CN105056969A - Preparation method of low-precious metal Au-Cu-TiO2/C catalyst for acetylene hydrochlorination reaction - Google Patents

Preparation method of low-precious metal Au-Cu-TiO2/C catalyst for acetylene hydrochlorination reaction Download PDF

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CN105056969A
CN105056969A CN201510469027.XA CN201510469027A CN105056969A CN 105056969 A CN105056969 A CN 105056969A CN 201510469027 A CN201510469027 A CN 201510469027A CN 105056969 A CN105056969 A CN 105056969A
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catalyst
tio
acetylene hydrochlorination
ethanolic solution
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CN105056969B (en
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胡瑞生
杜燕飞
贾云
孟婉婉
郭颖昕
张俊阁
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INNER MONGOLIA SANLIAN CHEMICAL CO.,LTD.
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Inner Mongolia University
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Abstract

The invention discloses a preparation method of low-precious metal Au-Cu-TiO2/C catalyst for an acetylene hydrochlorination reaction. The catalyst is used in the acetylene hydrochlorination reaction. The catalyst is prepared through an ultrasonic assisted impregnation process. The method comprises the following steps: adding pretreated particulate active carbon to an auric chloride acid, copper chloride and titanium dioxide mixed solution adopting anhydrous ethanol as a solvent, carrying out ultrasonic treatment for 30min, carrying out magnetic stirring at normal temperature for 3h to make active components be uniformly loaded on the above active carbon carrier, standing for 5h, heating in 70DEG C water bath until the above impregnation solution is completely evaporated, and drying the evaporated catalyst in a 100DEG C oven for 12h to obtain the Au-Cu-TiO2/C catalyst sample. Auric chloride acid, copper chloride and titanium dioxide are used according to a mass ratio of Au to Cu to TiO2 of 0-0.55:4:5-11, and most preferably 0.45:4:9. The preparation method of the catalyst has the advantages of simplicity, reduction of the content of precious metals, no pollution, and good catalysis activity and vinyl chloride selectivity in the acetylene hydrochlorination reaction.

