CN107042120A - 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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Abstract
The invention belongs to chemical technology field, 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 as carrier using ordered mesoporous material, and the catalyst includes following components：Double acetonitrile palladium chlorides, stannous chloride and ackd salt, wherein, the parts by weight of each above-mentioned component of the catalyst are：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 to loaded catalyst of the ordered mesoporous material as carrier, cyclotrimerization generation benzene can occur with catalyzing acetylene, and the conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the life-span of catalyst is able to maintain that longer time, suitable for industrial amplification production, there is good market application foreground.
Description
Technical field
The invention belongs to chemical technology field, and in particular to a kind of acetylene trimerization benzene catalyst and preparation method thereof and should
With.
Background technology
The light aromatics such as benzene, toluene and dimethylbenzene (three is referred to as BTX) extensively should as most basic Organic Chemicals
For producing the chemical products such as rubber, fiber, plastics, dyestuff.At present, in traditional handicraft, aromatic hydrocarbons is mainly derived from oil
Catalytic reforming and hydrocarbon cracking in work, account for the 90% of aromatic hydrocarbon resource, and only about 10% aromatic hydrocarbons derives from coal chemical industry.But
It is that preparing aromatic hydrocarbons using traditional handicraft has problems with：On the one hand, because petroleum resources in recent years are gradually decreased, cause
The cost of 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 of exploitation 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 has high reactivity, and its cyclotrimerization is thermodynamically strongly exothermic, can pass through catalysis
Agent promotees to bring it about polymerisation to prepare benzene.In the prior art, Tysoe et al. (J. Chem. Soc., Chem.
Commun. 1983,623) and Sesselmann et al. (Surf. Sci. 1983,135,128) has reported transition gold respectively
Belong to Pd has excellent acetylene cyclotrimerization performance at low temperature, it is found that acetylene is adsorbed in Pd at a temperature of 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, there is following defect in the technology：Catalyst needs single crystal forms, and needs to react under condition of ultralow temperature, and technique is set
Standby cost is higher, it is difficult to industrialize；The yield of benzene is too low, and only only 30%, gather while being likely to form four during the course of the reaction
Thing, pentamer, polymer etc..It is high that Xu Lei et al. (CA201510864201, CA201510860897) reports a kind of support type
Scattered palladium, ruthenium, rhodium composite transition metal catalyst, conversion ratio of the acetylene under constant-pressure and high-temperature greatly improve (up to 100%), together
When improve the selectivity (up to 82.2%) of benzene.But, there is following defect in this method：The life-span of catalyst is shorter, can only
The activity of several hours of maintenance；Catalyst mithridatism is poor, and the purity requirement to acetylene gas is very high, is unfavorable for industrialized reality
Apply.At present, the acetylene benzene of open report, which reacts, has above-mentioned drawback, such as severe reaction conditions need HTHP, 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
Go out a kind of raising conversion of alkyne and benzene selective, extension catalyst life, the benzene catalyst processed suitable for large-scale production come
Occurs cyclotrimerization generation benzene for catalyzing acetylene, as current urgent problem.
The content of the invention
For problems of the prior art, the invention provides a kind of acetylene trimerization benzene catalyst and its preparation side
Method and application, can be with catalyzing acetylene initial ring trimerization by using the loaded catalyst using ordered mesoporous material as carrier
Reaction generation benzene, and reaction in acetylene conversion ratio and benzene selectivity it is higher, and catalyst life-span be able to maintain that it is longer
Time, it is adaptable to industrial amplification production, have good market application foreground.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
The invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is to be used as carrier using ordered mesoporous material
Loaded catalyst, it is characterised in that the catalyst includes following components：Double acetonitrile palladium chlorides, stannous chloride and ackd salt,
Wherein, the parts by weight of each component are：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.
