CN107042120B - A kind of acetylene trimerization benzene catalyst and its preparation method and application - Google Patents
A kind of acetylene trimerization benzene catalyst and its preparation method and application Download PDFInfo
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- CN107042120B CN107042120B CN201710381805.9A CN201710381805A CN107042120B CN 107042120 B CN107042120 B CN 107042120B CN 201710381805 A CN201710381805 A CN 201710381805A CN 107042120 B CN107042120 B CN 107042120B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
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Abstract
The invention belongs to chemical technology fields, and in particular to a kind of acetylene trimerization benzene catalyst and its preparation method and application.The acetylene trimerization benzene catalyst is the loaded catalyst using ordered mesoporous material as carrier, the catalyst includes following components: double acetonitrile palladium chlorides, stannous chloride and ackd salt, wherein, the parts by weight of above-mentioned each component of the catalyst are as follows: the ackd salt of double acetonitrile palladium chlorides of 0.1-3 parts by weight, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight.Thus, by the present invention in that the loaded catalyst to ordered mesoporous material as carrier, cyclotrimerization can occur with catalyzing acetylene and generate benzene, and the conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the service life of catalyst is able to maintain that longer time, suitable for industrial amplification production, there is good market application prospect.
Description
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of acetylene trimerization benzene catalyst and preparation method thereof and answer
With.
Background technique
The light aromatics such as benzene, toluene and dimethylbenzene (three is referred to as BTX) are answered extensively as most basic Organic Chemicals
For producing the chemical products such as rubber, fiber, plastics, dyestuff.Currently, aromatic hydrocarbons is mainly derived from petroleum in traditional handicraft
Catalytic reforming and hydrocarbon cracking in work, account for about the 90% of aromatic hydrocarbon resource, and only about 10% aromatic hydrocarbons derives from coal chemical industry.But
It is that aromatic hydrocarbons is prepared using traditional handicraft and is had the following problems: on the one hand, since petroleum resources in recent years gradually decrease, causes
The cost for preparing raw material gradually increases；On the other hand, synthetic material and other fine chemicals demands is growing to aromatic hydrocarbons
Production forms higher demand.Therefore, the new technology for developing aromatics production is imperative.If acyclic simple point can be utilized
Son, such as methane, methanol, acetylene bring it about the light aromatics that aromatization is directly translated into high added value, will have weight
The strategic importance wanted.
Acetylene have high reactivity, cyclotrimerization be thermodynamically it is strongly exothermic, catalysis can be passed through
Agent rush brings it about polymerization reaction to prepare benzene.In the prior art, Tysoe et al. (J. Chem. Soc., Chem.
Commun. transition gold 1983,623) has been reported respectively with Sesselmann et al. (Surf. Sci. 1983,135,128)
Belong to Pd has excellent acetylene cyclotrimerization performance at low temperature, and discovery acetylene is adsorbed on Pd at a temperature of being less than 210K
(111) behind single crystalline catalyst surface, about 30% ADSORPTION STATE acetylene generation cyclotrimerization is converted into benzene in Temperature Programmed Processes.
But the technology has the following deficiencies: that catalyst needs single crystal forms, and needs to react under condition of ultralow temperature, technique is set
Standby higher cost, it is difficult to industrialize；The yield of benzene is too low, and only only 30%, while it is poly- to be likely to form four during the reaction
Object, pentamer, polymer etc..It is high that Xu Lei et al. (CA201510864201, CA201510860897) reports a kind of support type
Disperse palladium, ruthenium, rhodium composite transition metal catalyst, conversion ratio of the acetylene under constant-pressure and high-temperature greatly improves (up to 100%), together
When improve the selectivity (up to 82.2%) of benzene.But this method has the following deficiencies: that the service life of catalyst is shorter, it can only
Maintain several hours activity；Catalyst mithridatism is poor, very high to the purity requirement of acetylene gas, is unfavorable for industrialized reality
It applies.Currently, there is above-mentioned drawback in the acetylene benzene reaction of open report, as severe reaction conditions need high temperature and pressure, react into
Expect complex, catalyst easy in inactivation of component etc., and conversion of alkyne and benzene selective are relatively low.Therefore, how to design
It is a kind of out to improve conversion of alkyne and benzene selective, extend catalyst life, the benzene catalyst processed suitable for large-scale production
Cyclotrimerization occurs for catalyzing acetylene and generates benzene, becomes current urgent problem.
