CN103274359A - Method and device for recycling hydrogen from synthesis ammonia released air and preparing LNG (liquefied natural gas) with membrane separation and cryogenic integration technology - Google Patents
Method and device for recycling hydrogen from synthesis ammonia released air and preparing LNG (liquefied natural gas) with membrane separation and cryogenic integration technology Download PDFInfo
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- CN103274359A CN103274359A CN2013102323243A CN201310232324A CN103274359A CN 103274359 A CN103274359 A CN 103274359A CN 2013102323243 A CN2013102323243 A CN 2013102323243A CN 201310232324 A CN201310232324 A CN 201310232324A CN 103274359 A CN103274359 A CN 103274359A
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Abstract
The invention discloses a method and a device for recycling hydrogen from synthesis ammonia released air and preparing LNG (liquefied natural gas) with a membrane separation and cryogenic integration technology. The method is characterized in that the synthesis ammonia released air sequentially passes through three treatment units as follows: a synthesis ammonia released air pretreatment unit, a membrane separation and hydrogen recycling unit, and an LNG preparation unit with a cryogenic technology. The integration technology utilizes technical advantages of a membrane technology which is small in investment and high in hydrogen recovery rate and doesn't produce depressurized tail gas and technical advantages of the cryogenic technology which can prepare LNG, and simultaneously avoids technical defects that the cryogenic investment is large, the energy consumption is high, and a single membrane or PSA (Pressure Swing Adsorption) technology cannot simultaneously recycle H2 and CH4. By means of the integration technology, the technical problem that the synthesis ammonia released air cannot be economically, conveniently, efficiently and comprehensively utilized is solved; while the hydrogen is recycled, the LNG can be prepared; and a new energy-saving, emission-reduction and efficient technological process route is provided for a synthesis ammonia enterprise, and the integration technology has an excellent application prospect.
Description
Technical field
The present invention relates to the ammonia synthesizing industry field, specifically a kind of with membrane sepn and deep cooling integrated technology recover hydrogen and produce method and the device of LNG from synthetic ammonia emptying gas.
Background technology
At present, synthetic ammonia is an Essential Chemistry industry, occupies an important position in chemical industry.China's synthetic ammonia output surpasses 5,000 ten thousand tons/year at present, accounts for 1/3rd of global output.Increase along with global population, human demand to increasing crop yield has determined the increase to ammonia demand, and it is relative with it, because synthetic ammonia is the high energy consumption industry, and its raw materials for production are Nonrenewable resources such as coal, oil, Sweet natural gas, in today that resource day is becoming tight, environmental pollution is more and more serious, how to improve energy transformation efficiency, energy-saving and emission-reduction, minimizing pollutant emission, the raising economic benefit of enterprises of synthetic ammonia, become the developing direction of current ammonia synthesizing industry production technology.
In production of synthetic ammonia, in order to improve the transformation efficiency of ammonia, need a part of circulation gas of discharging to reduce noble gas content, the gas of this part discharging is called synthetic ammonia emptying gas.It contains a large amount of hydrogen and methane, and hydrogen is the reactor feed gas of synthetic ammonia, and methane is the main component of Sweet natural gas, and these two kinds of gases are reclaimed and utilize is the important measures of ammonia enterprise energy-saving and emission-reduction synergy.
The gas composition that the synthetic ammonia high pressure is dropped a hint is H
2, N
2, CH
4, Ar, NH
3Deng gas, this part gas purging amount is about 200Nm
3/ ton ammonia, wherein H
2Volume fraction be about 60%, CH
4Volume fraction be about 20%, all the other are N
2, gas such as Ar.At present, the common way of handling synthetic ammonia emptying gas is to adopt only recover hydrogen of membrane sepn or PSA technology, and gaseous combustion or discharging that other contain a large amount of methane so just cause the very big wasting of resources.Since the characteristics determined of technology itself can not adopt membrane sepn or PSA technology recover hydrogen and methane simultaneously separately, and adopt separately that cryogenics is big owing to facility investment, energy consumption is high, complicated operation, less economical etc. former thereby seldom be used.So simultaneously the method for recover hydrogen and methane and device rarely have and mention from drop a hint.
