CN107213910A - A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride - Google Patents
A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride Download PDFInfo
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- CN107213910A CN107213910A CN201710337934.8A CN201710337934A CN107213910A CN 107213910 A CN107213910 A CN 107213910A CN 201710337934 A CN201710337934 A CN 201710337934A CN 107213910 A CN107213910 A CN 107213910A
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- catalyst
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- hydrogen chloride
- methanol
- monochloro methane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride, and this method includes willAdd in liquor zinci chloridi, after mixing, drying, roasting obtains described catalyst, and its feature is, is dried and is calcined under hydrogen chloride atmosphere.The catalyst prepared by the inventive method can effectively overcome existing ZnCl2/
Description
Technical field
The invention belongs to monochloro methane synthesis field, and in particular to a kind of to synthesize urging for monochloro methane for methanol hydrogen chloride
The preparation method of agent.
Background technology
Monochloro methane is commonly called as chloromethanes, is usage amount larger chemical intermediate and industrial chemicals, mainly for the preparation of having
The raw material of machine silicon industry, methyl chlorosilane monomer, be also used for methylcellulose, quaternary ammonium compound, agricultural chemicals, organic compound it is molten
The production of agent and emulsifying agent etc., also acts as medical anesthetic.The intermediate raw material monochloro methane of methane chloride is than methane more
Active material, can synthesize the product in downstream as intermediate product, and it is acted on can be similar with the methanol of coal chemical industry.Closely
As organosilicon, the fast development of methane chloride industry, the demand of monochloro methane are also continuously increased over year.Monochloro methane
Preparation method mainly has：Methane chlorination method and methanol chloridising.Country's methane chloride production method is with methanol chloridising at present（First
Alcohol liquid catalytic and methanol vapor phase chloridising）Based on.Liquid catalytic is that methanol and hydrogen chloride are mixed into equipped with liquid phase
The reactor of catalyst carries out liquid phase reactor.Gas-phase methanol hydrogen chloride method is equipped with catalyst by gas methanol and hydrogen chloride
Reacted in fixed bed reactors.
Current methanol hydrogen chloride synthesis monochloro methane is main with commodity, molecular sieve, and load the business of zinc chloride
Product aluminum oxide and molecular sieve are catalyst.CommodityCheap, activity is relatively low, although molecular sieve activity has
Lifted, but selectivity is not so good as aluminum oxide.During methanol hydrogen chloride synthesis monochloro methane, methanol carbonization, in catalyst
Surface is accumulated, and causes catalyst duct to block so that catalyst inactivation.By loading ZnCl2Activity and selectivity is substantially carried afterwards
Rise, during load, ZnCl2The duct for easily causing catalyst is blocked, during roasting, part ZnCl2It is lost in, together
When the ZnCl that loads2Easily decompose as ZnO or Zn-O-Cl etc., do not reach expected results.
The content of the invention
The technical problem to be solved in the present invention is to overcome existing defect to be used for methanol hydrogen chloride synthesis one there is provided one kind
The preparation method of the catalyst of chloromethanes.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride, including willAdd zinc chloride
In solution, after mixing, drying, roasting obtains described catalyst, and its feature is, is dried and is roasted under hydrogen chloride atmosphere
Burn.
Preferably, the solvent of the liquor zinci chloridi is organic solvent, and zinc chloride can be effectively suppressed using organic solvent
Hydrolysis.
It is highly preferred that the organic solvent is methanol, ethanol, glycerine, acetone or ether.
Preferably, drying temperature is 30~80 DEG C, and sintering temperature is 300~600 DEG C.It is highly preferred that drying temperature is 50
DEG C, sintering temperature is 400 DEG C.Preferably, the heating rate of roasting is 1~10 DEG C/min, and roasting time is 2-4 hours.
Preferably, ZnCl in the catalyst2Load capacity be 8wt%~15wt%.
