CN101343580A - Method for preparing methanol synthesis gas with oven gas and blast furnace gas - Google Patents
Method for preparing methanol synthesis gas with oven gas and blast furnace gas Download PDFInfo
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- CN101343580A CN101343580A CNA2008100458669A CN200810045866A CN101343580A CN 101343580 A CN101343580 A CN 101343580A CN A2008100458669 A CNA2008100458669 A CN A2008100458669A CN 200810045866 A CN200810045866 A CN 200810045866A CN 101343580 A CN101343580 A CN 101343580A
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Abstract
The invention discloses a preparation method for methanol synthetic gas through coke oven gas and blast furnace gas. The preparation method adopts coke oven gas as the raw material, and H2 is extracted through pressure swing adsorption; the blast furnace gas with high yield and relatively low calorific value is adopted as the raw material, an adsorbent which can adsorb CO and CO2 is utilized to simultaneously extract and reclaim the CO and the CO2 in the blast furnace gas, and then the H2, the CO and the CO2 are mixed and prepared into the methanol synthetic gas. The hydrogencarbon ratio f value of the methanol synthetic gas prepared according to the method is within the optimum range of 2.05 to 2.60, and the contents of nitrogen gas and other impure gases are suitable for the methanol production. The by-product gas generated during the steel production process is utilized to prepare the methanol synthetic gas, the useful components in the gas are utilized, the discharging of harmful substances into the environment is reduced, and not only the chemical reaction can not occur during the process, but also the carbon adding is not required, the technical process is short, the process is simple, and the cost is low, so the preparation method is one of the preferable methods for the preparation of methanol synthetic gas.
Description
Technical field
The present invention relates to a kind of method of producing methyl methanol syngas, more particularly, relate to a kind of method of producing methyl methanol syngas with coke(oven)gas and blast furnace gas.
Background technology
By-product coke furnace gas, blast furnace gas and converter gas in the steel manufacture process have only reclaimed partial heat energy wherein at present, utilize its active principle with failing high benefit.The coke(oven)gas that is produced in the steel manufacture process, blast furnace gas and converter gas are rich in elements such as hydrogen, carbon, therefrom reclaim useful component, and in order to compounding methanol synthetic gas, production methyl alcohol, production cost is low, has favorable economic benefit, is one and effectively utilizes approach.Hydrogeneous (H in the coke(oven)gas
2) height, it is low to contain carbon monoxide (CO), and hydrogen-carbon ratio f value reaches about 6 { f=(H
2-CO
2)/CO+CO
2, with the direct synthesizing methanol of such gas, must earlier the methane conversion in the coke(oven)gas be become CO and H
2, the hydrogen-carbon ratio f value after the conversion is 2.7, also needs to utilize CO and carbonic acid gas (CO
2) replenish carbon, make the f value reach the scope of 2.05-2.10, could obtain quality product height, methyl methanol syngas that the side reaction resultant is few.Be rich in CO and CO in converter gas, the blast furnace gas
2, can be used as the source of carbon.Wherein the CO content of converter gas and calorific value be than blast furnace gas height, is methyl methanol syngas carbon source preferably, as Chinese patent (CN1803746A, 2006.7.19) disclosing a kind of is the technology that raw material is produced methyl alcohol with coke(oven)gas, converter gas; But the output of converter gas is little, and not enough methanol production is mended carbon and used, and the pressure of converter gas and component fluctuation are big, use so converter gas generally only is used for enterprise self heating.Blast furnace gas output is big, and can satisfy methanol production and mend the carbon use, but its CO content and calorific value are all lower, the inert gas content height, recovery difficult is big.Mainly utilize pressure swing absorption process from blast furnace gas, to reclaim CO at present, propose to utilize at first MDEA desulfurization of blast furnace gas, take off CO as Xie Guangquan (gas chemical industry's the 6th phase of nineteen ninety-five)
2After transformation adsorbing and extracting CO, CO is compressed, the part conversion, take off CO with MDEA
2, after smart desulfurization, with the PSA-H that exits that speeds
2The H that device comes
2The method of mixing back acquisition methyl methanol syngas; Chinese patent (CN1100588C, 1997.10.24) propose from blast furnace gas, to separate the two-phase method pressure swing adsorption that concentrates CO, remove strong absorbed component such as carbonic acid gas for first section, second section obtains CO fuel gas, is intended to solve and extracts the CO that does fuel from blast furnace gas; And in the blast furnace gas another can be used as the CO in methyl methanol syngas carbon source
2Then be discharged, not only environment impacted, and wasted resource as waste gas.