Description

A kind of acetylene hydrochlorination reaction low precious metal content Au-Cu-TiO 2the preparation method of/C catalyst
Technical field
The present invention relates to a kind of low precious metal content Au-Cu-TiO 2the preparation method of/C catalyst, refers to a kind of for the low precious metal content Au-Cu-TiO without mercury catalyzing acetylene hydrochlorination especially 2the preparation method of/C catalyst.
Background technology
Along with improving constantly of the growing of national economy and living standards of the people, the demand of polyvinyl chloride is increasing.Produce vinyl chloride with ethylene process and ethane method to compare, acetylene method produces the advantage that vinyl chloride has " settling at one go ", namely only reacts containing one and does not have accessory substance to produce.But ethylene process and ethane method comprise many side reactions, the separation reducing the productive rate of vinyl chloride and target product vinyl chloride is also very complicated.But acetylene method adopts HgCl always 2catalyst, in use mercury easily volatilizees environmental pollution seriously, and the mercuryvapour be mixed with in vinyl chloride have impact on the quality of product, seriously constrains the sustainable development of acetylene method.On January 19th, 2013, more than 140 country reached " Minamata mercury prevents and treats pact ", before the year two thousand twenty, reduced the production and trade of mercurous product gradually.Chinese Government promises to undertake that reducing mercury in the year two thousand twenty PVC industry consumes more than 50%, then prohibits mercury gradually.Therefore, development environment friendly catalyst without mercury is production of vinyl chloride by calcium carbide method industry problem demanding prompt solution.
At present, Au catalyst is paid close attention to widely owing to having very large application potential in acetylene hydrochlorination reaction.But Au catalyst is Au in course of reaction 3+easily be reduced to Au 0and inactivation.In order to improve the stability of Au catalyst, some researchers attempt to stop Au by adding the second metal chloride component 3+reduction, but result of study shows that adding of the second metal chloride does not significantly improve Au in catalyst 3+stability.On this basis, we study metal chloride and metal oxide simultaneously to the facilitation of Au catalyst, CuCl 2and TiO 2double-doped Au-Cu-TiO 2the research that/C catalyst is used for acetylene hydrochlorination reaction is also relatively less.Therefore this patent provides a kind of double-doped low precious metal content Au-Cu-TiO 2the preparation method of/C catalyst, for without mercury catalyzing acetylene hydrochlorination, and can increase substantially the catalytic activity of acetylene hydrochlorination catalysts.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of low precious metal content Au-Cu-TiO 2the preparation method of/C catalyst; this catalyst utilizes ultrasonic assistant soakage legal system standby; take absolute ethyl alcohol as dipping solution; chlorauric acid solution, copper chloride solution and titanium dioxide solids are used anhydrous alcohol solution simultaneously; again pretreated seed activity high-area carbon is added in above-mentioned mixed solution; through ultrasonic assistant soakage reaction, form Au-Cu-TiO 2/ C catalyst, reacts this catalyst application in acetylene hydrochlorination, higher conversion of alkyne can be reached and vinyl chloride selective.
The preparation method of catalyst of the present invention is with gold chloride, copper chloride, and titanium dioxide is active component, and pretreated granular activated carbon is carrier.Specific features is: first with a certain amount of anhydrous alcohol solution HAuCl 44H 2o is made into 0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, with a certain amount of anhydrous alcohol solution CuCl 22H 2o is made into 10wt%Cu 2+cuCl 22H 2o ethanolic solution, gets 54.35ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution and 2.31ml10wt%Cu 2+cuCl 22H 2o ethanolic solution mixes, and adds 0.5199g business TiO in mixed solution 2mix; add the ultrasonic 30min of the pretreated granular activated carbon of 5g again; normal temperature magnetic agitation 3h makes active component uniform load on absorbent charcoal carrier; then 5h is left standstill; in 70 DEG C of water-baths, the catalyst of evaporate to dryness, until maceration extract distilled-to-dryness, is put into after 100 DEG C of baking ovens dry 12h and is namely obtained Au (0.45%) Cu (4%) TiO by heating again 2(9%)/C catalyst sample.
Catalyst of the present invention obtains good catalytic effect in acetylene hydrochlorination course of reaction.Specific experiment operation is formerly weighed in WFS-3015 fixed bed reactors and is carried out, and under atmospheric pressure 180 DEG C of conditions, 1.0g catalyst is fixed to reaction bed center.Before the reaction, reactor N 2purge the moisture in removing reactor and air, the HCl of catalyst 11ml/min activates 0.5h, after reaction temperature is heated to 180 DEG C, and C 2h 2flow 10ml/min and HCl flow 11ml/min passes into reactor simultaneously, and first acetylene gas and hydrogen chloride gas remove moisture by the drier that anhydrous calcium chloride is housed.Product sodium hydroxide solution carries out product composition analysis by SP-6890 gas-chromatography after absorbing removing hydrogen chloride gas.Conversion of alkyne (X a) and the selective (S of vinyl chloride vC) as the evaluation criterion of catalytic activity, its account form is: wherein with the volume fraction of representative reaction residue acetylene respectively, the volume fraction of impurity and the volume fractions of VCM such as the air introduced before reaction.In addition, the thing phase composition of the D8ADVANCE type Powder X-ray Diffractometer detecting catalyst adopting German Bruker company to produce, the running parameter of this instrument is as follows: radiation source is CuK α(λ=0.15406nm), operating voltage is 36kV, and electric current is 20mA, sweep limits 10 ° ~ 80 °, sweep speed 2 °/min.
Low precious metal content Au-Cu-TiO of the present invention 2/ C catalyst is with different Au, Cu ratio, different Ti O 2doping catalyst as a comparison, wherein Au (0.45%) Cu (4%) TiO 2(9%)/C catalyst shows good catalytic activity in acetylene hydrochlorination reaction.
The present invention also adopts bi-component and single component catalyst as a comparison, and the acetylene hydrochlorination catalytic reaction only containing wherein one or both active constituent catalysts is active in Au (0.45%) Cu (4%) TiO 2(9%)/C catalyst.
Au, Cu and TiO selected by the present invention 2mass fraction ratio is 0 ~ 0.55: 4: 5 ~ 11.
Advantage of the present invention is: the low precious metal content Au-Cu-TiO prepared 2/ C catalyst, as acetylene hydrochlorination catalysts have good catalytic activity and vinyl chloride selective.And method for preparing catalyst is simple, reduces the content of noble metal, pollution-free.
Essential characteristics of the present invention is:
1. adopt low precious metal content Au (0.45%) Cu (4%) TiO that ultrasonic assistant soakage legal system is standby 2(9%)/C catalyst, this catalyst is used for acetylene hydrochlorination reaction, conversion of alkyne and vinyl chloride is selective is respectively 94.83% and 99.48%, and acetylene hydrochlorination catalytic reaction activity is far superior to other Au, Cu ratios, other TiO 2the catalyst of doping and bi-component and one pack system, and demonstrate TiO in XRD test 2, Au and active carbon three kinds of thing phases.