It is highly preferred that ZnCl in the catalyst2Load capacity be 11wt%.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and constitutes a part for specification, the reality with the present invention
Applying example is used to explain the present invention together, is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is catalyst performance evaluation experimental provision schematic diagram of the present invention, wherein, 1. methanol, 2. hydrogen chloride, 3. gaseous mixtures
CH4/N2, 4. heating furnaces, 5. catalyst, 6. thermocouples, in 7. and bottle.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that preferred reality described herein
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment 1
Aluminium isopropoxide powder is fully ground to fine powder, 17.1g sucrose is weighed and is dissolved in 90ml deionized water, stirs, makes
It fully dissolves, and is slowly added to the levigate aluminium isopropoxides of 10.2g, and strong mixing dissolves it.PH to 5.5 is adjusted, 48h, 80 is stirred
DEG C volatilization volatile components, obtain clear gel, 600 DEG C are warming up to 3 DEG C/min heating rate, be calcined 4h, obtain。
Weigh 0.136g ZnCl2It is dissolved in 2.5mL deionized waters, adds 0.1mL65w% concentrated nitric acid, make its abundant
Dissolving, adds the above-mentioned preparations of 1.02g, under HCl atmosphere protections, after 50 DEG C dry, it is transferred in quartz boat,
Tube furnace center is placed on, HCl is passed through, the air in quartz ampoule is replaced, 400 DEG C, roasting are warming up to 3 DEG C/min speed
180min, obtains zinc chloride load capacity for 11wt% catalyst.
Embodiment 2
Preparation be the same as Example 1.
Weigh 0.136g ZnCl2It is dissolved in 4mL absolute ethyl alcohols, fully dissolving, adds 1.02g, in HCl gas
Under atmosphere protection, after 50 DEG C dry, it is transferred in quartz boat, is placed on tube furnace center, HCl is passed through, by the air in quartz ampoule
Displacement, 400 DEG C are warming up to 3 DEG C/min speed, are calcined 180min, obtain zinc chloride load capacity for 11wt% catalyst.
Embodiment 3
Preparation be the same as Example 1.
Weigh 0.0907g ZnCl2It is dissolved in 4mL absolute ethyl alcohols, fully dissolving, adds 1.02g, in HCl
Under atmosphere protection, after 50 DEG C dry, it is transferred in quartz boat, is placed on tube furnace center, HCl is passed through, by the sky in quartz ampoule
Gas is replaced, and 400 DEG C are warming up to 3 DEG C/min speed, is calcined 180min, obtains zinc chloride load capacity for 8wt% catalyst.
Embodiment 4
Preparation be the same as Example 1.
Weigh 0.1813g ZnCl2It is dissolved in 4mL absolute ethyl alcohols, fully dissolving, adds 1.02g, in HCl
Under atmosphere protection, after 50 DEG C dry, it is transferred in quartz boat, is placed on tube furnace center, HCl is passed through, by the sky in quartz ampoule
Gas is replaced, and 400 DEG C are warming up to 3 DEG C/min speed, is calcined 180min, obtains zinc chloride load capacity for 15wt% catalyst.
Comparative example 1
Aluminium isopropoxide powder is fully ground to fine powder, 17.1g sucrose is weighed and is dissolved in 90ml deionized water, stirs, makes
It fully dissolves, and is slowly added to the levigate aluminium isopropoxides of 10.2g, and strong mixing dissolves it.Then 0.34g ZnCl are added2, by force
3h is stirred, pH to 5.5 is adjusted, 48h is stirred, volatilize volatile components at 80 DEG C, clear gel is obtained, with 3 DEG C/min heating
Speed is warming up to 600 DEG C, is calcined 4h, obtains zinc chloride doping for 11wt% catalyst.
Comparative example 2
Preparation be the same as Example 1.
Weigh 0.136g ZnCl2It is dissolved in 2.5mL deionized waters, fully dissolving, adds 1.02g, 50
DEG C drying（Air atmosphere）, zinc chloride load capacity is obtained for 11wt% catalyst.
Comparative example 3
Preparation be the same as Example 1.
Weigh 0.136g ZnCl2It is dissolved in 2.5mL deionized waters, fully dissolving, adds 1.02g γ-Al2O3, 50
DEG C drying（Air atmosphere）, 400 DEG C are warming up to 3 DEG C/min speed, 180min is calcined, obtaining zinc chloride load capacity is
11wt% catalyst.
