CN107008465A - A kind of acetylene hydrochlorination reaction copper-based catalysts with high-activity stable - Google Patents
A kind of acetylene hydrochlorination reaction copper-based catalysts with high-activity stable Download PDFInfo
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- CN107008465A CN107008465A CN201710208643.9A CN201710208643A CN107008465A CN 107008465 A CN107008465 A CN 107008465A CN 201710208643 A CN201710208643 A CN 201710208643A CN 107008465 A CN107008465 A CN 107008465A
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- copper
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- stabilizer
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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
- B01J27/08—Halides
- B01J27/122—Halides of copper
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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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1817—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with copper, silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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Abstract
Copper-based catalysts are reacted the present invention relates to a kind of acetylene hydrochlorination with high-activity stable, the copper-based catalysts are used as active component using mantoquita；One kind in copper chloride, copper nitrate, copper sulphate, cupric phosphate of the mantoquita and more than, it is characterised in that stabilizer is introduced in copper-based catalysts；One kind in guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethyl ammonium chloride, etamon chloride, trimethyl benzyl ammonia chloride, triethyl benzyl ammonia chloride, four methyl phosphonium chlorides, 4-butyl phosphonium chloride, methyl triphenyl phosphonium chloride, 1 butyl triphenyl phosphonium chloride of the stabilizer and more than.The present invention makes acetylene hydrochlorination copper-based catalysts stability be significantly improved by introducing the stabilizer with the advantage such as cost is low, toxicity is low, heat endurance good, vapour pressure is small in the catalyst.
Description
Technical field
It is more particularly to a kind of with high-activity stable the invention belongs to preparing chloroethylene by acetylene hydrochlorination technical field
Acetylene hydrochlorination reacts copper-based catalysts.
Background technology
China is the first big country of polyvinyl chloride (poly vinyl chloride, PVC) production in the world, accounts for global total
More than the 50% of production capacity.The production of polyvinyl chloride monomeric vinyl chloride (vinyl chloride monomer, VCM) has two mainly
Commercial routes, i.e. oil-ethylene process and coal-acetylene method.In China, acetylene method (also known as carbide) commercial routes have coal
Charcoal endowment of resources is abundant, in Atom economy height and cost advantage, therefore Chinese Production of PVC, the synthesis of acetylene method hydrogen chloride
Process for vinyl chloride occupies more than 70% proportion, and is still raising year by year.Core reaction therein is：
In the commercial Application of recent decades, the catalyst main active component of the reaction is mercury chloride.Mercury chloride is used for
This reaction have preferably activity, but there is also it is fatal the problem of.First, mercury chloride has hypertoxicity and volatility.According to statistics
With estimation, only just there are about 800 tons of mercury to be used in vinyl chloride production procedure every year in China, wherein there are about 200 tons or so nothings
Method is reclaimed and is directly entered environment, easily causes serious personal injury and environmental pollution.Secondly, mercury resource is due to long-term
Exploitation day is closely exhausted, further increase catalyst cost.Importantly, mercury pollution have become one it is global
The problem of, the limitation that international organization uses for mercury is increasingly strict.But at the same time, in for quite a long time, carbide
Process for vinyl chloride will be the main flow of PVC Industry.Therefore, searching performance is good, and price is low, the synthesis chloroethene of energy replacement for mercury
Alkene catalyst, the Green Sustainable for Chinese PVC industries is imperative and extremely urgent task.
At present, noble metal gold is predicted and confirmed with best acetylene hydrochlorination activity.Gold utensil has stably, efficiently, clearly
The advantage such as clean and recyclable, but its price is still of a relatively high, it is difficult to received by the relatively low PVC industries of added value itself.
Therefore, the industrialization of Au catalyst distance still has a segment distance.