Summary of the invention
The objective of the invention is to overcome above shortcomings in the prior art, a kind of physical separation method of utilizing transformation absorption is provided, from coke(oven)gas, extract H
2, in same stage pressure swing adsorption apparatus, from blast furnace gas, extract CO and CO simultaneously
2, make full use of the H in coke(oven)gas, the blast furnace gas
2, CO and CO
2Deng the available gas resource, make that hydrogen-carbon ratio reaches the stoichiometric(al) scope in the methyl methanol syngas, foreign gas content is few, can reduce synthesis pressure, reduce energy consumption and production costs, reduce the preparation method of the methyl methanol syngas of pollutant discharge amount.
To achieve these goals, the invention provides following technical scheme:
A kind ofly produce the method for methyl methanol syngas, may further comprise the steps with coke(oven)gas and blast furnace gas:
(1) with the coke(oven)gas is raw material, extracts H through pressure swing absorption process
2:
Coke(oven)gas is sent into the transformation absorption of being made up of at least 4 adsorption towers carry hydrogen production device, extract H
2Each adsorption tower that hydrogen production device is carried in transformation absorption experience successively absorption, all pressure drops, along put, contraryly put, wash or find time, all voltage rises, final all pressure-swing adsorption processes of pressure, adsorptive pressure is 0.1MPa～2.0MPa (all pressure units all is gauge pressure in the present patent application), temperature is 0～40 ℃, and sorbent material is one or more in activated alumina, silica gel, gac, the molecular sieve;
(2) with the blast furnace gas be raw material, extract rich CO and CO through transformation absorption I section and II section
2Gas:
Blast furnace gas removes water and a spot of carbonic acid gas through transformation absorption I section, transformation absorption I section apparatus is made up of at least 3 adsorption towers, each adsorption tower experiences absorption, all pressure drops, displacement successively, contraryly puts, washes or find time, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～1.0MPa, evacuation pressure is-0.09MPa～-0.02MPa, temperature is 0～40 ℃, and sorbent material is one or more in activated alumina, silica gel, gac, the molecular sieve;
Remove the residual gas that obtains after water and the amounts of carbon dioxide through transformation absorption I section after the pressure-swing adsorption process of transformation absorption II section, obtain rich CO and CO through finding time
2Gas, the pressure-swing absorption apparatus of transformation absorption II section is made up of at least 4 adsorption towers, each adsorption tower experience successively absorption, all pressure drops, along put, contraryly put, find time, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～1.0MPa, evacuation pressure is-0.09～-0.04MPa, sorbent material is one or more in copper modified adsorbent, activated alumina, gac, molecular sieve, the silica gel;
(3) the rich CO and the CO that are obtained of hydrogen that step (1) is extracted and step (2)
2Gas is 2.09～2.74: 1 mixed in molar ratio, obtains methyl methanol syngas.
Described copper modified adsorbent is that cuprous ion is loaded on formed sorbent material in activated alumina, silica gel, gac or the molecular sieve any one.
The volumn concentration of each component of coke(oven)gas is described in the step (1): H
2: 55～60%, N
2: 3～7%, CO:5～8%, CO
2: 1.5～3%, CH
4: 23～27%, CnHm:2～4%.Coke(oven)gas after pressurization again transformation adsorbing and extracting concentration greater than 98% hydrogen, all the other gases that are rich in methane with do fuel usefulness after converter gas mixes.Impurity such as naphthalene that the hydrogen process can also remove part in the coke(oven)gas, tar, sulphur, oxygen are carried in this transformation absorption, can simplify the operation of cleaning section.
Blast furnace gas described in the step (2) removes water and a spot of carbonic acid gas through transformation absorption I section, and the volumn concentration of each component of residual gas of acquisition is: H
2: 0.5～4.0%, N
2: 52～58%, CO:22～28%, CO
2: 11～18%, CH
4: 0.2～1.0%, all the other are CnHm.
Blast furnace gas described in the step (2) through transformation absorption I section, the absorption of II section after the rich CO and the CO that are obtained of finding time
2CO and CO in the gas
2The volume percent sum be 85～99.8%, wherein the volume percent of carbonic acid gas is 4.8～18.3%.