Summary of the invention
Aiming at the problems existing in the prior art, the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation sides
With catalyzing acetylene ring trimerization can occur for method and application by using the loaded catalyst using ordered mesoporous material as carrier
Reaction generate benzene, and react in acetylene conversion ratio and benzene selectivity it is higher, and the service life of catalyst be able to maintain that it is longer
Time, be suitable for industrial amplification production, have good market application prospect.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
The present invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is using ordered mesoporous material as load
The loaded catalyst of body, which is characterized in that the catalyst includes following components: double acetonitrile palladium chlorides, stannous chloride and acid
Property salt, wherein the parts by weight of each component are as follows: double acetonitrile palladium chloride 0.1-3 parts by weight, stannous chloride 25-70 parts by weight and
Ackd salt 27-75 parts by weight；Also, the mass ratio of the catalyst and the carrier is 0.1%-2%:1.
Inventors have found that passing through the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization can occur with catalyzing acetylene and generate benzene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the service life of catalyst is able to maintain that longer time, is suitable for
Industrial amplification production；Meanwhile the present invention carries out catalysis benzene processed by the loaded catalyst and reacts, required reactive component
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, and temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fastly
Speed, simple process reduce production cost, and can be realized higher conversion of alkyne and benzene selective, have good
Application prospect.
According to a particular embodiment of the invention, the ackd salt is at least one in ferric trichloride, ammonium chloride or copper chloride
Kind.
According to a particular embodiment of the invention, the ordered mesoporous material is in SBA-15 or MCM-41 mesopore molecular sieve
It is at least one.
According to a particular embodiment of the invention, in the ackd salt ammonium chloride and copper chloride mass ratio are as follows: 0.1-1:
0.1-0.5。
Meanwhile the present invention also provides the preparation methods of above-mentioned acetylene trimerization benzene catalyst, which is characterized in that including
Following steps:
(1) ordered mesoporous material is roasted in nitrogen atmosphere, after its cooling, is put into drier standby as carrier
With；
(2) double acetonitrile palladium chlorides of 0.1-3 parts by weight, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight are weighed
Ackd salt, and be mixed uniformly, configuration obtains catalyst aqueous solution, and ultrasonic treatment makes it be uniformly dispersed；
(3) ordered mesoporous material carrier is added in catalyst aqueous solution and is impregnated, it is then dry in air atmosphere, with
Afterwards after tabletting, being crushed and sieving, the loaded catalyst is obtained.
According to a particular embodiment of the invention, in step 1, the ordered mesoporous material is mesoporous point of SBA-15 or MCM-41
At least one of son sieve, described be roasted to roasts 2-4 hours at 700-800 DEG C.
According to a particular embodiment of the invention, in step 3, the time of the dipping is 6-12 hours.
According to a particular embodiment of the invention, in step 3, the screening is to be sized to 20-40 mesh.
Meanwhile the present invention also provides the methods of above-mentioned acetylene trimerization benzene catalyst benzene, which is characterized in that including
Following steps:
(1) loaded catalyst is fitted into fixed bed reactors, by the loaded catalyst anti-before reaction
It answers nitrogen on device to purge, guarantees that reaction environment is in anhydrous and oxygen-free state；
(2) using mixed with the acetylene of nitrogen as reaction gas, with acetylene volume space velocity 200-3000h-1Flow velocity be passed into
In fixed bed reactors, contact it with the loaded catalyst, and 150-300 DEG C at a temperature of, carry out acetylene trimerization
Benzene reaction processed.