Summary of the invention
According to the technical problem of above-mentioned proposition, and provide a kind of with membrane sepn and deep cooling integrated technology recover hydrogen and produce method and the device of LNG from synthetic ammonia emptying gas.
The technique means that the present invention adopts is as follows:
A kind of with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that passing through successively following three processing units:
1. synthetic ammonia emptying gas pretreatment unit;
2. membrane sepn hydrogen reclaims the unit;
3. cryogenics is produced the LNG unit.
As preferably, 1. described processing unit is to feed in the ammonia absorber through post-decompression synthetic ammonia emptying gas, absorb processing with de-salted water to it, enters in the well heater through gas-liquid separator then and heats.
Generally speaking, be from 15.0MPa～30.0MPa 11.0MPa～13.0MPa that reduces pressure with synthetic ammonia emptying gas, feed in the ammonia absorber then, by the de-salted water that pumps into the ammonia in dropping a hint is absorbed processing, process is washed the ammonia content of the gas behind the ammonia less than 10ppm, feeds gas-liquid separator then except the vaporific drop of deentrainment, feeds double-pipe exchanger then, the wiring core pipe of dropping a hint, low-pressure steam is walked pipe box.
As preferably, 2. described processing unit is that the gas after 1. treated unit is handled feeds membrane separation apparatus and handles, and the infiltration gas that wherein sees through film returns the synthesis cycle compressor, enters processing unit 3. after seeing through the tail gas decompression of film.
Hollow-fibre membrane in the described membrane separation apparatus can bear the pressure reduction of 11.0MPa and the pressure of the highest 16.0MPa.Wherein permeating gas and refer to see through the hydrogen of film, is that the gas that sees through film forms tail gas, and the methane content in the tail gas is not less than 45% and is advisable.
As preferably, 3. described processing unit is that the gas after 2. treated unit is handled feeds to feed in the interchanger behind the adsorbing tower with molecular sieve and lowers the temperature, and the gas that heat exchange is come out from interchanger enters decompressor to be continued to enter rectifying tower after the cooling.
Above-mentioned adsorbing tower with molecular sieve is removed ammonia and the water of trace in the gas, in case freeze during gas refrigeration.Because the water-content in the membrane sepn tail gas is extremely low, compares investment and the process cost that also can significantly reduce adsorbing tower with molecular sieve with independent employing deep cooling.
As preferably, described processing unit feed in 1. gas heating in the well heater more than 10 ℃ to 35 ℃～60 ℃.
As preferably, described processing unit 2. in the infiltration atmospheric pressure smaller or equal to 3.5MPa, suitable substantially with the gaseous tension that enters membrane separation apparatus through the tail gas pressure of membrane sepn, enter processing unit 3. as unstripped gas after tail gas is decompressed to 5.0～6.0MPa.
As preferably, described processing unit 3. in gas temperature behind interchanger be reduced to-130～-135 ℃; After being cooled to-155～-165 ℃, decompressor enters rectifying tower.
The gas temperature that will enter interchanger by external world's adding refrigeration agent drops to about-130 ℃, gas enters decompressor then, by the 5.0MPa 0.1MPa acting of expanding of reducing pressure, gas temperature is reduced to about-160 ℃ again and enters rectifying tower, liquid methane is discharged at the bottom of the tower and is obtained the LNG product, and the gas of cat head is discharged by cat head through after the heat exchange.
