CN100513301C - Purification process of raw material gas for production of synthetic ammonia or methanol production - Google Patents
Purification process of raw material gas for production of synthetic ammonia or methanol production Download PDFInfo
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- CN100513301C CN100513301C CNB2006101620581A CN200610162058A CN100513301C CN 100513301 C CN100513301 C CN 100513301C CN B2006101620581 A CNB2006101620581 A CN B2006101620581A CN 200610162058 A CN200610162058 A CN 200610162058A CN 100513301 C CN100513301 C CN 100513301C
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- desulfurization
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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
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention discloses a purifying technology of raw material of synthetic ammonia or carbinol, which comprises the following steps: setting the pressure of transforming gas from transforming system at 3.4-3.6Mpa; transmitting into the bottom of desulfurizing tower to contact with reflow steric hindrance amine desulfurizing liquid from top of tower; making H2S and partial CO2 adsorbed by solution; decarburizing; entering transforming gas with pressure at 3.3-3.5Mpa from desulfurizing segment into adsorbing tower from the bottom; contacting with reflow MDEA in the tower.
Description
Technical field
The present invention relates to a kind of gas purification treatment technology, be specially a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production.
Background technology
Low-temperature rectisol and domestic independently developed NHD solution gas purifying technique that German LURGI is mostly adopted in domestic in recent years newly-built methyl alcohol and synthetic ammonia installation, gas sweetening, supporting CLAUS sulfur recovery unit.
1, low-temperature rectisol need be bought patent license and key equipment, invests greatlyyer, is unfavorable for the popularization and the use of domestic proprietary technology.
2, NHD solution gas purifying technique is the domestic intellecture property that has, and invests also lower temperature methanol wash, but the working cost height is poor to the organosulfur receptivity.
3, since China's various places coal vary, so in the gas sulphur content also difference is bigger.After above-mentioned two kinds of process solvents regeneration, sour gas contains H
2S concentration is low, and the characteristics that tolerance is little so adopt single conventional CLAUS technology, can't satisfy national gaseous emission standard at all.
Summary of the invention
The present invention is in order to solve the gas purification cost height that exists in the prior art, adaptability problem and a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production is provided widely inadequately.
The present invention is realized that by following technical scheme a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production comprises the following steps
One, desulfurization, the conversion gas that comes from transformation system (is mainly CO, CO
2, H
2, H
2S, CH
4) pressure is 3.4～3.6MPa, at first sends into the thionizer bottom, with the bulky amine doctor solution counter current contact of going into tower from this tower top, the H in the gas
2S and portion C O
2By solution absorption.
Go out thionizer purified gas H
2S content is less than 10mg/Nm
3, remove decarbonization process.After the bulky amine liquid decompression of coming out at the bottom of the desulfuration absorbing tower, through the solution heat exchanger heat exchange, enter the solution flash groove, under the pressure of 0.4-0.6MPa, with the H in the solution
2, CO, and portion C O
2Flash distillation is come out, H in the flashed vapour
2S content is at 1000～1500mg/Nm
3, go out the flashed vapour (CO of regeneration overhead
2And H
2S) after water cooler and separator cool and isolate water of condensation, be sent to complexing iron desulfurization process.
Two, decarburization, the pressure that comes from desulfurization workshop section is that 3.3-3.5MPa (contains about CO
225%) conversion gas enters the absorption tower from bottom, decarburization absorption tower, with the MDEA solution counter current contact in the tower,
Be specially elder generation and MDEA (N methyldiethanol amine) the solution counter current contact that enters from the tower middle part, (the most of CO in the gas phase
2Be absorbed) again with the molten counter current contact of the MDEA that enters from tower top, finish the purification absorption process of carbonic acid gas.Purified gas (contains CO
2≤ 5.0%)
Regeneration: the solution that comes out at the bottom of the absorption tower enters one and dodges tower and carry out high pressure flash after decompression, and the gas that flashes off is delivered to complexing iron desulfurization process.MDEA (N methyldiethanol amine) solution that is come out by a sudden strain of a muscle tower bottom enters two sudden strain of a muscle towers, carries out low pressure flash, and the carbon dioxide that flash distillation is come out is delivered to complexing iron desulfurization process.The solution of gained carries out thermal regeneration after the desorb.