Inventor has found, the invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, passes through
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization generation benzene can occur with catalyzing acetylene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the life-span of catalyst is able to maintain that longer time, it is adaptable to
Industrial amplification production；Meanwhile, the present invention carries out being catalyzed benzene reaction processed, required reactive component by the loaded catalyst
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fast
Speed, technique is simple, reduces production cost, and can realize higher conversion of alkyne and benzene selective, with 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, the mass ratio of ammonium chloride and copper chloride is in the ackd salt：0.1-1:
0.1-0.5。
Meanwhile, present invention also offers the preparation method of above-mentioned acetylene trimerization benzene catalyst, it is characterised in that including
Following steps：
（1）Ordered mesoporous material is calcined in nitrogen atmosphere, after after its cooling, is put into standby as carrier in drier；
（2）Weigh the acid of the double acetonitrile palladium chlorides, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight of 0.1-3 parts by weight
Property salt, and be mixed uniform, configuration obtains aqueous catalyst solution, ultrasonically treated it is uniformly dispersed；
（3）Ordered mesoporous material carrier is added in aqueous catalyst solution and impregnated, then dries, is passed through after in air atmosphere
Cross tabletting, it is broken and after sieving, obtain the loaded catalyst.
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 is calcined 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, present invention also offers the method for above-mentioned acetylene trimerization benzene catalyst benzene, it is characterised in that including
Following steps：
（1）The loaded catalyst is fitted into fixed bed reactors, filled the loaded catalyst in reaction before reaction
Put nitrogen purging, it is ensured 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
In bed reactor, it is contacted with the loaded catalyst, and at a temperature of 150-300 DEG C, carry out acetylene trimerization benzene
Reaction.
According to a particular embodiment of the invention, step（2）In, 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 invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, the orderly of the present invention is used
Mesoporous material loaded catalyst, catalyzing acetylene occurs in cyclotrimerization generation benzene, the conversion ratio of acetylene and the selectivity of benzene
It is higher, and the life-span of catalyst be able to maintain that longer time, it is adaptable to industrial amplification production, there is good market to apply
Prospect.
（2）The invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, use the present invention's
Ordered mesoporous material loaded catalyst, catalyzing acetylene occurs in cyclotrimerization generation benzene, and required reactive component is few, only
Nitrogen and acetylene, required reaction condition are relatively mild, and temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is quick, technique
Simply, production cost is reduced, and higher conversion of alkyne and benzene selective can be realized, before good application
Scape.
（3）The invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, using order mesoporous
Material load type catalyst, the composition of the catalyst is simple, is readily available, and in catalyst large surface carrier to active component
Form preferably scattered.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For can be by the conventional products of acquisition purchased in market.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implies relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, define " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".In the description of the invention,
" multiple " are meant that two or more, unless otherwise specifically defined.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " connected ", " connection ", " fixation " etc.
Term should be interpreted broadly, for example, it may be fixedly connected or be detachably connected, or integrally；Can be that machinery connects
Connect or electrically connect；Can be joined directly together, can also be indirectly connected to by intermediary, can be in two elements
The connection in portion or the interaction relationship of two elements.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 invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is
Using loaded catalyst of the 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
Alkyne reaction generates the neccessary composition of benzene；Stannous chloride can improve benzene as co-catalyst by being incorporated stannous chloride
Selectivity, reduces the generation of impurity；And ackd salt can further improve reaction rate, the reaction time is reduced, reduction is produced into
This.The parts by weight of each above-mentioned component of the catalyst are：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 is using loaded catalyst of the ordered mesoporous material as carrier, and the composition of the catalyst is simple, is readily available,
And large surface carrier forms preferably scattered to active component in catalyst.
Inventor has found, the invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, passes through
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization generation benzene can occur with catalyzing acetylene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the life-span of catalyst is able to maintain that longer time, it is adaptable to
Industrial amplification production；Meanwhile, the present invention carries out being catalyzed benzene reaction processed, required reactive component by the loaded catalyst
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fast
Speed, technique is simple, reduces production cost, and can realize higher conversion of alkyne and benzene selective, with good
Application prospect.
According to a particular embodiment of the invention, the species for the ackd salt that the acetylene trimerization benzene catalyst is used not by
Especially limitation, those skilled in the art can be selected according to actual needs.According to some specific embodiments of the invention, institute
It is at least one of ferric trichloride, ammonium chloride or copper chloride to state ackd salt.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 is：0.1-1: 0.1-0.5；It is preferred that, institute
The mass ratio for stating the ammonium chloride in ackd salt and copper chloride is：0.9-1：0.4-0.5.Thus, it is possible to further improve reaction speed
Rate, reduces the reaction time, reduces production cost.