Blast furnace gas extracts CO and CO through the pressure-swing adsorption process of transformation absorption I section, II section
2After, remaining gas burning back emptying.
Methyl methanol syngas f value of the present invention after deoxidation treatment, can be sent into methanol sythesis reactor and carry out the synthetic production of methyl alcohol in 2.05～2.60 scopes.
Compared with prior art, beneficial effect of the present invention: of the present inventionly producing the method for methyl methanol syngas with coke(oven)gas and blast furnace gas, is raw material with the coke(oven)gas, through transformation adsorbing and extracting H
2, calorific value blast furnace gas lower, difficult treatment big with output is raw material, and utilization is CO absorption and CO simultaneously
2Sorbent material, with CO in the blast furnace gas and CO
2Extract simultaneously and reclaim, again with H
2With rich CO and CO
2The gas mixed preparing is a methyl methanol syngas.Utilization of the present invention is CO absorption and CO simultaneously
2Sorbent material, will be originally extract CO and CO respectively
2Two required cover pressure-swing absorption apparatuss of gas are reduced to a cover, have saved investment and process cost, and have made full use of the useful component in the gas, reduced the discharging of objectionable impurities to environment, this process had not both had chemical reaction and had taken place, and need not mend carbon again, flow process is short, and process is simple, and cost is low.The hydrogen-carbon ratio f value of the methyl methanol syngas of preparing by the inventive method is in 2.05～2.60 optimum range, and foreign gas content such as nitrogen are low.Because pressure swing adsorption is the dry method physical separating process, so this process is environmental friendliness, physical process simple to operate, does not have chemical reaction, having improved system operation stability, greatly reduced energy consumption and production cost, is one of preferred method of methyl methanol syngas preparation.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Embodiment
Further describe the present invention below by embodiment, therefore do not limit the present invention among the described scope of embodiments.
Embodiment 1
Fig. 1 is the process flow diagram that utilizes coke(oven)gas and blast furnace gas pressure swing adsorption process compounding methanol gas mixture.
(1) with the coke(oven)gas is raw material, extracts H through pressure swing absorption process
2:
Raw coke oven gas flow velocity 5500Nm
3/ h forms as shown in table 1ly, and it is compressed to the pressure range of 0.1～1.0MPa, carries the fuel gas that is separated into hydrogen and methane rich in the hydrogen production device in transformation absorption then.
The hydrogen unstripped gas is carried in the absorption of table 1 coke(oven)gas transformation and product gas is formed
The absorption of present embodiment coke(oven)gas transformation is carried hydrogen production device and is made up of 4 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with adsorbent activity aluminum oxide, gac in each adsorption tower from top to bottom, the height ratio of filling is an activated alumina: gac=2: 1; The pressure-swing adsorption process that each adsorption tower experiences absorption, step-down successively, washes, boosts in a loop cycle, adsorptive pressure 0.1MPa～1.0MPa, 0～40 ℃ of temperature, its program run sequential, each step gauge pressure value see Table 2.
Hydrogen work schedule table is carried in the absorption of table 2 coke(oven)gas transformation
| Time/s | 180 | 180 | 180 | 180 |
| Pressure/MPa | 0.1 | 0.05 | 0 | 0.1 |
| The A tower | Absorption | Step-down | Flushing | Boost |
| The B tower | Boost | Absorption | Step-down | Flushing |
| The C tower | Flushing | Boost | Absorption | Step-down |
| The D tower | Step-down | Flushing | Boost | Absorption |
The hydrogen volume percentage composition of coke(oven)gas transformation adsorbing and extracting is 98%, extracts that remaining gas is exactly high methane gas behind the hydrogen, and high methane gas contains methane can reach 51%, and the combustion heat value height can be used as the fuel gas of Iron and Steel Production.
