CN105883851B - A kind of Novel gasification and pyrolysis coupling coal gas multi-production process - Google Patents
A kind of Novel gasification and pyrolysis coupling coal gas multi-production process Download PDFInfo
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- CN105883851B CN105883851B CN201610212127.9A CN201610212127A CN105883851B CN 105883851 B CN105883851 B CN 105883851B CN 201610212127 A CN201610212127 A CN 201610212127A CN 105883851 B CN105883851 B CN 105883851B
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Abstract
The present invention relates to a kind of Novel gasification and pyrolysis coupling coal gas multi-production process, the raw gas that the technique is produced with gasification furnace is respectively after waste heat boiler and gasification gas cleaning device, a part melts down gas use as pyrolysis, and another part is used through desulfurizer as synthesis gas；Raw coke oven gas is pyrolyzed after being pyrolyzed gas cleaning device, be divided to two stocks not after the desulfurization of desulfurization and decarburization device and desulfurization and decarburization, one after desulfurization melts down gas use as pyrolysis oven, and one pyrolysis gas of desulfurization and decarburization enters ice chest, and separation of methane obtains LNG/CNG products；Remaining hydrogen-rich and the rich stock-traders' know-how pressure-variable adsorption of carbon monoxide one are carried after hydrogen, hydrogen converges into compressor and the nitrogen from space division and enters compressor, device is catalyzed and synthesized subsequently into synthesis ammonia to obtain synthesizing ammonolysis product, Utilization of PSA Relief Gas body converges with another strand of hydrogen-rich gas and remaining rich CO gas and the above from the synthesis gas of gasification respectively, enter compressor in the lump, then can be respectively synthesized the products such as CNG/ alcohol/ether through catalyzing and synthesizing device.Novel gasification and pyrolysis coupling coal gas multi-production process that pyrolysis high-quality coal gas is rationally utilized are realized to greatest extent the invention provides a kind of.
Description
Technical field
The present invention relates to a kind of coke-stove gas and the coupling of pure oxygen gasification coal gas, preparing synthetic gas produces alcohol, ether and LNG/CNG altogether
Deng the Novel gasification and pyrolysis coupling coal gas multi-production process of product.
Background technology
In coal gas multi-production process：One class is the method using coal as raw material pyrolytic gas making, the first purified dress of pyrolysis coal gas
Put and prepare synthesis gas production downstream product through catforming again after processing；Another kind of is using coal, semi-coke or coke as raw material
Gasification gas making puts method, transformed device prepares synthesis gas production downstream product again after gasification gas first purified device processing.
Coal gas is pyrolyzed by taking coke-stove gas as an example, its main component is：CH422 ~ 28%, H255 ~ 60 %, CO5 ~ 8%, CO2~ 4%,
Caloric value about 4000kcal/m3, the fuel gas that it is high-quality rich in methane is not only due to, more because its hydrogen content height is precious
Expensive chemical industry synthesis raw material.At present, have in the preparing synthetic gas method in preparing synthesis gas from coke oven gas Poly-generation, mainly used：Catalysis
Steam conversion, catalyzing part oxidation and non-catalytic partial oxidation method；And problem present in these methods has：1. using catalysis
Agent, 2. consumes amount of heat, and 3. hydrogen-carbon ratio is higher in product, and a large amount of hydrogen are contained in off-gas, and discharge capacity is big, hydrogen resources profit
With not reasonable.
Therefore, how oven gas scientifically and rationally to be carried out into composition segmentation to utilize, is coking industry urgent problem to be solved.
Gasification gas is using coke as raw material, and exemplified by pure oxygen fixed bed continuous gasification gas, its main component is CH4~
1.27%, H2~ 44.35%, CO ~ 35.73%, CO2~ 19.3%, 2300 ~ 2600kcal/m of caloric value3, due to its carbon monoxide and hydrogen
Gas component content height is good raw material of synthetic gas gas, but due in gasification product gas carbon monoxide and hydrogen than higher, synthesis
, it is necessary to carbon monoxide transformed reaction in part is changed into CO2 emission into air, to optimize during downstream product
C/Hratio, the process causes the waste of carbon resource.
Thus, with reference to pyrolysis coal gas advantage and gasification gas advantage, overall segmentation is carried out to coal gas and is utilized, pyrolysis can be avoided
The high energy consumption and the high problem of product gas hydrogen-carbon ratio of coal gas catalytic conversion unit, and converter unit in gasification gas can be avoided to make
Into carbon resource discharge waste problem, be the effective way for realizing hydrocarbon comprehensive utilization of resources.