2. adopt the low precious metal content Au-Cu-TiO that ultrasonic assistant soakage legal system is standby 2/ C catalyst, CuCl 2add strengthen catalyst to C 2h 2adsorption capacity, the TiO added 2there is provided electronics for Au thus strengthen Au to the adsorption capacity of hydrogen chloride, being so more conducive to the generation of acetylene hydrochlorination reaction, thus making Au-Cu-TiO 2/ C catalyst shows excellent catalytic activity in acetylene hydrochlorination reaction.
Accompanying drawing explanation
Fig. 1 is Au (0.45%) Cu (4%) TiO 2(9%)/C catalyst catalyzing acetylene hydrochlorination 50h time (1) vinyl chloride selectivity curve; (2) acetylene conversion rate curve.
Fig. 2 is (1) Au (0.45%) Cu (4%) TiO 2(9%)/C catalyst; (2) Au (0.45%) Cu (4%)/C catalyst; (3) Au (0.45%) TiO 2(9%)/C catalyst; (4) Cu (4%) TiO 2(9%)/C catalyst; (5) Au (0.45%)/C catalyst; (6) Cu (4%)/C catalyst; (7) TiO 2(9%) X ray diffracting spectrum of/C catalyst.
Conversion of alkyne when table 1 is each component inventory and the catalyzing acetylene hydrochlorination of different catalysts and vinyl chloride selective.
Detailed description of the invention
Embodiment 1:
Activated Carbon Pretreatment method: take the deionized water that a certain amount of granular activated carbon adds active carbon triploid long-pending and make the complete submergence of active carbon in deionized water; transfer to after magnetic stirring apparatus stirs 1h in centrifuge tube; supernatant liquid is outwelled in centrifuges after centrifugal 1h; and then rinsed five removings impurity wherein by deionized water, in the baking oven of 100 DEG C, finally dry 24h obtain pretreated granular activated carbon.
Catalyst preparation process: first with a certain amount of anhydrous alcohol solution HAuCl 44H 2o is made into 0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, with a certain amount of anhydrous alcohol solution CuCl 22H 2o is made into 10wt%Cu 2+cuCl 22H 2o ethanolic solution, gets 54.35ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution and 2.31ml10wt%Cu 2+cuCl 22H 2o ethanolic solution mixes, and adds 0.5199g business TiO in mixed solution 2mix; add the ultrasonic 30min of the pretreated granular activated carbon of 5g again; normal temperature magnetic agitation 3h makes active component uniform load on carrier; then 5h is left standstill; in 70 DEG C of water-baths, the catalyst of evaporate to dryness, until maceration extract distilled-to-dryness, is put into after 100 DEG C of baking ovens dry 12h and is namely obtained Au (0.45%) Cu (4%) TiO by heating again 2(9%)/C catalyst sample.
Comparative example 1: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 6.01ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.30ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5175g business TiO 2, the pretreated granular activated carbon of 5g, obtained Au (0.05%) Cu (4%) TiO 2(9%)/C catalyst sample.
Comparative example 2: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 18.06ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.30ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5181g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.15%) Cu (4%) TiO 2(9%)/C catalyst sample.
Comparative example 3: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 30.13ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.30ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5187g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.25%) Cu (4%) TiO 2(9%)/C catalyst sample.
Comparative example 4: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 42.23ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.31ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5193g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.35%) Cu (4%) TiO 2(9%)/C catalyst sample.
Comparative example 5: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 66.52ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.31ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5205g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.55%) Cu (4%) TiO 2(9%)/C catalyst sample.
Comparative example 6: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 51.96ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.21ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.2761g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.45%) Cu (4%) TiO 2(5%)/C catalyst sample.
Comparative example 7: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 53.13ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.26ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.3953g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.45%) Cu (4%) TiO 2(7%)/C catalyst sample.
Comparative example 8: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 55.65ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.37ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.6505g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.45%) Cu (4%) TiO 2(11%)/C catalyst sample.
Comparative example 9: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 49.24ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 2.09ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, the pretreated granular activated carbon of 5g, obtained Au (0.45%) Cu (4%)/C catalyst sample.
Comparative example 10: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 51.96ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, 0.4970g business TiO 2granular activated carbon pretreated with 5g, obtained Au (0.45%) TiO 2(9%)/C catalyst sample.
Comparative example 11: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 2.30ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, 0.5172g business TiO 2granular activated carbon pretreated with 5g, obtained Cu (4%) TiO 2(7%)/C catalyst sample.
Comparative example 12: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 47.26ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution, and the pretreated granular activated carbon of 5g, obtained Au (0.45%)/C catalyst sample.
Comparative example 13: Activated Carbon Pretreatment method and catalyst preparation process, with embodiment 1, get 2.08ml10wt%Cu 2+cuCl 22H 2o ethanolic solution, and the pretreated granular activated carbon of 5g, obtained Cu (4%)/C catalyst sample.
Comparative example 14: Activated Carbon Pretreatment method and catalyst preparation process with embodiment 1, with anhydrous alcohol solution 0.4945g business TiO 2after add the pretreated granular activated carbon of 5g again, obtained TiO 2(9%)/C catalyst sample.
Obtained catalyst carries out the test of catalytic activity according to the methods below:
Example 1, the catalyst 1.0000g that comparative example 1-14 obtains is fixed to reaction bed center.Before the reaction, reactor N 2purge the moisture in removing reactor and air, the HCl of catalyst 11ml/min activates 0.5h, after reaction temperature is heated to 180 DEG C, and C 2h 2flow 10ml/min and HCl flow 11ml/min passes into reactor simultaneously, and first acetylene gas and hydrogen chloride gas remove moisture by the drier that anhydrous calcium chloride is housed.Product sodium hydroxide solution carries out product composition analysis by SP-6890 gas-chromatography after absorbing removing hydrogen chloride gas.Conversion of alkyne (X a) and the selective (S of vinyl chloride vC) as the evaluation criterion of catalytic activity, its account form is: wherein with the volume fraction of representative reaction residue acetylene respectively, the volume fraction of impurity and the volume fractions of VCM such as the air introduced before reaction.