According to a particular embodiment of the invention, it in step (2), is specifically included mixed with the acetylene of nitrogen: 10-50% volume second
Alkynes and 50-90% volume nitrogen.
Beneficial effects of the present invention are as follows:
(1) the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, using of the invention
Ordered mesoporous material loaded catalyst, catalyzing acetylene occur cyclotrimerization and generate in benzene, the choosing of the conversion ratio and benzene of acetylene
Selecting property is higher, and the service life of catalyst is able to maintain that longer time, is suitable for industrial amplification production, there is good market
Application prospect.
(2) the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, using of the invention
Ordered mesoporous material loaded catalyst, catalyzing acetylene occur cyclotrimerization and generate in benzene, and required reactive component is few, only
Nitrogen and acetylene, required reaction condition is relatively mild, and temperature is at 150-300 degrees Celsius, synthesis under normal pressure, rapid reaction, technique
Simply, production cost is reduced, and can be realized higher conversion of alkyne and benzene selective, before there is application well
Scape.
(3) the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, use is order mesoporous
Material load type catalyst, the ingredient of the catalyst is simple, is easy to get, and in catalyst large surface carrier to active component
Form preferable dispersion.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or integral；It can be mechanical connect
It connects, is also possible to be electrically connected；It can be directly connected, can also can be in two elements indirectly connected through an intermediary
The interaction relationship of the connection in portion or two elements.It for the ordinary skill in the art, can be according to specific feelings
Condition understands the concrete meaning of above-mentioned term in the present invention.
According to an aspect of the present invention, the present invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is
Loaded catalyst using ordered mesoporous material as carrier, the catalyst includes following components: double acetonitrile palladium chlorides, chlorine
Change cuprous and ackd salt, wherein double acetonitrile palladium chlorides are the main actives of benzene catalyst processed, are benzene catalyst second processed
The neccessary composition of alkyne reaction generation benzene；Stannous chloride can be used as co-catalyst, and benzene can be improved by being incorporated stannous chloride
Selectivity, reduces the generation of impurity；And ackd salt can be further improved reaction rate, reduce the reaction time, reduction is produced into
This.The parts by weight of above-mentioned each component of the catalyst are as follows: double acetonitrile palladium chloride 0.1-3 parts by weight, stannous chloride 25-70
Parts by weight and ackd salt 27-75 parts by weight；Also, the mass ratio of the catalyst and the carrier is 0.1%-2%:1.By
This, the present invention uses loaded catalyst of the ordered mesoporous material as carrier, and the ingredient of the catalyst is simple, it is easy to get,
And large surface carrier forms preferable dispersion to active component in catalyst.
Inventors have found that passing through the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization can occur with catalyzing acetylene and generate benzene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the service life of catalyst is able to maintain that longer time, is suitable for
Industrial amplification production；Meanwhile the present invention carries out catalysis benzene processed by the loaded catalyst and reacts, required reactive component
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, and temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fastly
Speed, simple process reduce production cost, and can be realized higher conversion of alkyne and benzene selective, have good
Application prospect.
According to a particular embodiment of the invention, the type for the ackd salt that the acetylene trimerization benzene catalyst uses not by
Especially limitation, those skilled in the art can select according to actual needs.Specific some embodiments according to the present invention, institute
Stating ackd salt is at least one of ferric trichloride, ammonium chloride or copper chloride.Further, the ackd salt is ammonium chloride and chlorine
Change the mixture of copper, the mass ratio of ammonium chloride and copper chloride in the ackd salt are as follows: 0.1-1:0.1-0.5；Preferably, institute
State the mass ratio of the ammonium chloride and copper chloride in ackd salt are as follows: 0.9-1:0.4-0.5.Thus, it is possible to further increase reaction speed
Rate reduces the reaction time, reduces production cost.