According to a particular embodiment of the invention, the species for the ordered mesoporous material that the acetylene trimerization benzene catalyst is used
It is not particularly restricted, those skilled in the art can be selected according to actual needs.According to some specific realities of the invention
Example is applied, the ordered mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieves.Thus, it is possible to significantly improve
The catalytic activity of the benzene catalyst processed.
Meanwhile, the invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is to use ordered mesoporous material
As the loaded catalyst of carrier, the parts by weight of each component of the catalyst are：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 chlorides are benzene catalyst processed
Main active, is the neccessary composition that benzene catalyst acetylene reaction processed generates benzene；Stannous chloride can be used as co-catalysis
Agent, can improve the selectivity of benzene by being incorporated stannous chloride, reduce the generation of impurity；And ackd salt can be improved further instead
Speed is answered, the reaction time is reduced, production cost is reduced.Thus, the present invention uses the above-mentioned parts by weight system of each component
Standby catalyst, can further improve the catalytic activity of the benzene catalyst processed.
Meanwhile, the invention provides a kind of acetylene trimerization benzene catalyst, the catalyst is to use ordered mesoporous material
As the loaded catalyst of carrier, the parts by weight of each component of the catalyst are：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 chlorides are benzene catalyst processed
Main active, is the neccessary composition that benzene catalyst acetylene reaction processed generates benzene；Stannous chloride can be used as co-catalysis
Agent, can improve the selectivity of benzene by being incorporated stannous chloride, reduce the generation of impurity；And ackd salt can be improved further instead
Speed is answered, the reaction time is reduced, production cost is reduced.Thus, the present invention uses the above-mentioned parts by weight system of each component
Standby catalyst, can further improve the catalytic activity of the benzene catalyst processed.
According to another aspect of the present invention, present invention also offers a kind of system of above-mentioned acetylene trimerization benzene catalyst
Preparation Method, comprises the following steps：
（1）Ordered mesoporous material is calcined in nitrogen atmosphere, after after its cooling, is put into standby as carrier in drier.
According to a particular embodiment of the invention, the species for the ordered mesoporous material that the acetylene trimerization benzene catalyst is used
It is not particularly restricted, those skilled in the art can be selected according to actual needs.According to some specific realities of the invention
Example is applied, the ordered mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieves.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 calcined is as follows：It is described orderly
Mesoporous material is calcined 2-4 hours at 700-800 DEG C, and then, the cooling is to be down to less than 100 DEG C.
（2）Weigh the double acetonitrile palladium chlorides, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight of 0.1-3 parts by weight
Ackd salt, and be mixed uniform, configuration obtains aqueous catalyst solution, ultrasonically treated it is uniformly dispersed.
The present invention is prepared in the method for acetylene trimerization benzene catalyst, and the catalyst is to use 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 generation benzene it is necessary into
Point；Stannous chloride can improve the selectivity of benzene by being incorporated stannous chloride, reduce the life of impurity as co-catalyst
Into；And ackd salt can further improve reaction rate, the reaction time is reduced, production cost is reduced.Thus, the present invention is used and had
Sequence mesoporous material is as the loaded catalyst of carrier, and the composition of the catalyst simply, is readily available, and big table in catalyst
Face carrier forms preferably scattered to active component.
According to a particular embodiment of the invention, the parts by weight of each above-mentioned component of the catalyst are：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 each above-mentioned component of the catalyst are：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.Thus, the present invention carries out preparation catalysis using the above-mentioned parts by weight of each component
Agent, can further improve 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：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.Thus, the present invention prepares catalyst using the above-mentioned parts by weight progress of each component,
The catalytic activity of the benzene catalyst processed can further be improved.
