CN104801291A - Zn/mesoporous carbon catalyst for producing chloroethane and preparation method of Zn/mesoporous carbon catalyst - Google Patents
Zn/mesoporous carbon catalyst for producing chloroethane and preparation method of Zn/mesoporous carbon catalyst Download PDFInfo
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- CN104801291A CN104801291A CN201510138900.7A CN201510138900A CN104801291A CN 104801291 A CN104801291 A CN 104801291A CN 201510138900 A CN201510138900 A CN 201510138900A CN 104801291 A CN104801291 A CN 104801291A
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- mesoporous carbon
- catalyst
- chloroethanes
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Abstract
The invention discloses a Zn/mesoporous carbon catalyst. Mesoporous carbon is taken as a carrier, and a Zn active component precursor is supported on the carrier with an impregnation method and activated. The catalyst can be applied to preparation of chloroethane, wherein the active component precursor is zinc salt, and the carrier is mesoporous carbon. The invention further provides a preparation method of the Zn/mesoporous carbon catalyst for producing chloroethane. The preparation method comprises the preparation step of the carrier and the supporting step of Zn active component precursor. The catalyst has higher catalytic activity for the reaction between ethyl alcohol and hydrogen chloride for generation of chloroethane, and the reaction condition is relatively mild. The catalyst can improve the conversion rate and the yield when ethyl alcohol is used for synthetizing chloroethane, can be easily separated from a product and has good reutilization.
Description
Technical field
The present invention relates to a kind of employing and active component presoma is carried on mesoporous carbon supported catalyst, belong to chemical technology field.
Background technology
Chloroethanes is mainly used in the materials such as synthesis lead tetraethide, ethyl cellulose and ethyl carbazole dyestuff, also as preparing smoke agent, refrigerant, local anesthetic, pesticide, ethylating agent, olefinic polymerization solvent, gasoline knock-reducer etc., also can be used as the solvent of material such as synthesis polyacrylic catalyst and phosphorus, sulphur, grease, resin, wax etc.The production method of current chloroethanes mainly adopts alcohol method to produce, and its production technology is divided into: liquid catalytic and gas-phase catalysis.The former be by gaseous state alcohol and hydrogen chloride mixing pass into liquid catalyst is housed reactor in carry out catalytic reaction; The latter be by gaseous state alcohol and hydrogen chloride mixing pass into solid catalyst is housed fixed bed reactors in react.Reaction pressure needed for gas-phase catalysis, temperature are all very high and also have high requirement to the material of consersion unit, so most domestic enterprise all adopts liquid catalytic as the production technology of chloroethanes at present.But this method also has obvious defect: first raw materials for production are high concentration ethanol and the hydrochloric acid of high price; Secondly chloroethanes building-up process is reversible reaction, causes the productive rate of chloroethanes not high, finally also can produce a large amount of waste water.
Summary of the invention
When preparing chloroethanes for prior art, reaction temperature requires high, chloroethanes productive rate is low and can produce a large amount of useless water problem, the invention discloses a kind of Zn/ gold/mesoporous carbon catalyst, using mesoporous carbon as carrier, active component presoma to be carried on carrier and to activate, the efficient synthesis of chloroethanes can be realized.
In order to achieve the above object, the invention provides following technical scheme:
For the production of a Zn/ gold/mesoporous carbon catalyst for chloroethanes, it is characterized in that: Zn active component precursor is carried on carrier by described catalyst and activation obtains, and described active component precursor is zinc salt, and described carrier is mesoporous carbon.
Further, described zinc salt comprises Zn (OH)
2, Zn (CH
3cOO)
2, ZnCO
3, ZnCl
2in at least one.
Further, described active component is in Zn, and its quality is the 0.5%-20% of carrier quality.
For the production of a preparation method for the Zn/ gold/mesoporous carbon catalyst of chloroethanes, comprise the steps:
The preparation of carrier: commercially available mesoporous carbon be impregnated in the carrying out heating reflow treatment in alkaline solution, wherein mesoporous carbon aperture is 2nm ~ 100nm, and specific area is at 200-2000m
2/ g, then the mesoporous carbon after alkali treatment to be carried out after calcining and slow cooling to normal temperature, obtain required mesoporous carbon carrier;
The load of active component: mesoporous carbon be impregnated in the zinc salt precursor solution prepared; after drying the moisture in solution; first calcine under the protection of inert gas to decompose the zinc salt of load further, then pass into hydrogen reducing under the condition maintaining protection gas, obtain required catalyst.
