CN101455966B - Methanol synthesis gas desulfurizer and preparation method thereof - Google Patents
Methanol synthesis gas desulfurizer and preparation method thereof Download PDFInfo
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- CN101455966B CN101455966B CN 200710191187 CN200710191187A CN101455966B CN 101455966 B CN101455966 B CN 101455966B CN 200710191187 CN200710191187 CN 200710191187 CN 200710191187 A CN200710191187 A CN 200710191187A CN 101455966 B CN101455966 B CN 101455966B
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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 isreduced 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 products, also is a kind of important basic organic chemical industry raw material.At present, industrial synthesizing methanol extensively adopts the Cu-Zn-Al series catalysts, good, the selective height of this series catalysts activity, but very responsive to poisonous substance, easy poisoning and deactivation, the harm of its medium sulphide content 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 take zinc oxide as main, 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, the frequent catalyst for methanol is totally unfavorable to manufacturer, 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 such as rope company of Denmark Top is deep desulfurizer, the K306 moldeed depth degree desulfurizing agent that German southern chemical company produces.
Chinese patent CN 01135213.2 discloses protective agent of a kind of methanol synthesis catalyst and preparation method thereof, with spherical γ-Al
2O
3Be carrier, as Main Components, 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 the operations such as dipping, drying, roasting, and the protective agent that makes is used for carbonyl iron and the carbonyl nickel of methanol removal synthesis gas.
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
-1Lower 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 comprised of the oxide of three kinds or four kinds metals in copper, zinc, chromium, the aluminium.Take the gross weight of desulfurizing agent as benchmark, 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 ℃.The qualified rear filtration of the washing of precipitate that obtains, lower dry at 100 ℃～150 ℃, be broken into the particle of 1.0mm～2.0mm, add 0.5%～10% pore-creating auxiliary agent, such 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, under stirring solution B is added solution A, N-process control temperature is controlled endpoint pH 6.0～8.0 at 50 ℃～90 ℃.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 and lower 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 and lower 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
The desulfurizing agent 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, pass into first reducing gases (H
2: N
2=3: then 97) reduction passes into the methyl methanol syngas (sulfide content 10 * 10 that contains sulphur
-6～100 * 10
-6).At pressure 5.0MPa, 200 ℃～350 ℃ of temperature, air speed 2000h
-1～3000h
-1Lower, measure the outlet total sulfur.Record the outlet total sulfur and all be less than or equal to instrument minimum detected value 20 * 10
-9
Claims (2)
1. methanol synthesis gas desulfurizer, take the gross weight of desulfurizing agent as benchmark, active component consist of CuO 5%～30%, ZnO 5%～40%, Cr
2O
320%～50%, it is characterized in that using the following methods preparation: the soluble-salt solution with copper, zinc, chromium, carry out coprecipitation reaction with acid carbonate solution as precipitating reagent; Precipitation process control temperature is 50 ℃～90 ℃, the qualified rear filtration of the washing of precipitate that obtains, 100 ℃～150 ℃ lower dry, beat sheet after being broken into the particle of 1.0mm～2.0mm; The pore-creating auxiliary agent that adds when beating sheet, the pore-creating auxiliary agent counts 0.5%～5% with the gross weight of catalyst, and the pore-creating auxiliary agent is carbonate, ammonia salt; Then calcine, 200 ℃～500 ℃ of calcining heats, calcination time 1h～4h makes desulfurizing agent.
2. the preparation method of desulfurizing agent as claimed in claim 1 is characterized in that used metal soluble salt is nitrate, sulfate, acetate; Used acid carbonate be a kind of in sodium acid carbonate, saleratus, the carbonic hydroammonium or wherein two or three.
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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 CN101455966A (en) | 2009-06-17 |
| CN101455966B true CN101455966B (en) | 2013-01-30 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2876100A4 (en) * | 2012-07-23 | 2016-08-17 | Sekisui Chemical Co Ltd | Oxygenated product production system and oxygenated product production method |
| 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 |
| 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 |
| 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 |
| CN110586028B (en) * | 2019-10-08 | 2021-11-19 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035254A (en) * | 1987-11-05 | 1989-09-06 | 大阪瓦斯株式会社 | Make a kind of method of desulfurizing agent |
-
2007
- 2007-12-11 CN CN 200710191187 patent/CN101455966B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035254A (en) * | 1987-11-05 | 1989-09-06 | 大阪瓦斯株式会社 | Make a kind of method of desulfurizing agent |
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