CN1217735C - Catalyst for synthesizing dimethyl thioether and its prepn - Google Patents
Catalyst for synthesizing dimethyl thioether and its prepn Download PDFInfo
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- CN1217735C CN1217735C CN 02135619 CN02135619A CN1217735C CN 1217735 C CN1217735 C CN 1217735C CN 02135619 CN02135619 CN 02135619 CN 02135619 A CN02135619 A CN 02135619A CN 1217735 C CN1217735 C CN 1217735C
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- catalyst
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- active component
- balls
- dimethyl thioether
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Abstract
The present invention discloses a catalyst for synthesizing dimethyl thioether with H2S-contained acid gas and methanol as raw materials and a preparation method thereof. The catalyst is prepared from activated alumina as a supporter and alkali metal oxide as an active component. The preparation method of the catalyst comprises that firstly, alumina is heated and dissolved in an alkali solution to prepare a sodium aluminate solution, a spherical alumina supporter is soaked in the sodium aluminate solution, or a sodium metaaluminate solution is sprayed while aluminum hydroxide powder is rolled and formed into balls, or the aluminum hydroxide powder is uniformly mixed with composite metal oxides or minerals, such as pulverized facellite, etc., and then, the mixture is rolled and formed into balls; the balls are placed at room temperature for some time, and then, the balls are dried and calcined to obtain the catalyst. Compared with traditional catalysts, the catalyst has higher catalytic activity and higher average crushing strength, and is more favorable for synthesizing dimethyl thioether at high temperature of 400 DEG C with H2S and CH3OH as raw materials.
Description
Technical field
The present invention relates to a kind of catalyst and this Preparation of catalysts method for preparing dimethyl sulfide, refer more particularly to oil plant and contain H
2The Catalysts and its preparation method of the sour gas of S and methyl alcohol reaction synthesizing dimethyl thioether.
Background technology
The synthetic method of dimethyl sulfide mainly contains dimethyl suflfate method, carbon disulfide method, hydrogen sulfide method and black liquid method etc.Wherein the basic principle of hydrogen sulfide method is the reaction of following methyl alcohol and hydrogen sulfide:
Each hydrogenation plant of oil plant and a large amount of H of sewage stripper plant by-product
2S can only be converted into the extremely low elementary sulfur of added value by sulfur recovery facility in the past.And employing H
2S and CH
3OH reaction can the high dimethyl sulfide of production added value, we can say that rich producing contains H
2The oil plant of S sour gas adopts hydrogen sulfide method production dimethyl sulfide to have advantageous condition.With H
2S and CH
3OH is that the used catalyst of raw material synthesizing dimethyl thioether is mainly with γ-Al
2O
3Be main.Below to H
2S and CH
3OH is that synthetic relevant technology and the catalyst of dimethyl sulphide of raw material done a summary:
1. it is that the wolframic acid caesium of carrier impregnation 15～40% is the catalyst of active component synthesizing dimethyl thioether with the activated alumina that German Degussa has introduced a kind of in patent CN1178137, compares with adopting potassium tungstate salt, has improved activity and selectivity.
2.JP63057566 introduced a kind of with CS
2And CH
3OH is the catalyst of the synthetic dimethyl sulphide of raw material, and this catalyst is a crystalline aluminium silicon zeolite, compares CH with activated alumina
3SCH
3Yield brings up to 91.9% from 83.3%.
3.SU1414844 introduced a kind of with H
2S and CH
3OH is the method for the synthetic dimethyl sulphide of raw material, and the catalyst of employing is η-Al
2O
3
4.RU22056940 introduced a kind of synthetic with H
2S and CH
3OH is the catalyst of raw material synthesis of methyl mercaptan and dimethyl sulfide, this catalyst is to flood 7.5～10.0wt% potassium tungstate to be prepared from aluminium oxide, and in order to improve result of use, carrier adopts the form of aluminium borate, pore radius more than 100nm, specific pore volume 0.08～1.13ml/g.
5.US4302605 introduced a kind of with H
2S and CH
3OH is the technology that raw material is produced dimethyl sulfide, and the catalyst of employing is the less zeolite catalyst of alkali metal ion content measured.
6.JP58159456 introduced a kind of with H
2S and CH
3OH is the method for raw material synthesizing dimethyl thioether, and this method adopts two step reaction techniques, and the catalyst of employing is an activated alumina.Reaction temperature is 300～450 ℃.
7.Kushelev, introduced a kind of description among the P103-5 with H Deng in Khim.Prom-st (2)
2S and CH
3OH is the Mathematical Modeling of raw material synthesizing dimethyl thioether, and the catalyst of employing is the γ-Al of non-loading type
2O
3
8.CN1217326 introduced a kind of with H
2S and CH
3OH is the method for synthetic dimethyl sulphide of raw material and methyl mercaptan, and the catalyst of employing is γ-Al
2O
3Or the Alusil catalyst, its main feature is the H that adopts
2The concentration of S is 30～99%.
