CN104119975B - Coke-oven plant's combined production of methanol and the method for liquefied natural gas - Google Patents
Coke-oven plant's combined production of methanol and the method for liquefied natural gas Download PDFInfo
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Abstract
The invention belongs to oven gas technical field of comprehensive utilization, specially coke-oven plant's combined production of methanol and the method for liquefied natural gas (LNG).Oven gas is through purified treatment such as temp.-changing adsorption (TSA), desulfurization, Vacuum Pressure Swing Adsorption (VPSA), and through cryogenic liquefying isolated liquefied natural gas (LNG) product, the part not liquefied is mainly composed of (CO+H2), it being used for producing methanol as methyl methanol syngas, not enough carbon component is with H2On the basis of, the burnt continuous oxygen-enriched atmospheric gasification stove gas of the 7～24mm chopped cooked entrails of sheep supplement.The present invention realizes one of oven gas key component CH4Directly utilize, (CO+H2) it is directly used in methanol-fueled CLC, not enough carbon source uses normal pressure Gas-making Furnace, gas making raw material to be that the self-produced chopped cooked entrails of sheep in coke-oven plant are burnt, decrease main energy consumption workshop section and the devices with high investment such as intermolecular conversion, integrated artistic process simplification, the comprehensive energy consumption producing methanol and liquefied natural gas (LNG) is low, coal chemical enterprise whole economic efficiency can be improved, reduce investment outlay.
Description
Technical field
The invention belongs to oven gas technical field of comprehensive utilization, specially coke-oven plant's combined production of methanol and the method for liquefied natural gas (LNG).
Background technology
China is coke production big country, a large amount of oven gas of by-product in coke production, and the most independent coke-oven plant of large-scale coke-oven plant must the feasible effective oven gas comprehensive utilization device of auxiliary construction.Oven gas comparison of ingredients is complicated and unstable, and generally, the oven gas low heat value after purifying is 17580～18420kJ/m3, density is 0.45～0.48kg/m3, it is few that the main feature of component shows as the many carbon of hydrogen, according to volume fraction, and CH in oven gas4Nearly 25%, CO, CO2、CH4, CnHm add up to about 40%, H2May be up to 60%.
Component feature according to oven gas, utilization ways currently mainly, one is to be directly used in city domestic gas, and this approach is limited by the factors such as region, civilian tolerance, combustion cleaning, is the most progressively replaced by natural gas；Two is for gas turbine power generation, and the economic benefit of this utilization ways is limited by networking electricity price；Three is through converting, putting forward the different courses of processing such as hydrogen, the chemicals such as synthesizing methanol, synthesis ammonia；Four is through courses of processing such as methanations, produces the cleaning fuel such as synthetic natural gas (SNG), compressed natural gas (CNG) or liquefied natural gas (LNG).Owing to the chemicals such as methanol, synthesis ammonia are basic chemical industry raw materials, of many uses；Natural gas is the cleanest domestic gas and the raw material of industry, is also the best substitute of motor vehicle gasoline, has calorific value height, good environmental protection, the feature such as cheap, and therefore latter two approach is the Main way of oven gas comprehensive utilization.
The prior art processes flow process of oven gas LNG is illustrated as shown in Figure 1.
The method of existing oven gas preparing liquefied natural gas (LNG), for improving methane production, its core reaction is CO, CO2The methanation reaction of hydrogenation.CO, CO after oven gas purification2Content is mostly 7%～11%, and pressurization enters methanation device, CO and CO2React generation methane with hydrogen, simultaneously a small amount of oxygen also with hydrogen water generation reaction.Cooled separate water after, enter pressure-variable adsorption (PSA) segregation apparatus, obtain containing CH4The product gas (i.e. synthetic natural gas SNG) of 90%, compressed, decarburization, be dried, cryogenic liquefying obtains liquefied natural gas (LNG), the isolated hydrogen rich off gas of PSA needs comprehensive utilization.
