CN101455966A - Methanol synthesis gas desulfurizer and preparation method thereof - Google Patents
Methanol synthesis gas desulfurizer and preparation method thereof Download PDFInfo
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- CN101455966A CN101455966A CN 200710191187 CN200710191187A CN101455966A CN 101455966 A CN101455966 A CN 101455966A CN 200710191187 CN200710191187 CN 200710191187 CN 200710191187 A CN200710191187 A CN 200710191187A CN 101455966 A CN101455966 A CN 101455966A
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Abstract
The invention provides a methanol syngas desulfurizer and a preparation method thereof. The preparation method comprises the steps of adopting a coprecipitation method to prepare a mixture of zinc oxide, copper oxide, chromic oxide or alumina and adding a pore-forming agent to the mixture so as to prepare a deep desulfurizer with appropriate specific surface and aperture. The deep desulfurizer is reduced via hydrogen and then is used for the deep desulphurization of methanol syngas. The total sulfur content of the syngas after desulphurization is less than or equal to 20*10<-9>.
Description
Technical field: the invention belongs to catalysis technical field, be specifically related to a kind of methyl methanol syngas deep desulfurizer and preparation method thereof.
Background technology: methyl alcohol is a kind of broad-spectrum organic chemical industry's product, also is a kind of important basic Organic Chemicals.At present, industrial synthesizing methanol extensively adopts the Cu-Zn-Al series catalysts, and this series catalysts activity is good, selectivity is high, but very responsive to poisonous substance, easy poisoning and deactivation, and wherein the harm of sulfide is the most serious.So before advancing synthetic tower, all need smart desulfurization.The domestic production desulfurizing agent is various in style at present, mainly based on zinc oxide, also has iron oxide, activated carbon etc. and other composite.Desulfurization precision is less than 0.2 * 10
-6About, can not use as deep desulfurizer.
At present domestic and international methanol production forward large scale development is also had higher requirement to the purified synthesis gas technology that matches with it.Because maximization methyl alcohol is extremely complicated in processes such as filling, reduction, it is totally unfavorable to manufacturer frequently to change catalyst for methanol, loses huge.For making methanol device long period, the operation of high activity ground, external major company requires very strict to synthetic gas poisoning thing, and wherein total sulfur content requires to be less than 30 * 10
-9The MG-901 type Cu-Cr that produces as rope company of Denmark Top is a deep desulfurizer, the K306 moldeed depth degree desulfurizing agent that German southern chemical company produces.
Chinese patent CN01135213.2 discloses protective agent of a kind of methanol synthesis catalyst and preparation method thereof, with spherical γ-Al
2O
3Be carrier, as main component, go back at least a metal oxide in A bunch of metal of load regulation II as minor consistuent by one or more burnings among dip loading Mo, Cr, the Cu.Preparation process comprises operations such as dipping, drying, roasting, and the protective agent that makes is used for removing the carbonyl iron and the carbonyl nickel of methyl methanol syngas.
Chinese patent CN 1704143 discloses a kind of activated carbon desulphurization agent, contain active carbon 80%～95%, alkali metal compound 2%～10%, alkaline earth metal compound 3%～10%, by alkali metal compound and alkaline earth metal compound mix with active carbon, extrusion gets, and it is said that this desulfurizing agent can be at normal temperature, normal pressure and 1000h
-1Down the total sulfur in the gas is removed to 30 * 10
-9
Summary of the invention: the object of the present invention is to provide a kind of copper base methyl methanol syngas deep desulfurizer, be used at 200 ℃～350 ℃ of temperature, pressure 2.0MPa～8.0MPa, air speed 2000h
-1～3000h
-1, the deep desulfuration of realization methyl methanol syngas makes through the methyl methanol syngas total sulfur content after the desulfurization to be less than or equal to 20 * 10
-9
The methyl methanol syngas deep desulfurizer that this invention provides is made up of the oxide of three kinds or four kinds metals in copper, zinc, chromium, the aluminium.Gross weight with catalyst is a benchmark, and it consists of: CuO 5%～30%, and ZnO 5%～40%, Cr
2O
320%～50% or Al
2O
320%～50%.
Methyl methanol syngas deep desulfurizer provided by the invention adopts the coprecipitation method preparation: with the soluble-salt solution of copper, zinc, chromium (or aluminium), carry out coprecipitation reaction with acid carbonate solution as precipitating reagent, the precipitation that obtains through washing, drying, granulation, beat sheet, calcination process and get.