Summary of the invention
The present invention aims to provide a kind of oil plant that utilizes and contains H
2S sour gas and methyl alcohol reaction generate catalyst and this Preparation of catalysts method of dimethyl sulfide.
This catalyst is carrier with the activated alumina, and the main form of activated alumina can be one or more a mixture of transition state of alumina such as γ, δ, κ, ρ, η, and the specific area of aluminium oxide is 250～350m
2/ g, preferably 280～320m
2/ g, pore volume are between 0.3～0.5ml/g, preferably between 0.35～0.45ml/g; With the alkali metal compound is active constituent; Active constituent can be oxide or the salt of Na, K, is preferably NaAlO
2, NaAl (OH)
4Deng alkaline metal salt or kaliophilite (K
2OAl
2O
32SiO
2) wait composite metal oxide or natural minerals etc., preferred NaAlO
2, NaAl (OH)
4, KAlO
2, KAl (OH)
4, kaliophilite (K
2OAl
2O
32SiO
2), potassic feldspar (K
2OAl
2O
36SiO
2), albite (Na
2OAl
2O
36SiO
2) in one or more; Alkali metal content is with Na in the active constituent
2O or K
2O content meter accounts for 1～10% of catalyst gross weight, and preferably 2～7%.
Method for preparing catalyst is aluminium hydroxide to be dissolved in be made into sodium aluminate solution in the sodium hydroxide solution dipping ball-aluminium oxide carrier under heating; Or sodium aluminate solution limit roller forming is sprayed on the limit in aluminium hydroxide dry powder roller forming process; Perhaps aluminium hydroxide dry powder is mixed the back roller forming with the oxide or the salt of sodium that contains active constituent or potassium; Place a period of time in room temperature, dry then, roasting makes catalyst.In preparation process, NaAlO
2Or kaliophilite (K
2OAl
2O
32SiO
2) the isoreactivity component can adopt equivalent impregnation or in the process of roller forming the mode with solution add; Perhaps by abrasive dust to greater than joining in the catalyst in mixed uniformly mode behind 200 orders.Need behind the shaping of catalyst to place 8～36 hours preferably 12～24 hours in room temperature; At 100～130 ℃, preferably dried 1～12 hour for 110～120 ℃, preferably 2～6 hours, again at 300～600 ℃ preferably 400～500 ℃, roasting 2～4 hours.
Compare with traditional catalyst, the catalytic activity and the average crushing strength of the catalyst of the present invention's preparation all improve a lot, and more help with H
2S and CH
3OH is raw material synthetic dimethyl sulphide under 400 ℃ high temperature.Simultaneously because with H
2S and CH
3OH is that the reaction of raw material synthesizing dimethyl thioether is a dehydration, and the surface alkalinty that suitably increases catalyst helps impelling balance to be carried out to the direction that generates dimethyl sulfide, moreover, because this reaction generates a large amount of water, common alkali metal oxide such as Na
2O, K
2Thereby O etc. run off easily life of catalyst are reduced, and catalyst of the present invention has adopted alkali metal compound such as NaAlO
2, NaAl (OH)
4, KAlO
2Or natural Alkaline minerals such as kaliophilite (K
2OAl
2O
32SiO
2), potassic feldspar (K
2OAl
2O
36SiO
2), albite (Na
2OAl
2O
36SiO
2) etc., in use there is not the losing issue of active constituent, thereby prolonged life of catalyst.The catalyst of the present invention preparation is used for the carbon disulfide legal system and gets the technology of dimethyl sulfide and compare with conventional method and compare, can reduce cost, synergy is remarkable, market prospects are wide, and aspect environmental protection, also has positive role, this technology combines with sulfur recovery facility, and the waste gas of discharge is further handled by sulfur recovery facility, can eliminate environmental pollution.
Embodiment
The following examples have been carried out concrete description to the present invention, but the present invention is not limited to embodiment itself.
Embodiment 1
Accurately take by weighing industrial aluminium hydroxide Al (OH)
3Dry powder 305g, through being dissolved in the aqueous solution that contains 258gNaOH after the heating, the sodium aluminate solution A that is made into total amount and is 1000g is standby.
Take by weighing the aluminium hydroxide dry powder 200g that adopts high temperature fast dewatering explained hereafter, roller forming adds 50g sodium aluminate solution A in the spin process, particle size is Φ 4～6mm, room temperature was placed 16 hours, dried 12 hours for 120 ℃, and 450 ℃ of roastings promptly got catalyst sample 1 in 3 hours.The average crushing strength of this sample be 140 newton/, specific area is 280m
2/ g, specific pore volume are 0.40ml/g, wherein NaAlO
2Content is the 10g/100g catalyst.