According to a particular embodiment of the invention, the type for the ordered mesoporous material that the acetylene trimerization benzene catalyst uses
It is not particularly restricted, those skilled in the art can select according to actual needs.Specific some realities according to the present invention
Example is applied, the ordered mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieve.Thus, it is possible to significantly improve
The catalytic activity of the benzene catalyst processed.
Meanwhile the present invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is using ordered mesoporous material
As the loaded catalyst of carrier, the parts by weight of each component of the catalyst are as follows: double acetonitrile palladium chloride 0.5-2.5 weights
Measure part, stannous chloride 40-70 parts by weight and ackd salt 30-60 parts by weight；Wherein, double acetonitrile palladium chloride benzene catalyst
Main active is the neccessary composition that benzene catalyst acetylene reaction processed generates benzene；Stannous chloride can be used as co-catalysis
Agent can be improved the selectivity of benzene by being incorporated stannous chloride, reduce the generation of impurity；And ackd salt can be further improved instead
Rate is answered, the reaction time is reduced, reduces production cost.The present invention uses the above-mentioned parts by weight system of each component as a result,
Standby catalyst, can be further improved the catalytic activity of the benzene catalyst processed.
Meanwhile the present invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is using ordered mesoporous material
As the loaded catalyst of carrier, the parts by weight of each component of the catalyst are as follows: double acetonitrile palladium chloride 0.6-1.5 weights
Measure part, stannous chloride 45-65 parts by weight and ackd salt 30-45 parts by weight；Wherein, double acetonitrile palladium chloride benzene catalyst
Main active is the neccessary composition that benzene catalyst acetylene reaction processed generates benzene；Stannous chloride can be used as co-catalysis
Agent can be improved the selectivity of benzene by being incorporated stannous chloride, reduce the generation of impurity；And ackd salt can be further improved instead
Rate is answered, the reaction time is reduced, reduces production cost.The present invention uses the above-mentioned parts by weight system of each component as a result,
Standby catalyst, can be further improved the catalytic activity of the benzene catalyst processed.
According to another aspect of the present invention, the present invention also provides a kind of systems of above-mentioned acetylene trimerization benzene catalyst
Preparation Method, comprising the following steps:
(1) ordered mesoporous material is roasted in nitrogen atmosphere, after its cooling, is put into drier standby as carrier
With.
According to a particular embodiment of the invention, the type for the ordered mesoporous material that the acetylene trimerization benzene catalyst uses
It is not particularly restricted, those skilled in the art can select according to actual needs.Specific some realities according to the present invention
Example is applied, the ordered mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieve.Thus, it is possible to significantly improve
The catalytic activity of the benzene catalyst processed.The specific operation process that the ordered mesoporous material is roasted is as follows: described orderly
Mesoporous material roasts 2-4 hours at 700-800 DEG C, and then, the cooling is to be down to 100 DEG C or less.
(2) double acetonitrile palladium chlorides of 0.1-3 parts by weight, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight are weighed
Ackd salt, and be mixed uniformly, configuration obtains catalyst aqueous solution, and ultrasonic treatment makes it be uniformly dispersed.
The present invention is prepared in the method for acetylene trimerization benzene catalyst, and the catalyst is using ordered mesoporous material conduct
The loaded catalyst of carrier, the catalyst includes following components: double acetonitrile palladium chlorides, stannous chloride and ackd salt, wherein
Double acetonitrile palladium chlorides are the main actives of benzene catalyst processed, be benzene catalyst acetylene reaction processed generate benzene it is necessary at
Point；Stannous chloride can be used as co-catalyst, and the selectivity of benzene can be improved by being incorporated stannous chloride, reduce the life of impurity
At；And ackd salt can be further improved reaction rate, reduce the reaction time, reduce production cost.The present invention uses and has as a result,
Loaded catalyst of the sequence mesoporous material as carrier, the ingredient of the catalyst is simple, is easy to get, and big table in catalyst
Face carrier forms preferable dispersion to active component.