The present invention is achieved like this: three kinds or the water-soluble mixed solution that is mixed with of four kinds of soluble-salts (can be nitrate, sulfate, acetate) of copper, zinc, chromium, aluminium, carry out co-precipitation with acid carbonate solution as precipitating reagent.Used acid carbonate solution can be a kind of solution in sodium acid carbonate, saleratus, the carbonic hydroammonium, also can be two or three mixture solution wherein.Precipitation process control temperature is 50 ℃～90 ℃.Filter the qualified back of the washing of precipitate that obtains, dry down at 100 ℃～150 ℃, be broken into the particle of 1.0mm～2.0mm, add 0.5%～10% pore-creating auxiliary agent, as carbonate, ammonia salt, can be carbonic hydroammonium, graphite etc., compressing tablet, through 200 ℃～500 ℃ roasting 1h～4h, make the desulfurizing agent in suitable specific surface and aperture again.
The specific embodiment: following embodiment is in order to further specify content of the present invention:
Embodiment 1:
2L is contained 120g Cu (NO
3)
2, 145gZn (NO
3)
2With 245g Cr (NO
3)
3Mixed solution A, be heated to 50～90 ℃ stand-by, make precipitating reagent with the sodium bicarbonate solution B of concentration 55g/L, be heated to 50～90 ℃ stand-by, stir down solution B added solution A, N-process control temperature is at 50 ℃～90 ℃, control endpoint pH 6.0～8.0.Neutralization is carried out in stirring all the time.Then slip after filtration, washing, the filter cake that obtains is broken into the particle of 1.0mm～2.0mm 100 ℃～150 ℃ oven dry, adds auxiliary agent, carries out compressing tablet, and at 200 ℃～500 ℃ roasting 3h, makes desulfurizing agent I.
Embodiment 2:
2L is contained 145g Cu (NO
3)
2, 150gZn (NO
3)
2With 236g Al (NO
3)
3Mixed solution A, be heated to 50～90 ℃ stand-by, make precipitating reagent with the sodium bicarbonate solution B of concentration 55g/L, be heated to 50～90 ℃ stand-by, stir down solution B added solution A, N-process control temperature is at 50 ℃～90 ℃, control endpoint pH 6.0～8.0.Neutralization is carried out in stirring all the time.Then slip after filtration, washing, the filter cake that obtains is broken into the particle of 1.0mm～2.0mm 100 ℃～150 ℃ oven dry, adds auxiliary agent, carries out compressing tablet, and at 200 ℃～500 ℃ roasting 3h, makes desulfurizing agent II.
Embodiment 3:
2L is contained 120g Cu (NO
3)
2, 135Zn (NO
3)
2, 180g Al (NO
3)
3And 100gCr (NO
3)
3Mixed solution A, be heated to 50～90 ℃ stand-by, make precipitating reagent with the sodium bicarbonate solution B of concentration 55g/L, be heated to 50～90 ℃ stand-by, stir down solution B added solution A, N-process control temperature is at 50 ℃～90 ℃, control endpoint pH 6.0～8.0.Neutralization is carried out in stirring all the time.Then slip after filtration, washing, the filter cake that obtains is broken into the particle of 1.0mm～2.0mm 100 ℃～150 ℃ oven dry, adds auxiliary agent, carries out compressing tablet, and at 200 ℃～500 ℃ roasting 3h, makes desulfurizing agent III.
Sample test
Catalyst sample: it is 0.425mm～1.180mm that desulfurizing agent I, II and III are crushed to granularity, fills in the fixed bed reactors.Before the test activity, feed reducing gases (H earlier
2: N
2=3: 97) reduction feeds the methyl methanol syngas (sulfide content 10 * 10 that contains sulphur then
-6～100 * 10
-6).At pressure 5.0MPa, 200 ℃～350 ℃ of temperature, air speed 2000h
-1～3000h
-1Measure the outlet total sulfur down.Record the outlet total sulfur and all be less than or equal to instrument minimum detected value 20 * 10
-9
Claims (6)
1. a methanol synthesis gas desulfurizer is characterized in that the gross weight with catalyst is a benchmark, active component consist of CuO 5%～30%, ZnO 5%～40%, Cr
2O
3Or Al
2O
320%～50%.
2. the preparation method of desulfurizing agent according to claim 1, it is characterized in that soluble-salt solution with copper, zinc, chromium or aluminium, carry out coprecipitation reaction with acid carbonate solution as precipitating reagent, the precipitation that obtains is passed through washing, drying, granulation, is beaten sheet, calcination process, makes desulfurizing agent.
3. as the preparation method of desulfurizing agent as described in the claim 2, it is characterized in that used metal soluble salt is nitrate, sulfate, acetate; Used acid carbonate precipitating reagent is a kind of in sodium acid carbonate, saleratus, the carbonic hydroammonium or two or three mixture solution wherein.
