CN101050390B - CO conversion technique matched to coal gasification - Google Patents

CO conversion technique matched to coal gasification Download PDF

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Publication number
CN101050390B
CN101050390B CN2007100684010A CN200710068401A CN101050390B CN 101050390 B CN101050390 B CN 101050390B CN 2007100684010 A CN2007100684010 A CN 2007100684010A CN 200710068401 A CN200710068401 A CN 200710068401A CN 101050390 B CN101050390 B CN 101050390B
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China
Prior art keywords
gas
conversion
shift converter
condensate
introducing
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CN2007100684010A
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Chinese (zh)
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CN101050390A (en
Inventor
郑明峰
李海洋
李德武
张骏驰
孙海燕
蒋德军
李鹏
林宝起
费伟水
操斌
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中国石化集团宁波工程有限公司
中国石油化工股份有限公司
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Priority to CN2007100684010A priority Critical patent/CN101050390B/en
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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
    • Y02P20/10Process efficiency
    • 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
    • Y02P20/10Process efficiency
    • Y02P20/129Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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 bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

This invention discloses a process for converting CO in pulverized coal gasification. The process comprises: introducing crude synthesis gas from pulverized coal gasification into a gas-liquid separator, mixing the gas from separator top with outside middle-pressure overheated steam, middle-pressure steam and a small amount of condensate from steam stripping, introducing into a pre-conversion furnace, controlling the temperature increase, introducing the converted gas into 1# conversion furnace, performing in-depth CO conversion, introducing high-temperature shift gas into a middle-pressure waste boiler to generate4.0 MPa steam with the condensate produced in the process, introducing all middle-pressure steam into fresh converted gas for recycling, quenching with the condensate for humidification, converting in 2# conversion furnace, cooling he converted gas by a water preheater, introducing into 3# conversion furnace, recovering waste heat until the output gas is less than or equal to 40 DEG C, and introducing into the following procedures. The CO concentration is decreased from 60-65 mol. % to less than or equal to 0.4 mol. %. The pre-conversion furnace can prevent catalyst poisoning. The pressure decrease of the conversion system is reduced, thus can ensure the pressure at the inlet of the synthesis gas compressor.

