CN107519872A - A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method - Google Patents
A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
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- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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Abstract
The technical problem to be solved in the present invention is to provide a kind of boron nitrogen codope acetylene hydrochlorination catalyst.Main preparation process is that first activated carbon, boric acid, urea and appropriate deionized water are put into beaker, and up to being evaporated, obtained sample is calcined 5 hours under 500 DEG C, nitrogen atmosphere for heating response in 60 DEG C of water-baths.HAuCl is added dropwise into the sample after roasting again4·4H2O ethanol solution, then impregnated at 25 DEG C 24 hours, finally dried 12 hours at 140 DEG C, prepare boron, nitrogen codope acetylene hydrochlorination catalyst, and be applied in fixed bed reactors.Method for preparing catalyst technique is simple；Cost is cheap；The reaction that the catalyst prepared is applied to acetylene hydrochlorination preparing chloroethylene has preferable catalytic activity and stability, conversion of alkyne 83.5%, and vinyl chloride is selectively 99.7%.
Description
Technical field
The present invention relates to a kind of preparation method of acetylene hydrochlorination catalyst, refers in particular to a kind of acetylene hydrochlorination that is used for and reacts
Boron, the preparation method of nitrogen codope activated carbon low content Au-based catalyst.
Background technology
Vinyl chloride (VCM) is synthesizing polyvinyl chloride (PVC) monomer, and the almost all of vinyl chloride (98%) in the whole world is all to use
To produce polyvinyl chloride.Polyvinyl chloride is one of five big general synthetic resins, has good physical and mechanical properties, for producing
Construction material, packaging material, electronic material and daily necessities, it is widely used in industry, agricultural, transportation, packaging etc.
Each field, China Plastics Industry have formed the more complete industrial system of class, turn into and are run neck and neck with steel, cement, timber
Basic material industry, as a kind of new material, it has much surmounted above-mentioned three kinds of materials using field, be agricultural, industry,
The indispensable important material of all fields of national economy such as the energy, communications and transportation, information industry or even cosmic space and ocean development
One of material.
The production method of vinyl chloride (VCM) mainly has an ethylene process and carbide, and China is that petroleum reserves is less, coal resources
The country of relative abundance, so carbide turns into the main method of China PVC productions.Calcium carbide process PVC production mainly uses acetylene
With the technique productions vinyl chloride of HCl additions, the technique makees catalyst with activated carbon supported mercury chloride.Mercury chloride easily distils, poison
Property it is big, catalyst easily causes to inactivate because of distillation during the course of the reaction, and be lost in mercury chloride can to biology and environment make
Into murder by poisoning, therefore, the anti-applications catalyst of acetylene hydrochlorination of exploitation environment-friendly type mercury-free series is the innovation of calcium carbide process PVC industrial technology
One of core topic.How in course of production of chloroethylene caused catalyst pollution is reduced, to better adapt to nation-building
The requirement of resource-conserving and environment-friendly society, it has also become whole carbide acetylene method produces PVC Industry faces one
Individual urgent problem to be solved.
Currently, domestic and international acetylene hydrochlorination reaction catalyst without mercury research is different according to active component, is broadly divided into non-expensive
Metallic catalyst and the major class of noble metal catalyst two.Catalyst without mercury is reacted for base metal acetylene hydrochlorination, early in 1994
Year, NEC chemical industry Co., Ltd. attempted a variety of halide as acetylene hydrochlorination reaction catalyst without mercury activearm
Point, find SnCl2The catalytic effect reacted acetylene hydrochlorination is best, but the catalyst activity and life-span can not meet that industry should
Use demand.In recent years there is document report using silica as carrier, bismuth copper and the bimetallic catalyst that bismuth zinc is active component
BiPO4-Cu3(PO4)/SiO2And BiPO4-Zn3(PO4)2/SiO2, there is preferable activity to acetylene hydrochlorination reaction, but it is initial anti-
Should active be the 1/3 of activated carbon supported mercury chloride industrial catalyst.
It is relatively more active for the relative non-precious metal catalyst of noble metal acetylene hydrochlorination reaction catalyst without mercury research, greatly
Most literature research finds, the reaction of the reactivity of noble metal catalyst close to activated carbon supported mercury chloride industrial catalyst
Activity, but because its bullion content is higher (mostly more than 1%) so that catalyst cost is very high, and noble metal catalyst
Catalytic activity is also up for further improving.Therefore, bullion content is reduced, it is urgently to solve to improve acetylene hydrochlorination reactivity
Key issue certainly.
