direct utilization, (CO+H 2) to be directly used in methyl alcohol synthetic, it is self-produced chopped cooked entrails of sheep Jiao in coke-oven plant that not enough carbon source adopts normal pressure Gas-making Furnace, gas making raw material, main energy consumption workshop section and the devices with high investment such as intermolecular conversion are reduced, integrated artistic process simplification, the comprehensive energy consumption of methanol and natural gas liquids (LNG) is low, can improve coal chemical enterprise whole economic efficiency, reduce investment outlay.
Technical scheme of the present invention:
The method of coke-oven plant's combined production of methanol and natural gas liquids, comprises the steps:
Gas holder transports that 40 DEG C, 0～10kPa coke(oven)gas are compressed enters Temp .-changing adsorption pretreatment process (TSA) to 1.05MPa; Then through hydrogenating desulfurization and smart desulfurization organic sulfide removal and hydrogen sulfide, enter Vacuum Pressure Swing Adsorption operation (VPSA), remove CO 2, the heavy hydrocarbon such as ammonia and benzene, enter cryogenic liquefying operation and obtain natural gas liquids (LNG) product, the ice chest discharge gas main component after purification LNG is CO, H 2, send the synthetic compression section of methyl alcohol as methyl methanol syngas, transport water-gas with the burnt gas operation processed of 7～24mm chopped cooked entrails of sheep and merge for the production of methyl alcohol;
The step of the described burnt gas operation processed of 7～24mm chopped cooked entrails of sheep is: the oxygen of 7～24mm chopped cooked entrails of sheep Jiao, 0.3MPa steam and purity 99.6% enters the continuous Gas-making Furnace of normal pressure oxygen enrichment, and water produced coal gas enters buffer gas tank through dust-removal and desulfurizing rough purification operation; Compressed wet desulphurization, the smart desulfurization depth cleaning section of entering of this rough purification gas, after deep purifying with above-mentioned purification LNG after ice chest discharge gas preparation hydrogen-carbon ratio be 2.10～2.15 methyl methanol syngas, the synthetic methanol product of compressed, methyl alcohol.
Described Temp .-changing adsorption pretreatment process (TSA), comprise pretreater, resurgent gases well heater, the steps include: to enter after Temp .-changing adsorption (TSA) pretreatment process from 40 DEG C of compressor outlet, 1.05MPa coke(oven)gas, alternately realize coke(oven)gas and purify by absorption, regeneration by pretreater; Naphthalene, tar and part NH in coke(oven)gas 3, H 2s and other heavy hydrocarbons impurity are adsorbed at normal temperatures, desorption after heater via is heated to 180 DEG C, and desorption stripping gas is sent the comprehensive utilization of coke oven heating pipe network back to, and the coke(oven)gas after purification removes hydrogenating desulfurization, smart desulfurization process.
Described hydrogenating desulfurization is for adopting secondary hydrogenation iron molybdenum conversion catalyst, and 280～320 DEG C of temperature, pressure 2.5MPa, for removing COS, thiophene and other organosulfur of coke(oven)gas; Warm Zinc oxide desulfurizer during described smart desulfurization adopts, 350 DEG C of temperature, pressure 2.4MPa, for removing H 2s, the two configured in series, desulfurization precision reaches H 2s content is less than 0.1ppm.
Described Vacuum Pressure Swing Adsorption operation (VPSA), comprises adsorption tower and vacuum pump, the steps include: under 40 DEG C, 2.3MPa pressure the CO in desulfurizing and purifying gas 2, the impurity such as ammonia absorbed by silica type, the agent of molecular sieve combine adsorption, the component not being adsorbed is discharged and is entered cryogenic liquefying operation, the CO being adsorbed from tower top 2, the foreign gas such as ammonia, benzene sends into the comprehensive utilization of coke oven heating pipe network after by desorption desorb.By all pressure, step-downs, vacuumize desorption and the adsorbent reactivation of realizing foreign gas, the hocket absorption, regenerative operation of multiple adsorption towers can realize the object of continuous imurity-removal.
