CN1903723A - Method of producing liquid ammonia, urea and methanol using metallurgical waste gas - Google Patents

Method of producing liquid ammonia, urea and methanol using metallurgical waste gas Download PDF

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Publication number
CN1903723A
CN1903723A CNA2006100892979A CN200610089297A CN1903723A CN 1903723 A CN1903723 A CN 1903723A CN A2006100892979 A CNA2006100892979 A CN A2006100892979A CN 200610089297 A CN200610089297 A CN 200610089297A CN 1903723 A CN1903723 A CN 1903723A
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gas
ammonia
urea
hydrogen
nitrogen
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CNA2006100892979A
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冯俊小
梁凯丽
陈四仿
王绳
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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Abstract

The present invention relates to a method for producing liquid ammonia, urea and methyl alcohol by utilizing metallurgical waste gas. It is characterized by that (1), the coke oven gas is undergone the processes of fine desulfurization and pressurization, then assed through the hydrogen separation equipment so as to obtain the hydrogen gas whose purity is greater than 90%, said hydrogen gas can be used as raw material gas for making synthetic ammonia, other gas can be back returned into gas pipe network; (2), the nitrogen gas required for making synthetic ammonia can be directly from polluted nitrogen produced by oxygen gas plant, said polluted nitrogen is pressurized and filtered, then fed into synthetic ammonia system, said hydrogen gas and nitrogen gas can produce synthesis reaction to obtain ammonia, the unreacted gas can be undergone the process of circulating compression and can be reused; (3), the carbon dioxide produced by calcining lime and dolomite is undergone the process of purification, then the purified carbon dioxide and ammonia are undergone the process of steam stripping treatment so as to produce urea, etc. and (4), said invention can make the waste gases of coke oven gas, carbon dioxide and polluted 4nitrogen of metallurgical plant obtain comprehensive utilization and raise their economic value.

