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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CN1903723A
CN1903723A CN 200610089297 CN200610089297A CN1903723A CN 1903723 A CN1903723 A CN 1903723A CN 200610089297 CN200610089297 CN 200610089297 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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CN 200610089297
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Chinese (zh)
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冯俊小
梁凯丽
陈四仿
王绳
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北京科技大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/51Bulk chemicals
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/58Recycling
    • Y02P20/582Recycling of unreacted starting or intermediate materials

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

一种利用冶金废气生产液氨、尿素及甲醇的生产方法 Utilizing metallurgical method of producing an exhaust gas producing ammonia, urea and methanol

技术领域 FIELD

本发明属于冶金化工领域,特别涉及一种利用冶金废气生产液氨、尿素及甲醇的生产方法,可实现冶金废气资源的综合利用。 The present invention belongs to the field of metallurgy industry, in particular, relates to an exhaust gas utilization utilizing metallurgical process for producing a liquid ammonia, urea and methanol, the exhaust gas can be achieved metallurgical resources.

背景技术 Background technique

冶金行业是高能耗,高污染排放的行业之一。 Metallurgical industry is one of high energy consumption, high pollution industries. 我国目前有大小冶金企业几百家,2005年全国钢铁产量达3.5亿吨,居世界第一位。 China currently has hundreds of the size of the metallurgical enterprises in 2005, the national steel output reached 350 million tons, ranking first in the world. 在冶金生产过程中,焦化工序产生大量的焦炉煤气,这些高热值的焦炉气通常作为普通燃料气被烧掉,不仅降低了其经济价值,而且污染环境;有些厂还由于燃料气过剩而将焦炉煤气白白放散掉。 In the metallurgical production process, a large amount of coking step coke oven gas, coke oven gas and the high calorific value fuel is usually burned as a normal gas, not only reduces its economic value, but also pollute the environment; some plants and also because an excess of fuel gas the coke oven gas in vain to put dissipated. 石灰石和白云石的焙烧会排放大量二氧化碳,氧气制备过程会排放大量的污氮,均被作为废气排放。 Calcination of limestone and dolomite can emit large quantities of carbon dioxide, oxygen preparation process can emit large quantities of waste nitrogen, are discharged as waste gas. 这样不仅浪费了资源和能源,增加了企业的生产成本,同时也对环境造成了污染。 This is not only a waste of resources and energy, increased production costs, but also on the environment caused by pollution. 从资源综合利用、保护环境以及经济效益等角度出发,冶金企业废气的问题亟待解决。 From the comprehensive utilization of resources, environmental protection and economic efficiency point of view, the problem metallurgical enterprises of the exhaust gas to be solved.

发明内容 SUMMARY

本发明从资源综合利用、保护环境以及经济效益等角度出发,提出了一条冶金废气综合、高效、环保的利用捷径,提高资源的综合利用率,减少CO2温室气体等污染物的排放。 The present invention is based on comprehensive utilization of resources, environmental protection and economic efficiency point of view, put forward a comprehensive metallurgical waste gas, efficient and environmentally friendly use of shortcuts, improve the comprehensive utilization of resources, reduce emissions of CO2 and other greenhouse gases.

一种冶金废气生产液氨、尿素及甲醇的生产方法,其特征是:(1)制取作为合成氨的主原料气之一的H2:对来自冶金企业焦化生产过程中的焦炉煤气进行精脱硫以脱除有机硫和无机硫,脱硫方法采用湿法脱硫或干法脱硫,湿法脱硫包括:改良MDEA法、栲胶法、PDS法;干法脱硫包括:加氢转化、活性炭法、氧化铁法、氧化锌法、锰矿法等。 A metallurgical waste gas producing ammonia, methanol and urea production process, characterized in that: (1) Preparation of one H2 as main material gas of ammonia: for metallurgical coke production from the coke oven gas desulfurization to remove organic and inorganic sulfur, wet desulfurization using the desulfurization method or dry desulfurization, wet desulfurization comprising: MDEA improved method, tannin extract, the PDS method; dry desulfurization comprising: hydroconversion, activated carbon, iron oxide method, oxidation of zinc, manganese or the like. 对脱硫后的焦炉煤气加压送入分离系统。 Desulfurization of coke oven gas pressure into the separation system. 分离系统为物理法、化学法或物理化学组合法。 Separation system physical, chemical or physicochemical methods in combination. 包括变压吸附法等方法。 The method includes a pressure swing adsorption method or the like. 分离系统的有效气体H2分离效率≥90%,H2纯度≥95%。 The effective gas H2 separation efficiency system ≥90%, H2 purity of ≥95%.