Described LNG cryogenic liquefying operation is divided into drying section, demercuration workshop section and deep cooling workshop section, as follows in detail:
A) drying section
Drying process before ice chest is made up of one group of Temp .-changing adsorption pre-treatment (TSA) drying tower, comprises pretreater, resurgent gases well heater, for adsorbing and removing H 20 and CO 2;
B) demercuration workshop section
Process drying process is by H in gas 2o is removed to 1ppm, CO 2be removed to after 10ppm, purified gas enters demercuration reactor again the Trace Mercury containing in unstripped gas is removed, and to protect follow-up ice chest not to be corroded, then send deep cooling workshop section;
After above-mentioned purification and dry, demercuration are processed, enter impurity in the purified gas of deep cooling workshop section and reach following index: water < 1ppm(V), CO 2< 10ppm(V), mercury < 0.01 μ g/m 3, aromatics < 10ppm(V), dust < 5 μ m;
C) deep cooling workshop section
Cryogenic technology adopts the not circulation of the mix refrigerant with precooling (MRC) and nitrogen auxiliary cooling, cryogenic temperature-160～-175 DEG C, pressure 1.5～4.5MPa.
The burnt gas operation processed of described 7～24mm chopped cooked entrails of sheep is selected the continuous Gas-making Furnace of normal pressure oxygen enrichment gas processed, and tolerance processed is discharged gas as benchmark taking the ice chest after purification LNG, the methyl methanol syngas that preparation hydrogen-carbon ratio is 2.10～2.15.
Described rough purification operation adopts Venturi scrubber, carbon to wash tower scrubbing dust collection desulfurization; Described deep purifying operation adopts MDEA method, NHD method, tannin extract method or modified ADA method wet desulphurization decarburization, and smart desulfurization adopts zinc oxide method, H in the methyl methanol syngas after purification 2s content is less than 0.1ppm.
Methyl alcohol synthesizes in employing, low pressure methanol synthesis technique, and 210～270 DEG C of synthesis pressure 5.0～13.0MPa, temperature, adopt Cu-series catalyst.
The synthetic stove heating pipe network comprehensive utilization that defocuses of speeding to exit of methyl alcohol.
Beneficial effect of the present invention is:
1. the present invention has realized by coke(oven)gas methanol coproduction LNG, has reduced methanation workshop section and conversion section, process simplification, and simple to operate, energy consumption is low, invests low.
2. the present invention has realized the direct utilization of coke(oven)gas active principle, realizes " molecule economy ", i.e. active principle CH in coke(oven)gas 4directly produce natural gas liquids (LNG), CO, H through pressure-variable adsorption 2component is for the production of methyl alcohol, and not enough carbon component is with H 2for benchmark, to be supplemented by the burnt oxygen enrichment gas processed continuously of 7～24mm chopped cooked entrails of sheep, whole economic efficiency is high, invests lowly, has stopped the strong exothermal reaction steps such as intermolecular conversion, and art breading is simplified, reduced investment.
3. methanol of the present invention, has reduced conversion section, does not need auxiliary construction large-scale space division device, and the simple and investment of flow process reduces.
4. the present invention has taken into full account that the burnt price of the self-produced 7～24mm chopped cooked entrails of sheep of coal chemical enterprise is low, the reality of sales difficulty, proposes coke(oven)gas and separates after LNG for the production of carbon component not enough in the synthetic gas of methyl alcohol with H 2for benchmark, to be supplemented by the burnt oxygen enrichment gas processed continuously of self-produced 7～24mm chopped cooked entrails of sheep, whole economic efficiency is high, invests low.