(2) with the blast furnace gas be raw material, through rich CO of two sections transformation adsorbing and extracting and CO
2Gas:
With flow velocity 3500Nm
3The blast furnace gas of/h is compressed to 0.2MPa～1.0MPa, removes water and a spot of carbonic acid gas through transformation absorption I section.The pressure-swing absorption apparatus of transformation absorption I section is made up of 3 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with activated alumina in each adsorption tower, each adsorption tower experience successively absorption, all pressure drops, along put, contraryly put, wash, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～1.0MPa, and temperature is 0～40 ℃;
The residual gas composition that obtains after transformation absorption I section sees Table 4, and this residual gas after the pressure-swing adsorption process of transformation absorption II section, obtains rich CO and CO again through finding time
2Gas.The pressure-swing absorption apparatus of transformation absorption II section is made up of 4 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with the silica gel absorber of adsorbent activity aluminum oxide, gac, copper modification in each adsorption tower from top to bottom, the silica gel absorber of this copper modification is that 50% cuprous chloride and 50% silica gel are formed by weight percent.The height ratio of sorbent material filling is: activated alumina: gac: the silica gel absorber of copper modification=1: 1: 6.The pressure-swing adsorption process that each adsorption tower experiences absorption, step-down successively, replaces, finds time, boosts, adsorptive pressure is 0.2MPa～1.0MPa, evacuation pressure is-0.09～-0.04MPa, temperature is 0～40 ℃, its program run sequential, each step gauge pressure value see Table 3.
Table 3 blast furnace gas transformation absorption II section 4 tower time-scales
Rich CO and CO that blast furnace gas obtains through two sections pressure-swing adsorption processes
2The composition of gas sees Table 4, wherein CO and CO
2The volumn concentration sum be 99.8%, other foreign matter contents are few, help reducing methyl alcohol synthesis pressure and energy consumption, enhance productivity, and reduce equipment manufacturing cost.
Two sections transformation adsorption productions of table 4 embodiment 1 blast furnace gas gas is formed
(3) with the hydrogen 2810Nm of above-mentioned acquisition
3/ h and rich CO and CO
2Gas 1300Nm
3/ h mixes, and obtains methyl methanol syngas, and this methyl methanol syngas f value is 2.05, can be for producing 10000 tons of uses of methyl alcohol per year, and its component sees Table 5.
Table 5 embodiment 1 methyl methanol syngas is formed
Embodiment 2
(1) with the coke(oven)gas is raw material, extracts H through pressure swing absorption process
2:
Raw coke oven gas flow velocity 45000Nm
3/ h forms as shown in table 6ly, and it is compressed to the pressure range of 0.1～1.0MPa, carries hydrogen production device in transformation absorption then and extracts H
2The absorption of present embodiment coke(oven)gas transformation is carried hydrogen production device and is made up of 8 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with sorbent material silica gel and gac in each adsorption tower from top to bottom, the height ratio of filling is a silica gel: gac=1: 3; Coke(oven)gas enters 2 adsorption tower absorption simultaneously, each adsorption tower experiences absorption A successively in a loop cycle, four equal pressure drop E1D, E2D, E3D, E4D are along putting PP, the contrary D of putting, flushing P, four equal voltage rise E4R, E3R, E2R, E1R finally all press the pressure-swing adsorption process of FR, adsorptive pressure 0.2MPa～2.0MPa, 0～40 ℃ of temperature, its program run sequential, each step gauge pressure value see Table 7.
The hydrogen unstripped gas is carried in the absorption of table 6 coke(oven)gas transformation and product gas is formed
The hydrogen volume percentage composition of coke(oven)gas transformation adsorbing and extracting is 99%, sees Table 6.
Hydrogen 8 tower time-scales are carried in the absorption of table 7 coke(oven)gas transformation
(2) with the blast furnace gas be raw material, through rich CO of two sections transformation adsorbing and extracting and CO
2Gas:
With flow velocity 30000Nm
3The blast furnace gas of/h is compressed to 0.2MPa～0.6MPa, removes water and a spot of carbonic acid gas through transformation absorption I section.The pressure-swing absorption apparatus of transformation absorption I section is made up of 6 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with silica gel and gac in each adsorption tower, ratio is a silica gel: gac=1: 2, each adsorption tower experience successively absorption A, all pressure drop ED, along put PP, contraryly put D, the V that finds time, all voltage rise ER, finally all press the pressure-swing adsorption process of FR, adsorptive pressure is 0.2MPa～0.6MPa, and temperature is 0～40 ℃; The residual gas composition that obtains after transformation absorption I section sees Table 9, and residual gas after the pressure-swing adsorption process of transformation absorption II section, obtains rich CO and CO again through finding time
2Gas.Transformation absorption II section is made up of 8 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with the gac and the molecular sieve of sorbent material silica gel, copper modification in each adsorption tower from top to bottom, its loading height ratio is: silica gel: the copper modified activated carbon: molecular sieve=1: 2: 4.The acticarbon of copper modification is that 5% cuprous chloride and 95% gac are formed by weight percentage.Each adsorption tower experiences absorption A successively, twice equal pressure drop E1D, E2D, along putting PP, contrary put D, twice V that finds time, twice equal voltage rise ER, final pressure-swing adsorption process of all pressing FR, adsorptive pressure is 0.2MPa～0.6MPa, evacuation pressure is-0.08～-0.04MPa, temperature is 0～40 ℃, its program run sequential, each step gauge pressure value see Table 8.