(2)合成氨,选取来自氧气生产过程放散的污氮作为氮气源,污氮在进入氨合成系统前经过滤器脱除其中的杂质,脱除杂质后的污氮与从分离系统分理出的氢气一起压缩进入氨合成系统,氨合成系统可采用高压、中压、低压合成技术,合成压力8.0-15MPa,进入氨合成系统的氮气和氢气经流量调节器控制,使合成回路中的氢氮摩尔比约为3∶1。 (2) ammonia, an impurity selected from oxygen, nitrogen pollution releasing of the production process as a source of nitrogen, wherein the nitrogen pollution removal through the filter before entering the ammonia synthesis system, after the removal of waste nitrogen impurities from the hydrogen gas separation system sub-sort of together with the compression system into the ammonia synthesis, ammonia synthesis systems employed a high-pressure, medium-pressure, low-pressure synthesis techniques, synthetic pressure 8.0-15MPa, into the ammonia synthesis system by nitrogen and hydrogen flow control regulator, that the molar ratio of hydrogen to nitrogen in the synthesis loop about 3:1.

由于采用纯的氢气和氮气作为原料,因此单程合成转化率可高达20%以上,其特点是:氨净值高,驰放气量小;在较低的合成压力下,可以取得较高的氨收率。 Since pure hydrogen and nitrogen as the raw material, and therefore the synthesis pass conversion rate as high as 20%, which is characterized by: high ammonia net, a small purge gas; synthesis at lower pressures, can achieve a higher yield of ammonia . 因而和其他工艺相比,能耗也最低。 Compared to other processes and thus, the lowest energy consumption.

(3)合成的液氨可以同冶金企业的另外一种废气CO2气体一起作为尿素或其它氨加工生产装置的原料,原料CO2气体可通过物理法、化学法或物理化学法提纯到99%以上以满足工艺要求。 (3) can be synthesized with additional ammonia to an exhaust gas with CO2 gas as a raw material metallurgical urea, ammonia or other processing apparatus, a raw material gas CO2 by physical, chemical or physicochemical methods to purify 99% or more meet the technical requirements.

(4)出分离系统富含甲烷和一氧化碳等组分的另一部分气体,可送回原焦炉煤气管网作为冶金企业的燃料气体。 (4) another portion of the separation system enriched gas components methane and carbon monoxide, it can be returned to the original coke oven gas as a fuel gas pipeline metallurgical enterprises. 或再经过部分转化或蒸汽转化法将其中甲烷转化为氢气和一氧化碳,然后送入气体分离系统,将其中的氢气进行再回收,用于生产合成氨,也可用氢气和一氧化碳通过低压、中压等甲醇工艺技术生产甲醇。 Or go through steam reforming or partial conversion method of methane into hydrogen and carbon monoxide, and then fed to the gas separation system, in which the hydrogen gas recycling for the production of ammonia, hydrogen and carbon monoxide can also be used by low pressure, medium pressure, etc. Methanol technology to produce methanol.

本工艺路线是在现有单项成熟技术的基础上开发出的一种冶金化工联合生产新工艺。 This route is developed on the basis of the existing single mature technology, based on a metallurgical joint production of new chemical processes. 流程简单,投资低。 Simple process, low investment. 依托冶金企业建设一套同类规模的装置,其投资仅为新建传统工艺的30~40%,经济效益明显。 Metallurgical enterprises to build a similar sized device support, new investment is only 30 to 40% of the traditional process of economic benefit.