Embodiment 2
Take by weighing the aluminium hydroxide dry powder 500g of high temperature fast dewatering explained hereafter, (main component is K less than 200 purpose 50g kaliophilites to add granularity
2OAl
2O
32SiO
2) dry powder, spray 5% HNO Yi Bian mix the back
3Roller forming is to Φ 3～6mm particle on one side for solution, and room temperature was placed after 12 hours, dried 2 hours for 120 ℃, and 450 roastings promptly got catalyst sample 2 in 2 hours.The average crushing strength of sample 2 be 130 newton/, specific area is 300m
2/ g, specific pore volume 0.35ml/g.K in the finished catalyst
2O content is 3%.
Embodiment 3
Get the metatitanic acid dry powder 100g of Production By Sulfuric Acid Process, add Ca (NO
3)
24H
2O 17g, enriching H
2SO
42g mixes the back and pass through φ 4mm orifice plate extruded moulding on the twin-screw banded extruder, and room temperature was placed 12 hours, dried 12 hours for 120 ℃, and 400 roastings promptly got catalyst sample 3 in 2 hours.The average crushing strength of sample 3 be 100 newton/, specific area is 100m
2/ g, pore volume are 0.25ml/g.TiO in the catalyst
2Content＞85%.
Embodiment 4
Take by weighing the aluminium hydroxide dry powder 100g of high temperature fast dewatering explained hereafter, add the sodium aluminate solution A25g among the embodiment 1, mix the back and on the twin-screw banded extruder, pass through φ 4mm orifice plate extruded moulding, room temperature was placed 8 hours, dried 4 hours for 120 ℃, 500 roastings promptly got catalyst sample 4 in 2 hours.
Embodiment 5
Take by weighing the aluminium hydroxide dry powder 100g of high temperature fast dewatering explained hereafter, add water 40g and mix the back φ 4mm orifice plate extruded moulding that passes through on the twin-screw banded extruder, room temperature was placed 12 hours, dried 4 hours for 120 ℃, and 500 roastings promptly got catalyst sample 5 in 2 hours.
Embodiment 6
(Haiyang Chemical Plant, Qingdao produces, and φ 4mm white is spherical, specific area 120m to get commercial silicon dioxide carrier 100g
2/ g, bulk density 0.65g/ml), the sodium aluminate solution A of dipping 25g embodiment 1 preparation, room temperature was placed after 24 hours, dried 4 hours for 120 ℃, and 400 roastings promptly got catalyst sample 6 in 2 hours.The NaAlO of sample 6
2Content is the 10g/100g catalyst.
Embodiment 7
Take by weighing the aluminium hydroxide dry powder 200g of high temperature fast dewatering explained hereafter, add water 80g roller forming to φ 4mm spheric granules, room temperature was placed 12 hours, dried 4 hours for 120 ℃, and 500 roastings promptly got catalyst sample 7 in 2 hours.The specific area of this sample is 290m
2/ g, pore volume are 0.38ml/g, average crushing strength be 140 newton/.
Embodiment 8
Get the sample 7 that 100g embodiment 7 makes and be carrier, the sodium aluminate solution A of dipping 25g embodiment 1 preparation, room temperature was placed after 24 hours, 120 ℃ of oven dry 4 hours, 400 ℃ of roastings promptly got catalyst sample 8 in 3 hours.The specific area of this sample is 260m
2/ g, pore volume are 0.32ml/g, average crushing strength be 150 newton/.
Embodiment 9
Get industrial zirconium hydroxide 100g (production of Zibo, Shandong Province oxidation zirconium plant), on the twin-screw banded extruder, become φ 4mm bar shaped catalyst after adding water 30g by 4mm orifice plate extruded moulding, room temperature is placed after 12 hours 120 ℃ of oven dry 3 hours, and 450 ℃ of roastings promptly got catalyst sample 9 in 2 hours.The specific area of this sample is 80m
2/ g, pore volume are 0.22ml/g, average crushing strength be 100 newton/.
Embodiment 10
With
For index is reflected on the continuous-flow reaction unit catalytic activity of above-mentioned catalyst sample is estimated, reactor is that the stainless steel tube of 4mm is made by internal diameter, and catalyst loading amount 5ml, catalyst grain size are 40～60 orders, 350 ℃ of reaction temperatures.Inlet gas is formed: H
2S1.25%, CH
3OH1.25%, all the other are N
2Gas volume air speed 1200h
-1Adopt GC-14B gas chromatograph analysis inlet and exit gas to form.The activity of different catalysts sample is shown in following table 1.By table 1 data as can be seen, the activity of activated alumina catalyst is better than SiO
2, TiO
2Catalyst.And the catalytic activity of having added the alkali-metal catalyst sample of the present invention of difficult losses such as sodium metaaluminate and kaliophilite more is better than the pure alumina catalyst, illustrates that catalyst of the present invention is to H
2S and CH
3OH is that the synthetic dimethyl sulphide of raw material has catalytic action preferably.