Being all strong exothermal reaction due to methanation reaction, temperature rise ratio is relatively big, and the adiabatic temperature rise often converting 1%CO is about 63 DEG C, often converts 1%CO2Adiabatic temperature rise be about 50.5 DEG C, along with temperature raise, CO and CO2Equilibrium conversion reduce.Owing to CO content is high in oven gas, directly carrying out methanation reaction with oven gas, outlet temperature is up to more than 650 DEG C, and this is unfavorable to methanation reaction, CO and CO2Conversion ratio relatively low.In order to avoid reaction outlet temperature is too high, taking multistage to react, i.e. the cooling of reaction intermediate heat transfer, walks heat with steam zone, and to control temperature rise, or the gas taked portion of methane loops back to dilute raw coke oven gas, thus reduces import CO concentration.
There is obvious shortcoming in above-mentioned technological process, although methanation reaction can increase gas production, but it is to sacrifice gross energy as cost.Because methanation is by CO, CO in oven gas2(accounting for about 10%) hydrogenation becomes CH4, methanation actually oven gas component readjusts the process of combination, i.e. to CH4、CO、CO2、H2Four kinds of effective gas composition restructuring, will produce effective gas CO, CO of methanol2、H2It is converted into CH by methanation4, it is not that effective gas composition is directly utilized, does not possesses " molecular economy ", and methanation energy loss is huge, although the energy of loss reclaims major part with the form producing steam, but still lose more than gain.
At present, oven gas produces the existing technological process signal of methanol as shown in Figure 2.
Owing to oven gas contains the CH of about 25%4, rich in H2, it is used for producing methanol and has to pass through conversion section and be converted into and mainly have CO, CO2And H2It is the synthesis gas of 2.10～2.15 Deng composition, hydrogen-carbon ratio.Therefore, conversion section is the core workshop section of this technique, generally uses the Technology of " heat exchange type oven gas pressurized catalysis partial oxidation process producing synthesis gas ", and conversion temperature maintains essentially in about 1000 DEG C.In order to improve CH4Equilibrium conversion, and prevent on catalyst occur analysis charcoal reaction, cause catalysqt deactivation, need to add a large amount of steam.Oven gas after conversion section, purification enters heating furnace preheating after saturator adjusts vapour coke ratio, carries out partial oxidation reaction with the pure oxygen from space division subsequently into reburner and convert under the effect of catalyst.Pyrolytic conversion gas gives up pot and low pressure is given up pot by-product middle pressure steam and low-pressure saturated steam respectively through high pressure, converts gas afterwards and send compression section synthesic gas compressor after boiler water-suppling heater, desalted water heater, water cooler cooling again.CO, CO in synthesis gas2With H2Synthesizing methanol under the effect of catalyst, releases big calorimetric by-product middle pressure steam simultaneously.
This technique there is the problem that to improve methanol output, oven gas need to be largely converted into methyl methanol syngas, one is to need by conversion section, oven gas is converted into methyl methanol syngas, and conversion process energy consumption is high, safety operation degree requires height, does not possesses " molecular economy "；Two is that conversion section needs pure oxygen, needs auxiliary construction large-scale space division device, and investment is greatly increased, and for 200,000 t/a preparing methanol from coke oven gas devices, converts and the investment of supporting space division workshop section accounts for the 1/3 of whole investment in fixed assets.
Summary of the invention
The present invention is directed to oven gas component feature, good in conjunction with coal chemical enterprise self-produced 7～24mm chopped cooked entrails of sheep coke inherent quality, price is low, the practical situation of sales difficulty, integrated by process optimization, it is provided that coke-oven plant's combined production of methanol and the method for liquefied natural gas (LNG).Oven gas is through purified treatment such as temp.-changing adsorption (TSA), desulfurization, Vacuum Pressure Swing Adsorption (VPSA), and through cryogenic liquefying isolated liquefied natural gas (LNG) product, the part not liquefied is mainly composed of (CO+H2), it being used for producing methanol as methyl methanol syngas, not enough carbon component is with H2On the basis of, the burnt continuous oxygen-enriched atmospheric gasification stove gas of the 7～24mm chopped cooked entrails of sheep supplement.The present invention realizes one of oven gas key component CH4Directly utilize, (CO+H2) it is directly used in methanol-fueled CLC, not enough carbon source uses normal pressure Gas-making Furnace, gas making raw material to be that the self-produced chopped cooked entrails of sheep in coke-oven plant are burnt, decrease main energy consumption workshop section and the devices with high investment such as intermolecular conversion, integrated artistic process simplification, the comprehensive energy consumption producing methanol and liquefied natural gas (LNG) is low, coal chemical enterprise whole economic efficiency can be improved, reduce investment outlay.