Description

A kind of production method of utilizing metallurgic waste gas to produce liquefied ammonia, urea and methyl alcohol
Technical field
The invention belongs to field of metallurgy and chemical engineering, particularly a kind of production method of utilizing metallurgic waste gas to produce liquefied ammonia, urea and methyl alcohol can realize the comprehensive utilization of metallurgic waste gas resource.
Background technology
Metallurgy industry is a high energy consumption, one of industry of high pollution discharging.China has big or small smelter several hundred families at present, and national iron and steel output reached 3.5 hundred million tons in 2005, ranked first in the world.In the metallurgical production process, coking process produces a large amount of coke-oven gas, and the coke(oven)gas of these high heating values is burnt as conventional fuel gas usually, has not only reduced its economic worth, and contaminate environment; Some factory also diffuses coke-oven gas in vain because fuel gas is superfluous.The roasting meeting discharging great amount of carbon dioxide of Wingdale and rhombspar, the oxygen preparation process can be discharged a large amount of dirty nitrogen, all is used as exhaust gas emission.So not only waste the resource and the energy, increased the production cost of enterprise, also environment has been caused pollution simultaneously.From comprehensive utilization of resources, protection environment and economic benefit equal angles, the problem of smelter waste gas needs to be resolved hurrily.
Summary of the invention
The present invention is from comprehensive utilization of resources, protection environment and economic benefit equal angles, proposed that metallurgic waste gas is comprehensive, efficient, environmental protection utilize shortcut, improve the comprehensive utilization ratio of resource, reduce CO 2The discharging of pollutents such as greenhouse gases.
A kind of metallurgic waste gas is produced the production method of liquefied ammonia, urea and methyl alcohol, it is characterized in that:
(1) produces the H of one of main raw material gas as synthetic ammonia 2: to carrying out smart desulfurization with organic sulfide removal and inorganic sulfur from the coke-oven gas in the smelter coking production process, sulfur method adopts wet desulphurization or dry desulfurization, and wet desulphurization comprises: improvement MDEA method, tannin extract method, PDS method; Dry desulfurization comprises: hydrocracking, activated carbon method, iron oxide process, zinc oxide method, manganese ore method etc.Separation system is sent in pressurization to the coke-oven gas after the desulfurization.Separation system is physics method, chemical method or physical chemistry combined method.Comprise methods such as pressure swing adsorption process.The available gas H of separation system 2Separation efficiency 〉=90%, H 2Purity 〉=95%.
(2) synthetic ammonia, choose the dirty nitrogen that diffuses from the oxygen production process as source nitrogen, dirty nitrogen process filter before entering ammonia synthesis system removes impurity wherein, removing dirty nitrogen behind the impurity compresses with the hydrogen that goes out from the separation system sub-argument and enters ammonia synthesis system, ammonia synthesis system can adopt high pressure, middle pressure, low pressure synthetic technology, synthesis pressure 8.0-15MPa, the nitrogen and the hydrogen that enter ammonia synthesis system are controlled through flow regulator, make the hydrogen nitrogen mol ratio in the synthesis loop be about 3: 1.
Owing to adopt pure hydrogen and nitrogen as raw material, so the one way Synthesis conversion can be characterized in up to more than 20%: the ammonia net value height, the discharge quantity of speeding is little; Under lower synthesis pressure, can obtain higher ammonia yield.Thereby compare with other technologies, energy consumption is also minimum.
(3) synthetic liquefied ammonia can be with another waste gas CO of smelter 2Gas is together as the raw material of urea or other ammonia producing unit, raw material CO 2Gas can be purified to more than 99% to satisfy processing requirement by physics method, chemical method or physico-chemical processes.
(4) go out another part gas that separation system is rich in components such as methane and carbon monoxide, can send the fuel gas of former coke-oven gas pipe network back to as smelter.Transform through part again or steam reforming wherein methane conversion be hydrogen and carbon monoxide, send into gas separation system then, hydrogen is wherein reclaimed again, be used to produce synthetic ammonia, also available hydrogen and carbon monoxide are produced methyl alcohol by methanol technics technology such as low pressure, middle pressures.
This operational path is a kind of chemical metallurgy novel process of joint production of developing on the basis of existing individual event mature technology.Flow process is simple, invests low.Rely on smelter to build the device of the similar scale of a cover, its investment is 30～40% of a newly-built traditional technology only, and economic benefit is obvious.
Description of drawings
Fig. 1 utilizes metallurgic waste gas to produce the technological process of production figure of liquefied ammonia and urea
Fig. 2 utilizes metallurgic waste gas to produce the technological process of production figure of liquefied ammonia, urea and methyl alcohol
Embodiment
Embodiment one: coke-oven gas is pressurized to 1～4MPa after desulfurization, carries out Hydrogen Separation (purity is more than 90%) by transformation absorption, and remaining gas is returned gas line.To be pressurized to 7～15MPa behind the dirty nitrogen ultra-clean filtering and removing impurity, send into ammonia synthesis system synthetic ammonia with isolated hydrogen (regulating about 3: 1 of hydrogen nitrogen mol ratio) again.
Embodiment two: coke-oven gas is pressurized to 1～4MPa after desulfurization, carry out Hydrogen Separation (purity is more than 95%) by transformation absorption, remaining gas is passed through conversion again after vapor portion transforms, the gas after the conversion is sent into gas separation system again and carried out the hydrogen separation.To be pressurized to 7～15MPa behind the dirty nitrogen ultra-clean filtering and removing impurity, send into ammonia synthesis converter synthetic ammonia with isolated hydrogen (regulating about 3: 1 of hydrogen nitrogen mol ratio) again.
Embodiment three: coke-oven gas is pressurized to 1～4MPa after desulfurization, carries out Hydrogen Separation (purity is more than 95%) by transformation absorption, and remaining gas is isolated hydrogen through sending into gas separation system after the conversion again after vapor portion transforms.To be pressurized to 7～15MPa behind the dirty nitrogen ultra-clean filtering and removing impurity, send into ammonia synthesis system synthetic ammonia with isolated hydrogen (regulating about 3: 1 of hydrogen nitrogen mol ratio) again.
Isolated CO in synthetic ammonia and the stove waste gas 2Produce urea through stripping process.

Claims (4)