Table 8 blast furnace gas transformation absorption II section 8 tower time-scales
Rich CO and CO that blast furnace gas obtains through two sections pressure-swing adsorption processes
2The composition of gas sees Table 9, wherein CO and CO
2The volumn concentration sum be 85%.
Two sections transformation adsorption productions of table 9 embodiment 2 blast furnace gas gas is formed
(3) with the 23000Nm of above-mentioned acquisition
3/ h hydrogen and rich CO and CO
2Gas 11000Nm
3/ h obtains methyl methanol syngas through mixing the back, and component sees Table 10, and the f value is 2.20, can be for producing 100000 tons of uses of methyl alcohol per year.
Table 10 embodiment 2 methyl methanol syngas are formed
Embodiment 3
(1) with the coke(oven)gas is raw material, extracts H through pressure swing absorption process
2:
Raw coke oven gas flow velocity 93000Nm
3/ h forms as shown in table 11ly, and it is compressed to the pressure range of 0.2～2.0MPa, carries hydrogen production device in transformation absorption then and extracts H
2Present embodiment coke(oven)gas transformation absorption is carried hydrogen production device and is made up of 10 adsorption towers, is filled with adsorbent activity aluminum oxide and molecular sieve in each adsorption tower from top to bottom, and the height ratio of filling is an activated alumina: molecular sieve=1: 5; Coke(oven)gas enters 3 adsorption tower absorption simultaneously, each adsorption tower in a loop cycle successively experience absorption A, all pressure drop ED, along put PP, contrary put D, flushing P, all voltage rise ER, finally all press the pressure-swing adsorption process of FR, adsorptive pressure 0.2MPa～2.0MPa, 0～40 ℃ of temperature, its program run sequential, each step gauge pressure value see Table 12.
The hydrogen unstripped gas is carried in the absorption of table 11 coke(oven)gas transformation and product gas is formed
The hydrogen volume percentage composition of coke(oven)gas transformation adsorbing and extracting is 98.5%, sees Table 11.
Hydrogen 10 tower time-scales are carried in the absorption of table 12 coke(oven)gas transformation
(2) with the blast furnace gas be raw material, through rich CO of two sections transformation adsorbing and extracting and CO
2Gas:
With flow velocity 52000Nm
3The blast furnace gas of/h is compressed to 0.4MPa～1.0MPa, removes water and a spot of carbonic acid gas through transformation absorption I section.The pressure-swing absorption apparatus of transformation absorption I section is made up of 8 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with activated alumina and gac in each adsorption tower, ratio is an activated alumina: gac=1: 1, each adsorption tower experience successively absorption, all pressure drops, along put, contraryly put, find time, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.4MPa～1.0MPa, evacuation pressure is-0.08～-0.02MPa, temperature is 0～40 ℃.
The residual gas composition that obtains after transformation absorption I section sees Table 13, and residual gas after the pressure-swing adsorption process of transformation absorption II section, obtains rich CO and CO again through finding time
2Gas.The pressure-swing absorption apparatus of transformation absorption II section is made up of 14 adsorption towers, be connected with program-controlled valve by corresponding pipeline between tower and the tower, be filled with sorbent material silica gel, molecular sieve and copper modified aluminas sorbent material in each adsorption tower from top to bottom, copper modified aluminas sorbent material is that 15% cuprous chloride and 85% aluminum oxide are formed by weight percentage.Sorbent material filling ratio is: silica gel: molecular sieve: copper modified aluminas=1: 2: 6.Each adsorption tower experiences absorption A successively, twice equal pressure drop E1D, E2D, along putting PP, contrary put D, twice V that finds time, twice equal voltage rise ER, final pressure-swing adsorption process of all pressing FR, adsorptive pressure is 0.4MPa～1.0MPa, evacuation pressure is-0.08～-0.02MPa, temperature is 0～40 ℃, its program run sequential, each step gauge pressure value see Table 15.