Technical scheme:
Coke-oven plant's combined production of methanol and the method for liquefied natural gas, comprise the steps:
It is compressed to 1.05MPa entrance temp.-changing adsorption pretreatment process (TSA) that gas holder conveying comes 40 DEG C, 0～10kPa oven gas；The most hydrogenated desulfurization and fine de-sulfur remove organic sulfur and hydrogen sulfide, enter Vacuum Pressure Swing Adsorption operation (VPSA), remove CO2, the heavy hydrocarbon such as ammonia and benzene, entering cryogenic liquefying operation obtains liquefied natural gas (LNG) product, purifies the discharge gas of the ice chest after LNG and is mainly composed of CO, H2, send methanol-fueled CLC compression section as methyl methanol syngas, carry out water gas with 7～24mm chopped cooked entrails of sheep Jiao's gas operation conveyings and merge for producing methanol；
The step of 7～24mm described chopped cooked entrails of sheep Jiao's gas operations is: the oxygen of 7～24mm chopped cooked entrails of sheep Jiao, 0.3MPa steam and purity 99.6% enters the oxygen-enriched continuous Gas-making Furnace of normal pressure, and water produced coal gas removing dust desulfurization preliminary purification operation enters buffer gas tank；The compressed entrance wet desulphurization of this preliminary purification gas, fine de-sulfur deep purifying operation, 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, compressed, methanol-fueled CLC produces methanol product.
Described temp.-changing adsorption pretreatment process (TSA), including pretreater, regeneration gas heater, after the steps include: that 40 DEG C from compressor outlet, 1.05MPa oven gas enter temp.-changing adsorption (TSA) pretreatment process, pretreater alternately realize oven gas by absorption, regeneration and purify；Naphthalene, tar and part NH in oven gas3、H2S and other heavy hydrocarbons impurity are adsorbed at normal temperatures, and heater via is desorbed after being heated to 180 DEG C, and desorption stripping gas is sent coke oven heating pipeline coordination back to and utilized, and the oven gas after purification goes hydrodesulfurization, fine de-sulfur operation.
Described hydrodesulfurization is for using secondary hydrogenation ferrum molybdenum conversion catalyst, and temperature 280～320 DEG C, pressure 2.5MPa, for removing COS, thiophene and other organic sulfur in oven gas；Described fine de-sulfur uses middle temperature Zinc oxide desulfurizer, temperature 350 DEG C, pressure 2.4MPa, is used for removing H2S, the two arranged in series, desulfurization precision reaches H2S content is less than 0.1ppm.
Described Vacuum Pressure Swing Adsorption operation (VPSA), including adsorption tower and vacuum pump, the steps include: 40 DEG C, under 2.3MPa pressure, the CO in desulfurizing and purifying gas2, the impurity such as ammonia absorbed by silica type, molecular sieve combine adsorption agent, component not to be adsorbed is discharged into cryogenic liquefying operation, adsorbed CO from tower top2, ammonia, the foreign gas such as benzene utilizes by sending into coke oven heating pipeline coordination after desorption desorbing.Realized desorption and the adsorbent reactivation of foreign gas by all pressures, blood pressure lowering, evacuation, multiple adsorption towers alternately adsorb, regenerative operation can realize the purpose of continuous imurity-removal.