Catalyst performance evaluation is tested：By above-mentioned preparationAnd loaded zinc chlorideCatalyst
Sieving, obtains the catalyst granules of 40-60 mesh.Reacted in fixed bed reactors.Reaction temperature is 280 DEG C, and HCl flows are
6mL/min, methanol flow is 0.01mL/min, gaseous mixture CH4/N2(VCH4/VN2=flow 1%) is 20mL/min, nitrogen conduct
Inert component, corrosion of the reduction HCl to device, CH4As interior gas, to methanol, monochloro methane and dimethyl ether carry out quantitative scoring
Calculate.As a result it is as follows：
The above results show, ZnCl is can obviously improve using the method for the present invention2/The catalytic activity of catalyst.
The present invention is not limited to what is prepared using the above method, existing other methods are prepared or commercially availableIt is equally applicable, the various embodiments described above are using self-controlSimply chlorine is added for preferably examination on different opportunitys
Change influence of the zinc for catalytic activity.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride, including willAdd chlorination
In zinc solution, after mixing, drying, roasting obtains described catalyst, it is characterised in that carried out under hydrogen chloride atmosphere drying and
Roasting.
2. preparation method according to claim 1, it is characterised in that：The solvent of the liquor zinci chloridi is organic solvent.
3. preparation method according to claim 2, it is characterised in that：The organic solvent is methanol, ethanol, glycerine, third
Ketone or ether.
4. preparation method according to claim 1, it is characterised in that：Drying temperature is 30~80 DEG C, and sintering temperature is 300
~600 DEG C.
5. preparation method according to claim 4, it is characterised in that：The heating rate of roasting is 1~10 DEG C/min, roasting
Time is 2~4 hours.
6. preparation method according to claim 1, it is characterised in that：ZnCl in the catalyst2Load capacity for 8wt%~
15wt%。
7. preparation method according to claim 6, it is characterised in that：ZnCl in the catalyst2Load capacity be 11wt%.
8. a kind of catalyst prepared according to any methods describeds of claim 1-7.
9. the purposes of catalyst described in claim 8, it is characterised in that methanol gas and hydrogen chloride gas are in the catalyst
Under catalysis, reaction generation monochloro methane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710337934.8A CN107213910A (en) | 2017-05-15 | 2017-05-15 | A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride |
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| CN201710337934.8A CN107213910A (en) | 2017-05-15 | 2017-05-15 | A kind of preparation method for the catalyst that monochloro methane is synthesized for methanol hydrogen chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225234A (en) * | 2018-09-19 | 2019-01-18 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN116196965A (en) * | 2023-04-25 | 2023-06-02 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982267A (en) * | 2005-12-13 | 2007-06-20 | 山东东岳氟硅材料有限公司 | Method for converting carbon tetrachloride into methane chloride |
-
2017
- 2017-05-15 CN CN201710337934.8A patent/CN107213910A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1982267A (en) * | 2005-12-13 | 2007-06-20 | 山东东岳氟硅材料有限公司 | Method for converting carbon tetrachloride into methane chloride |
Non-Patent Citations (3)
| Title |
|---|
| SUBHA KUMARASWAMY PILLAI ET AL.: "Metathesis of methyloleate over methyltrioxorhenium supported on ZnCl2-promoted mesoporous alumina", 《APPLIED CATALYSIS A: GENERAL》 * |
| 宋立新等: "合成氯甲烷的负载型ZnCl2/γ-Al2O3催化剂的研制", 《化工科技》 * |
| 廖清江: "《无机药物化学》", 30 April 1957, 人民卫生出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109225234A (en) * | 2018-09-19 | 2019-01-18 | 石河子大学 | A kind of composition for carbon catalytic hydrogenation methane |
| CN116196965A (en) * | 2023-04-25 | 2023-06-02 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
| CN116196965B (en) * | 2023-04-25 | 2023-08-15 | 山东东岳氟硅材料有限公司 | Gamma-Al 2 O 3 C-N catalyst and preparation method thereof |
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