附图说明 BRIEF DESCRIPTION

图1为利用冶金废气生产液氨及尿素的生产工艺流程图图2为利用冶金废气生产液氨、尿素及甲醇的生产工艺流程图具体实施方式实施例一:焦炉煤气经脱硫后加压到1~4MPa,通过变压吸附进行氢气分离(纯度90%以上),其余气体返回煤气管道。 Example 1 is the use of ammonia and urea production exhaust metallurgical production process using FIG 2 is a metallurgical exhaust ammonia production, methanol production process in FIG urea and a particular embodiment: the desulfurized coke oven gas was pressurized to 1 ~ 4MPa, hydrogen gas separation (purity 90%) by pressure swing adsorption, the remaining gas return gas pipe. 将污氮超净过滤脱除杂质后加压到7~15MPa,再与已分离出的氢(调节氢氮摩尔比约3∶1)送入氨合成系统合成氨。 The nitrogen pollution removal of impurities filtered clean pressurized to 7 ~ 15MPa, and then separated out and the hydrogen (molar ratio of hydrogen to nitrogen adjustment about 3) ammonia into the ammonia synthesis system.

实施例二:焦炉煤气经脱硫后加压到1~4MPa,通过变压吸附进行氢气分离(纯度95%以上),其余气体经蒸汽部分转化后,再经过变换,变换之后的气体再送入气体分离系统进行氢分离。 Example Two: gas after desulfurization coke oven gas was pressurized to 1 ~ 4MPa, hydrogen gas separation (purity 95%) by pressure swing adsorption, the vapor remaining after partial conversion gas, and then the converted, and then converted into a gas separation system for separating hydrogen. 将污氮超净过滤脱除杂质后加压到7~15MPa,再与已分离出的氢(调节氢氮摩尔比约3∶1)送入氨合成塔合成氨。 The nitrogen pollution removal of impurities filtered clean pressurized to 7 ~ 15MPa, and then separated out and the hydrogen (molar ratio of hydrogen to nitrogen adjustment about 3) ammonia into the ammonia synthesis tower.

实施例三:焦炉煤气经脱硫后加压到1~4MPa,通过变压吸附进行氢气分离(纯度95%以上),其余气体经蒸汽部分转化后,再经过变换后送入气体分离系统进行分离出氢气。 Third Embodiment: The desulfurized coke oven gas pressurized to 1 ~ 4MPa, hydrogen gas separation (purity 95%) by pressure swing adsorption, the vapor remaining after partial conversion gas, then after converting into a gas separation system for separating hydrogen gas. 将污氮超净过滤脱除杂质后加压到7~15MPa,再与已分离出的氢(调节氢氮摩尔比约3∶1)送入氨合成系统合成氨。 The nitrogen pollution removal of impurities filtered clean pressurized to 7 ~ 15MPa, and then separated out and the hydrogen (molar ratio of hydrogen to nitrogen adjustment about 3) ammonia into the ammonia synthesis system.

合成氨与炉窑废气中分离出的CO2经汽提工艺生产尿素。 Ammonia and kiln exhaust gas separated by the CO2 stripping urea producing process.

Claims (4)