Described LNG cryogenic liquefying operation is divided into drying section, demercuration workshop section and deep cooling workshop section, as follows:
A) drying section
Drying process before ice chest is made up of one group of temp.-changing adsorption pretreatment (TSA) drying tower, including pretreater, regeneration gas heater, is used for adsorbing and removing H20 and CO2；
B) demercuration workshop section
Through drying process by H in gas2O is removed to 1ppm, CO2After being removed to 10ppm, purify gas and enter back into the Trace Mercury removing that demercuration reactor will contain in unstripped gas, to protect follow-up ice chest not to be corroded, then send deep cooling workshop section；
Through above-mentioned purification be dried, after demercuration processes, enter impurity in the purification gas of deep cooling workshop section and reach following index: water ＜ 1ppm(V), CO2＜ 10ppm(V), hydrargyrum ＜ 0.01 μ g/m3, aromatic compound ＜ 10ppm(V), dust ＜ 5 μm；
C) deep cooling workshop section
Cryogenic technology uses the mixed-refrigerant cycle (MRC) without pre-cooling and nitrogen auxiliary cooling, cryogenic temperature-160～-175 DEG C, pressure 1.5～4.5MPa.
7～24mm described chopped cooked entrails of sheep Jiao's gas operations select the oxygen-enriched continuous Gas-making Furnace gas of normal pressure, and on the basis of the tolerance processed ice chest discharge gas after purifying LNG, preparation hydrogen-carbon ratio is the methyl methanol syngas of 2.10～2.15.
Described preliminary purification operation uses Venturi scrubber, carbon to wash tower cleaning dust desulfurization；Described deep purifying operation uses MDEA method, NHD method, tannin process or modified ADA method wet desulphurization decarburization, and fine de-sulfur uses zinc oxide method, H in the methyl methanol syngas after purification2S content is less than 0.1ppm.
Methanol-fueled CLC use in, low pressure methanol synthesis technique, synthesis pressure 5.0～13.0MPa, temperature 210～270 DEG C, use Cu-series catalyst.
Methanol-fueled CLC periodic off-gases goes coke oven heating pipeline coordination to utilize.
The invention have the benefit that
1. present invention achieves and produced methanol with joint production LNG by oven gas, decrease methanation workshop section and conversion section, process simplification, simple to operate, energy consumption is low, invests low.
2. present invention achieves directly utilizing of oven gas active component, it is achieved the active component CH in " molecular economy ", i.e. oven gas4It is directly over pressure-variable adsorption and produces liquefied natural gas (LNG), CO, H2Component is used for producing methanol, and not enough carbon component is with H2On the basis of, the burnt continuous oxygen-enriched gas processed of the 7～24mm chopped cooked entrails of sheep to supplement, whole economic efficiency is high, invests low, has stopped the strong exothermal reaction steps such as intermolecular conversion, and PROCESS FOR TREATMENT simplifies, reduced investment.
3. the present invention produces methanol, decreases conversion section, it is not necessary to auxiliary construction large-scale space division device, and flow process is simple and investment reduces.
4. the present invention has taken into full account that coal chemical enterprise self-produced 7～24mm chopped cooked entrails of sheep Jiao's price is low, the reality of sales difficulty, proposes carbon component not enough in the synthesis gas producing methanol after oven gas separates LNG with H2On the basis of, the burnt continuous oxygen-enriched gas processed in self-produced 7～the 24mm chopped cooked entrails of sheep to supplement, whole economic efficiency is high, invests low.
5. the present invention has taken into full account that the large-scale coal chemical enterprise of oven gas per unit area yield methanol implements the probability of technological transformation, be conducive to such enterprise implement technological transformation, not only can increase liquefied natural gas (LNG) new product, adjust the product mix, improve product specification, also ensure that original methanol production scale does not reduces, existing air separation unit can be to prepare liquefied natural gas (LNG) to provide cold, it is that the burnt continuous oxygen-enriched air stripping processed of the 7～24mm chopped cooked entrails of sheep is for required oxygen simultaneously, improve enterprise energy, assets and device utilization ratio, effectively reduce investment for trnasforming urban land.
