CN104801291B - Zn/ gold/mesoporous carbon catalysts for producing chloroethanes and preparation method thereof - Google Patents
Zn/ gold/mesoporous carbon catalysts for producing chloroethanes and preparation method thereof Download PDFInfo
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- CN104801291B CN104801291B CN201510138900.7A CN201510138900A CN104801291B CN 104801291 B CN104801291 B CN 104801291B CN 201510138900 A CN201510138900 A CN 201510138900A CN 104801291 B CN104801291 B CN 104801291B
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Abstract
The invention discloses a kind of Zn/ gold/mesoporous carbon catalysts, using mesoporous carbon as carrier, Zn active component precursors are carried on carrier and activated using infusion process.The catalyst can be used for preparing chloroethanes, and wherein active component precursor is zinc salt, and carrier is mesoporous carbon.Present invention also offers a kind of preparation method for being used to produce the Zn/ gold/mesoporous carbon catalysts of chloroethanes, include the load steps of the preparation process Zn active component precursors of carrier.This catalyst has a high catalytic activity to ethanol and hcl reaction generation chloroethanes, and reaction condition is gentleer；This catalyst can improve the conversion ratio and yield of ethanol synthesis chloroethanes, and easily be separated with product, have good reusing.
Description
Technical field
The present invention relates to one kind using active component presoma is carried on into mesoporous carbon supported catalyst, belong to chemical industry
Technical field.
Background technology
Chloroethanes is mainly used in synthesizing the materials such as lead tetraethide, ethyl cellulose and ethyl carbazole dyestuff, also serves as preparation
Smoke agent, refrigerant, local anesthetic, insecticide, ethylating agent, olefinic polymerization solvent, gasoline knock-reducer etc., are alternatively arranged as closing
Into the solvent of the material such as polyacrylic catalyst and phosphorus, sulphur, grease, resin, wax.The production method of chloroethanes is mainly adopted at present
Produced with alcohol method, its production technology is divided into：Liquid catalytic and gas-phase catalysis.The former is to mix gaseous state alcohol and hydrogen chloride to lead to
Enter and catalytic reaction is carried out in the reactor equipped with liquid catalyst；The latter is to mix gaseous state alcohol and hydrogen chloride to be passed through equipped with solid-state
Reacted in the fixed bed reactors of catalyst.Because the reaction pressure needed for gas-phase catalysis, temperature are very high and right
The material of consersion unit also has high requirement, so most domestic enterprise uses liquid catalytic as chloroethene at present
The production technology of alkane.But the method also has the defects of obvious：Raw materials for production are the high concentration ethanol and hydrochloric acid of high price first；
Secondly chloroethanes building-up process is reversible reaction, causes the yield of chloroethanes not high, finally can also produce a large amount of waste water.
The content of the invention
Reaction temperature requires high when preparing chloroethanes for prior art, chloroethanes low yield and can produce a large amount of waste water
Problem, the invention discloses a kind of Zn/ gold/mesoporous carbon catalysts, and using mesoporous carbon as carrier, active component presoma is carried on
On carrier and activated, efficiently synthesizing for chloroethanes can be realized.
In order to achieve the above object, the present invention provides following technical scheme：
A kind of Zn/ gold/mesoporous carbon catalysts for being used to produce chloroethanes, it is characterised in that：The catalyst is by Zn activearms
Divide precursor to be carried on carrier and activate what is obtained, the active component precursor is zinc salt, and the carrier is mesoporous carbon.
Further, the zinc salt includes Zn (OH)2、Zn(CH3COO)2、ZnCO3 、ZnCl2At least one of.
Further, for the active component in terms of Zn, its quality is the 0.5%-20% of carrier quality.
A kind of preparation method for being used to produce the Zn/ gold/mesoporous carbon catalysts of chloroethanes, comprises the following steps：
The preparation of carrier：By commercially available mesoporous carbon be impregnated in alkaline solution carry out be heated to reflux handling, wherein mesoporous carbon
Aperture is 2nm ~ 100nm, and specific surface area is in 200-2000m2/ g, then after the mesoporous carbon after alkali process is calcined and slowly
Normal temperature is cooled to, produces required mesoporous carbon carrier；
The load of active component：Mesoporous carbon is impregnated in the zinc salt precursor solution prepared, dries the water in solution
/ after, calcined first under the protection of inert gas further to decompose the zinc salt of load, then in the bar for maintaining protection gas
Hydrogen reducing is passed through under part, produces required catalyst.
Further, the zinc salt includes Zn (OH)2、Zn(CH3COO)2、ZnCO3 、ZnCl2At least one of.
Further, the alkaline solution includes KOH, NaOH, K2CO3In one or more of mixed liquors.
Further, for the active component in terms of Zn, its quality is the 0.5%-20% of carrier quality.