Two sections transformation adsorption productions of table 13 embodiment 3 blast furnace gas gas is formed
Rich CO and CO
2CO and CO in the gas
2The volumn concentration sum is 95.2%, and nitrogen and methane content are higher, see Table 13.
(3) with the hydrogen 48000Nm of above-mentioned acquisition
3/ h and rich CO and CO
2Gas 20100Nm
3/ h mixes, and obtains methyl methanol syngas, and this methyl methanol syngas component sees Table 14, and its f value is 2.31 can be for 200,000 tons of uses of annual output methyl alcohol.
Table 14 embodiment 3 methyl methanol syngas are formed
Table 15 blast furnace gas transformation absorption II section 14 tower time-scales
Embodiment 4
With 53000Nm
3/ h coke(oven)gas is at first through overdraft, carry the fuel gas that is separated into hydrogen and methane rich in the hydrogen production device in transformation absorption then, the pressure-swing absorption apparatus of present embodiment is made up of 8 adsorption towers, each adsorption tower experiences absorption successively, four equal pressure drops, along putting, contrary putting, flushing, four equal voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～2.0MPa, temperature is 0～40 ℃, adopt pipeline and valve to link between tower and the tower, the bottom of each adsorption tower is filled with the adsorbent activity aluminum oxide, the upper strata is filled with gac, and the ratio of the two is 1: 2; The composition of coke(oven)gas, hydrogen sees Table 16.
The hydrogen unstripped gas is carried in the absorption of table 16 coke(oven)gas transformation and product gas is formed
With 30000Nm
3/ h blast furnace gas adsorbs rich CO of recovery and CO in the II section in transformation absorption I section that 5 adsorption towers are formed and the transformation of being made up of 8 adsorption towers after overdraft
2Gas, rich CO and CO
2CO and CO in the gas
2The content sum is 99.6%, sees Table 17.
Two sections transformation adsorption productions of table 17 embodiment 4 blast furnace gas gas is formed
Be filled with activated alumina and molecular sieve in the adsorption tower of transformation absorption I section, ratio is an activated alumina: molecular sieve=1: 3, be filled with sorbent material aluminum oxide and copper modified molecular screen sorbent material in the adsorption tower of transformation absorption II section, the adsorbent of molecular sieve of copper modification is that 60% cuprous chloride and 40% molecular sieve are formed by weight percent.The filling ratio of sorbent material is an aluminum oxide: copper modified molecular screen=1: 10.The time-scale of transformation absorption II section sees Table 18.
Table 18 blast furnace gas transformation absorption II section 8 tower time-scales
The hydrogen 26400Nm of above-mentioned acquisition
3/ h and rich CO and CO
2Gas 9650Nm
3/ h obtains methyl methanol syngas through mixing the back, and this synthesis gas components sees Table 19, and its f value is 2.60, can be for producing 100000 tons of uses of methyl alcohol per year.
Table 19 embodiment 4 methyl methanol syngas are formed
Embodiment 5
With 500000Nm
3/ h coke(oven)gas is at first through overdraft, carry the fuel gas that is separated into hydrogen and methane rich in the hydrogen production device in transformation absorption then, the pressure-swing absorption apparatus of present embodiment is made up of 32 adsorption towers, per 8 adsorption towers are one group, pressure-swing adsorption process among the time sequential routine of each group such as the embodiment 2, each adsorption tower experiences absorption successively, all pressure drops, along putting, contrary putting, flushing, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.6MPa～2.0MPa, temperature is 0～40 ℃, adopt pipeline and valve to link between tower and the tower, at least be filled with activated alumina in each adsorption tower, gac, adsorbent of molecular sieve, its filling ratio is an activated alumina: gac: molecular sieve=2: 2: 1; The composition of coke(oven)gas, hydrogen, high methane gas sees Table 6.