4. as the preparation method of desulfurizing agent as described in the claim 2, it is characterized in that precipitation process control temperature is 50 ℃～90 ℃, filter the qualified back of the washing of precipitate that obtains, dry down at 100 ℃～150 ℃, beat sheet after being broken into the particle of 1.0mm～2.0mm, make desulfurizing agent through 200 ℃～500 ℃ roasting 1h～4h again.
5. as the preparation method of desulfurizing agent as described in the claim 2, it is characterized in that when beating sheet, adding the pore-creating auxiliary agent, calcine then.
6. as the preparation method of desulfurizing agent as described in claim 2 or 5, it is characterized in that the pore-creating auxiliary agent that adds counts 0.5%～5% with the gross weight of catalyst when beating sheet, the pore-creating auxiliary agent is carbonate, ammonia salt.
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| CN 200710191187 CN101455966B (en) | 2007-12-11 | 2007-12-11 | Methanol synthesis gas desulfurizer and preparation method thereof |
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|---|---|---|---|
| CN 200710191187 CN101455966B (en) | 2007-12-11 | 2007-12-11 | Methanol synthesis gas desulfurizer and preparation method thereof |
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| CN101455966A true CN101455966A (en) | 2009-06-17 |
| CN101455966B CN101455966B (en) | 2013-01-30 |
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Cited By (7)
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|---|---|---|---|---|
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN104640828A (en) * | 2012-07-23 | 2015-05-20 | 积水化学工业株式会社 | Oxygenated product production system and oxygenated product production method |
| CN105289713A (en) * | 2015-12-14 | 2016-02-03 | 夏百庆 | Triphase composite catalyst used for gasoline desulfurization |
| CN110272021A (en) * | 2018-03-13 | 2019-09-24 | 国家能源投资集团有限责任公司 | Catalyst for methanol protective agent and preparation method thereof |
| CN110586028A (en) * | 2019-10-08 | 2019-12-20 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method and application thereof |
| CN110876935A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Methanol synthesis catalyst protective agent and preparation method thereof |
| CN110898840A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4985074A (en) * | 1987-11-05 | 1991-01-15 | Osaka Gas Company Limited | Process for producing a desulfurization agent |
-
2007
- 2007-12-11 CN CN 200710191187 patent/CN101455966B/en active Active
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104640828A (en) * | 2012-07-23 | 2015-05-20 | 积水化学工业株式会社 | Oxygenated product production system and oxygenated product production method |
| JP2018048199A (en) * | 2012-07-23 | 2018-03-29 | 積水化学工業株式会社 | Manufacturing system of oxygenated article and manufacturing method of oxygenated article |
| US9975105B2 (en) | 2012-07-23 | 2018-05-22 | Sekisui Chemical Co., Ltd. | System for producing oxygenate and method for producing oxygenate |
| CN103525474A (en) * | 2013-10-30 | 2014-01-22 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN103525474B (en) * | 2013-10-30 | 2014-10-08 | 西南化工研究设计院有限公司 | Ultrafine desulfurization agent and preparation method thereof |
| CN105289713A (en) * | 2015-12-14 | 2016-02-03 | 夏百庆 | Triphase composite catalyst used for gasoline desulfurization |
| CN110272021A (en) * | 2018-03-13 | 2019-09-24 | 国家能源投资集团有限责任公司 | Catalyst for methanol protective agent and preparation method thereof |
| CN110272021B (en) * | 2018-03-13 | 2021-04-13 | 国家能源投资集团有限责任公司 | Methanol catalyst protective agent and preparation method thereof |
| CN110876935A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Methanol synthesis catalyst protective agent and preparation method thereof |
| CN110876935B (en) * | 2018-09-06 | 2023-06-30 | 中国石油化工股份有限公司 | Protective agent for methanol synthesis catalyst and preparation method thereof |
| CN110898840A (en) * | 2018-09-18 | 2020-03-24 | 中国石油化工股份有限公司 | Methanol synthesis catalyst and preparation method thereof |
| CN110586028A (en) * | 2019-10-08 | 2019-12-20 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method and application thereof |
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Address after: Baoying County, Jiangsu province 225824 Yangzhou City Xia Ji Zhen Guo Xia Road No. 18 Patentee after: Nanhua Group Corp. Address before: 210048 Jiangsu Province, Nanjing city Liuhe District Dachang geguan Road No. 699 Patentee before: Nanhua Group Corp. |
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Address after: No.18 Guoxia Road, Xiaji Town, Baoying County, Nanjing City, Jiangsu Province 225824 Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Baoying County, Jiangsu province 225824 Yangzhou City Xia Ji Zhen Guo Xia Road No. 18 Patentee before: Nanhua Group Research Institute |