5. the present invention has taken into full account the possibility of the large-scale coal chemical enterprise enforcement technological transformation of coke(oven)gas per unit area yield methyl alcohol, be conducive to such enterprise implement technological transformation, not only can increase natural gas liquids (LNG) product innovation, adjust the product mix, improve product specification, can also ensure that original methanol production scale does not reduce, existing air separation facility can provide cold for preparing natural gas liquids (LNG), be that the burnt oxygen enrichment continuously of 7～24mm chopped cooked entrails of sheep air lift processed is for required oxygen simultaneously, improve enterprise energy, assets and device utilising efficiency, effectively reduce investment for trnasforming urban land.
In a word, processing method of the present invention, has realized effective utilization of resource, and the enterprise present situation taking into full account, is beneficial to corporation improvement and production, under minimum invest in the transformation of real estate, obtains very high interests and benefit, also meets the call of current energy-saving and emission-reduction.
Brief description of the drawings
Fig. 1 is the prior art processes schema of the coke(oven)gas LNG processed of background technology record.
Fig. 2 is the existing process flow sheet of the coke(oven)gas methanol of background technology record.
embodiment
Below by specific embodiment, technical scheme of the present invention is described in detail.
Embodiment
From the coke(oven)gas 55000Nm of coking system gas holder 3/ h, 40 DEG C of temperature, pressure 0～10kPa, component (v%): H 261.88, CH 424.52, CO 7.25, CO 22.0, N 24.29, O 20.06, H 2s 100mg/Nm 3, ammonia 270 mg/Nm 3, tar 10mg/Nm 3, naphthalene 150mg/Nm 3, organosulfur 200mg/Nm 3, benzene 3150mg/Nm 3.To 1.05MPa, enter Temp .-changing adsorption pretreatment process (TSA) through coke(oven)gas compressor compresses, in the time that service temperature is 40 DEG C, remove naphthalene, tar and part NH by pretreater absorption 3, H 2the impurity such as S, benzene, desorption after pretreater heater via is heated to 180 DEG C, desorption stripping gas is sent the comprehensive utilization of coke oven heating pipe network back to.In coke(oven)gas after pre-treatment purifies, remain at impurity H 2s 80mg/Nm 3, ammonia 162 mg/Nm 3, organosulfur 120mg/Nm 3, benzene 2520mg/Nm 3, under 300 DEG C of temperature, pressure 2.5MPa condition, COS, thiophene and other organosulfur in secondary hydrogenation iron molybdenum conversion catalytic eliminating coke(oven)gas, through the middle temperature Zinc oxide desulfurizer of configured in series, under 350 DEG C of temperature, pressure 2.4MPa condition, remove H 2s, makes H in coke(oven)gas 2s content is less than 0.1ppm.Purified gas after above-mentioned desulfurization, under 40 DEG C, 2.3MPa pressure, enters Vacuum Pressure Swing Adsorption (VPSA) operation, CO 2, the impurity such as ammonia, benzene is adsorbed agent and absorbs, and by all pressure, step-downs, vacuumize desorption and the adsorbent reactivation of realizing foreign gas, at this moment forms desorption gas 1769Nm 3/ h, mainly contains the CO being adsorbed 2, impurity and a small amount of H such as ammonia, benzene 2, CH 4, the inflammable gas such as CO, send into the comprehensive utilization of coke oven heating pipe network, purified gas 53097Nm 3/ h discharges and enters cryogenic liquefying operation from tower top.In cryogenic liquefying operation, first the TSA drying tower of drying workshop section further adsorbs and removes H 20 and CO 2, by H in gas 2o is removed to below 1ppm, CO 2be removed to below 10ppm, then the demercuration reactor that enters demercuration workshop section removes the Trace Mercury that may contain in purified gas, for protecting follow-up ice chest not to be corroded, take off the 0.01 μ g/m to mercury < 3, finally in temperature-170 DEG C, under pressure 2.5MPa condition, carry out cryogenic liquefying separation, obtain natural gas liquids (LNG) product 12896Nm 3/ h, wherein CH 4content (v%) is greater than 99.9; Obtain hydrogen-rich synthetic gas 40201Nm 3/ h, component (v%): H 284.06, CH 40.49, CO 9.70, CO 20.01, N 25.74, for compounding methanol synthetic gas.