According to a particular embodiment of the invention, the species for the ackd salt that the acetylene trimerization benzene catalyst is used not by
Especially limitation, those skilled in the art can be selected according to actual needs.According to some specific embodiments of the invention, institute
It is at least one of ferric trichloride, ammonium chloride or copper chloride to state ackd salt.Further, the ackd salt is ammonium chloride and chlorine
Change the mixture of copper；It is preferred that, the mass ratio of ammonium chloride and copper chloride in the ackd salt is：0.1-1: 0.1-0.5.By
This, can further improve reaction rate, reduce the reaction time, reduce production cost.
（3）Ordered mesoporous material carrier is added in aqueous catalyst solution and impregnated, is then dried in air atmosphere, with
Afterwards by tabletting, broken and after sieving, the loaded catalyst is obtained.
According to a particular embodiment of the invention, in step 3, the time that the ordered mesoporous material carrier is impregnated is：
6-12 hours；The condition that ordered mesoporous material carrier after dipping is dried is：The 100-120 DEG C of dry 6- in air atmosphere
12 hours；The condition of the screening is：It is sized to 20-40 mesh.Thus, by the present invention in that being used as load to ordered mesoporous material
The loaded catalyst of body, can occur cyclotrimerization generation benzene with catalyzing acetylene, and in reaction acetylene conversion ratio and benzene
Selectivity is higher, and the life-span of catalyst is able to maintain that longer time, with good application prospect；Meanwhile, the present invention
Carry out being catalyzed benzene reaction processed by the loaded catalyst, required reactive component is few, and required reaction condition is relatively mild, instead
Should be quick, technique is simple, reduces production cost, and the benzene yield and purity that prepare are higher, with single-minded product zone
Field selectivity, it is adaptable to industrial amplification production.
According to another aspect of the present invention, above-mentioned acetylene trimerization benzene catalyst is used present invention also offers a kind of
The method of benzene processed, comprises the following steps：
（1）The loaded catalyst is fitted into fixed bed reactors, filled the loaded catalyst in reaction before reaction
Put nitrogen purging, it is ensured that reaction environment is in anhydrous and oxygen-free state.According to a particular embodiment of the invention, step（1）In, institute
The time for stating 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, it is contacted with the loaded catalyst, and at a temperature of 150-300 DEG C, carry out acetylene trimerization
Benzene reaction processed.According to a particular embodiment of the invention, step（2）In, the concrete component mixed with the acetylene of nitrogen is：10-50% bodies
Product acetylene and 50-90% volume nitrogen.Thus, it is possible to further improve the yield and selectivity of the benzene prepared.Thus, originally
By using the loaded catalyst using ordered mesoporous material as carrier cyclotrimerization life can occur with catalyzing acetylene for invention
The conversion ratio of acetylene and the selectivity of benzene are higher into benzene, and reaction, and the life-span of catalyst is able to maintain that longer time,
With good application prospect；Meanwhile, the present invention carries out being catalyzed benzene reaction processed, required reaction group by the loaded catalyst
Divide few, required reaction condition is relatively mild, reaction is quick, technique is simple, reduce production cost, and the benzene prepared is produced
Rate and purity are higher, with single-minded product area selectivity, it is adaptable to industrial amplification production.
Embodiment 1
The preparation of supported catalyst
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 3, the mg of stannous chloride 700, the mg of ferric trichloride 297, and it is mixed uniform, configuration 50mL catalyst
The aqueous solution, makes it be uniformly dispersed after ultrasound.The SBA-15 mesopore molecular sieve normal temperature that 50 grams of roasting pretreatments of weighing are crossed is isometric
It is added in aqueous catalyst solution and impregnates 6 hours, then 120 degrees Celsius of dryings produces supported catalyst in 12 hours in air atmosphere again
Agent.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 70%, and the selectivity of benzene is 82%.
Embodiment 2
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, the mg of ammonium chloride 201, the mg of copper chloride 90, and be mixed uniformly, match somebody with somebody
50mL aqueous catalyst solutions are put, it is uniformly dispersed after ultrasound.Weigh the SBA-15 mesoporous moleculars that 50 grams of roasting pretreatments are crossed
Sieve normal temperature is added in aqueous catalyst solution in equal volume impregnates 6 hours, then 120 degrees Celsius of dryings 12 hours in air atmosphere again
Produce supported catalyst.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 77%, and the selectivity of benzene is 84%.