It is a kind of with membrane sepn and deep cooling integrated technology recover hydrogen and produce the device of LNG from synthetic ammonia emptying gas that the present invention also provides, and it is characterized in that:
Comprise the synthetic ammonia emptying gas pretreatment unit of being formed by ammonia absorber, gas-liquid separator and well heater; The membrane sepn hydrogen that membrane separation apparatus is formed reclaims the unit; Produce the LNG unit by the deep cooling that adsorbing tower with molecular sieve, interchanger, decompressor and rectifying tower are formed;
The synthetic ammonia emptying gas pneumatic tube feeds the filler bottom of described ammonia absorber, the de-salted water input tube feeds the filler top of described ammonia absorber, the top of described ammonia absorber is taken over and is connected with the entrance of described gas-liquid separator, and export ammoniacal liquor by the ammoniacal liquor output tube bottom of described ammonia absorber; The top of described gas-liquid separator is taken over and is connected with described well heater, the outlet pipe of described well heater is connected with the entrance of described membrane separation apparatus, the infiltration gas output tube of described membrane separation apparatus links to each other with device synthetic compressor outward, and the tail gas outlet pipe of described membrane separation apparatus feeds the filler bottom of described adsorbing tower with molecular sieve; The top of described adsorbing tower with molecular sieve is taken over and is connected with described interchanger, the outlet pipe of described interchanger links to each other with the entrance of described decompressor, the outlet pipe of described decompressor feeds the filler bottom of described rectifying tower, the top of described rectifying tower is taken over and is connected with the non-condensable gas output tube, and export the LNG product by the LNG output tube bottom of described rectifying tower.
On described synthetic ammonia emptying gas pneumatic tube, described ammoniacal liquor output tube, described infiltration gas output tube, described tail gas outlet pipe, described non-condensable gas output tube and the described LNG output tube variable valve and on-line detector table are installed all.
As preferably, by variable valve and on-line detector table pressure, temperature, liquid level, flow are controlled; Pressure, liquid level, temperature are detected demonstration automatically and establish the overload alarm interlocking; LNG product flow at the bottom of infiltration gas, tail gas, rectifying tower cat head non-condensable gas, the rectifying Tata is carried out online detection.
Compare than prior art, the present invention has the following advantages:
1, compares with single employing film or PSA technology, the invention solves above-mentioned two kinds of monotechnicses recovery H of economy simultaneously
2, CH
4Technological deficiency.
2, compare with independent employing cryogenics, the present invention adopt membrane separation technique will drop a hint earlier in most of hydrogen recovery, the tail gas of membrane sepn is as the unstripped gas of deep cooling, advantage is that the processing tolerance of cryogenic unit has reduced more than 60%, methane content has promoted about 1 times simultaneously, and the investment of deep cooling can reduce also reduction greatly of energy consumption about 50% or more, the while deep cooling like this.The present invention has overcome that the Deep Cooling Method facility investment is big, energy consumption is high, complicated operation, shortcoming such as less economical.
3, compare with the deep cooling integrated technology with PSA, the present invention except membrane sepn investment that synthetic ammonia emptying gas hydrogen reclaims still less, hydrogen recovery rate is higher, operation is more convenient, economy higher, most important reason is that the parsing atmospheric pressure after the PSA recover hydrogen is normal pressure substantially, and the tail gas pressure after the membrane sepn recover hydrogen does not reduce substantially, thereby can be that the cryogenic unit of back segment cuts down the consumption of energy by throttling expansion.
To sum up, a kind of integrated technology provided by the invention---utilize less investment, hydrogen recovery rate height, not step-down of tail gas and the cryogenics of membrane technique can produce the technical superiority of LNG, evaded simultaneously that the deep cooling investment is big, energy consumption is high and film or PSA monotechnics can not reclaim H simultaneously
2, CH
4Film and the deep cooling integrated technology of technological deficiency, this integrated technology has solved the economy of synthetic ammonia emptying gas, technical barrier convenient, that fully utilize efficiently---can produce LNG in the time of recover hydrogen, for ammonia enterprise provides a kind of new technological process route of energy-saving and emission-reduction synergy, has fabulous application prospect.
Description of drawings
The present invention is further detailed explanation below in conjunction with the drawings and specific embodiments.
Fig. 1 is the present invention with membrane sepn and deep cooling integrated technology recover hydrogen and produce the structural representation of the employed device of method of LNG from synthetic ammonia emptying gas.
Among the figure: 1, ammonia absorber 2, gas-liquid separator 3, well heater 4, membrane separation apparatus 5, adsorbing tower with molecular sieve 6, interchanger 7, decompressor 8, rectifying tower 9, variable valve 10, on-line detector table;
A, de-salted water input tube B, synthetic ammonia emptying gas pneumatic tube C, ammoniacal liquor output tube D, steam inlet tube E, infiltration gas output tube F, refrigeration agent input tube G, non-condensable gas output tube H, LNG output tube.