The content of the invention
It is an object of the invention to overcome above-mentioned two kinds of independent pathways in the prior art to prepare synthesis gas production downstream product
During the irrational problem of the hydrocarbon utilization of resources provide and a kind of realize what pyrolysis high-quality coal gas was rationally utilized to greatest extent
Novel gasification and pyrolysis coupling coal gas multi-production process.
The technical proposal of the invention is realized in this way：A kind of Novel gasification and pyrolysis coupling coal gas multi-production process, should
The raw gas that technique is produced using gasification furnace is raw material, respectively through waste heat boiler, gasification gas purifier and gasification coal gas desulfurization
After device, a part melts down gas use as pyrolysis, and another part is used as synthesis gas；Raw coke oven gas is pyrolyzed through being pyrolyzed gas purification dress
Postpone, be divided to two stocks not through the desulfurization of desulfurization and decarburization device and desulfurization and decarburization, one after desulfurization melts down gas as pyrolysis oven to be used, separately
Pyrolysis gas after one desulfurization and decarburization obtains LNG/CNG products into ice chest device separation of methane；Remaining hydrogen-rich and richness one are aoxidized
Two strands of pyrolysis gas of carbon, wherein hydrogen-rich pyrolysis gas are divided to two strands, and a stock-traders' know-how pressure-variable adsorption is carried after hydrogen, and hydrogen enters compressor with coming from
The nitrogen of space division converges, and catalyzing and synthesizing device subsequently into synthesis ammonia obtains synthesizing ammonolysis product；Utilization of PSA Relief Gas body is distinguished
Converge with another strand of hydrogen-rich gas and remaining rich CO gas and the above from the synthesis gas of gasification, pressure is entered in the lump
Contracting machine, then through catalyzing and synthesizing device synthesis CNG, alcohol or ether product；After periodic off-gases after catalyzing and synthesizing carry hydrogen through pressure-variable adsorption,
Hydrogen is used to enter synthesis ammonia compressor for synthesizing ammonia, and residual gas is recycled.
The gasification furnace is mainly pure oxygen fixed bed gasification, and other gasification technologies are equally applicable, raw materials used mainly to have
Raw coal, semi-coke and coke, gasification oxidant used mainly have pure oxygen, carbon dioxide and water vapour；The pyrolysis installation is mainly
Coke oven；The gasification gas main component is：CH4~ 1.9%, H2~ 41%, CO ~ 37%, CO2~18%；Being pyrolyzed coal gas main component is：
CH422 ~ 28%, H255 ~ 60 %, CO5 ~ 8%, CO2~4%。
It is mainly that low-temp methanol washes technology, other activative MDEA technologies and NHD skills to be pyrolyzed coal gas desulfurization decarbonization device technology
Art is equally applicable；Wherein, two strands of pyrolyzing coal qi leel respectively enters desulfurization and decarburization device, and wherein firing tunnel in coking furnace only carries out desulfurization, separately
One carries out desulfurization and decarburization, and the carbon dioxide of abjection enters back into gasification after being mixed with the pure oxygen from space division into gas mixing tank
Stove, produces carbon monoxide；Gasification gas desulfurizer technology mainly has a wet desulphurization and dry desulfurization, and it is also same that low-temp methanol is washed etc.
Sample is applicable；Gasificating desulfurization device and the sulphur of desulfurization and decarburization device abjection enter sulfur recovery unit and are used to produce sulphur or sulphuric acid production
Product.
Partial gasification coal gas replacement partial thermal decomposition coal gas melts down heating for pyrolysis installation and used, and its mixed gas calorific value is not
Less than 3000kcal/m3。
The catalytic synthetic techniques mainly have methane synthetic technology, methanol synthesis technology, synthetic technology of ethylene glycol and diformazan
Ether synthetic technology.
The good effect that technical scheme is produced is as follows：1. partial thermal decomposition is replaced with more low-quality gasification gas
Gas-fired, realizes the reasonable utilization of pyrolysis high-quality coal gas to greatest extent；2. the pyrolysis coal gas after purifying is successively through desulfurization
Decarbonization device and ice chest device isolate methane gas, hydrogen rich gas gas and rich CO gas, and methane gas is used to produce
LNG/CNG, hydrogen rich gas gas is divided to two strands, and a stock-traders' know-how pressure-variable adsorption, which carries hydrogen after hydrogen, to be used to produce synthesis ammonia etc., remaining desorption
Qi leel is not converged with the gasification gas after another strand of hydrogen rich gas gas and rich carbon monoxide gas and purification, then is used for after compression
Produce downstream product, not only take full advantage of the methane gas of pyrolysis wherein high-quality, also fully combine pyrolysis gas hydrogen-rich and
The advantage of the rich carbon of the gas that gasifies；3. the carbon dioxide of desulfurization and decarburization device abjection gasifies as gasification oxidant for gasification furnace, keeps away
Carbon emission is exempted from.