Embodiment 3
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, the mg of ammonium chloride 297, and it is mixed uniform, configuration 50mL catalyst water
Solution, makes it be uniformly dispersed after ultrasound.The MCM-41 mesopore molecular sieve normal temperature that 50 grams of roasting pretreatments of weighing are crossed adds in equal volume
Enter into aqueous catalyst solution dipping 6 hours, then 120 degrees Celsius of dryings produce supported catalyst in 12 hours in air atmosphere again
Agent.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 20% C will be passed through2H2+80%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 86%, and the selectivity of benzene is 80%.
Embodiment 4
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, the mg of copper chloride 297, and it is mixed uniform, configuration 50mL catalyst water
Solution, makes it be uniformly dispersed after ultrasound.Weigh MCM-41 mesoporous moleculars and the pre- place of 25 grams of roastings that 25 grams of roasting pretreatments are crossed
The MCM-41 mesopore molecular sieves managed, are mixed rear normal temperature and are added to dipping 6 hours in aqueous catalyst solution in equal volume, then
120 degrees Celsius of dryings produce supported catalyst in 12 hours in air atmosphere again.Through tabletting, broken and sieve as 20-40 mesh standby
With.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 20% C will be passed through2H2+80%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 81%, and the selectivity of benzene is 70%.
Embodiment 5
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, the mg of ammonium chloride 150, the mg of ferric trichloride 150, and be mixed uniformly,
50 mL aqueous catalyst solutions are configured, it is uniformly dispersed after ultrasound.Weigh mesoporous point of the MCM-41 that 50 grams of roasting pretreatments are crossed
Son sieve normal temperature is added in aqueous catalyst solution in equal volume to be impregnated 6 hours, and then 120 degrees Celsius of dryings 12 are small in air atmosphere again
When produce supported catalyst.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 20%C will be passed through2H2+80%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 82%, and the selectivity of benzene is 74%.
Embodiment 6
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, ammonium chloride 110 mg, ferric trichloride 110mg, copper chloride 75mg, and by its
It is well mixed, 50mL aqueous catalyst solutions are configured, it is uniformly dispersed after ultrasound.Weigh the MCM- that 50 grams of roasting pretreatments are crossed
41 mesopore molecular sieve normal temperature are added in aqueous catalyst solution in equal volume to be impregnated 6 hours, then again 120 degrees Celsius in air atmosphere
Drying produces supported catalyst in 12 hours.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 20%C will be passed through2H2+80%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 4 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 64%, and the selectivity of benzene is 79%.
Comparative example 1
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of ammonium chloride 297, and uniform, configuration 50mL aqueous catalyst solutions are mixed, make after ultrasound
It is uniformly dispersed.The SBA-15 mesopore molecular sieve normal temperature that 50 grams of roasting pretreatments of weighing are crossed is added to aqueous catalyst solution in equal volume
Middle dipping 6 hours, then 120 degrees Celsius of dryings produce supported catalyst in 12 hours in air atmosphere again.Through tabletting, broken and sieve
It is divided into standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 10 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 61%, and the selectivity of benzene is 21%.
It can to sum up state, when being added without stannous chloride in reaction, the reaction time brings up to 10 hours, not only second alkyne conversion
Rate is reduced, and the selectivity of benzene can degradation.
Comparative example 2
By macro porous silica gel molecular sieve in nitrogen atmosphere 500 degrees Celsius of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, and it is mixed uniform, configuration 50mL aqueous catalyst solutions, after ultrasound
It is made to be uniformly dispersed.It is water-soluble that the SBA-15 mesopore molecular sieves normal temperature that 50 grams of roasting pretreatments of weighing are crossed is added to catalyst in equal volume
Impregnated 6 hours in liquid, then 120 degrees Celsius of dryings produce supported catalyst in 12 hours in air atmosphere again.Through tabletting, crush simultaneously
Sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 250 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 3 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 37%, and the selectivity of benzene is 95%.