On the other side to be, base metal has the characteristics of reserves are extensive, price is relatively low.What base metal was prepared urges
Agent, which is applied to industry, has more obvious cost advantage.Therefore, current base metal acetylene hydrochlorination catalyst is also obtained
Certain research, wherein being that the catalyst of main active component has more excellent performance using copper.Deng state ability et al. is with bag
The catalyst that the base metal chloride including copper has prepared low cost as active component is included, the catalyst after optimization is matched somebody with somebody
Side can be in 30h-1Show the conversion ratio more than 98% under acetylene volume space velocity operating condition, but catalyst stability compared with
Difference.In CN101670293A, using silica as carrier, the composition metal including copper is entered as catalyst activity component
Row load, and by introducing the activity of part raising catalyst, this catalyst inactivation using recirculating fluidized bed quickly, it is necessary to be carried out
Regeneration.
The most general problem is that the stability of catalyst present in the research of current copper-based acetylene hydrochlorination catalyst
It is not ideal enough.Want to realize the long period commercial Application of catalyst, the stability of lifting catalyst is that must solve one asks
Topic.The method for effectively improving acetylene hydrochlorination copper-based catalysts stability is found, its crucial institute for moving towards practical application is to speed up
.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of acetylene hydrochlorination reaction with high-activity stable is copper-based
Catalyst.
It is a kind of with high-activity stable acetylene hydrochlorination reaction copper-based catalysts, its using mantoquita as active component,
And stabilizer is introduced in copper-based catalysts；One kind in copper chloride, copper nitrate, copper sulphate, cupric phosphate of the mantoquita and
More than；The stabilizer is selected from guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethyl ammonium chloride, etamon chloride, trimethyl
Benzyl ammonium chloride, triethyl benzyl ammonia chloride, four methyl phosphonium chlorides, 4-butyl phosphonium chloride, methyl triphenyl phosphonium chloride, 1- butyl
One kind in triphenyl phosphonium chloride and more than.
A kind of embodiment is that the mass fraction of the stabilizer in the catalyst is 1~10wt%.
A kind of embodiment is that the mass fraction of copper in the catalyst is 1~15wt%.
A kind of embodiment is, the copper-based catalysts are using activated carbon as carrier, and the activated carbon is selected from coconut carbon, wooden
Carbon, one kind in ature of coal carbon and more than.
A kind of embodiment is that the granular size of the activated carbon is 30~200 mesh, and specific surface area is 200~1200m2/
G, density is 300~1000kg/m3, pore volume is 0.4~0.8mL/g.
Beneficial effects of the present invention are：
The present invention by introducing with the advantage such as cost is low, toxicity is low, heat endurance good, vapour pressure is small in the catalyst
Stabilizer, makes acetylene hydrochlorination copper-based catalysts stability be significantly improved.The catalyst prepared can keep high
On the premise of selectivity (more than 99%), conversion ratio does not decline substantially after continuous long-time use, so as to better adapt to
Industrialize long-term operation requirement.This catalyst has the characteristics of cost is low, safe, performance is good concurrently, with sufficient development
Potentiality.
Brief description of the drawings
Fig. 1 is change curve of the conversion of alkyne in embodiment 1, embodiment 2, comparative example 1, comparative example 2 with the reaction time.
Fig. 2 is change curve of the conversion of alkyne in embodiment 10 with the reaction time.
Embodiment
The present invention will be further described with reference to the accompanying drawings and detailed description.It is emphasized that the description below
It is merely exemplary, the scope being not intended to be limiting of the invention and its application.
The preparation method of catalyst is：Mass fraction according to setting calculates the usage amount of mantoquita and stabilizer, and presses
Consumption adds load weighted mantoquita and stabilizer in deionized water like this, and being stirred vigorously dissolves component.After being completely dissolved,
It is stirred vigorously the lower load weighted absorbent charcoal carrier of addition.Products therefrom is placed in room temperature atmospheric pressure environment and kept for 6 hours, Ran Hou
Dried 12 hours at 110 DEG C, obtain finished catalyst.
It is listed below in embodiment, comparative example, the coconut carbon used is：Commercially available, granular size is 40~100 mesh, compares table
Area is 800m2/ g, density is 500kg/m3, pore volume is 0.7mL/g；The wooden carbon used is：Commercially available, granular size is 30 mesh,
Specific surface area is 500m2/ g, density is 500kg/m3, pore volume is 0.5mL/g.