The oxygen 9000Nm of 7～24mm chopped cooked entrails of sheep burnt 16.875t/h, 0.3MPa steam 27t/h and purity 99.6% 3/ h enters the continuous Gas-making Furnace of normal pressure oxygen enrichment, and water produced coal gas is washed the rough purifications such as tower scrubbing dust collection desulfurization through Venturi scrubber, carbon, obtain 40 DEG C, 0.104MPa water-gas 36000Nm 3/ h enters buffer gas tank storage, component (v%): H 235.0, CO 45.8, CO 217.5, CH 40.5, N 20.9, O 20.3, H 2s 40mg/Nm 3, organosulfur 120mg/Nm 3.Gas holder comes that 30 DEG C of rough purification gas is compressed enters NHD desulfurization and decarburization, zinc oxide essence desulfurization even depth cleaning section to 2.45MPa, by H 2s content takes off to 0.1ppm, obtains synthetic gas 30667Nm 3/ h, component (v%): H 240.67, CO 53.23, CO 24.13, CH 40.57, N 21.05, O 20.35.40201Nm after this purified gas and said extracted LNG 3/ h hydrogen-rich synthetic gas merges, the methyl methanol syngas that preparation hydrogen-carbon ratio is 2.15.Methyl methanol syngas is compressed to 5.5MPa, under 250 DEG C of temperature, Cu-series catalyst condition, and synthesizing methanol 30t/h, the synthetic 5635Nm that exits that speeds of methyl alcohol 3/ h stove heating pipe network the comprehensive utilization that defocuses.

Claims (9)

1. the method for coke-oven plant's combined production of methanol and natural gas liquids, comprises the steps:
Gas holder transports that 40 DEG C, 0～10kPa coke(oven)gas are compressed enters Temp .-changing adsorption pretreatment process to 1.05MPa; Then through hydrogenating desulfurization and smart desulfurization organic sulfide removal and hydrogen sulfide, enter Vacuum Pressure Swing Adsorption operation, remove CO 2, the heavy hydrocarbon such as ammonia and benzene, enter cryogenic liquefying operation and obtain liquefied natural gas product, the ice chest discharge gas main component after purification LNG is CO, H 2, send the synthetic compression section of methyl alcohol as methyl methanol syngas, transport water-gas with the burnt gas operation processed of 7～24mm chopped cooked entrails of sheep and merge for the production of methyl alcohol;
The step of the described burnt gas operation processed of 7～24mm chopped cooked entrails of sheep is: the oxygen of 7～24mm chopped cooked entrails of sheep Jiao, 0.3MPa steam and purity 99.6% enters the continuous Gas-making Furnace of normal pressure oxygen enrichment, and water produced coal gas enters buffer gas tank through dust-removal and desulfurizing rough purification operation; Compressed wet desulphurization, the smart desulfurization depth cleaning section of entering of this rough purification gas, after deep purifying with above-mentioned purification LNG after ice chest discharge gas preparation hydrogen-carbon ratio be 2.10～2.15 methyl methanol syngas, the synthetic methanol product of compressed, methyl alcohol.
2. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, it is characterized in that, described Temp .-changing adsorption pretreatment process, comprise pretreater, resurgent gases well heater, the steps include: to enter after Temp .-changing adsorption treatment process from 40 DEG C of compressor outlet, 1.05MPa coke(oven)gas, alternately realize coke(oven)gas and purify by absorption, regeneration by pretreater; Naphthalene, tar and part NH in coke(oven)gas 3, H 2s and heavy hydrocarbons impurity are adsorbed at normal temperatures, desorption after heater via is heated to 180 DEG C, and desorption stripping gas is sent the comprehensive utilization of coke oven heating pipe network back to, and the coke(oven)gas after purification removes hydrogenating desulfurization, smart desulfurization process.
3. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, it is characterized in that, described hydrogenating desulfurization is for adopting secondary hydrogenation iron molybdenum conversion catalyst, and 280～320 DEG C of temperature, pressure 2.5MPa, for removing COS, thiophene and other organosulfur of coke(oven)gas; Warm Zinc oxide desulfurizer during described smart desulfurization adopts, 350 DEG C of temperature, pressure 2.4MPa, for removing H 2s, the two configured in series.
4. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, it is characterized in that, described Vacuum Pressure Swing Adsorption operation (VPSA), comprises adsorption tower and vacuum pump, the steps include: under 40 DEG C, 2.3MPa pressure the CO in desulfurizing and purifying gas 2, the impurity such as ammonia absorbed by silica type, the agent of molecular sieve combine adsorption, the component not being adsorbed is discharged and is entered cryogenic liquefying operation from tower top.
5. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, is characterized in that, described LNG cryogenic liquefying operation is divided into drying section, demercuration workshop section and deep cooling workshop section, as follows in detail:
A) drying section
Drying process before ice chest is made up of one group of Temp .-changing adsorption pre-treatment drying tower, comprises pretreater, resurgent gases well heater, for adsorbing and removing H 20 and CO 2;
B) demercuration workshop section
Process drying process is by H in gas 2o is removed to 1ppm, CO 2be removed to after 10ppm, purified gas enters demercuration reactor again the Trace Mercury containing in unstripped gas is removed, and to protect follow-up ice chest not to be corroded, then send deep cooling workshop section;
C) deep cooling workshop section
Cryogenic technology adopts the not circulation of the mix refrigerant with precooling and nitrogen auxiliary cooling, cryogenic temperature-160～-175 DEG C, pressure 1.5～4.5MPa.
6. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, it is characterized in that, the burnt gas operation processed of described 7～24mm chopped cooked entrails of sheep is selected the continuous Gas-making Furnace of normal pressure oxygen enrichment gas processed, tolerance processed is discharged gas as benchmark taking the ice chest after purification LNG, the methyl methanol syngas that preparation hydrogen-carbon ratio is 2.10～2.15.
7. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, is characterized in that, described rough purification operation adopts Venturi scrubber, carbon to wash tower scrubbing dust collection desulfurization; Described deep purifying operation adopts MDEA method, NHD method, tannin extract method or modified ADA method wet desulphurization decarburization, and smart desulfurization adopts zinc oxide method.
8. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, is characterized in that, methyl alcohol synthesizes in employing, low pressure methanol synthesis technique, and 210～270 DEG C of synthesis pressure 5.0～13.0MPa, temperature, adopt Cu-series catalyst.
9. the method for coke-oven plant according to claim 1 combined production of methanol and natural gas liquids, is characterized in that, the synthetic stove heating pipe network comprehensive utilization that defocuses of speeding to exit of methyl alcohol.
CN201410313760.8A 2014-07-03 2014-07-03 Coke-oven plant's combined production of methanol and the method for liquefied natural gas CN104119975B (en)

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CN105110291A (en) * 2015-07-21 2015-12-02 河南环宇石化装备科技股份有限公司 Method for preparation of LNG from recovered coke oven gas and co-production of synthetic ammonia
CN105152864A (en) * 2015-07-31 2015-12-16 赛鼎工程有限公司 Technology for producing low carbon alcohol as well as by-product natural gas and liquefied ammonia from coke oven gas and synthetic gas
CN105176612A (en) * 2015-07-31 2015-12-23 赛鼎工程有限公司 Technology for preparing low-carbon alcohol and by-products of natural gas and hydrogen from coke oven gas
CN105296036A (en) * 2015-12-03 2016-02-03 南京国昌化工科技有限公司 Polygeneration method for synthesizing methanol, natural gas and ammonia
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CN106241736A (en) * 2016-08-03 2016-12-21 西南化工研究设计院有限公司 A kind of technique utilizing coke-stove gas extraction metallurgy reducing gases
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