Description

A kind of and the supporting CO conversion process of coal gasification
Technical field
The present invention relates to a kind of CO conversion process, the particularly a kind of and supporting CO conversion process of coal gasification.
Background technology
The CO conversion process is widely used on synthetic ammonia installation and the device for producing hydrogen, a major portion that belongs to purification process, its technology position is arranged on after gasification or the conversion procedure, according to the catalyzer of selecting for use anti-sulphur whether, is divided into two kinds of technologies of sulfur-resisting transformation and non-sulfur-resisting transformation; According to the use temperature of catalyzer, be divided into middle temperature transformation and low temperature shift.Different conversion process is mainly reflected in the variation of transformationreation hop count, temperature of reaction, heat recuperation mode three aspects, and this depends primarily on the performance of transformation catalyst, factors such as the system gas raw material that industrial production adopts, gas-made technology, follow-up purification process.
It is the synthesis ammonia plant that raw material is produced synthetic gas that sulfur resistant conversion process is mainly used in residual oil and coal, and the purification process path combination is CO conversion-desulfurization-decarburization; It is in the synthetic ammonia installation of raw material that non-sulfur resistant conversion process is mainly used in petroleum naphtha and Sweet natural gas, also is used for the synthetic ammonia installation that residual oil and coal are raw material.Being used for petroleum naphtha and Sweet natural gas is that the synthetic ammonia installation purification process of raw material is combined as conversion-decarburization.Be used for the synthetic ammonia installation that residual oil and coal are raw material, purification process is combined as desulfurization-conversion-decarburization.
Existingly can handle the conversion process that the higher conversion process of CO content surely belongs to coal water slurry gasification, its flow process is seen Fig. 1, the crude synthesis gas scale of handling is equivalent to the unstripped gas of 1000 ton per day synthetic ammonia, adopt in two sections anti-sulphur and become, CO content is reduced to 1.5% (mol) by~50% (mol) in the crude synthesis gas, low more than 10 percentage point of carbon monoxide content in the crude synthesis gas that its CO content that enters one section shift converter comes out than the shell coal gasification, the CO content of conversion outlet will exceed more than 1% than the present invention, and reaction conditions is comparatively gentle.Its flow setting is: crude synthesis gas enters 1# shift converter (2), gas after the conversion enters middle pressure steam superheater (3), inlet/outlet gas-gas heat exchanger (1), the useless pot of middle pressure (4) recovery heat successively, be provided with feedwater well heater (6), the useless pot of low pressure (8), de-salted water preheater a series of interchanger such as (10) in 2# shift converter (5) outlet, conversion temperature degree is reduced to about 110 ℃, (7) (9) behind each section conversion gas separatory, be cooled to 40 ℃ through final water cooler (11), process gas is delivered to lower procedure.
But above-mentioned CO conversion process can only be used for following condition:
1, in the raw gas CO concentration less than 60% (V butt).
2, system pressure drop can change within the specific limits.
Fine coal gasification process by the exploitation of Shell company is the clean new technology of releasing in recent years of gasification, and coal gas turnover ratio height is good in economic efficiency, but only limits to so far be used in the gas-steam combined circulation electric generating apparatus.Its crude synthesis gas has following characteristics:
1, the crude synthesis gas amount is big, is equivalent to produce the tolerance of 1500 ton per day synthetic ammonia;
2, CO and H2S content height, CO concentration is up to 61.71% (V butt) in the raw gas, and H2S content reaches 1.20% (V butt);
3, system pressure drop is constant, because the upstream vapor pressure determines that the inlet pressure of downstream synthesic gas compressor (original) is dead by limit, the pressure of whole purification process falls fully and is fixed.
Therefore, present CO conversion process fully can not be supporting with it, is badly in need of a kind of supporting CO conversion process of developing with Shell company of coal gasification of development.
Summary of the invention
Technical problem to be solved by this invention is to overcome the above-mentioned defective of prior art and a kind of and the supporting CO conversion process of coal gasification are provided, and makes it can be used for the condition that definite coal gasification falls in CO concentration height, packing pressure.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of and the supporting CO conversion process of coal gasification, comprise following flow process: the crude synthesis gas that comes from coal gasification enters gas-liquid separator, isolated process condensate is discharged to sewage disposal outward, the process gas at separator top with after pressing in outside the battery limit (BL) middle pressure steam of pressing useless pot by-product in superheated vapour, this technology and a small amount of process condensate behind the stripping to mix, enter pre-shift converter, control temperature rise to be limited in<30 ℃ of scopes in; The conversion gas that leaves pre-shift converter enters the 1# shift converter and carries out degree of depth CO transformationreation, leave and become gas in the high temperature of 1# shift converter and press in entering useless pot with self process condensate generation 4.0MPa steam, middle pressure steam all enters in the fresh conversion gas and recycles, then through process condensate quenching humidification, enter the 2# shift converter and proceed transformationreation, 2# shift converter outlet conversion gas is after boiler water preheater heat exchange cooling, enter the 3# shift converter, the exit gas recovery waste heat was delivered to lower procedure after reaction was finished after≤40 ℃.