The catalyst prepared passes through by flow control system, reactor, heating kettle, condensing unit, drying device, gas
The reaction evaluating equipment that phase chromatogram and device for absorbing tail gas are constituted is evaluated, and wherein gas-chromatography is used for determining second alkyne conversion
Rate and selectivity, its recording frequency be every 15 minutes once.
It is listed below reaction condition common in embodiment 1-9, comparative example 1-2：180 DEG C of reaction temperature, reaction pressure is
Normal pressure, the volume space velocity of acetylene is 180h-1, the useful load of catalyst is 1.0g, the volume flow of acetylene and hydrogen chloride gas it
Than for 1:1.1.
Embodiment 1
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and trimethyl benzyl ammonia chloride so that urge
The mass fraction of copper is 5% in agent, and the mass fraction of trimethyl benzyl ammonia chloride is 2.5%.In above-mentioned reaction condition
Lower to be reacted, conversion ratio declines Value Data and charges to table 1 by catalyst initial conversion and after 12 hours, Catalyst Conversion with
Reaction time change curve is shown in Fig. 1.
Comparative example 1
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate so that the quality of copper point in catalyst
Number is 5%.Reacted under the above-described reaction conditions, by catalyst initial conversion and after 12 hours, conversion ratio declines Value Data
Table 1 is charged to, Catalyst Conversion is shown in Fig. 1 with reaction time change curve.
Embodiment 2
Using coconut carbon as carrier, catalyst is prepared using cupric phosphate and trimethyl benzyl ammonia chloride so that in catalyst
The mass fraction of copper is 5%, and the mass fraction of trimethyl benzyl ammonia chloride is 2.5%.Carry out under the above-described reaction conditions
Reaction, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 1, when Catalyst Conversion is with reaction
Between change curve see Fig. 1.
Comparative example 2
Using coconut carbon as carrier, catalyst is prepared using cupric phosphate so that the mass fraction of copper is in catalyst
5%.Reacted under the above-described reaction conditions, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data is charged to
Table 1, Catalyst Conversion is shown in Fig. 1 with reaction time change curve.
Embodiment 3
Using wooden carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and trimethyl benzyl ammonia chloride so that urge
The mass fraction of copper is 5% in agent, and the mass fraction of trimethyl benzyl ammonia chloride is 2.5%.In above-mentioned reaction condition
Lower to be reacted, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 2.
Embodiment 4
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and trimethyl benzyl ammonia chloride so that urge
The mass fraction of copper is 5% in agent, and the mass fraction of trimethyl benzyl ammonia chloride is 10%.Under the above-described reaction conditions
Reacted, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 2.
Embodiment 5
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and tetramethyl ammonium chloride so that catalyst
The mass fraction of middle copper is 10%, and the mass fraction of tetramethyl ammonium chloride is 2.5%.Carry out under the above-described reaction conditions anti-
Should, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 2.
Embodiment 6
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and four methyl phosphonium chlorides so that catalyst
The mass fraction of middle copper is 5%, and the mass fraction of four methyl phosphonium chlorides is 2.5%.Carry out under the above-described reaction conditions anti-
Should, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 2.
Embodiment 7
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and 4-butyl phosphonium chloride so that catalyst
The mass fraction of middle copper is 5%, and the mass fraction of 4-butyl phosphonium chloride is 2.5%.Carry out under the above-described reaction conditions anti-
Should, by catalyst initial conversion and after 12 hours, conversion ratio decline Value Data charges to table 2.
Embodiment 8
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and tetramethylethylenediamine hydrochloride so that
The mass fraction of copper is 5% in catalyst, and the mass fraction of tetramethylethylenediamine hydrochloride is 2.5%.In above-mentioned reaction
Under the conditions of reacted, conversion ratio declines Value Data and charges to table 2 by catalyst initial conversion and after 12 hours.
Embodiment 9
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and guanidine hydrochloride so that copper coin in catalyst
The mass fraction of element is 5%, and the mass fraction of guanidine hydrochloride is 2.5%.Reacted under the above-described reaction conditions, by the beginning of catalyst
Beginning conversion ratio and after 12 hours conversion ratio decline Value Data charge to table 2.