According to a particular embodiment of the invention, the parts by weight of above-mentioned each component of the catalyst are as follows: double acetonitrile chlorine
Change palladium 0.1-3 parts by weight, stannous chloride 25-70 parts by weight and ackd salt 27-75 parts by weight；Also, the catalyst and institute
The mass ratio for stating carrier is 0.1%-2%:1.
According to a particular embodiment of the invention, the parts by weight of above-mentioned each component of the catalyst are as follows: double acetonitrile chlorine
Change palladium 0.5-2.5 parts by weight, stannous chloride 40-70 parts by weight and ackd salt 30-60 parts by weight；Also, the catalyst with
The mass ratio of the carrier is 0.1%-2%:1.The present invention carries out preparation catalysis using the above-mentioned parts by weight of each component as a result,
Agent can be further improved the catalytic activity of the benzene catalyst processed.
According to a particular embodiment of the invention, the parts by weight of each component of the catalyst are as follows: double acetonitrile palladium chlorides
0.6-1.5 parts by weight, stannous chloride 45-65 parts by weight and ackd salt 30-45 parts by weight；Also, the catalyst with it is described
The mass ratio of carrier is 0.1%-2%:1.The present invention carries out preparing catalyst using the above-mentioned parts by weight of each component as a result,
It can be further improved the catalytic activity of the benzene catalyst processed.
According to a particular embodiment of the invention, the type for the ackd salt that the acetylene trimerization benzene catalyst uses not by
Especially limitation, those skilled in the art can select according to actual needs.Specific some embodiments according to the present invention, institute
Stating ackd salt is at least one of ferric trichloride, ammonium chloride or copper chloride.Further, the ackd salt is ammonium chloride and chlorine
Change the mixture of copper；Preferably, the mass ratio of the ammonium chloride in the ackd salt and copper chloride are as follows: 0.1-1:0.1-0.5.By
This, can be further improved reaction rate, reduce the reaction time, reduce production cost.
(3) ordered mesoporous material carrier is added in catalyst aqueous solution and is impregnated, it is then dry in air atmosphere, with
Afterwards after tabletting, being crushed and sieving, the loaded catalyst is obtained.
According to a particular embodiment of the invention, in step 3, time that the ordered mesoporous material carrier is impregnated are as follows:
6-12 hours；The condition that ordered mesoporous material carrier after dipping is dried are as follows: the 100-120 DEG C of dry 6- in air atmosphere
12 hours；The condition of the screening are as follows: be sized to 20-40 mesh.As a result, by the present invention in that ordered mesoporous material as load
Cyclotrimerization can be occurred with catalyzing acetylene and generate benzene for the loaded catalyst of body, and in reacting acetylene conversion ratio and benzene
Selectivity is higher, and the service life of catalyst is able to maintain that longer time, has a good application prospect；Meanwhile the present invention
Catalysis benzene reaction processed is carried out by the loaded catalyst, required reactive component is few, and required reaction condition is relatively mild, instead
Should quickly, simple process reduces production cost, and the benzene yield and purity that are prepared are higher, has single-minded product zone
Field selectivity is suitable for industrial amplification production.
According to another aspect of the present invention, the present invention also provides a kind of using above-mentioned acetylene trimerization benzene catalyst
The method of benzene processed, comprising the following steps:
(1) loaded catalyst is fitted into fixed bed reactors, by the loaded catalyst anti-before reaction
It answers nitrogen on device to purge, guarantees that reaction environment is in anhydrous and oxygen-free state.According to a particular embodiment of the invention, step (1)
In, the time of the nitrogen purging is 20 minutes.