At present, boron, the low content of two kinds of nonmetal doping modified activated carbons of nitrogen to being reacted used in acetylene hydrochlorination
The research of Au-based catalyst does not have also.Therefore, this patent provides a kind of boron, nitrogen codope activated carbon low content Au-based catalyst,
The catalyst has preferable acetylene hydrochlorination reactivity, in larger air speed 770h-1, under conditions of 150 DEG C, the conversion ratio of acetylene
Reach 83.5%, the selectivity of vinyl chloride reaches 99.7%.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of boron, nitrogen codope activated carbon for acetylene hydrochlorination reaction
The preparation method of low content Au-based catalyst.The catalyst has higher conversion of alkyne and vinyl chloride selectivity.
The technical problem to be solved in the present invention is realized by following scheme：First by granular activated carbon (Chinese medicines group chemistry
Reagent Co., Ltd) use the HNO that concentration is 65%3At room temperature wash 2 hours, obtain suspension through filtering and spend from
Sub- water washing, untill reaching neutrality, obtained activated carbon dries 12 hours at 85 DEG C, the activity that 6g is treated
Carbon, 0.338g boric acid (H3BO)3, 1.286g urea (CO (NH2)2) and 50mL deionized waters be put into beaker, and in 60 DEG C of water-baths
Until solution distilled-to-dryness, finally, sample is calcined 5 hours under 500 DEG C, nitrogen atmosphere, obtains boron, nitrogen codope for evaporation in pot
Activated carbon sample, the percentage that boron accounts for absorbent charcoal carrier in catalyst sample is 1%, and the percentage that nitrogen accounts for absorbent charcoal carrier is
5%.
Supported Au catalysts use equi-volume impregnating, by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in
In 100ml absolute ethyl alcohols, the golden ethanol solution that amount containing Au is 0.00497g/ml is made into, it is 0.00497g/ml to take 3.0ml concentration
HAuCl4·4H2O(assay：49.7%) ethanol solution, dripped while stirring until gold into boron, nitrogen codope activated carbon sample
The percentage for accounting for absorbent charcoal carrier is 0.25%.Obtained sample is impregnated 24 hours at room temperature, and 12 are finally dried at 140 DEG C
Hour, obtain boron, nitrogen codope activated carbon Au-based catalyst sample.
Catalyst prepared by the present invention is applied in acetylene hydrochlorination reaction, has obtained preferable result.Activity test makes
It is fixed bed reactors, is carried out under the conditions of atmospheric pressure and 150 DEG C, 2 milliliters of catalyst samples is loaded in reactor
Center.Before reactions, with nitrogen purge to remove the water and air in reaction system, and it is 13.8ml/ with flow velocity
Min hydrogen chloride gas activated catalyst sample 0.5 hour.After reactor is heated to 150 DEG C, by the second that flow velocity is 12ml/min
Alkynes and the hydrogen chloride that flow velocity is 13.8ml/min are added in the reactor of heating together.Acetylene gas passes through silica-gel desiccant, chlorine
Change hydrogen by 5A molecular sieve desiccants, to remove mixing water.By product by sodium hydroxide tank with except de-chlorine hydride.Pass through
The composition of chromatographic product.Use XA=(φA0-φA1)/φA0× 100% and SVC=φVC/(φA0-φA1)×
100% (φA0For the volume fraction of acetylene in unstrpped gas, φA1For the volume fraction of remaining acetylene, φVCFor VCM volume integral
Number) calculate the conversion ratio (X of acetyleneA) and selectivity (SVC) to VCM.
It is an advantage of the invention that：Boron, the nitrogen codope activated carbon low content Au-based catalyst prepared, enter under big air speed
Row acetylene hydrochlorination reacts, and has preferable catalytic activity.And method for preparing catalyst is simple, cost is cheap.It is provided by the invention
Acetylene hydrochlorination catalyst has following essential characteristics compared with existing catalyst：
(1) preparation method of catalyst of the present invention is first to prepare boron nitrogen codope activated-carbon catalyst, then using isometric
Infusion process, boron, nitrogen codope activated carbon low content Au-based catalyst are obtained, the catalyst preparation is simple to operate, has preferable
Catalytic activity, the conversion ratio to acetylene are 83.5%.
(2) catalyst due to the codope of boron, nitrogen make catalyst activity and stability be improved, reduce simultaneously
The content of gold, reduces cost.
(3) the catalyst acetylene hydrochlorination reaction velocity is larger, is 770h-1, there is PRODUCTION TRAITS value.
Brief description of the drawings
Fig. 1 is (1) 0.25%/1B/5N-AC of Au, (2) Au 0.25%1B/3N-AC, (3) Au 0.25%1B/7N-AC,
(4) the catalytic activity test chart of the acetylene hydrochlorination of Au 0.25%1B/1N-AC (5) Au 0.25%-AC catalyst.