Specific area, activity and the selectivity of table 1 different catalysts sample
| Catalyst sample | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 |
| CH 3OH conversion ratio % | 90 | 91 | 54 | 90 | 89 | 47 | 88 | 85 | 39 |
| (CH 3) 2S selectivity % | 95 | 93 | 53 | 94 | 92 | 60 | 92 | 93 | 67 |
| (CH 3) 2S yield % | 85.5 | 85 | 28.6 | 84.6 | 81.9 | 28.2 | 81 | 79 | 26.1 |
Claims (5)
1, a kind of catalyst that is used for synthesizing dimethyl thioether is characterized in that catalyst is a carrier with the activated alumina, is active component with the alkali metal compound, and the specific area of active aluminum oxide carrier is 250～350m
2/ g, pore volume are selected from one or more mixture of γ, δ, κ, ρ or η transition state of alumina between 0.3～0.5ml/g, active component is oxide or the salt of Na, K, and alkali metal content is with Na in the active component
2O or K
2O content meter accounts for 2～7% of catalyst gross weight.
2, catalyst according to claim 1, the specific area that it is characterized in that activated alumina is 280～320m
2/ g, pore volume is between 0.35～0.45ml/g.
3, catalyst according to claim 1 is characterized in that described active component is NaAlO
2, NaAl (OH)
4, KAlO
2, KAl (OH)
4, kaliophilite K
2OAl
2O
32SiO
2, K-feldspar K
2OAl
2O
36SiO
2, albite Na
2OAl
2O
36SiO
2In one or more mixtures,
4, the described Preparation of catalysts method that is used for synthesizing dimethyl thioether of one of a kind of claim 1～3 is characterized in that aluminium hydroxide is dissolved in and is made into sodium aluminate solution in the sodium hydroxide solution under the condition of heating, dipping ball-aluminium oxide carrier; Perhaps aluminium hydroxide dry powder is mixed back roller forming or active component abrasive dust with the solution of active component extremely greater than evenly mixing with aluminium hydroxide dry powder behind 200 orders, then while spraying the nitric acid roller forming, at room temperature placed 8～36 hours, and descended oven dry 1～12 hour at 100～130 ℃ then, made catalyst in 2～4 hours 300～600 ℃ of following roastings again.
5, Preparation of catalysts method according to claim 4 is characterized in that at room temperature placing 12～24 hours behind the shaping of catalyst, then 110～120 ℃ of down oven dry 2～6 hours, again 400～500 ℃ of following roastings 2～4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135619 CN1217735C (en) | 2002-09-30 | 2002-09-30 | Catalyst for synthesizing dimethyl thioether and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02135619 CN1217735C (en) | 2002-09-30 | 2002-09-30 | Catalyst for synthesizing dimethyl thioether and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1486786A CN1486786A (en) | 2004-04-07 |
| CN1217735C true CN1217735C (en) | 2005-09-07 |
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|---|---|---|---|
| CN 02135619 Expired - Fee Related CN1217735C (en) | 2002-09-30 | 2002-09-30 | Catalyst for synthesizing dimethyl thioether and its prepn |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014210115A1 (en) * | 2013-06-27 | 2014-12-31 | Shell Oil Company | Systems and methods for producing dimethyl sulfide from gasified coke |
| CN103992253B (en) * | 2014-06-05 | 2016-03-02 | 刘成旭 | A kind of preparation method utilizing industrial gaseous waste to generate electronic-grade dimethyl thioether |
| CN111072535A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Method for preparing dimethyl sulfide by utilizing refinery acid gas |
| CN111185192A (en) * | 2018-11-15 | 2020-05-22 | 河南城建学院 | Catalyst carrier and catalyst for synthesizing dimethyl oxalate |
| CN109201067B (en) * | 2018-11-23 | 2021-08-31 | 中石化炼化工程（集团）股份有限公司 | Denitration catalyst, preparation method thereof and method for reducing emission of nitrogen oxides of circulating fluidized bed boiler |
| CN113527159B (en) * | 2020-04-17 | 2023-03-28 | 中国石油化工股份有限公司 | Method for utilizing refinery acid gas |
| CN113941322B (en) * | 2021-11-22 | 2022-08-09 | 西南化工研究设计院有限公司 | Preparation method of alumina-coated transesterification catalyst |
| CN117398985B (en) * | 2023-10-19 | 2024-05-24 | 北京铝能清新环境技术有限公司 | Active alumina carrier sphere in hydrolysis catalyst and preparation method thereof |
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