Embodiment
As shown in Figure 1, a kind of with membrane sepn and deep cooling integrated technology recover hydrogen and produce the device of LNG from synthetic ammonia emptying gas, comprise the synthetic ammonia emptying gas pretreatment unit of being made up of ammonia absorber 1, gas-liquid separator 2 and well heater 3, described well heater 3 adopts sheath tube heater; The membrane sepn hydrogen that membrane separation apparatus 4 is formed reclaims the unit; Produce the LNG unit by the deep cooling that adsorbing tower with molecular sieve 5, interchanger 6, decompressor 7 and rectifying tower 8 are formed;
Synthetic ammonia emptying gas pneumatic tube B feeds the filler bottom of described ammonia absorber 1, de-salted water input tube A feeds the filler top of described ammonia absorber 1, the top of described ammonia absorber 1 is taken over and is connected with the entrance of described gas-liquid separator 2, and export ammoniacal liquor by ammoniacal liquor output tube C the bottom of described ammonia absorber 1; The top of described gas-liquid separator 2 is taken over and is connected with described well heater 3, low-pressure steam is entered in the sheath tube heater 3 gas heating by steam inlet tube D, the outlet pipe of described well heater 3 is connected with the entrance of described membrane separation apparatus 4, the infiltration gas output tube E of described membrane separation apparatus 4 links to each other with device synthetic compressor outward, and the tail gas outlet pipe of described membrane separation apparatus 4 feeds the filler bottom of described adsorbing tower with molecular sieve 5; The top of described adsorbing tower with molecular sieve 5 is taken over and is connected with described interchanger 6, refrigeration agent is input in the described interchanger 6 wherein gas cooling by refrigeration agent input tube F, the outlet pipe of described interchanger 6 links to each other with the entrance of described decompressor 7, the outlet pipe of described decompressor 7 feeds the filler bottom of described rectifying tower 8, the top of described rectifying tower 8 is taken over and is connected with non-condensable gas output tube G, and export the LNG product by LNG output tube F the bottom of described rectifying tower 8.
On described synthetic ammonia emptying gas pneumatic tube B, described ammoniacal liquor output tube C, described infiltration gas output tube E, described tail gas outlet pipe, described non-condensable gas output tube G and the described LNG output tube H variable valve 9 and on-line detector table 10 are installed all, described steam inlet tube D also is provided with variable valve 9 and on-line detector table 10, above-mentioned variable valve 9 and on-line detector table 10 can be arranged on to be needed to be not limited to the setting of above-mentioned pipeline on the isoparametric pipeline of monitoring flow.
Control by variable valve 9 and on-line detector table 10 pair pressure, temperature, liquid level, flow; Parameters such as pressure, liquid level, temperature are detected demonstration automatically and establish the overload alarm interlocking; LNG product flow at the bottom of infiltration gas, tail gas, rectifying tower cat head non-condensable gas, the rectifying Tata is carried out online detection.
Embodiment 1
Synthetic ammonia emptying gas at first enters ammonia absorber 1 through the reducing valve 12.0MPa that reduces pressure, gas in high efficiency packing formula ammonia absorber with the de-salted water counter current contact that pumps into, become ammoniacal liquor after the ammonia in the gas is absorbed by water and at the bottom of tower, discharge.Wash and enter gas-liquid separator 2 after gas behind the ammonia is discharged by ammonia absorber 1 cat head, separate the entrainment that produces in the water washing process.Enter sheath tube heater 3 then, the general temperature rise of gas after heater via 3 heating is selected to be heated to 40 ℃ more than 10 ℃ in the present embodiment.The purpose of heating has two, and one is for making through washing back gas away from the water saturation dew point, its two working order of regulating membrane separation apparatus 4.Gas after the heating is sent into membrane separation apparatus 4, and all gases is impellent with the inside and outside both sides of hollow-fibre membrane partial pressure difference, sees through film by steps such as dissolving, diffusion, parsings.It is faster that hydrogen sees through the speed of film, make the inboard formation of hollow-fibre membrane hydrogen rich stream, and the film outside forms hydrogen-depleted gas stream.The former is called infiltration gas, and the latter is called tail gas.The compressed synthesis system that turns back to of infiltration gas, tail gas enters described deep cooling through decompression to 5.0MPa and produces the LNG unit, namely enters adsorbing tower with molecular sieve 5, and water and the ammonia of contained trace in the tail gas are removed, and avoids freezing because of freezing.Gas is taken over to enter outside installing through the top of adsorbing tower with molecular sieve 5 and is provided in the interchanger 6 of low-temperature receiver, after reducing the temperature to-130 ℃ behind the interchanger 6, enter decompressor 7 again, after temperature being dropped to again-161 ℃ by throttling expansion, enter rectifying tower 8 again, discharge the LNG product from rectifying tower 8 bottoms and send the product can, noncondensable gas is through discharging the battery limit (BL) from rectifying tower 8 tops after the heat exchange.