In above example 1-9 and comparative example 1-2, the selectivity of vinyl chloride is all higher than 99%.
Embodiment 10
Using coconut carbon as carrier, catalyst is prepared using Copper dichloride dihydrate and trimethyl benzyl ammonia chloride so that urge
The mass fraction of copper is 5% in agent, and the mass fraction of trimethyl benzyl ammonia chloride is 2.5%.In reaction temperature 180
DEG C, reaction pressure is normal pressure, and the volume space velocity of acetylene is 75h-1, the useful load of catalyst is 2.4g, acetylene and hydrogen chloride gas
The ratio between volume flow be 1:Long reaction is carried out under 1.1 reaction condition, the selectivity of vinyl chloride is maintained at more than 99%, 90
Hour Catalyst Conversion is shown in Fig. 2 with reaction time change curve, and catalyst initial conversion is catalysis after 74.0%, 90 hours
Agent conversion ratio is 83.68%, it can be seen that catalyst has high activity stability.
Catalyst performance is contrasted before and after table 1 introduces stabilizer
Table 2 introduces the performance of stabilizer rear catalyst
Claims (5)
1. it is a kind of with high-activity stable acetylene hydrochlorination reaction copper-based catalysts, the copper-based catalysts using mantoquita as
Active component；One kind in copper chloride, copper nitrate, copper sulphate, cupric phosphate of the mantoquita and more than, it is characterised in that
Stabilizer is introduced in copper-based catalysts；The stabilizer be selected from guanidine hydrochloride, tetramethylethylenediamine hydrochloride, tetramethyl ammonium chloride,
Etamon chloride, trimethyl benzyl ammonia chloride, triethyl benzyl ammonia chloride, four methyl phosphonium chlorides, 4-butyl phosphonium chloride, methyl
Triphenyl phosphonium chloride, one kind in 1- butyl triphenyl phosphonium chlorides and more than.
2. catalyst according to claim 1, it is characterised in that the mass fraction of the stabilizer in the catalyst is 1
~10wt%.
3. catalyst according to claim 1, it is characterised in that the mass fraction of copper in the catalyst is 1~
15wt%.
4. catalyst according to claim 1, it is characterised in that the copper-based catalysts are described using activated carbon as carrier
One kind in coconut carbon, wooden carbon, ature of coal carbon of activated carbon and more than.
5. catalyst according to claim 4, it is characterised in that the granular size of the activated carbon is 30~200 mesh, than
Surface area is 200~1200m2/ g, density is 300~1000kg/m3, pore volume is 0.4~0.8mL/g.
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| CN201710208643.9A CN107008465B (en) | 2017-03-31 | 2017-03-31 | Copper-based catalyst with high activity and stability for hydrochlorination of acetylene |
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| CN201710208643.9A CN107008465B (en) | 2017-03-31 | 2017-03-31 | Copper-based catalyst with high activity and stability for hydrochlorination of acetylene |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847802A (en) * | 2019-02-13 | 2019-06-07 | 石河子大学 | A kind of Au hetero atom composition catalyst and its preparation method and application for acetylene hydrochlorination reaction |
| CN110694653A (en) * | 2019-10-23 | 2020-01-17 | 那珊 | Catalyst for vinyl chloride synthesis and preparation method and application thereof |
| CN112961027A (en) * | 2021-02-24 | 2021-06-15 | 石河子大学 | Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
| CN115430425A (en) * | 2022-09-21 | 2022-12-06 | 清华大学 | High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, and preparation and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109847802A (en) * | 2019-02-13 | 2019-06-07 | 石河子大学 | A kind of Au hetero atom composition catalyst and its preparation method and application for acetylene hydrochlorination reaction |
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| CN112961027A (en) * | 2021-02-24 | 2021-06-15 | 石河子大学 | Insoluble copper complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
| CN115430425A (en) * | 2022-09-21 | 2022-12-06 | 清华大学 | High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, and preparation and application thereof |
| CN115430425B (en) * | 2022-09-21 | 2023-09-19 | 清华大学 | High-stability copper-based catalyst for catalyzing hydrochlorination of acetylene, preparation and application thereof |
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