(2) using mixed with the acetylene of nitrogen as reaction gas, with acetylene volume space velocity 200-3000h-1Flow velocity be passed into
In fixed bed reactors, contact it with the loaded catalyst, and 150-300 DEG C at a temperature of, carry out acetylene trimerization
Benzene reaction processed.According to a particular embodiment of the invention, in step (2), mixed with the concrete component of the acetylene of nitrogen are as follows: 10-50% body
Product acetylene and 50-90% volume nitrogen.Thus, it is possible to further increase the yield and selectivity for the benzene being prepared.As a result, originally
It is raw with catalyzing acetylene cyclotrimerization can to occur for invention by using the loaded catalyst using ordered mesoporous material as carrier
At benzene, and in reaction, the conversion ratio of acetylene and the selectivity of benzene are higher, and the service life of catalyst is able to maintain that longer time,
It has a good application prospect；Meanwhile the present invention carries out catalysis benzene processed by the loaded catalyst and reacts, required reaction group
Divide less, required reaction condition is relatively mild, rapid reaction, simple process, and the benzene for reducing production cost, and being prepared produces
Rate and purity are higher, with single-minded product area selectivity, are suitable for industrial amplification production.
Embodiment 1
The preparation of supported catalyst
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 3 mg, 700 mg of stannous chloride, 297 mg of ferric trichloride are weighed, and are mixed uniformly, configuration 50mL is urged
Agent aqueous solution, makes it be uniformly dispersed after ultrasound.Weigh the SBA-15 mesopore molecular sieve room temperature etc. that 50 grams of roasting pretreatments are crossed
Volume, which is added in catalyst aqueous solution, to be impregnated 6 hours, then 120 degrees Celsius of dryings load to obtain the final product in 12 hours in air atmosphere again
Catalyst.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 70%, the selectivity of benzene is 82%.
Embodiment 2
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, 201 mg of ammonium chloride, 90 mg of copper chloride are weighed, and are mixed
It is even, 50mL catalyst aqueous solution is configured, so that it is uniformly dispersed after ultrasound.It is mesoporous to weigh the SBA-15 that 50 grams of roasting pretreatments are crossed
Molecular sieve room temperature, which is added in equal volume in catalyst aqueous solution, to be impregnated 6 hours, then 120 degrees Celsius of dryings 12 in air atmosphere again
Hour is up to supported catalyst.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reaction
Gas space velocity is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control, reaction 4 in experiment
As a child sampling was using gas chromatograph detection product afterwards, and conversion of alkyne 77%, the selectivity of benzene is 84%.
Embodiment 3
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, 297 mg of ammonium chloride are weighed, and are mixed uniformly, configuration 50mL catalysis
Agent aqueous solution, makes it be uniformly dispersed after ultrasound.Weigh the bodies such as the MCM-41 mesopore molecular sieve room temperature that 50 grams of roasting pretreatments are crossed
Product, which is added in catalyst aqueous solution, to be impregnated 6 hours, and then 120 degrees Celsius of dryings are urged for 12 hours in air atmosphere up to load again
Agent.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 20% C will be passed through2H2+80%N2The reaction gas of (volume composition), reaction
Gas space velocity is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control, reaction 4 in experiment
As a child sampling was using gas chromatograph detection product afterwards, and conversion of alkyne 86%, the selectivity of benzene is 80%.
Embodiment 4
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, 297 mg of copper chloride are weighed, and are mixed uniformly, configuration 50mL catalysis
Agent aqueous solution, makes it be uniformly dispersed after ultrasound.Weigh the MCM-41 mesoporous molecular and 25 grams of roastings that 25 grams of roasting pretreatments are crossed
Pretreated MCM-41 mesopore molecular sieve, is mixed rear room temperature and is added in catalyst aqueous solution in equal volume and impregnate 6 hours,
Then again in air atmosphere 120 degrees Celsius of dryings 12 hours up to supported catalyst.Through tabletting, it is crushed and sieves as 20-40 mesh
It is spare afterwards.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 20% C will be passed through2H2+80%N2The reaction gas of (volume composition), reaction
Gas space velocity is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control, reaction 4 in experiment
As a child sampling was using gas chromatograph detection product afterwards, and conversion of alkyne 81%, the selectivity of benzene is 70%.