After testing, hydrogen recovery rate of the present invention reaches 95.74%, and the molecular fraction of recover hydrogen is 90.45%; The total yield of methane reaches 80.95%.Concrete data see Table 1.
Table 1
Can draw from test data, recover hydrogen from synthetic ammonia emptying gas is feasible with the method for producing LNG with membrane sepn and deep cooling integrated technology in the present invention, and its payback period was less than 1 month.Even calculate separately the pure profit of LNG can reach 10,000 yuan/time, i.e. 8,000 ten thousand yuan/year pure profit.Technical and economy all obviously is better than additive method, has fabulous social benefit and economic benefit, has fabulous popularization and using value.
The above; only be the preferable embodiment of the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to replacement or change according to technical scheme of the present invention and inventive concept thereof, all should be encompassed within protection scope of the present invention.
Claims (9)
1. one kind with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that passing through successively following three processing units:
1. synthetic ammonia emptying gas pretreatment unit;
2. membrane sepn hydrogen reclaims the unit;
3. cryogenics is produced the LNG unit.
2. according to claim 1 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: 1. described processing unit is to feed in the ammonia absorber through post-decompression synthetic ammonia emptying gas, with de-salted water it is absorbed processing, enter in the well heater through gas-liquid separator then and heat.
3. according to claim 1 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: 2. described processing unit is that the gas after 1. treated unit is handled feeds the membrane separation apparatus processing, wherein the infiltration gas that sees through film returns the synthesis cycle compressor, enters processing unit 3. after the tail gas decompression through film.
4. according to claim 1 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: 3. described processing unit is that the gas after 2. treated unit is handled feeds to feed in the interchanger behind the adsorbing tower with molecular sieve and lowers the temperature, and the gas that heat exchange is come out from interchanger enters decompressor to be continued to enter rectifying tower after the cooling.
5. according to claim 2 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: described processing unit feeds gas heating to 35 ℃ in the well heater～60 ℃ in 1..
6. according to claim 3 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: 2. middle infiltration atmospheric pressure is smaller or equal to 3.5MPa for described processing unit, and 3. tail gas enter processing unit after being decompressed to 5.0～6.0MPa.
7. according to claim 4 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the method for LNG from synthetic ammonia emptying gas, it is characterized in that: described processing unit 3. in gas temperature behind interchanger be reduced to-130～-135 ℃; After being cooled to-155～-165 ℃, decompressor enters rectifying tower.
8. one kind with membrane sepn and deep cooling integrated technology recover hydrogen and produce the device of LNG from synthetic ammonia emptying gas, it is characterized in that:
Comprise the synthetic ammonia emptying gas pretreatment unit of being formed by ammonia absorber, gas-liquid separator and well heater; The membrane sepn hydrogen that membrane separation apparatus is formed reclaims the unit; Produce the LNG unit by the deep cooling that adsorbing tower with molecular sieve, interchanger, decompressor and rectifying tower are formed;
The synthetic ammonia emptying gas pneumatic tube feeds the filler bottom of described ammonia absorber, the de-salted water input tube feeds the filler top of described ammonia absorber, the top of described ammonia absorber is taken over and is connected with the entrance of described gas-liquid separator, and export ammoniacal liquor by the ammoniacal liquor output tube bottom of described ammonia absorber; The top of described gas-liquid separator is taken over and is connected with described well heater, the outlet pipe of described well heater is connected with the entrance of described membrane separation apparatus, the infiltration gas output tube of described membrane separation apparatus links to each other with device synthetic compressor outward, and the tail gas outlet pipe of described membrane separation apparatus feeds the filler bottom of described adsorbing tower with molecular sieve; The top of described adsorbing tower with molecular sieve is taken over and is connected with described interchanger, the outlet pipe of described interchanger links to each other with the entrance of described decompressor, the outlet pipe of described decompressor feeds the filler bottom of described rectifying tower, the top of described rectifying tower is taken over and is connected with the non-condensable gas output tube, and export the LNG product by the LNG output tube bottom of described rectifying tower.