Fig. 2 is (1) 0.25%/1B/1N-AC of Au, (2) 0.25%/3B/1N-AC of Au, (3) 0.25%/5B/1N- of Au
The catalytic activity test chart of the acetylene hydrochlorination of AC, (4) 0.25%/7B/1N-AC of Au, (5) Au 0.25%-AC catalyst.
Fig. 3 is the Au 0.25%-AC after (1) use, and 0.25%/1B/5N-AC of Au after (2) use, (3) are fresh
Au 0.25%-AC, the X ray diffracting spectrum of (4) fresh Au 0.25%/1B/5N-AC catalyst.
Embodiment
Embodiment 1：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 0.338g H 6g treated3BO3、1.286g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 1%, and nitrogen accounts for work
Property high-area carbon percentage be 5%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Comparative example 1：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, being made into amount containing Au is
0.00497g/ml golden ethanol solution, take the HAuCl that 3.0ml concentration is 0.00497g/ml4·4H2O(assay：49.7%) second
Alcoholic solution, to 6g treat activated carbon in drip while stirring until gold account for absorbent charcoal carrier percentage be 0.25%.Obtain
Sample impregnate 24 hours at room temperature, finally dried 12 hours at 140 DEG C, obtain golden load type active carbon catalyst sample.
Comparative example 2：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 0.338g H 6g treated3BO3、0.257g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 1%, and nitrogen accounts for work
Property high-area carbon percentage be 1%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Comparative example 3：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 0.338g H 6g treated3BO3、0.771g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 1%, and nitrogen accounts for work
Property high-area carbon percentage be 3%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Comparative example 4：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 0.338g H 6g treated3BO3、1.8g CO(NH2)2With 50mL deionized waters
It is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, then, sample roasts under 500 DEG C, nitrogen atmosphere
Burn 5 hours, obtain boron, nitrogen codope activated carbon sample, the percentage that boron accounts for absorbent charcoal carrier in sample is 1%, and nitrogen accounts for activity
The percentage of high-area carbon is 7%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, is made into
Amount containing Au is 0.00497g/ml golden ethanol solution, takes the HAuCl that 3.0ml concentration is 0.00497g/ml4·4H2O(assay：
49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for the percentage of absorbent charcoal carrier
For 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtains boron, nitrogen codope
Activated carbon Au-based catalyst sample.
Comparative example 5：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 1.015g H 6g treated3BO3、0.257g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 3%, and nitrogen accounts for work
Property high-area carbon percentage be 1%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Comparative example 6：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 1.691g H 6g treated3BO3、0.257g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 5%, and nitrogen accounts for work
Property high-area carbon percentage be 1%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Comparative example 7：First, by granular activated carbon (Chemical Reagent Co., Ltd., Sinopharm Group) HNO that concentration is 65%3
Wash 2 hours at room temperature, filter and be washed with deionized, untill reaching neutrality, obtained activated carbon is at 85 DEG C
Dry 12 hours.Secondly, activated carbon, 2.367g H 6g treated3BO3、0.257g CO(NH2)2With 50mL deionizations
Water is put into beaker, and evaporation is until solution distilled-to-dryness in 60 DEG C of water-baths, and then, sample is under 500 DEG C, nitrogen atmosphere
Roasting 5 hours, obtains boron, nitrogen codope activated carbon sample, and the percentage that boron accounts for absorbent charcoal carrier in sample is 7%, and nitrogen accounts for work
Property high-area carbon percentage be 1%.Again by 1g HAuCl4·4H2O(assay：49.7%) it is dissolved in 100ml absolute ethyl alcohols, matches somebody with somebody
Into the golden ethanol solution that amount containing Au is 0.00497g/ml, the HAuCl that 3.0ml concentration is 0.00497g/ml is taken4·4H2O
(assay：49.7%) ethanol solution, dripped while stirring into boron, nitrogen codope activated carbon sample until gold accounts for absorbent charcoal carrier
Percentage be 0.25%.Obtained sample impregnates 24 hours at room temperature, is finally dried 12 hours at 140 DEG C, obtain boron,
Nitrogen codope activated carbon Au-based catalyst sample.
Obtained catalyst carries out the test of catalytic activity according to the methods below：
Embodiment 1, comparative example 1,2,3,4,5,6 and 7：Using fixed bed reactors, enter under the conditions of atmospheric pressure and 150 DEG C
OK, 2 milliliters of catalyst are loaded in the center of reactor.Before reactions, with nitrogen purge to remove reaction system
In water and air, and the hydrogen chloride gas activated catalyst sample 0.5 hour for being 13.8ml/min with flow velocity.Reactor heats
To after 150 DEG C, the hydrogen chloride that acetylene and flow velocity that flow velocity is 12ml/min are 13.8ml/min is added to the anti-of heating together
Answer in device.Record and calculate the conversion ratio of acetylene.