Claims (1)

1. an acetylene hydrochlorination reaction low precious metal content Au-Cu-TiO 2the preparation method of/C catalyst, is characterized in that, first with a certain amount of anhydrous alcohol solution HAuCl 44H 2o is made into 0.048wt%Au 3+hAuCl44H 2o ethanolic solution, with a certain amount of anhydrous alcohol solution CuCl 22H 2o is made into 10wt%Cu 2+cuCl 22H 2o ethanolic solution, gets 54.35ml0.048wt%Au 3+hAuCl 44H 2o ethanolic solution and 2.31ml10wt%Cu 2+cuCl 22H 2o ethanolic solution mixes, and adds 0.5199g business TiO in mixed solution 2mix; add the ultrasonic 30min of the pretreated granular activated carbon of 5g again; normal temperature magnetic agitation 3h makes active component uniform load on carrier; then 5h is left standstill; in 70 DEG C of water-baths, the catalyst of evaporate to dryness, until maceration extract distilled-to-dryness, is put into after 100 DEG C of baking ovens dry 12h and is obtained a kind of Au-Cu-TiO by heating again 2/ C catalyst sample, Au, Cu and TiO in this catalyst 2optimum quality mark than for Au: Cu: TiO 2=0.45: 4: 9, this catalyst application is reacted its conversion of alkyne up to 94.83% in acetylene hydrochlorination, and vinyl chloride is selective up to 99.48%.
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CN107442118A (en) * 2017-08-04 2017-12-08 内蒙古大学 A kind of preparation method of acetylene hydrochlorination preparing chloroethylene tantalum base catalyst
CN107519872A (en) * 2017-08-04 2017-12-29 内蒙古大学 A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method
CN110548499A (en) * 2019-08-16 2019-12-10 西安凯立新材料股份有限公司 Composite carrier catalyst for acetylene hydrochlorination and application thereof
CN110743624A (en) * 2019-09-29 2020-02-04 浙江工业大学 Acetylene hydrochlorination copper-based catalyst and preparation method and application thereof
CN111111709A (en) * 2020-01-06 2020-05-08 山东鲁泰化学有限公司 Acetylene hydrochlorination non-mercury catalyst taking titanium dioxide nanotube as carrier
CN116920883A (en) * 2023-07-21 2023-10-24 中国地质大学（武汉） TiO capable of efficiently producing hydrogen peroxide activity 2 /MoS x Preparation method and application of-Au photocatalyst

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CN107442118A (en) * 2017-08-04 2017-12-08 内蒙古大学 A kind of preparation method of acetylene hydrochlorination preparing chloroethylene tantalum base catalyst
CN107519872A (en) * 2017-08-04 2017-12-29 内蒙古大学 A kind of boron, nitrogen codope acetylene hydrochlorination catalyst preparation method
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CN116920883A (en) * 2023-07-21 2023-10-24 中国地质大学（武汉） TiO capable of efficiently producing hydrogen peroxide activity 2 /MoS x Preparation method and application of-Au photocatalyst

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