Three, complexing iron desulfurization, with step 1 and or two in the flash steam gas that produces adopt the desulfurization of complexing iron, pressure is 0.06～0.07Map, enters complexing iron absorption tower, with complexing iron doctor solution counter current contact.
Resurgent gases H
2S content is less than 10mg/Nm
3The configuration proportion of complexing iron doctor solution is to add 10～20kg complexing iron sweetening agent, 30～40kg soda ash, 30～40kg sodium bicarbonate, 10～20kg ferrous salt in the 1000kg water.Ferrous salt such as ferrous sulfate, iron protochloride etc.Complexing iron sweetening agent generally uses the graduate product of southization.
Complexing iron doctor solution rich solution and air thorough mixing enter regeneration tank after reaction, further oxidation regeneration in regeneration tank, (H
2S+O
2=H
2The elemental sulfur overflow of O+S) separating out in the regeneration tank enters the sulphur foam chute, sends into the sulfur melting kettle recovery sulphur by the sulphur foam pump again.
Compared with prior art, the present invention is directed to H in the gas
2The situation that S content is not too high, if adopt low-temperature rectisol or the supporting again CLAUS carbon of NHD gas sweetening to reclaim technology, though invest excessively, emission gases can't guarantee to reach discharging standards besides.This project adopts flow process to be: process gas comes out directly to enter transformation system after dedusting from two sections stoves, adopts bulky amine and the decarburization of MDEA double-stage desulfurizing after the conversion, to satisfy the methanol production requirement.(wherein major part is CO to stripping gas
2), take complexing iron to absorb wherein H
2S is to guarantee CO
2For urea, liquid CO
2Producing needs.The complexing ferrous solution is taked jet oxidative regeneration, and the sulfur recovery continuous sulfur melting obtains elemental sulfur. and this flow process, bulky amine and MDEA adopt heating decompression regeneration, do not have any liquefaction discharging, and be environmentally friendly.
Embodiment
Embodiment 1: a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production comprises the following steps
One, desulfurization, the conversion gas that comes from transformation system (is mainly CO, CO
2, H
2, H
2S, CH
4) pressure is 3.4MPa, at first sends into the thionizer bottom, with the bulky amine doctor solution counter current contact of going into tower from this tower top, the H in the gas
2S and portion C O
2By solution absorption.Go out thionizer purified gas H
2S content is less than 10mg/Nm
3, remove decarbonization process.After the bulky amine liquid decompression of coming out at the bottom of the desulfuration absorbing tower, through the solution heat exchanger heat exchange, enter the solution flash groove, under the pressure of 0.6MPa, with the H in the solution
2, CO, and portion C O
2Flash distillation is come out, H in the flashed vapour
2S content is at 1000～1500mg/Nm
3, go out the flashed vapour (CO of regeneration overhead
2And H
2S) after water cooler and separator cool and isolate water of condensation, be sent to complexing iron desulfurization process.The preparation of bulky amine doctor solution, the mass ratio of bulky amine and water are 1:2～2.5.
Two, decarburization, the pressure that comes from desulfurization workshop section is that 3.3MPa (contains about CO
225%) conversion gas enters the absorption tower from bottom, decarburization absorption tower, with MDEA (N methyldiethanol amine) the solution counter current contact in the tower,
Be specially elder generation and MDEA (N methyldiethanol amine) the solution counter current contact that enters from the tower middle part, (the most of CO in the gas phase
2Be absorbed) again with the molten counter current contact of the MDEA that enters from tower top, finish the purification absorption process of carbonic acid gas.Purified gas (contains CO
2≤ 5.0%) proportioning of MDEA (N methyldiethanol amine) solution is, MDEA and quality ratio 1:1～1.5.