Embodiment 5
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, 150 mg of ammonium chloride, 150 mg of ferric trichloride are weighed, and are mixed
Uniformly, 50 mL catalyst aqueous solutions are configured, so that it is uniformly dispersed after ultrasound.Weigh the MCM-41 that 50 grams of roasting pretreatments are crossed
Mesopore molecular sieve room temperature, which is added in equal volume in catalyst aqueous solution, impregnates 6 hours, then again in air atmosphere 120 degrees Celsius it is dry
Dry 12 hours up to supported catalyst.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 20%C will be passed through2H2+80%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 82%, the selectivity of benzene is 74%.
Embodiment 6
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, ammonium chloride 110 mg, ferric trichloride 110mg, copper chloride 75mg are weighed, and
It is mixed uniformly, configures 50mL catalyst aqueous solution, so that it is uniformly dispersed after ultrasound.Weigh what 50 grams of roasting pretreatments were crossed
MCM-41 mesopore molecular sieve room temperature, which is added in equal volume in catalyst aqueous solution, impregnates 6 hours, then 120 takes the photograph in air atmosphere again
Family name's degree dry 12 hours up to supported catalyst.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 20%C will be passed through2H2+80%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 64%, the selectivity of benzene is 79%.
Comparative example 1
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 297 mg of ammonium chloride are weighed, and are mixed uniformly, 50mL catalyst aqueous solution are configured, through ultrasound
After so that it is uniformly dispersed.It weighs the SBA-15 mesopore molecular sieve room temperature that 50 grams of roasting pretreatments are crossed and is added to catalyst water in equal volume
Impregnate 6 hours in solution, then again in air atmosphere 120 degrees Celsius drying 12 hours up to supported catalyst.Through tabletting, it is crushed
And it is spare after 20-40 mesh for sieving.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 10 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 61%, the selectivity of benzene is 21%.
It can to sum up state, when being added without stannous chloride in reaction, the reaction time is increased to 10 hours, not only second alkyne conversion
Rate reduces, and the selectivity of benzene can degradation.
Comparative example 2
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride are weighed, and are mixed uniformly, 50mL catalyst aqueous solution are configured, through super
It is set to be uniformly dispersed after sound.It weighs the SBA-15 mesopore molecular sieve room temperature that 50 grams of roasting pretreatments are crossed and is added to catalyst in equal volume
Impregnate 6 hours in aqueous solution, then again in air atmosphere 120 degrees Celsius drying 12 hours up to supported catalyst.Through tabletting, break
Broken and screening is spare after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 3 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 37%, the selectivity of benzene is 95%.
It can to sum up state, when ackd salt is not added in system, reaction detected product after 3 hours, although the selectivity of benzene is still
It is higher, but the conversion ratio of acetylene substantially reduces.
Comparative example 3
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius to be down to room temperature after roasting 6 hours spare, then successively
Double acetonitrile palladium chloride 10 mg, 700 mg of stannous chloride, 297 mg of ammonium chloride are weighed, and are mixed uniformly, configuration 50mL catalysis
Agent aqueous solution, makes it be uniformly dispersed after ultrasound.Weigh the bodies such as the SBA-15 mesopore molecular sieve room temperature that 50 grams of roasting pretreatments are crossed
Product, which is added in catalyst aqueous solution, to be impregnated 6 hours, and then 120 degrees Celsius of dryings are urged for 12 hours in air atmosphere up to load again
Agent.Through tabletting, it is broken and after sieving as 20-40 mesh it is spare.
Acetylene benzene reaction evaluating
Acetylene preparation reaction carries out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactor, reaction pressure
Normal pressure.2g supported catalyst is fitted into fixed bed reactors, by catalyst, nitrogen purges 20 points on reaction unit before reaction
Clock makes reaction environment guarantee anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reaction gas
Body air speed is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 1 is small
When after sampling using gas chromatograph detect product, conversion of alkyne 45%, the selectivity of benzene is 69%.