Claims (1)
1. the preparation method of catalyst of the present invention is mainly characterized by：First by granular activated carbon concentration be 65% HNO3
Persistently being stirred at 25 DEG C 2 hours, suspension is filtrated to get the activated carbon of preliminary treatment, and is washed with deionized, until
Untill reaching PH=7, the activated carbon of obtained preliminary treatment dries 12 hours at 85 DEG C.Secondly, by 6g preliminary treatments
Activated carbon, 0.338g boric acid (H3BO3), 1.286g urea (CO (NH2)2) and 50mL deionized waters be put into beaker, and 60
Heating response is evaporated in DEG C water-bath, and until solution distilled-to-dryness, then that the sample being evaporated is calcined under 500 DEG C, nitrogen atmosphere to 5 is small
When, obtain boron, nitrogen codope Mixture of Activated Carbon, the percentage that boron accounts for activated carbon in mixture is 1%, and nitrogen accounts for the hundred of activated carbon
Divide than being 5%.Then by 1g HAuCl4·4H2O is dissolved in 100ml absolute ethyl alcohols, is made into the gold that amount containing Au is 0.00497g/ml
Ethanol solution, take the HAuCl that 3.0ml concentration is 0.00497g/ml4·4H2O ethanol solutions, are added dropwise under conditions of being stirred continuously
Into boron, nitrogen codope Mixture of Activated Carbon, obtained sample impregnates 24 hours at 25 DEG C, then drying 12 is small at 140 DEG C
When, obtain prepared boron, nitrogen codope acetylene hydrochlorination catalyst, the percentage that gold accounts for absorbent charcoal carrier in catalyst is
0.25%.The catalyst is reacted applied to acetylene hydrochlorination, its conversion of alkyne reaches 83.5%, and the selectivity of vinyl chloride is high
Up to 99.7%.
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| CN108199055A (en) * | 2018-01-02 | 2018-06-22 | 珠海光宇电池有限公司 | Nitrogen co-doped carbon supported platinum catalyst of a kind of boron and preparation method thereof |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
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| CN116159579A (en) * | 2022-12-07 | 2023-05-26 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof |
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| CN108199055A (en) * | 2018-01-02 | 2018-06-22 | 珠海光宇电池有限公司 | Nitrogen co-doped carbon supported platinum catalyst of a kind of boron and preparation method thereof |
| CN109331869A (en) * | 2018-09-28 | 2019-02-15 | 内蒙古自治区石油化工监督检验研究院 | A kind of low ruthenium content ruthenium-based catalyst for acetylene hydrochlorination reaction |
| CN111715253A (en) * | 2019-03-22 | 2020-09-29 | 南开大学 | Copper-based catalyst for preparing vinyl chloride through acetylene hydrochlorination and preparation and use methods thereof |
| CN110560123B (en) * | 2019-08-23 | 2022-10-25 | 安徽师范大学 | Preparation method and application of metal-free non-porous catalyst material |
| CN110560123A (en) * | 2019-08-23 | 2019-12-13 | 安徽师范大学 | preparation method and application of metal-free non-porous catalyst material |
| CN112191244A (en) * | 2020-08-31 | 2021-01-08 | 浙江工业大学 | Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation |
| CN112191244B (en) * | 2020-08-31 | 2023-03-31 | 浙江工业大学 | Activated carbon-supported gold-based catalyst, preparation method thereof and application thereof in acetylene hydrogenation |
| CN112121840A (en) * | 2020-09-30 | 2020-12-25 | 李通 | Activated carbon of catalyst for preparing chloroethylene by calcium carbide method and preparation method thereof |
| CN112473744A (en) * | 2020-11-27 | 2021-03-12 | 浙江工业大学 | Front-rear stage two-section type combined catalyst and application thereof |
| CN112473744B (en) * | 2020-11-27 | 2021-11-30 | 浙江工业大学 | Front-rear stage two-section type combined catalyst and application thereof |
| CN112973799A (en) * | 2021-03-01 | 2021-06-18 | 内蒙古大学 | Preparation method and application of uracil modified gold-based catalyst |
| CN115155573A (en) * | 2022-08-04 | 2022-10-11 | 中盐吉兰泰氯碱化工有限公司 | Method for applying nitrogen-sulfur modified ultralow-content gold-based catalyst to reaction of preparing vinyl chloride through fixed bed acetylene hydrochlorination |
| CN115155573B (en) * | 2022-08-04 | 2023-08-08 | 中盐吉兰泰氯碱化工有限公司 | Method for preparing vinyl chloride by hydrochlorination of acetylene in fixed bed by using ultralow-content gold-based catalyst modified by nitrogen and sulfur |
| CN116159579A (en) * | 2022-12-07 | 2023-05-26 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | Acetylene hydrochlorination low-temperature mercury-free catalyst and preparation method thereof |
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