1. a metallurgic waste gas is produced the production method of liquefied ammonia, urea and methyl alcohol, it is characterized in that:
(1) produces the H of one of main raw material gas as synthetic ammonia 2: to carrying out smart desulfurization with organic sulfide removal and inorganic sulfur from the coke-oven gas in the coking production process, separation system is sent in pressurization to the coke-oven gas after the desulfurization, requires the H of separation system 2Separation efficiency 〉=90%, H 2Purity 〉=95%;
(2) produce two N as the main raw material gas of synthetic ammonia 2, choose the dirty nitrogen that diffuses from the oxygen production process as source nitrogen, dirty nitrogen after entering the impurity that removes through filter wherein as synthesis material;
(3) synthetic ammonia; The H that has prepared 2And N 2Enter ammonia synthesis system separately or after being compressed to synthesis pressure together after mixing, ammonia synthesis system pressure 7.0-15MPa, the dirty nitrogen and the hydrogen that enter ammonia synthesis system are controlled through flow regulator, and making the hydrogen nitrogen mol ratio in the ammonia synthesis loop is 3: 1.
2. a kind of metallurgic waste gas according to claim 1 is produced the production method of liquefied ammonia, urea and methyl alcohol, it is characterized in that synthetic liquefied ammonia another waste gas CO with smelter 2Gas is together as the raw material of urea or other ammonia producing unit, as the CO of urea 2Gas raw material requires to be purified to more than 99% by physics method, chemical method or physico-chemical processes.
3. a kind of metallurgic waste gas according to claim 1 is produced the production method of liquefied ammonia, urea and methyl alcohol, it is characterized in that separation system is rich in another part gas of methane, is hydrogen and carbon monoxide through partial oxidation or steam reforming with methane conversion, gas after the conversion can be sent into gas separation system, hydrogen is wherein recycled, be used to produce synthetic ammonia, also available hydrogen and carbon monoxide are by low pressure methanol technology, and liquid phase methyl alcohol technique means is produced methyl alcohol.
4. the production method that described a kind of metallurgic waste gas according to claim 1 is produced liquefied ammonia, urea and methyl alcohol is characterized in that sulfur method adopts wet desulphurization or dry desulfurization, and wet desulphurization comprises: improvement ADA method, tannin extract method, PDS method; Dry desulfurization comprises: hydrocracking, activated carbon method, iron oxide process, zinc oxide method, manganese ore method etc.; Separation system is physics method, chemical method or physical chemistry combined method, comprises pressure swing adsorption process, improvement thermokalite method, propene carbonate method, polyamine process method.
CNA2006100892979A 2006-08-15 2006-08-15 Method of producing liquid ammonia, urea and methanol using metallurgical waste gas Pending CN1903723A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348264B (en) * 2008-09-05 2010-04-14 黄鸿宁 Clean low energy consumption synthesis ammonia production method
CN101368010B (en) * 2008-09-25 2011-01-26 曲靖众一精细化工股份有限公司 Method for producing semi-reinforcing hydrocarbon black, methanol, liquid ammonia with coke oven gas
CN102101644A (en) * 2010-12-20 2011-06-22 昆明理工大学 Method for preparing ammonia synthesis gas from iron alloy smoke
CN102101643A (en) * 2010-12-20 2011-06-22 昆明理工大学 Method for preparing ammonia synthesis gas from oxygen-enriched blast furnace gas
CN101704712B (en) * 2009-10-29 2012-09-05 山西焦化股份有限公司 Technological method for preparing methanol by combining coke oven gas with water gas
CN102897798A (en) * 2012-06-08 2013-01-30 李宽义 Environmental-protection cleaning technology for producing hydrocyanic acid derivatives by comprehensive utilization of coke oven gas
CN103482648A (en) * 2013-09-16 2014-01-01 贵州金正大生态工程有限公司 Method of producing synthesis ammonia by using furnace gas produced when phosphoric acid is produced in kiln method or blast furnace method
CN104772031A (en) * 2015-04-14 2015-07-15 河南心连心化肥有限公司 Direct vehicle urea solution production device and production method thereof
CN105732323A (en) * 2016-02-18 2016-07-06 中国庆华能源集团有限公司 System for preparing methyl alcohol with coke oven gas and method for preparing methyl alcohol through system
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

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101348264B (en) * 2008-09-05 2010-04-14 黄鸿宁 Clean low energy consumption synthesis ammonia production method
CN101368010B (en) * 2008-09-25 2011-01-26 曲靖众一精细化工股份有限公司 Method for producing semi-reinforcing hydrocarbon black, methanol, liquid ammonia with coke oven gas
CN101704712B (en) * 2009-10-29 2012-09-05 山西焦化股份有限公司 Technological method for preparing methanol by combining coke oven gas with water gas
CN102101644B (en) * 2010-12-20 2013-11-27 昆明理工大学 Method for preparing ammonia synthesis gas from iron alloy smoke
CN102101643A (en) * 2010-12-20 2011-06-22 昆明理工大学 Method for preparing ammonia synthesis gas from oxygen-enriched blast furnace gas
CN102101644A (en) * 2010-12-20 2011-06-22 昆明理工大学 Method for preparing ammonia synthesis gas from iron alloy smoke
CN102101643B (en) * 2010-12-20 2013-11-27 昆明理工大学 Method for preparing ammonia synthesis gas from oxygen-enriched blast furnace gas
CN102897798A (en) * 2012-06-08 2013-01-30 李宽义 Environmental-protection cleaning technology for producing hydrocyanic acid derivatives by comprehensive utilization of coke oven gas
WO2013182071A1 (en) * 2012-06-08 2013-12-12 Li Kuanyi Environmentally friendly and clean process for producing hydrocyanic acid derivate by comprehensive utilization of coke oven gas
CN103482648A (en) * 2013-09-16 2014-01-01 贵州金正大生态工程有限公司 Method of producing synthesis ammonia by using furnace gas produced when phosphoric acid is produced in kiln method or blast furnace method
CN103482648B (en) * 2013-09-16 2015-12-23 金正大诺泰尔化学有限公司 A kind of furnace gas utilizing kiln method or blast furnace process to produce phosphoric acid produces the method for synthetic ammonia
CN104772031A (en) * 2015-04-14 2015-07-15 河南心连心化肥有限公司 Direct vehicle urea solution production device and production method thereof
CN105732323A (en) * 2016-02-18 2016-07-06 中国庆华能源集团有限公司 System for preparing methyl alcohol with coke oven gas and method for preparing methyl alcohol through system
CN105732323B (en) * 2016-02-18 2018-04-06 中国庆华能源集团有限公司 The method for preparing the system of methanol with oven gas and methanol being prepared with the system
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

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