Compared with prior art, the invention has the advantages that:
1, improved the processing power of changing device.
2, adopt in one section pre-conversion, two sections anti-sulphur become, one section sulfur resistant conversion process flow process, prolonged the work-ing life of catalyzer, efficiently solve speed of response and molecular balance problem, guaranteeing that the carbon monoxide concentration of assurance crude synthesis gas after conversion reduced to≤0.4% (mol) by 60~65% (mol) under the little prerequisite of the short system pressure drop of reaction process.
3, set up pre-shift converter, inside adds the pre-conversion of cheap catalyst protective material, ash disposal, prevents that primary reformer from advancing grey coking, prevents that the micro heavy component prevents poisoning of catalyst to the influence of CO transformation catalyst in the crude synthesis gas.
4, employing axial-radial flow reactor filling catalyst particle axially loads large granular catalyst in the stove, and the pressure that has reduced transformation system falls, the augmenting response impellent, and assurance enters the requirement of synthesic gas compressor inlet pressure.
5, phlegma is pressed useless pot to pay in self-produced low-pressure steam stripping rear section enters and is produced the middle pressure steam recycle, and part is delivered to gasification installation and recycled.
Adopt foregoing invention fully can be supporting the bed pulverized coal gasification technology of Shell company, be applied to " coal for replacing oil " reconstruction and extension project of existing nitrogen fertilizer plant, possess skills, many-sided comprehensive advantages such as economy, fund.
Description of drawings
Fig. 1 is the schema of existing CO conversion process.
Fig. 2 is the schema of CO conversion process of the present invention.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
As shown in Figure 2, a kind of and the supporting CO conversion process of coal gasification, its flow process comprises: the crude synthesis gas 1 that comes from coal gasification enters gas-liquid separator 2, isolated process condensate is discharged to sewage disposal outward, the process gas at separator top with after pressing in outside the battery limit (BL) middle pressure steam of pressing useless pot by-product in superheated vapour, this flow process and a small amount of process condensate behind the stripping to mix, enter pre-shift converter 3, stop solid impurities such as coal dust, carbon black on the one hand, absorption AS, Cl-etc. are to the component of the toxic effect of catalyzer, protection sulfur-resistant transformation catalyst; Carry out appropriate transformationreation on the other hand, the control temperature rise is limited in<30 ℃ of scopes in; The conversion gas that leaves pre-shift converter 3 enters 1# shift converter 4 and carries out degree of depth CO transformationreation, work off one's feeling vent one's spleen in CO content reduce to≤0.4%, leave and become gas in the high temperature of 1# shift converter and press useless pot 5 by-product middle pressure steams in entering, then through process condensate quenching humidification, enter 2# shift converter 6 and proceed just to change reaction, CO content is further reduced, 2# shift converter outlet conversion gas is after boiler water preheater 7 heat exchange cooling, enter 3# shift converter 8, after reaction is finished in the exit gas CO content reduce to 0.40% (V), recovery waste heat through water cooler reduce to≤deliver to lower procedure after 40 ℃.
Be provided with gas-liquid separator 2 in the above-mentioned technology, in order to removing liquid in the crude synthesis gas, solid matter, to improve the quality of crude synthesis gas, reducing influences subsequent handling its liquid that may carry secretly, solid, poisonous substance etc.
Above-mentioned technology is according to the requirement of feature and each section reaction outlet CO concentration arrangement and the final CO concentration of catalyzer, and the vapour of conversion unstripped gas 1/gas ratio elects 1.3~1.5 as.
In order effectively to reduce systemic resistance, increase the shift conversion rate, reduce the loadings of catalyzer relatively, reduce the size of reactor, reduce the plant modification investment, 1# shift converter 4,2# shift converter 6 adopt the diameter of axle to shift converter, add catalyst particle, improve the intensity of catalyzer internal diffusion efficiency factor, reactive behavior and catalyzer, increased the shift conversion rate.
Set up pre-shift converter 3 in the above-mentioned technology; be filled with the lower sulfur resistant catalyst protective material of some amount active ingredient in the stove; prevent that the micro heavy component prevents poisoning of catalyst to the influence of CO transformation catalyst in the crude synthesis gas, its temperature in is controlled at 240~280 ℃.
Above-mentioned three sections conversion, one section conversion temperature in is controlled at 240~280 ℃, and two sections conversion temperature ins are controlled at 230~260 ℃, and three sections conversion temperature ins are controlled at 210~230 ℃.
The above-mentioned middle pot that gives up of pressing can reclaim high-quality heat, with self process condensate generation 4.0MPa steam, all enters in the fresh conversion gas and recycles the participation transformationreation.
In order to prevent that CO from penetrating, guarantee the methanation safety operation, adopted the diameter of axle to the array configuration that is used in combination with axial flow reactor, axially filling large granular catalyst in the stove, further reduce pressure drop, guarantee to enter the synthetic gas pressure 〉=26.5kgf/cm2 of synthesis loop.
60 ℃ of the crude synthesis gas that the SHELL fine coal gasification process provides, 3.7MPa crude synthesis gas, CO content 60~65%mol, after above-mentioned technology conversion CO content reduce to≤0.4%.