Regeneration: the solution that comes out at the bottom of the absorption tower enters one and dodges tower and carry out high pressure flash after decompression, and the gas that flashes off is delivered to complexing iron desulfurization process.MDEA (N methyldiethanol amine) solution that is come out by a sudden strain of a muscle tower bottom enters two sudden strain of a muscle towers, carries out low pressure flash, and the carbon dioxide that flash distillation is come out is delivered to complexing iron desulfurization process.The solution of gained carries out thermal regeneration after the desorb.
Three, complexing iron desulfurization is adopted the desulfurization of complexing iron with the flash steam gas that produces among step 1 and two, and pressure is about 0.05Map, enters complexing iron absorption tower, with complexing iron doctor solution counter current contact.Resurgent gases H
2S content is less than 10mg/Nm
3, complexing iron doctor solution is an industry material commonly used, generally contains total alkali 35 grams per liters, total iron 3 grams per liters, complexing agent 12 grams per liters, pH value 8-8.5.The configuration proportion of complexing iron doctor solution is to add 10～20kg complexing iron sweetening agent, 30～40kg soda ash, 30～40kg sodium bicarbonate, 10～20kg ferrous salt in the 1000kg water.Ferrous salt such as ferrous sulfate, iron protochloride etc.Complexing iron sweetening agent generally uses the graduate product of southization.
Complexing iron doctor solution rich solution and air thorough mixing enter regeneration tank after reaction, further oxidation regeneration in regeneration tank, (H
2S+O
2=H
2The elemental sulfur overflow of O+S) separating out in the regeneration tank enters the sulphur foam chute, sends into the sulfur melting kettle recovery sulphur by the sulphur foam pump again.
Embodiment 2: a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production comprises the following steps
One, desulfurization, the conversion gas that comes from transformation system (is mainly CO, CO
2, H
2, H
2S, CH
4) pressure is 3.6MPa, at first sends into the thionizer bottom, with the bulky amine doctor solution counter current contact of going into tower from this tower top, the H in the gas
2S and portion C O
2By solution absorption.Go out thionizer purified gas H
2S content is less than 10mg/Nm
3, remove decarbonization process.After the bulky amine liquid decompression of coming out at the bottom of the desulfuration absorbing tower, through the solution heat exchanger heat exchange, enter the solution flash groove, under the pressure of 0.6MPa, with the H in the solution
2, CO, and portion C O
2Flash distillation is come out, H in the flashed vapour
2S content is at 1000～1500mg/Nm
3, go out the flashed vapour (CO of regeneration overhead
2And H
2S) after water cooler and separator cool and isolate water of condensation, be sent to complexing iron desulfurization process.
Two, decarburization, the pressure that comes from desulfurization workshop section is that 3.5MPa (contains about CO
225%) conversion gas enters the absorption tower from bottom, decarburization absorption tower, with MDEA (N methyldiethanol amine) the solution counter current contact in the tower,
Be specially elder generation and MDEA (N methyldiethanol amine) the solution counter current contact that enters from the tower middle part, (the most of CO in the gas phase
2Be absorbed) again with the molten counter current contact of the MDEA that enters from tower top, finish the purification absorption process of carbonic acid gas.Purified gas (contains CO
2≤ 5.0%)
Regeneration: the solution that comes out at the bottom of the absorption tower enters one and dodges tower and carry out high pressure flash after decompression, and the gas that flashes off is delivered to complexing iron desulfurization process.The MDEA solution that is come out by a sudden strain of a muscle tower bottom enters two sudden strain of a muscle towers, carries out low pressure flash, and the carbon dioxide that flash distillation is come out is delivered to complexing iron desulfurization process.The solution of gained carries out thermal regeneration after the desorb.
Three, complexing iron desulfurization is adopted the desulfurization of complexing iron with the flash steam gas that produces among step 1 and two, and pressure is 0.07Map, enters complexing iron absorption tower, with complexing iron doctor solution counter current contact.Resurgent gases H
2S content is less than 10mg/Nm
3,
Complexing iron doctor solution rich solution and air thorough mixing enter regeneration tank after reaction, further oxidation regeneration in regeneration tank, (H
2S+O
2=H
2The elemental sulfur overflow of O+S) separating out in the regeneration tank enters the sulphur foam chute, sends into the sulfur melting kettle recovery sulphur by the sulphur foam pump again.