Can to sum up state, when reacted between it is too short if, the conversion ratio of benzene can also reduce, and the selectivity of benzene can be slightly worse, centainly
Reaction time facilitate the promotion of conversion ratio.
Inventors have found that passing through the present invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization can occur with catalyzing acetylene and generate benzene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the service life of catalyst is able to maintain that longer time, is suitable for
Industrial amplification production；Meanwhile the present invention carries out catalysis benzene processed by the loaded catalyst and reacts, required reactive component
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, and temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fastly
Speed, simple process reduce production cost, and can be realized higher conversion of alkyne and benzene selective, have good
Application prospect.
The present invention is described in detail above, principle and embodiment of the embodiment to the application used herein
It is expounded, the description of the example is only used to help understand the method for the present application and its core ideas；Meanwhile for
Those of ordinary skill in the art have change according to the thought of the application in specific embodiments and applications
Place, in conclusion the contents of this specification should not be construed as limiting the present application.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (9)
1. a kind of acetylene trimerization benzene catalyst, the catalyst is the supported catalyst using ordered mesoporous material as carrier
Agent, which is characterized in that the catalyst includes following components: double acetonitrile palladium chlorides, stannous chloride and ackd salt, wherein each group
The parts by weight divided are as follows: double acetonitrile palladium chloride 0.1-3 parts by weight, stannous chloride 25-70 parts by weight and ackd salt 27-75 weight
Part；Also, the mass ratio of the catalyst and the carrier is 0.1%-2%:1,
The ackd salt is at least one of ferric trichloride, ammonium chloride or copper chloride.
2. acetylene trimerization benzene catalyst as described in claim 1, which is characterized in that the ordered mesoporous material is SBA-15
Or at least one of MCM-41 mesopore molecular sieve.
3. acetylene trimerization benzene catalyst as claimed in claim 2, which is characterized in that ammonium chloride and chlorination in the ackd salt
The mass ratio of copper are as follows: 0.1-1:0.1-0.5.
4. a kind of preparation method of acetylene trimerization benzene catalyst as claimed in any one of claims 1-3, which is characterized in that
The following steps are included:
(1) ordered mesoporous material is roasted in nitrogen atmosphere, after its cooling, is put into drier spare as carrier；
(2) acid of double acetonitrile palladium chlorides of 0.1-3 parts by weight, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight is weighed
Property salt, and be mixed uniformly, configuration obtains catalyst aqueous solution, and ultrasonic treatment makes it be uniformly dispersed；
(3) ordered mesoporous material carrier is added in catalyst aqueous solution and is impregnated, it is then dry in air atmosphere, it is passed through after
After crossing tabletting, being crushed and sieve, the loaded catalyst is obtained.
5. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 4, which is characterized in that described to have in step 1
Sequence mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieve, and described be roasted to roasts at 700-800 DEG C
2-4 hours.
6. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 4, which is characterized in that in step 3, the leaching
The time of stain is 6-12 hours.
7. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 4, which is characterized in that in step 3, the sieve
It is divided into and is sized to 20-40 mesh.
8. a kind of method using acetylene trimerization benzene catalyst benzene as claimed in any one of claims 1-3, feature
It is, comprising the following steps:
(1) loaded catalyst is fitted into fixed bed reactors, fills the loaded catalyst in reaction before reaction
Nitrogen purging is set, guarantees that reaction environment is in anhydrous and oxygen-free state；
(2) using mixed with the acetylene of nitrogen as reaction gas, with acetylene volume space velocity 200-3000h-1Flow velocity be passed into fixation
Bed reactor in, contact it with the loaded catalyst, and 150-300 DEG C at a temperature of, carry out acetylene trimerization benzene
Reaction.
9. method according to claim 8, which is characterized in that in step (2), specifically included mixed with the acetylene of nitrogen: 10-
50% volume acetylene and 50-90% volume nitrogen.
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