Brief description of the drawings
Fig. 1 is the process chart of Novel gasification of the present invention and pyrolysis coupling coal gas multi-production process.
Embodiment
The present invention can be further detailed with reference to drawings and Examples to the present invention.
A kind of Novel gasification and pyrolysis coupling coal gas multi-production process, as shown in figure 1, with production metallurgy it is burnt 1,300,000 tons/
Year, coke-stove gas about 6 ten thousand steres/hour, 3.2 ten thousand steres of pure oxygen fixed bed gasification equipment production gasification gas/hour, first
About 100,000 tons/year of alcohol, synthesizes about 50,000 tons/year of ammonia, is realized exemplified by the enterprise of LNG7 ~ 80,000 ton/year.
The present invention implementation be 3.2 ten thousand steres of the raw gas/hour for producing gasification furnace respectively through waste heat boiler,
After gasification gas purifier and gasification gas desulfurizer, a part of about 2.2 ten thousand steres/hour melts down gas as pyrolysis
With another part about 1 ten thousand stere/hour after desulfurizer, is used as synthesis gas；Pyrolysis raw coke oven gas about 6 ten thousand stere/small
When after being pyrolyzed gas cleaning device, be divided to two stocks not after the desulfurization of desulfurization and decarburization device and desulfurization and decarburization, one after desulfurization
About 1 ten thousand stere/hour melts down the pyrolysis gas after gas use, another stock about 5 ten thousand steres/hour desulfurization and decarburization about as pyrolysis oven
4.7 ten thousand steres/hour enters ice chest device, and separation of methane obtains 9.05 ton hour LNG/CNG products, remaining hydrogen-rich 3.2
Ten thousand stere/hour and rich carbon monoxide 0.3 ten thousand stere/two strands of hour pyrolysis gas, wherein hydrogen-rich pyrolysis gas are divided to two strands,
After one about 1.3 ten thousand steres/hour carries hydrogen through pressure-variable adsorption, hydrogen about 1 ten thousand stere/hour enters compressor with coming from space division
Nitrogen converge and enter compressor, catalyzing and synthesizing device subsequently into synthesis ammonia obtains synthesizing ammonolysis product, Utilization of PSA Relief Gas
0.3 ten thousand stere of body/hour respectively with another 1.9 ten thousand steres of stock/hour hydrogen-rich gas and remaining 0.3 ten thousand stere/hour
Rich CO gas and the above are converged from about 1 ten thousand stere/hour synthesis gas of gasification, in the lump into compressor,
Then the methanol product of about 12.58 ton hours can be synthesized through catalyzing and synthesizing device；About 0.78 ten thousand stere after catalyzing and synthesizing/
After hour periodic off-gases carry hydrogen through pressure-variable adsorption, hydrogen about 0.3 ten thousand stere/hour is used to enter synthesis ammonia compressor for synthesizing
Ammonia, residual gas is recycled.Wherein, carbon dioxide about 0.17 ten thousand stere/hour of desulfurization and decarburization device abjection is with coming from
0.7 ten thousand stere of pure oxygen/hour of space division enters gasification installation after entering blending tank mixing；Gasificating desulfurization device and desulfurization and decarburization
The sulphur of device abjection enters sulfur recovery unit and can be used for production sulphur or the ton hour product of sulfuric acid 1.48.
According to above-mentioned implementation, gasification gas composition H2~ 41%, CO ~ 37%, CH4~ 1.9%, CO2~18%；Coke-stove gas group
Into H2~ 57%, CO ~ 8.5%, CH4~ 22%, CO2~ 3.7%, CnHm ~ 2%.