Embodiment 3: a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production comprises the following steps
One, desulfurization, the conversion gas that comes from transformation system (is mainly CO, CO
2, H
2, H
2S, CH
4) pressure is 3.5MPa, at first sends into the thionizer bottom, with the bulky amine doctor solution counter current contact of going into tower from this tower top, the H in the gas
2S and portion C O
2By solution absorption.Go out thionizer purified gas H
2S content is less than 10mg/Nm
3, remove decarbonization process.After the bulky amine liquid decompression of coming out at the bottom of the desulfuration absorbing tower, through the solution heat exchanger heat exchange, enter the solution flash groove, under the pressure of 0.5MPa, with the H in the solution
2, CO, and portion C O
2Flash distillation is come out, H in the flashed vapour
2S content is at 1000～1500mg/Nm
3, go out the flashed vapour (CO of regeneration overhead
2And H
2S) after water cooler and separator cool and isolate water of condensation, be sent to complexing iron desulfurization process.
Two, decarburization, the pressure that comes from desulfurization workshop section is that 3.4MPa (contains about CO
225%) conversion gas enters the absorption tower from bottom, decarburization absorption tower, with MDEA (N methyldiethanol amine) the solution counter current contact in the tower,
Be specially elder generation and MDEA (N methyldiethanol amine) the solution counter current contact that enters from the tower middle part, (the most of CO in the gas phase
2Be absorbed) again with the molten counter current contact of the MDEA that enters from tower top, finish the purification absorption process of carbonic acid gas.Purified gas (contains CO
2≤ 5.0%)
Regeneration: the solution that comes out at the bottom of the absorption tower enters one and dodges tower and carry out high pressure flash after decompression, and the gas that flashes off is delivered to complexing iron desulfurization process.The MDEA solution that is come out by a sudden strain of a muscle tower bottom enters two sudden strain of a muscle towers, carries out low pressure flash, and the carbon dioxide that flash distillation is come out is delivered to complexing iron desulfurization process.The solution of gained carries out thermal regeneration after the desorb.
Three, complexing iron desulfurization, with step 1 and or two in the flash steam gas that produces adopt the desulfurization of complexing iron, pressure is about 0.06MPa, enters complexing iron absorption tower, with complexing iron doctor solution counter current contact.Resurgent gases H
2S content is less than 10mg/Nm
3,
Complexing iron doctor solution rich solution and air thorough mixing enter regeneration tank after reaction, further oxidation regeneration in regeneration tank, (H
2S+O
2=H
2The elemental sulfur overflow of O+S) separating out in the regeneration tank enters the sulphur foam chute, sends into the sulfur melting kettle recovery sulphur by the sulphur foam pump again.
Claims (5)
1, a kind of purification process that is applied to the unstripped gas of synthetic ammonia or methanol production is characterized in that: comprise the following steps
One, desulfurization, the conversion atmospheric pressure that comes from transformation system is 3.4～3.6MPa, at first sends into the thionizer bottom, with the bulky amine doctor solution counter current contact of going into tower from this tower top, the H in the gas
2S and portion C O
2By solution absorption,
Two, decarburization, the pressure that comes from desulfurization workshop section is the conversion gas of 3.3-3.5MPa, enters the absorption tower from bottom, decarburization absorption tower, with the MDEA liquid counter current contact in the tower,
After the bulky amine liquid decompression of coming out at the bottom of the desulfuration absorbing tower,, enter the solution flash groove with the H in the solution through the solution heat exchanger heat exchange
2, CO, and portion C O
2Flash distillation is come out, and goes out the resurgent gases CO of regeneration overhead
2And H
2S is sent to complexing iron desulfurization process after water cooler and separator cool and isolate water of condensation, the resurgent gases pressure that comes from the bulky amine desulfurization process is 0.06～0.07MPa, enters complexing iron absorption tower, with complexing iron doctor solution counter current contact.