  1. 1.一种冶金废气生产液氨、尿素及甲醇的生产方法,其特征是:(1)制取作为合成氨的主原料气之一的H2:对来自焦化生产过程中的焦炉煤气进行精脱硫以脱除有机硫和无机硫,对脱硫后的焦炉煤气加压送入分离系统,要求分离系统的H2分离效率≥90%,H2纯度≥95%;(2)制取作为合成氨的主原料气之二的N2,选取来自氧气生产过程放散的污氮作为氮气源,污氮在进入经过滤器脱除其中的杂质后作为合成原料;(3)合成氨;已制备好的H2和N2单独或混合后一起压缩到合成压力后进入氨合成系统,氨合成系统压力7.0-15MPa,进入氨合成系统的污氮和氢气经流量调节器控制,使氨合成回路中的氢氮摩尔比为3∶1。 1. A metallurgical waste gas producing ammonia, methanol and urea production process, characterized in that: (1) Preparation of one H2 as main material gas of ammonia: production of coke from the coke oven gas during desulfurization to remove organic and inorganic sulfur, coke oven gas desulfurized pressurized to a separation system that requires the separation system H2 separation efficiency ≥90%, H2 purity ≥95%; (2) Preparation of raw material ammonia as a main bis N2 gas, selected from oxygen, nitrogen pollution releasing of the production process as a source of nitrogen, waste nitrogen removal through the filter after entering as an impurity wherein the synthetic material; (3) ammonia; H2 and N2 have been prepared separately or as a mixture compressed together after the pressure into the ammonia synthesis system of the synthesis, ammonia synthesis system pressure 7.0-15MPa, into the ammonia synthesis system of hydrogen and nitrogen pollution control through flow regulator, that the molar ratio of hydrogen to nitrogen for ammonia synthesis loop 3:1.
  2. 2.根据权利要求1所述的一种冶金废气生产液氨、尿素及甲醇的生产方法,其特征在于合成的液氨同冶金企业的另外一种废气CO2气体一起作为尿素或其它氨加工生产装置的原料,作为尿素的CO2气体原料要求通过物理法、化学法或物理化学法提纯到99%以上。 2. A metallurgical production of ammonia an exhaust gas according to claim 1, the method for producing methanol and urea, wherein the ammonia synthesis together with another exhaust gas CO2 metallurgical enterprises as ammonia, urea or other processing means the raw material, the raw material urea as CO2 gas purification requirements by 99% or more physical, chemical or physicochemical methods.
  3. 3.根据权利要求1所述的一种冶金废气生产液氨、尿素及甲醇的生产方法,其特征在于出分离系统富含甲烷的另一部分气体,经过部分氧化或蒸汽转化法将甲烷转化为氢气和一氧化碳,转化后的气体可送入气体分离系统,将其中的氢气进行回收利用,用于生产合成氨,也可用氢气和一氧化碳通过低压甲醇工艺,液相甲醇技术手段生产甲醇。 3. A metallurgical production of ammonia an exhaust gas, according to a method of producing urea and methanol claim, wherein a further portion of the methane-rich gas separation system, via partial oxidation or steam reforming of methane into hydrogen and carbon monoxide gas can be converted into the gas separation system, in which hydrogen recycling, for the production of ammonia, hydrogen and carbon monoxide can also be used by low pressure methanol process to produce methanol, the methanol phase techniques.
  4. 4.根据权利要求1所述的所述的一种冶金废气生产液氨、尿素及甲醇的生产方法,其特征在于脱硫方法采用湿法脱硫或干法脱硫,湿法脱硫包括:改良ADA法、栲胶法、PDS法;干法脱硫包括:加氢转化、活性炭法、氧化铁法、氧化锌法、锰矿法等;分离系统为物理法、化学法或物理化学组合法,包括变压吸附法、改良热碱法、碳酸丙烯脂法、多胺法方法。 4. A metallurgical exhaust gas according to the claim 1, ammonia production, methanol production process and urea, characterized in that the wet desulfurization using the desulfurization method or dry desulfurization, wet desulfurization comprising: Modified ADA process, tannin extract, the PDS method; dry desulfurization comprising: hydroconversion, activated carbon, iron oxide method, oxidation of zinc, manganese and the like methods; separation system for the physical, chemical or physicochemical methods in combination, comprising a pressure swing adsorption , improved hot alkaline carbonate, propylene lipid, polyamines method method.
CN 200610089297 2006-08-15 2006-08-15 Method of producing liquid ammonia, urea and methanol using metallurgical waste gas CN1903723A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
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
CN102101644B (en) 2010-12-20 2013-11-27 昆明理工大学 Method for preparing ammonia synthesis gas from iron alloy smoke
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 process for producing phosphoric acid or a method using a blast furnace kiln furnace gas ammonia production
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 System for producing coke oven gas with methanol and methods of making the system with methanol

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