Further, described zinc salt comprises Zn (OH)
2, Zn (CH
3cOO)
2, ZnCO
3, ZnCl
2in at least one.
Further, described alkaline solution comprises KOH, NaOH, K
2cO
3in the mixed liquor of one or more.
Further, described active component is in Zn, and its quality is the 0.5%-20% of carrier quality.
Beneficial effect:
Zn/ gold/mesoporous carbon catalyst provided by the invention generates chloroethanes to ethanol and hydrochloric acid or hcl reaction and has high catalytic activity, and reaction condition is gentleer, obviously can reduce reaction temperature; This catalyst can improve conversion ratio and the productive rate of ethanol synthesis chloroethanes, and easy and separation of products.This catalyst has good reusing, with ZnCl
2catalyst is compared, and greatly reduces containing ZnCl2 wastewater discharge, reduces environmental hazard, can be used as the basis of industrial applications.
Detailed description of the invention
Below with reference to specific embodiment, technical scheme provided by the invention is described in detail, following detailed description of the invention should be understood and be only not used in for illustration of the present invention and 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 area is at 200-2000m
2/ g) impregnated in alkaline solution carrying out heating reflow treatment, then calcine 3 h under the mesoporous carbon after alkali treatment being placed in 600 DEG C of conditions and slow cooling to normal temperature, obtain required mesoporous carbon carrier; Certainly, also NaOH, K can be adopted
2cO
3deng other alkaline solutions as activator.
Step 2, the preparation of Zn/ gold/mesoporous carbon catalyst
By active component presoma Zn (CH
3cOO)
2add in the aqueous solution, stirring and dissolving, add the mesoporous carbon carrier obtained in step 1 after to be dissolved and stir 2h, dry 8-10h at 90-110 DEG C of temperature subsequently, grind to form fine powder, then in nitrogen atmosphere under 220 DEG C ~ 400 DEG C (this example preferably 300 DEG C) roasting 2h, obtain catalyst precursor; Described catalyst precursor is placed in hydrogen atmosphere in 200 DEG C ~ 800 DEG C (this example preferably 300 DEG C) reduction treatment 2h, reduction pressure is 0.1-0.2MPa, hydrogen flowing quantity 40-50ml/min, by Zn (CH
3cOO)
2be reduced into metal simple-substance, namely obtain required catalyst.Zn (the CH mentioned in this step
3cOO)
2as just a kind of example, we also can adopt other zinc salts, as Zn (OH)
2or ZnCO
3or ZnCl
2in one carry out alternative Zn (CH
3cOO)
2, the mixture of several different zinc salt can also be adopted as active component presoma.Aforesaid reaction condition also can adjust along with using the difference of activator and zinc salt, in fact, is carried on by active component presoma zinc salt and mesoporous carbon carrier also activates the catalyst obtained all belongs to protection category of the present invention.
In order to absolutely prove catalyst effect provided by the invention, the catalyst that above-mentioned steps prepares by we is further used for chloroethanes synthesis.Zn/ gold/mesoporous carbon catalyst step 2 prepared and 30g ethanol add in reaction unit.Reaction unit can adopt the reactor of a built-in cooling coil and agitating device, passes into hydrogen chloride gas and is vented 3 times, then pass into the hydrogen chloride gas of aequum and seal in reactor, is warming up to predetermined temperature (30 DEG C ~ 120 DEG C) and starts stirring reaction.The addition of Zn/C catalyst is the 0.5-10% of ethanol quality.Reaction is stopped when the conversion ratio of ethanol reaches more than 95%.Refrigerated brine ester temperature of reaction kettle is passed into-5 in built-in condenser
oc, gained liquid is chloroethanes and utilizes gas-chromatography analysis, and separated reaction mixture, obtain chloroethanes and reclaim responseless ethanol.We adopt Zn/ gold/mesoporous carbon catalyst provided by the invention to carry out many groups of experiments at different conditions respectively, and carry out the synthesis of chloroethanes, experimental result is as follows:
Table 1
Response parameter when reaction temperature in table 1 and reaction time are all synthesis chloroethanes, reaction raw materials is ethanol and hydrogen chloride gas, catalyst is Zn/ mesoporous carbon, catalyst amount refers to the mass ratio of catalyst and ethanol, active component addition refers to that the quality of Zn accounts for the percentage of carrier quality, interpolation scope is 0.5%-20%, the mole of ethanol in mole/raw material that chloroethanes productive rate=chloroethanes generates.