Beneficial effect：
Zn/ gold/mesoporous carbon catalysts provided by the invention have high to ethanol with hydrochloric acid or hcl reaction generation chloroethanes
Catalytic activity, reaction condition is gentleer, can obviously reduce reaction temperature；This catalyst can improve ethanol synthesis chloroethanes
Conversion ratio and yield, and easily separated with product.The catalyst has good reusing, with ZnCl2Catalyst is compared,
Greatly reduce wastewater discharge containing ZnCl2, reduce environmental hazard, can be as the basis of industrial applications.
Embodiment
Technical scheme provided by the invention is described in detail below with reference to specific embodiment, it should be understood that following specific
Embodiment is only illustrative of the invention and is not intended to limit the scope of the invention.
Catalyst provided by the invention is prepared by following steps：
Step 1, the preparation of mesoporous carbon carrier
By commercially available mesoporous carbon（Aperture is 2nm ~ 100nm, and specific surface area is in 200-2000m2/g）It is impregnated in alkaline solution
Carry out be heated to reflux handling, then the mesoporous carbon after alkali process is placed under the conditions of 600 DEG C and calcines 3 h and slow cooling is to normal
Temperature, produce required mesoporous carbon carrier；It is of course also possible to use NaOH, K2CO3Deng other alkaline solutions as activator.
Step 2, the preparation of Zn/ gold/mesoporous carbon catalysts
By active component presoma Zn (CH3COO)2Add in the aqueous solution, stirring and dissolving, added after to be dissolved in step 1
Obtained mesoporous high-area carbon stirring 2h, 8-10h is then dried at a temperature of 90-110 DEG C, is ground into fine powder, then in nitrogen atmosphere
In in 220 DEG C~400 DEG C（Preferably 300 DEG C of this example）Lower roasting 2h, obtains catalyst precursor；The catalyst precursor is put
In 200 DEG C~800 DEG C in hydrogen atmosphere（Preferably 300 DEG C of this example）Reduction treatment 2h, reduction pressure are 0.1-0.2MPa, hydrogen
Flow 40-50ml/min, by Zn (CH3COO)2Metal simple-substance is reduced into, that is, obtains required catalyst.The Zn mentioned in this step
(CH3COO)2As just a kind of example, we can also use other zinc salts, such as Zn (OH)2Or ZnCO3Or ZnCl2In one
Plant to substitute Zn (CH3COO)2, the mixture of several different zinc salts can also be used as active component presoma.Foregoing is anti-
Condition is answered to be adjusted with the difference using activator and zinc salt, in fact, active component presoma zinc salt is born
It is loaded on mesoporous carbon carrier and activates the protection category that obtained catalyst belongs to the present invention.
In order to absolutely prove catalyst effect provided by the invention, the catalyst that above-mentioned steps are prepared for we enters one
Walk and synthesized for chloroethanes.Zn/ gold/mesoporous carbon catalysts and 30g ethanol prepared by step 2 is added in reaction unit.Reaction unit
The reactor of cooling coil and agitating device built in one can be used, hydrogen chloride gas is passed through into reactor and is vented 3 times, then is passed through
The desired amount of hydrogen chloride gas simultaneously seals, and is warming up to predetermined temperature（30 DEG C~120 DEG C）Start stirring reaction.Zn/C catalyst
Addition is the 0.5-10% of ethanol quality.Stop reaction when the conversion ratio of ethanol reaches more than 95%.Into built-in condenser
Refrigerated brine ester temperature of reaction kettle is passed through to -5oC, gained liquid is chloroethanes and analyzed using gas-chromatography, and is steamed
Cut obtains chloroethanes and reclaims responseless ethanol from reaction mixture.We are mesoporous using Zn/ provided by the invention
C catalyst has carried out multigroup experiment at different conditions respectively, carries out the synthesis of chloroethanes, and experimental result is as follows：
Table 1
Reaction temperature and reaction time in table 1 are all response parameters when synthesizing chloroethanes, reaction raw materials be ethanol and
Hydrogen chloride gas, catalyst are Zn/ mesoporous carbons, and catalyst amount refers to the mass ratio of catalyst and ethanol, active component addition
Amount refers to that Zn quality accounts for the percentage of carrier quality, and addition scope is 0.5%-20%, and chloroethanes yield=chloroethanes generation rubs
The mole of ethanol in your amount/raw material.