Claims (5)
1. a kind of Novel gasification and pyrolysis coupling coal gas multi-production process, it is characterised in that：The technique with gasification furnace produce it is thick
Coal gas is raw material, and respectively after waste heat boiler, gasification gas purifier and gasification gas desulfurizer, a part is used as pyrolysis
Gas use is melted down, another part is used as synthesis gas；Raw coke oven gas is pyrolyzed after being pyrolyzed gas cleaning device, is divided to two stocks not through desulfurization
Decarbonization device desulfurization and desulfurization and decarburization, one after desulfurization melt down the pyrolysis after gas use, another strand of desulfurization and decarburization as pyrolysis oven
Gas obtains LNG/CNG products into ice chest device separation of methane；Two strands of pyrolysis gas of remaining hydrogen-rich and rich carbon monoxide, wherein
Hydrogen-rich pyrolysis gas is divided to two strands, and a stock-traders' know-how pressure-variable adsorption is carried after hydrogen, and hydrogen converges into compressor with the nitrogen from space division, then
Device is catalyzed and synthesized into synthesis ammonia to obtain synthesizing ammonolysis product；Utilization of PSA Relief Gas body respectively with another strand of hydrogen-rich gas and surplus
Remaining rich CO gas and the above are converged from the synthesis gas of gasification, in the lump into compressor, then through catalyzing and synthesizing
Device synthesis CNG, alcohol or ether product；After periodic off-gases after catalyzing and synthesizing carry hydrogen through pressure-variable adsorption, hydrogen is used to enter synthesis ammonia
Compressor is used to synthesize ammonia, and residual gas is recycled.
2. a kind of Novel gasification according to claim 1 and pyrolysis coupling coal gas multi-production process, it is characterised in that：It is described
Gasification furnace is pure oxygen fixed bed gasification, and raw materials used including raw coal, semi-coke and coke, gasification oxidant used includes pure oxygen, two
Carbonoxide and water vapour；The pyrolysis installation is coke oven；The gasification gas main component is：CH41.9%, H241%, CO
37%, CO218%；Being pyrolyzed coal gas main component is：CH422 ~ 28%, H255 ~ 60 %, CO5 ~ 8%, CO2 4%。
3. a kind of Novel gasification according to claim 1 and pyrolysis coupling coal gas multi-production process, it is characterised in that：Pyrolysis
Coal gas desulfurization decarbonization device technology is that low-temp methanol washes technology, activative MDEA technology or NHD technologies；Wherein, pyrolyzing coal qi leel
Two strands respectively enter desulfurization and decarburization device, and wherein firing tunnel in coking furnace only carries out desulfurization, another strand of progress desulfurization and decarburization, the dioxy of abjection
Change after carbon is mixed with the pure oxygen from space division into gas mixing tank and enter back into gasification furnace, produce carbon monoxide；Gasification of coal qi exhaustion
Sulphur device technique is that wet desulphurization, dry desulfurization or low-temp methanol are washed；What gasificating desulfurization device and desulfurization and decarburization device were deviate from
Sulphur enters sulfur recovery unit and is used to produce sulphur or sulfuric acid product.
4. a kind of Novel gasification according to claim 1 and pyrolysis coupling coal gas multi-production process, it is characterised in that：Part
Gasification gas replacement partial thermal decomposition coal gas melts down heating for pyrolysis installation and used, and its mixed gas calorific value is not less than
3000kcal/m3。
5. a kind of Novel gasification according to claim 1 and pyrolysis coupling coal gas multi-production process, it is characterised in that：It is described
Catalytic synthetic techniques include methane synthetic technology, methanol synthesis technology, synthetic technology of ethylene glycol and Dimethyl Ether Synthesis Technology.
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| CN107043089B (en) * | 2017-05-19 | 2019-06-04 | 福州大学化肥催化剂国家工程研究中心 | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals |
| CN113956905A (en) * | 2020-06-29 | 2022-01-21 | 杨皓 | Improved process for preparing ammonia and CNG from coke oven gas |
| CN116177564A (en) * | 2022-12-08 | 2023-05-30 | 金能科技股份有限公司 | Method for preparing methanol and co-producing synthetic ammonia and extracting ammonia from coke oven gas |
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Inventor after: Li Mao Inventor after: Yu Yuanhang Inventor after: Hao Yingxuan Inventor after: Li Guangmin Inventor after: Li Hongchao Inventor after: Ai Humin Inventor after: Ren Yunliang Inventor after: Peng Yawei Inventor after: Zhang Hongen Inventor after: Bi Yamei Inventor after: Niu Xin Inventor before: Li Hongchao Inventor before: Ren Yunliang Inventor before: Peng Yawei Inventor before: Zhang Hongen Inventor before: Bi Yamei Inventor before: Niu Xin Inventor before: Yu Yuanhang Inventor before: Hao Yingxuan |
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Effective date of registration: 20170111 Address after: Hung Road Shilong District of Pingdingshan City, Henan province 467045 No. 2 Applicant after: Henan Zhonghong Group Coal Chemical Industry Co., Ltd. Applicant after: China Pingmei Shenma Energy Chemical Group Co., Ltd. Address before: Hung Road Shilong District of Pingdingshan City, Henan province 467045 No. 2 Applicant before: Henan Zhonghong Group Coal Chemical Industry Co., Ltd. |
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