On described synthetic ammonia emptying gas pneumatic tube, described ammoniacal liquor output tube, described infiltration gas output tube, described tail gas outlet pipe, described non-condensable gas output tube and the described LNG output tube variable valve and on-line detector table are installed all.
9. according to claim 8 with membrane sepn and deep cooling integrated technology recover hydrogen and produce the device of LNG from synthetic ammonia emptying gas, it is characterized in that: by variable valve and on-line detector table pressure, temperature, liquid level, flow are controlled; Pressure, liquid level, temperature are detected demonstration automatically and establish the overload alarm interlocking; LNG product flow at the bottom of infiltration gas, tail gas, rectifying tower cat head non-condensable gas, the rectifying Tata is carried out online detection.
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| CN103539603A (en) * | 2013-10-10 | 2014-01-29 | 山东润银生物化工股份有限公司 | Method for preparing liquefied methane by using synthesis ammonia vent gas and purge gas |
| CN103940198A (en) * | 2013-09-21 | 2014-07-23 | 贵州兴化化工股份有限公司 | Method for recovering tail gas and preparing liquefied natural gas |
| CN105174288A (en) * | 2015-08-24 | 2015-12-23 | 河南心连心化肥有限公司 | Synthetic ammonia waste gas recovering and utilizing device and recovering and utilizing method thereof |
| CN105585425A (en) * | 2015-12-30 | 2016-05-18 | 七台河宝泰隆煤化工股份有限公司 | Hydrogen recycling device |
| CN107055570A (en) * | 2017-03-21 | 2017-08-18 | 武汉金中石化工程有限公司 | Low-pressure synthetic ammonia equipment and low-pressure synthetic ammonia method |
| CN108774099A (en) * | 2018-06-01 | 2018-11-09 | 河南广硕化工科技有限公司 | A kind of method of exhaust carbon dioxide comprehensive utilization production liquid methane |
| CN109612203A (en) * | 2018-11-22 | 2019-04-12 | 山东润银生物化工股份有限公司 | A kind of processing method of discharge gas in ammonia synthesis |
| CN112279216A (en) * | 2020-11-16 | 2021-01-29 | 河南骏化发展股份有限公司 | Device and process for preparing hydrogen for fuel cell by using synthetic ammonia purge gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103940198A (en) * | 2013-09-21 | 2014-07-23 | 贵州兴化化工股份有限公司 | Method for recovering tail gas and preparing liquefied natural gas |
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| CN105174288A (en) * | 2015-08-24 | 2015-12-23 | 河南心连心化肥有限公司 | Synthetic ammonia waste gas recovering and utilizing device and recovering and utilizing method thereof |
| CN105585425A (en) * | 2015-12-30 | 2016-05-18 | 七台河宝泰隆煤化工股份有限公司 | Hydrogen recycling device |
| CN107055570A (en) * | 2017-03-21 | 2017-08-18 | 武汉金中石化工程有限公司 | Low-pressure synthetic ammonia equipment and low-pressure synthetic ammonia method |
| CN108774099A (en) * | 2018-06-01 | 2018-11-09 | 河南广硕化工科技有限公司 | A kind of method of exhaust carbon dioxide comprehensive utilization production liquid methane |
| CN109612203A (en) * | 2018-11-22 | 2019-04-12 | 山东润银生物化工股份有限公司 | A kind of processing method of discharge gas in ammonia synthesis |
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Application publication date: 20130904 |