In a word, the process of the present invention, it is achieved that effective utilization of resource, and the enterprise present situation taken into full account, beneficially corporation improvement and production, under minimum investment transformation, obtains the highest interests and benefit, also complies with the call of current energy-saving and emission-reduction.
Accompanying drawing explanation
Fig. 1 is the prior art processes flow chart of the oven gas LNG that background technology is recorded.
Fig. 2 is the existing process chart that the oven gas that background technology is recorded produces methanol.
Detailed description of the invention
Below by specific embodiment, technical scheme is described in detail:
Embodiment
Oven gas 55000Nm from coking system gas holder3/ h, temperature 40 DEG C, pressure 0～10kPa, component (v%): H261.88,CH424.52,CO7.25,CO22.0,N24.29,O20.06,H2S100mg/Nm3, ammonia 270mg/Nm3, tar 10mg/Nm3, naphthalene 150mg/Nm3, organic sulfur 200mg/Nm3, benzene 3150mg/Nm3.Through oven gas compressor compresses to 1.05MPa, enter temp.-changing adsorption pretreatment process (TSA), removed naphthalene, tar and part NH when operating temperature and being 40 DEG C by pretreater absorption3、H2The impurity such as S, benzene, pretreater heater via is desorbed after being heated to 180 DEG C, and desorption stripping gas is sent coke oven heating pipeline coordination back to and utilized.Oven gas after pretreatment purification remains at impurity H2S80mg/Nm3, ammonia 162mg/Nm3, organic sulfur 120mg/Nm3, benzene 2520mg/Nm3, under the conditions of temperature 300 DEG C, pressure 2.5MPa, COS, thiophene and other organic sulfur in secondary hydrogenation ferrum molybdenum shift catalyst removing oven gas, it is concatenated the middle temperature Zinc oxide desulfurizer of configuration, under the conditions of temperature 350 DEG C, pressure 2.4MPa, removes H2S, makes H in oven gas2S content is less than 0.1ppm.Purification gas after above-mentioned desulfurization 40 DEG C, under 2.3MPa pressure, enter Vacuum Pressure Swing Adsorption (VPSA) operation, CO2, ammonia, the impurity such as benzene be adsorbed by adsorbent, realized desorption and the adsorbent reactivation of foreign gas by all pressures, blood pressure lowering, evacuation, at this moment form desorption gas 1769Nm3/ h, mainly contains adsorbed CO2, ammonia, the impurity such as benzene and a small amount of H2、CH4, the fuel gas such as CO, send into coke oven heating pipeline coordination and utilize, purified gas 53097Nm3/ h is discharged into cryogenic liquefying operation from tower top.TSA drying tower in cryogenic liquefying operation, first drying workshop section adsorbs further and removes H20 and CO2, by H in gas2O is removed to below 1ppm, CO2Being removed to below 10ppm, the demercuration reactor entering back into demercuration workshop section will purify the Trace Mercury removing that may contain in gas, for protecting follow-up ice chest not to be corroded, take off to hydrargyrum ＜ 0.01 μ g/m3, under the conditions of temperature-170 DEG C, pressure 2.5MPa, finally carry out cryogenic liquefying separation, obtain liquefied natural gas (LNG) product 12896Nm3/ h, wherein CH4Content (v%) is more than 99.9；Obtain hydrogen-rich synthetic gas 40201Nm3/ h, component (v%): H284.06,CH40.49,CO9.70,CO20.01,N25.74, for compounding methanol synthesis gas.