Meanwhile we carry out contrast test under the equal synthesis condition of above-described embodiment, it is mesoporous that Zn/ is substituted using zinc chloride
For carbon as catalyst, remaining reaction condition is identical, obtains following comparative test result：
Table 2
From table 1 it follows that during using Zn/ gold/mesoporous carbon catalysts, at a lower temperature（50 DEG C~80 DEG C）Still can
Enough to keep higher chloroethanes yield, the synthetic yield of chloroethanes more may be up to more than 90% in the range of 50 DEG C~60 DEG C, and instead
It is shorter between seasonable.It is obvious that this catalyst can reduce reaction temperature, shorten the reaction time, the table 2 of contrast table 1 is it can be found that originally
Invention is compared under equal conditions that zinc chloride is close to each other as catalyst progress chloroethanes synthetic yield.Prepared by the present invention urges
Agent is reusable, advantageously reduces discharge of wastewater.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned embodiment, in addition to
Formed technical scheme is combined by above technical characteristic.It should be pointed out that for those skilled in the art
For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (5)
- A kind of 1. Zn/ gold/mesoporous carbon catalysts for being used to produce chloroethanes, it is characterised in that：The catalyst is by Zn active components Presoma is carried on carrier and activates what is obtained, and the active component presoma is zinc compound, and the carrier is mesoporous carbon, The zinc compound includes Zn (OH)2、Zn(CH3COO)2、ZnCO3 、ZnCl2At least one of；The catalyst is made by the steps：The preparation of carrier：Commercially available mesoporous carbon is impregnated in alkaline solution and carries out being heated to reflux handling, wherein mesoporous carbon aperture is 2nm ~ 100nm, specific surface area is in 200-2000m2/ g, then after the mesoporous carbon after alkali process is calcined and slow cooling extremely Normal temperature, produce required mesoporous carbon carrier；The load of active component：Mesoporous carbon is impregnated in the zinc compound precursor solution prepared, dries the water in solution / after, calcined first under the protection of inert gas further to decompose the zinc compound of load, then maintaining to protect gas Under conditions of be passed through hydrogen reducing, produce required catalyst.
- 2. the Zn/ gold/mesoporous carbon catalysts according to claim 1 for being used to produce chloroethanes, it is characterised in that：The activity For component in terms of Zn, its quality is the 0.5%-20% of carrier quality.
- 3. the preparation method of the Zn/ gold/mesoporous carbon catalysts for producing chloroethanes, it is characterised in that：Comprise the following steps：The preparation of carrier：Commercially available mesoporous carbon is impregnated in alkaline solution and carries out being heated to reflux handling, wherein mesoporous carbon aperture is 2nm ~ 100nm, specific surface area is in 200-2000m2/ g, then after the mesoporous carbon after alkali process is calcined and slow cooling extremely Normal temperature, produce required mesoporous carbon carrier；The load of active component：Mesoporous carbon is impregnated in the zinc compound precursor solution prepared, dries the water in solution / after, calcined first under the protection of inert gas further to decompose the zinc compound of load, then maintaining to protect gas Under conditions of be passed through hydrogen reducing, produce required catalyst, the zinc compound includes Zn (OH)2、Zn(CH3COO)2、ZnCO3 、ZnCl2At least one of.
- 4. the preparation method according to claim 3 for being used to produce the Zn/ gold/mesoporous carbon catalysts of chloroethanes, its feature exist In：The alkaline solution includes KOH, NaOH, K2CO3In one or more of mixed liquors.
- 5. the preparation method according to claim 3 for being used to produce the Zn/ gold/mesoporous carbon catalysts of chloroethanes, its feature exist In：For the active component in terms of Zn, its quality is the 0.5%-20% of carrier quality.
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| US2140549A (en) * | 1937-03-19 | 1938-12-20 | Dow Chemical Co | Preparation of 1, 1, 2-trichloroethane |
| US5196618A (en) * | 1991-03-01 | 1993-03-23 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of methyl chloride from carbon tetrachloride and methyl alcohol |
| CN1070633A (en) * | 1991-08-26 | 1993-04-07 | 纳慕尔杜邦公司 | 1,1,1-three chloro-2,2, the catalytic production method of 2-Halothane |
| CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| CN102671656A (en) * | 2012-05-22 | 2012-09-19 | 常州大学 | Pt-load catalyst taking mesoporous carbon as carrier, as well as preparation method and usage thereof |
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| CN102049256B (en) * | 2009-10-27 | 2013-05-01 | 中国石油化工股份有限公司 | Waste water treatment catalyst and preparation method thereof |
| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
| CN102744055A (en) * | 2012-07-20 | 2012-10-24 | 武汉大学 | Active carbon loaded zinc oxide catalyst and application thereof in degradation of organic pollutant |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2140549A (en) * | 1937-03-19 | 1938-12-20 | Dow Chemical Co | Preparation of 1, 1, 2-trichloroethane |
| US5196618A (en) * | 1991-03-01 | 1993-03-23 | Shin-Etsu Chemical Co., Ltd. | Method for the preparation of methyl chloride from carbon tetrachloride and methyl alcohol |
| CN1070633A (en) * | 1991-08-26 | 1993-04-07 | 纳慕尔杜邦公司 | 1,1,1-three chloro-2,2, the catalytic production method of 2-Halothane |
| CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| CN102671656A (en) * | 2012-05-22 | 2012-09-19 | 常州大学 | Pt-load catalyst taking mesoporous carbon as carrier, as well as preparation method and usage thereof |
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