Claims (1)

  1. One kind with the supporting CO conversion process of coal gasification, it is characterized in that: comprise following flow process: the crude synthesis gas (1) that comes from coal gasification enters gas-liquid separator (2), isolated process condensate is discharged to sewage disposal outward, the process gas at separator top with after pressing in outside the battery limit (BL) middle pressure steam of pressing useless pot by-product in superheated vapour, this technology and a small amount of process condensate behind the stripping to mix, enter pre-shift converter (3), control temperature rise to be limited in<30 ℃ of scopes in; The conversion gas that leaves pre-shift converter (3) enters 1# shift converter (4) and carries out degree of depth CO transformationreation, leave and become gas in the high temperature of 1# shift converter and press in entering useless pot (5) with self process condensate generation 4.0MPa steam, middle pressure steam all enters in the fresh conversion gas and recycles, then through process condensate quenching humidification, enter 2# shift converter (6) and proceed transformationreation, 2# shift converter outlet conversion gas is after boiler water preheater (7) heat exchange cooling, enter 3# shift converter (8), the exit gas recovery waste heat was delivered to lower procedure after reaction was finished after≤40 ℃, the vapour of conversion unstripped gas (1)/gas ratio is 1.3~1.5, described 1# shift converter (4) temperature in is controlled at 240~280 ℃, 2# shift converter temperature in is controlled at 230~260 ℃, 3# shift converter (8) temperature in is controlled at 210~230 ℃, described 1# shift converter (4), 2# shift converter (6) adopts the diameter of axle to shift converter, adds catalyst particle.
CN2007100684010A 2007-04-27 2007-04-27 CO conversion technique matched to coal gasification CN101050390B (en)

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US8673034B2 (en) 2008-02-21 2014-03-18 General Electric Company Methods and systems for integrated boiler feed water heating
CN102002403B (en) * 2010-11-09 2013-06-19 中国石油化工股份有限公司 Low water-air ratio and middle water-air ratio carbon monoxide (CO) conversion process
CN102102040B (en) * 2010-12-20 2014-03-05 中国石油化工股份有限公司 Ash coal gasification low water/gas ratio total low temperature chilling CO sulfur resistant shifting technology
CN102304390B (en) * 2011-08-08 2013-10-16 安徽淮化股份有限公司 Recovery process and recovery equipment of drain vent gas in CO changer
CN102337162B (en) * 2011-08-30 2013-11-27 中国石油化工股份有限公司 Low-water-steam-ratio saturated hot water tower CO transformation process
CN102337159B (en) * 2011-08-30 2013-09-04 中国石油化工股份有限公司 Saturated hot water tower high-water-steam-ratio CO transformation process
CN102337161B (en) * 2011-08-30 2013-12-04 中国石油化工股份有限公司 Low water-to-gas ratio serial saturation tower and hot water tower CO conversion process
CN102732329A (en) * 2012-06-12 2012-10-17 中国石油化工股份有限公司 Fine coal gasification product crude synthetic gas CO sulfur-tolerant shift technology
CN103449364B (en) * 2012-11-12 2015-09-30 山东齐鲁科力化工研究院有限公司 A kind of process for converting high-concentration CO-tolerant sulfur and device making full use of reaction heat
CN102992264B (en) * 2012-11-12 2014-08-06 内蒙古伊泰煤制油有限责任公司 Partial conversion system for carbonic oxide and process control method thereof
JP6025603B2 (en) * 2013-02-21 2016-11-16 三菱重工業株式会社 CO shift reaction apparatus and CO shift conversion method
CN103881768B (en) * 2014-03-24 2015-05-27 中石化宁波工程有限公司 Cyclic CO (carbon monoxide) transformation process
CN103922280B (en) * 2014-04-18 2017-10-20 四川省达科特能源科技股份有限公司 A kind of flexicoking gasification gas hydrogen manufacturing technique
CN104030241A (en) * 2014-06-27 2014-09-10 清华大学 Adsorbing strengthening steam conversion technology with pre-transform reactor for processing CO gas
CN104085854B (en) * 2014-07-01 2015-12-30 中国华能集团清洁能源技术研究院有限公司 A kind of synthetic gas sulfur resistant conversion process of economy and system
CN105645354B (en) * 2015-12-30 2018-03-16 福州大学化肥催化剂国家工程研究中心 Sulfur-tolerant water gas shift equipment and sulfur-resistant conversion technical method
CN112195041A (en) * 2020-10-23 2021-01-08 中国石油化工股份有限公司 Coal water slurry purification pre-transformation furnace

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Address after: 315103 Ningbo high tech Zone, Zhejiang, academician Road, No. 660

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