With 270000Nm
3/ h blast furnace gas after overdraft, rich CO of recovery and CO in the transformation of 16 adsorption towers absorption I section and the II section formed by 32 adsorption towers
2Gas, 32 adsorption towers of blast furnace gas transformation absorption II section are divided into 4 groups, are made up of 8 adsorption towers for every group, and its time sequential routine is seen embodiment 2.Each adsorption tower filling silica gel, copper modified activated carbon and acticarbon, copper modified adsorbent is that 70% cuprous chloride and 30% gac are formed by weight percent.The filling ratio of sorbent material is for filling out silica gel: the copper modified activated carbon: gac=2: 1: 3, rich CO and CO
2The gas component sees Table 9.
The hydrogen 240000Nm of above-mentioned acquisition
3/ h and rich CO and CO
2Gas 110000Nm
3/ h mixes the back and obtains methyl methanol syngas, and its component sees Table 20, and the f value of this methyl methanol syngas is 2.30, can be for producing 1000000 tons of uses of methyl alcohol per year.
Table 20 embodiment 5 methyl methanol syngas are formed
Claims (4)
1, a kind ofly produce the method for methyl methanol syngas, it is characterized in that may further comprise the steps with coke(oven)gas and blast furnace gas:
(1) with the coke(oven)gas is raw material, extracts H through pressure swing absorption process
2:
Coke(oven)gas is sent into the transformation absorption of being made up of at least 4 adsorption towers carry hydrogen production device, extract H
2Each adsorption tower that hydrogen production device is carried in transformation absorption experience successively absorption, all pressure drops, along put, contraryly put, wash or find time, all voltage rises, final all pressure-swing adsorption processes of pressure, adsorptive pressure is 0.1MPa～2.0MPa, temperature is 0～40 ℃, and sorbent material is one or more in activated alumina, silica gel, gac, the molecular sieve;
(2) with the blast furnace gas be raw material, extract rich CO and CO through transformation absorption I section and II section
2Gas:
Blast furnace gas removes water and a spot of carbonic acid gas through transformation absorption I section, transformation absorption I section apparatus is made up of at least 3 adsorption towers, each adsorption tower experiences absorption, all pressure drops, displacement successively, contraryly puts, washes or find time, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～1.0MPa, evacuation pressure is-0.09MPa～-0.02MPa, temperature is 0～40 ℃, and sorbent material is one or more in activated alumina, silica gel, gac, the molecular sieve;
Remove the residual gas that obtains after water and the amounts of carbon dioxide through transformation absorption I section after the pressure-swing adsorption process of transformation absorption II section, obtain rich CO and CO through finding time
2Gas, the pressure-swing absorption apparatus of transformation absorption II section is made up of at least 4 adsorption towers, each adsorption tower experience successively absorption, all pressure drops, along put, contraryly put, find time, all voltage rises, final pressure-swing adsorption process of all pressing, adsorptive pressure is 0.2MPa～1.0MPa, evacuation pressure is-0.09～-0.04MPa, sorbent material is one or more in copper modified adsorbent, activated alumina, gac, molecular sieve, the silica gel;
(3) the rich CO and the CO that are obtained of hydrogen that step (1) is extracted and step (2)
2Gas is 2.09～2.74: 1 mixed in molar ratio, obtains methyl methanol syngas.
2, according to claim 1ly produce the method for methyl methanol syngas with coke(oven)gas and blast furnace gas, it is characterized in that: described copper modified adsorbent is that cuprous ion is loaded on formed sorbent material in activated alumina, silica gel, gac or the molecular sieve any one.
3, the method for producing methyl methanol syngas with coke(oven)gas and blast furnace gas according to claim 1, it is characterized in that: blast furnace gas described in the step (2) removes water and a spot of carbonic acid gas through transformation absorption I section, and the volumn concentration of each component of residual gas of acquisition is: H
2: 0.5～4.0%, N
2: 52～58%, CO:22～28%, CO
2: 11～18%, CH
4: 0.2～1.0%, all the other are CnHm.
4, according to claim 1ly produce the method for methyl methanol syngas, it is characterized in that: rich CO and the CO of obtaining that after transformation absorption I section, the absorption of II section, find time of blast furnace gas described in the step (2) with coke(oven)gas and blast furnace gas
2CO and CO in the gas
2The volume percent sum be 85～99.8%, wherein the volume percent of carbonic acid gas is 4.8～18.3%.
Priority Applications (1)
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| CNA2008100458669A CN101343580A (en) | 2008-08-22 | 2008-08-22 | Method for preparing methanol synthesis gas with oven gas and blast furnace gas |
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