7～24mm chopped cooked entrails of sheep Jiao 16.875t/h, 0.3MPa steam 27t/h and the oxygen 9000Nm of purity 99.6%3/ h enters the oxygen-enriched continuous Gas-making Furnace of normal pressure, and water produced coal gas is washed the preliminary purifications such as tower cleaning dust desulfurization through Venturi scrubber, carbon, obtained 40 DEG C, 0.104MPa water gas 36000Nm3/ h enters buffer gas tank storage, component (v%): H235.0,CO45.8,CO217.5,CH40.5, N20.9,O20.3,H2S40mg/Nm3, organic sulfur 120mg/Nm3.It is compressed to 2.45MPa entrance NHD desulfurization and decarburization, zinc oxide fine de-sulfur even depth cleaning procedure, by H that gas holder carrys out 30 DEG C of preliminary purification gas2S content takes off to below 0.1ppm, obtains synthesis gas 30667Nm3/ h, component (v%): H240.67,CO53.23,CO24.13,CH40.57, N21.05,O20.35.40201Nm after this purification gas and said extracted LNG3/ h hydrogen-rich synthetic gas merges, and preparation hydrogen-carbon ratio is the methyl methanol syngas of 2.15.Methyl methanol syngas is compressed to 5.5MPa, under the conditions of temperature 250 DEG C, Cu-series catalyst, synthesizing methanol 30t/h, methanol-fueled CLC periodic off-gases 5635Nm3/ h goes coke oven heating pipeline coordination to utilize.
Claims (7)
1. coke-oven plant's combined production of methanol and the method for liquefied natural gas, comprise the steps:
It is compressed to 1.05MPa entrance temp.-changing adsorption pretreatment process that gas holder conveying comes 40 DEG C, 0～10kPa oven gas；The most hydrogenated desulfurization and fine de-sulfur remove organic sulfur and hydrogen sulfide, enter Vacuum Pressure Swing Adsorption operation, remove CO2, ammonia and benzene heavy hydrocarbon, enter cryogenic liquefying operation and obtain liquefied natural gas product, purify the discharge gas of the ice chest after LNG and be mainly composed of CO, H2, send methanol-fueled CLC compression section as methyl methanol syngas, carry out water gas with 7～24mm chopped cooked entrails of sheep Jiao's gas operation conveyings and merge for producing methanol；
The step of 7～24mm described chopped cooked entrails of sheep Jiao's gas operations is: the oxygen of 7～24mm chopped cooked entrails of sheep Jiao, 0.3MPa steam and purity 99.6% enters the oxygen-enriched continuous Gas-making Furnace of normal pressure, and water produced coal gas removing dust desulfurization preliminary purification operation enters buffer gas tank；The compressed entrance wet desulphurization of this preliminary purification gas, fine de-sulfur deep purifying operation, 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, compressed, methanol-fueled CLC produces methanol product；
Described Vacuum Pressure Swing Adsorption operation (VPSA), including adsorption tower and vacuum pump, the steps include: 40 DEG C, under 2.3MPa pressure, the CO in desulfurizing and purifying gas2, ammonia impurity absorbed by silica type, molecular sieve combine adsorption agent, component not to be adsorbed is discharged into cryogenic liquefying operation from tower top；
Methanol-fueled CLC periodic off-gases goes coke oven heating pipeline coordination to utilize.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterized in that, described temp.-changing adsorption pretreatment process, including pretreater, regeneration gas heater, after the steps include: that 40 DEG C from compressor outlet, 1.05MPa oven gas enter temp.-changing adsorption treatment process, pretreater alternately realize oven gas by absorption, regeneration and purify；Naphthalene, tar and part NH in oven gas3、H2S and heavy hydrocarbons impurity are adsorbed at normal temperatures, and heater via is desorbed after being heated to 180 DEG C, and desorption stripping gas is sent coke oven heating pipeline coordination back to and utilized, and the oven gas after purification goes hydrodesulfurization, fine de-sulfur operation.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterized in that, described hydrodesulfurization is for using secondary hydrogenation ferrum molybdenum conversion catalyst, and temperature 280～320 DEG C, pressure 2.5MPa, for removing COS, thiophene and other organic sulfur in oven gas；Described fine de-sulfur uses middle temperature Zinc oxide desulfurizer, temperature 350 DEG C, pressure 2.4MPa, is used for removing H2S, the two arranged in series.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterised in that described LNG cryogenic liquefying operation is divided into drying section, demercuration workshop section and deep cooling workshop section, as follows:
A) drying section
Drying process before ice chest is made up of one group of temp.-changing adsorption pretreatment drying tower, including pretreater, regeneration gas heater, is used for adsorbing and removing H20 and CO2；
B) demercuration workshop section
Through drying process by H in gas2O is removed to 1ppm, CO2After being removed to 10ppm, purify gas and enter back into the Trace Mercury removing that demercuration reactor will contain in unstripped gas, to protect follow-up ice chest not to be corroded, then send deep cooling workshop section；
C) deep cooling workshop section
Cryogenic technology uses the mixed-refrigerant cycle without pre-cooling and nitrogen auxiliary cooling, cryogenic temperature-160～-175 DEG C, pressure 1.5～4.5MPa.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterized in that, 7～24mm described chopped cooked entrails of sheep Jiao's gas operations select the oxygen-enriched continuous Gas-making Furnace gas of normal pressure, on the basis of the tolerance processed ice chest discharge gas after purifying LNG, preparation hydrogen-carbon ratio is the methyl methanol syngas of 2.10～2.15.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterised in that described preliminary purification operation uses Venturi scrubber, carbon to wash tower cleaning dust desulfurization；Described deep purifying operation uses MDEA method, NHD method, tannin process or modified ADA method wet desulphurization decarburization, and fine de-sulfur uses zinc oxide method.
Coke-oven plant the most according to claim 1 combined production of methanol and the method for liquefied natural gas, it is characterised in that methanol-fueled CLC use in, low pressure methanol synthesis technique, synthesis pressure 5.0～13.0MPa, temperature 210～270 DEG C, use Cu-series catalyst.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280235A (en) * | 2008-05-21 | 2008-10-08 | 太原理工天成科技股份有限公司 | Method for preparing liquefied natural gas from coke oven gas |
| CN101323799A (en) * | 2008-07-29 | 2008-12-17 | 四川天一科技股份有限公司 | Coke oven gas dry cleaning temperature swing adsorption process |
| CN101434879A (en) * | 2008-12-15 | 2009-05-20 | 四川天一科技股份有限公司 | Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal |
| CN102079999A (en) * | 2011-01-21 | 2011-06-01 | 成都赛普瑞兴科技有限公司 | Method for producing liquefied natural gas and synthetic gas by taking coke oven gas as raw material |
| CN102585951A (en) * | 2012-03-07 | 2012-07-18 | 四川天一科技股份有限公司 | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas |
| CN102690169A (en) * | 2012-05-25 | 2012-09-26 | 四川天一科技股份有限公司 | Method for cogeneration of methanol, CNG (compressed natural gas) and LNG (liquefied natural gas) from coke-oven gas and converter gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280235A (en) * | 2008-05-21 | 2008-10-08 | 太原理工天成科技股份有限公司 | Method for preparing liquefied natural gas from coke oven gas |
| CN101323799A (en) * | 2008-07-29 | 2008-12-17 | 四川天一科技股份有限公司 | Coke oven gas dry cleaning temperature swing adsorption process |
| CN101434879A (en) * | 2008-12-15 | 2009-05-20 | 四川天一科技股份有限公司 | Method for preparing methyl alcohol synthesis gas and compressed natural gas from coke oven gas and coal |
| CN102079999A (en) * | 2011-01-21 | 2011-06-01 | 成都赛普瑞兴科技有限公司 | Method for producing liquefied natural gas and synthetic gas by taking coke oven gas as raw material |
| CN102585951A (en) * | 2012-03-07 | 2012-07-18 | 四川天一科技股份有限公司 | Novel process for co-production of liquefied synthesis gas, pure hydrogen and methanol from coke-oven gas |
| CN102690169A (en) * | 2012-05-25 | 2012-09-26 | 四川天一科技股份有限公司 | Method for cogeneration of methanol, CNG (compressed natural gas) and LNG (liquefied natural gas) from coke-oven gas and converter gas |
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