2, the purification process that is applied to the unstripped gas of synthetic ammonia or methanol production according to claim 1 is characterized in that:
The MDEA solution counter current contact that decarburization is specially earlier and enters from the tower middle part again with the molten counter current contact of the MDEA that enters from tower top, is finished the purification absorption process of carbonic acid gas.
3, the purification process that is applied to the unstripped gas of synthetic ammonia or methanol production according to claim 1 is characterized in that:
The complexing iron doctor solution rich solution and the air thorough mixing that produce enter regeneration tank after reaction, further oxidation regeneration in regeneration tank, and the elementary sulfur overflow of separating out in the regeneration tank enters the sulphur foam chute, sends into the sulfur melting kettle recovery sulphur by the sulphur foam pump again.
4, the purification process that is applied to the unstripped gas of synthetic ammonia or methanol production according to claim 1 is characterized in that:
The bulky amine liquid decompression back of coming out at the bottom of the desulfuration absorbing tower is flash distillation under 0.4-0.6MPa at pressure.
5, the purification process that is applied to the unstripped gas of synthetic ammonia or methanol production according to claim 1 is characterized in that:
The desulfurization of step 1, the conversion atmospheric pressure that comes from transformation system is 3.5MPa, the decarburization of step 2, the conversion atmospheric pressure that comes from desulfurization workshop section is 3.4MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101620581A CN100513301C (en) | 2006-12-11 | 2006-12-11 | Purification process of raw material gas for production of synthetic ammonia or methanol production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101620581A CN100513301C (en) | 2006-12-11 | 2006-12-11 | Purification process of raw material gas for production of synthetic ammonia or methanol production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962414A CN1962414A (en) | 2007-05-16 |
| CN100513301C true CN100513301C (en) | 2009-07-15 |
Family
ID=38081671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101620581A Expired - Fee Related CN100513301C (en) | 2006-12-11 | 2006-12-11 | Purification process of raw material gas for production of synthetic ammonia or methanol production |
Country Status (1)
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|---|---|
| CN (1) | CN100513301C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214922B (en) * | 2007-12-26 | 2010-06-02 | 罗庆洪 | Combined purifying technique for ammonia preparation from natural gas, ammonia preparation from coal and methanol preparation from coal |
| CN104667714A (en) * | 2013-12-03 | 2015-06-03 | 中国科学院过程工程研究所 | Device and method for deep removal of acid gas in industrial mixed gas |
| CN110228792B (en) * | 2019-06-30 | 2022-07-12 | 新乡中新化工有限责任公司 | Deep decarburization process for synthesis gas |
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2006
- 2006-12-11 CN CNB2006101620581A patent/CN100513301C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1962414A (en) | 2007-05-16 |
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Owner name: SHANXI YANGMEI FENGXI FERTILIZER INDUSTRY (GROUP) Free format text: FORMER OWNER: SHANXI YANGMEI FENGXI FERTILIZER INDUSTRY (GROUP) CO., LTD. LINYI BRANCH CO.,LTD. Effective date: 20100205 |
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Owner name: SHANXI YANGMEI FENGXI FERTILIZER INDUSTRY (GROUP) Free format text: FORMER NAME: SHANXI FEIXI FERTILIZER INDUSTRY ( GROUP ) CO., LTD. LINYI BRANCH |
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Address after: Shanxi Linyi Fenxi Road West, No. 2000 Patentee after: Shanxi Yangmei Fengxi fertilizer industry (Group) Co.,Ltd. Linyi Branch Address before: Shanxi Linyi Zhai Road No. 3 Patentee before: SHANXI FENGXI FERTILIZER Group |
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Effective date of registration: 20100205 Address after: Shanxi province Yuncheng Economic Development Zone Yudu library Road No. 1 Patentee after: SHANXI YANGMEI FENGXI FERTILIZER INDUSTRY GROUP Co.,Ltd. Address before: Shanxi Linyi Fenxi Road West, No. 2000 Patentee before: Shanxi Yangmei Fengxi fertilizer industry (Group) Co.,Ltd. Linyi Branch |
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