Meanwhile, we carry out contrast test under the equal synthesis condition of above-described embodiment, and adopt zinc chloride to substitute Zn/ mesoporous carbon as catalyst, remaining reaction condition is identical, obtains following comparative test result:
Table 2
As can be seen from Table 1, when using Zn/ gold/mesoporous carbon catalyst, (50 DEG C ~ 80 DEG C) still can keep higher chloroethanes productive rate at a lower temperature, and within the scope of 50 DEG C ~ 60 DEG C, the synthetic yield of chloroethanes more can up to more than 90%, and the reaction time is shorter.Clearly, this catalyst can reduce reaction temperature, Reaction time shorten, and contrast table 1 table 2 can find that the present invention compares that zinc chloride to be carried out chloroethanes synthetic yield as catalyst under equal conditions close to each other.Catalyst prepared by the present invention is reusable, is conducive to reducing discharge of wastewater.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned embodiment, also comprises the technical scheme be made up of above technical characteristic.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (7)
1. for the production of a Zn/ gold/mesoporous carbon catalyst for chloroethanes, it is characterized in that: Zn active component precursor is carried on carrier by described catalyst and activation obtains, and described active component precursor is zinc salt, and described carrier is mesoporous carbon.
2. the Zn/ gold/mesoporous carbon catalyst for the production of chloroethanes according to claim 1, is characterized in that: described zinc salt comprises Zn (OH)
2, Zn (CH
3cOO)
2, ZnCO
3, ZnCl
2in at least one.
3. the Zn/ gold/mesoporous carbon catalyst for the production of chloroethanes according to claim 1 and 2, is characterized in that: described active component is in Zn, and its quality is the 0.5%-20% of carrier quality.
4., for the production of the preparation method of the Zn/ gold/mesoporous carbon catalyst of chloroethanes, it is characterized in that: comprise the steps:
The preparation of carrier: commercially available mesoporous carbon be impregnated in the carrying out heating reflow treatment in alkaline solution, wherein mesoporous carbon aperture is 2nm ~ 100nm, and specific area is at 200-2000m
2/ g, then the mesoporous carbon after alkali treatment to be carried out after calcining and slow cooling to normal temperature, obtain required mesoporous carbon carrier;
The load of active component: mesoporous carbon be impregnated in the zinc salt precursor solution prepared; after drying the moisture in solution; first calcine under the protection of inert gas to decompose the zinc salt of load further, then pass into hydrogen reducing under the condition maintaining protection gas, obtain required catalyst.
5. the preparation method of the Zn/ gold/mesoporous carbon catalyst for the production of chloroethanes according to claim 4, is characterized in that: described zinc salt comprises Zn (OH)
2, Zn (CH
3cOO)
2, ZnCO
3, ZnCl
2in at least one.
6. the preparation method of the Zn/ gold/mesoporous carbon catalyst for the production of chloroethanes according to claim 4, is characterized in that: described alkaline solution comprises KOH, NaOH, K
2cO
3in the mixed liquor of one or more.
7. the preparation method of the Zn/ gold/mesoporous carbon catalyst for the production of chloroethanes according to claim 4, is characterized in that: described active component is in Zn, and its quality is the 0.5%-20% of carrier quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397102A (en) * | 2016-08-29 | 2017-02-15 | 山东同成医药股份有限公司 | Halogenated hydrocarbon product and sealed heat insulation pressurized production method thereof |
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| 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 |
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| 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 |
| 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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2015
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Patent Citations (8)
| 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 |
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| CN101780952A (en) * | 2010-03-26 | 2010-07-21 | 上海交通大学 | Method for preparing loading functional oxide porous carbon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397102A (en) * | 2016-08-29 | 2017-02-15 | 山东同成医药股份有限公司 | Halogenated hydrocarbon product and sealed heat insulation pressurized production method thereof |
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