It can to sum up state, when being not added with ackd salt in system, reaction detects 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 of roastings to be down to room temperature after 6 hours standby, then weigh successively
Double mg of acetonitrile palladium chloride 10, the mg of stannous chloride 700, the mg of ammonium chloride 297, and it is mixed uniform, configuration 50mL catalyst water
Solution, makes it be uniformly dispersed after ultrasound.The SBA-15 mesopore molecular sieve normal temperature that 50 grams of roasting pretreatments of weighing are crossed adds in equal volume
Enter into aqueous catalyst solution dipping 6 hours, then 120 degrees Celsius of dryings produce supported catalyst in 12 hours in air atmosphere again
Agent.Through tabletting, broken and sieve to be standby after 20-40 mesh.
Acetylene benzene reaction evaluating
Acetylene prepares reaction and carried out on fixed-bed reactor, uses internal diameter 28mm stainless steel reactors, reaction pressure normal pressure.
2g supported catalysts are fitted into fixed bed reactors, by catalyst, nitrogen is purged 20 minutes on reaction unit before reaction, is made
Reaction environment ensures anhydrous and oxygen-free state.Then 30%C will be passed through2H2+70%N2The reaction gas of (volume composition), reacting gas is empty
Speed is 600h-1, reaction temperature is 200 degrees Celsius.The flow of gas has mass flowmenter control in experiment, and reaction 1 was as a child
Sampling detects product using gas chromatograph afterwards, and conversion of alkyne is 45%, and 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 be reduced, and the selectivity of benzene can be slightly worse, necessarily
Reaction time contribute to the lifting of conversion ratio.
Inventor has found, the invention provides a kind of acetylene trimerization benzene catalyst and its preparation method and application, passes through
The loaded catalyst using ordered mesoporous material as carrier is used, cyclotrimerization generation benzene can occur with catalyzing acetylene, and
The conversion ratio of acetylene and the selectivity of benzene are higher in reaction, and the life-span of catalyst is able to maintain that longer time, it is adaptable to
Industrial amplification production；Meanwhile, the present invention carries out being catalyzed benzene reaction processed, required reactive component by the loaded catalyst
Lack, only nitrogen and acetylene, required reaction condition is relatively mild, temperature is at 150-300 degrees Celsius, and synthesis under normal pressure, reaction is fast
Speed, technique is simple, reduces production cost, and can realize higher conversion of alkyne and benzene selective, with good
Application prospect.
The present invention is described in detail above, used herein principle and embodiment of the embodiment to the application
It is set forth, the explanation of above example is only intended to help and understands the present processes and its core concept；Simultaneously for
Those of ordinary skill in the art, according to the thought of the application, have change in specific embodiments and applications
Place, in summary, this specification content should not be construed as the limitation to the 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 to combine specific features, structure, material or the spy that the embodiment or example are described
Point is contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the not be the same as Example or the feature of example and non-be the same as Example or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. a kind of acetylene trimerization benzene catalyst, the catalyst is the supported catalyst as carrier using ordered mesoporous material
Agent, it is characterised in that the catalyst includes following components：Double acetonitrile palladium chlorides, stannous chloride and ackd salt, wherein, each group
Point parts by weight be：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.
2. acetylene trimerization benzene catalyst as claimed in claim 1, it is characterised in that the ackd salt is ferric trichloride, chlorine
Change at least one of ammonium or copper chloride.
3. acetylene trimerization benzene catalyst as claimed in claim 1, it is characterised in that the ordered mesoporous material is SBA-15
At least one of or MCM-41 mesopore molecular sieves.
4. acetylene trimerization benzene catalyst as claimed in claim 2, it is characterised in that ammonium chloride and chlorine in the ackd salt
Change copper mass ratio be：0.1-1: 0.1-0.5.
5. a kind of preparation method of acetylene trimerization benzene catalyst as any one of claim 1-4, it is characterised in that
Comprise the following steps：
（1）Ordered mesoporous material is calcined in nitrogen atmosphere, after after its cooling, is put into standby as carrier in drier；
（2）Weigh the acid of the double acetonitrile palladium chlorides, the stannous chloride of 25-70 parts by weight and 27-75 parts by weight of 0.1-3 parts by weight
Property salt, and be mixed uniform, configuration obtains aqueous catalyst solution, ultrasonically treated it is uniformly dispersed；
（3）Ordered mesoporous material carrier is added in aqueous catalyst solution and impregnated, then dries, is passed through after in air atmosphere
Cross tabletting, it is broken and after sieving, obtain the loaded catalyst.
6. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 5, it is characterised in that described to have in step 1
Sequence mesoporous material is at least one of SBA-15 or MCM-41 mesopore molecular sieves, and described be roasted to is calcined at 700-800 DEG C
2-4 hours.
7. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 5, it is characterised in that in step 3, the leaching
The time of stain is 6-12 hours.
8. the preparation method of acetylene trimerization benzene catalyst as claimed in claim 5, it is characterised in that in step 3, the sieve
It is divided into and is sized to 20-40 mesh.
9. a kind of method of acetylene trimerization benzene catalyst benzene using as any one of claim 1-4, its feature
It is, comprises the following steps：
（1）The loaded catalyst is fitted into fixed bed reactors, filled the loaded catalyst in reaction before reaction
Put nitrogen purging, it is ensured 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
In bed reactor, it is contacted with the loaded catalyst, and at a temperature of 150-300 DEG C, carry out acetylene trimerization benzene
Reaction.
10. method as claimed in claim 9, it is characterised in that step（2）In, specifically included mixed with the acetylene of nitrogen：10-
50% volume acetylene and 50-90% volume nitrogen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570204A (en) * | 2017-09-18 | 2018-01-12 | 北京华福工程有限公司 | Acetylene ring trimerization benzene catalyst and its preparation method and application |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN115055201A (en) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498759A (en) * | 2015-12-01 | 2016-04-20 | 中国科学院大连化学物理研究所 | High-performance catalyst for preparation of benzene by cyclotrimerization of acetylene as well as preparation method and application thereof |
| CN105498757A (en) * | 2015-12-01 | 2016-04-20 | 中国科学院大连化学物理研究所 | Catalyst for preparation of benzene through cyclotrimerization of acetylene and preparation method of benzene |
-
2017
- 2017-05-26 CN CN201710381805.9A patent/CN107042120B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498759A (en) * | 2015-12-01 | 2016-04-20 | 中国科学院大连化学物理研究所 | High-performance catalyst for preparation of benzene by cyclotrimerization of acetylene as well as preparation method and application thereof |
| CN105498757A (en) * | 2015-12-01 | 2016-04-20 | 中国科学院大连化学物理研究所 | Catalyst for preparation of benzene through cyclotrimerization of acetylene and preparation method of benzene |
Non-Patent Citations (5)
| Title |
|---|
| CHARLES H. PATTERSON ET AL.: "Molecular Mechanisms In the Cyclotrlmerlzatlon of Acetylene to Benzene on Palladium (111)", 《THE JOURNAL OF PHYSICAL CHEMISTRY》 * |
| ZHE-PENG DENG ET AL.: "Acetylene cyclotrimerization catalyzed by PdCl2 and CuCl2 in the gas phase:A theoretical study", 《COMPUTATIONAL AND THEORETICAL CHEMISTRY》 * |
| 孙守恒等: "拨基钻簇合物催化苯乙炔三聚反应的研究", 《催化学报》 * |
| 程金生等: "一种温和高效的钯催化乙炔的环三聚", 《广州化学》 * |
| 鞠廷勇等: "Ni原子催化乙炔三聚环化反应机理的理论研究", 《化学研究与应用》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107570204A (en) * | 2017-09-18 | 2018-01-12 | 北京华福工程有限公司 | Acetylene ring trimerization benzene catalyst and its preparation method and application |
| CN113559924A (en) * | 2021-07-28 | 2021-10-29 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN113559924B (en) * | 2021-07-28 | 2023-10-03 | 绍兴七轩新材料科技有限公司 | Ionic liquid catalyst and preparation method and application thereof |
| CN115055201A (en) * | 2022-05-18 | 2022-09-16 | 汕尾职业技术学院 | Catalyst for preparing benzene through acetylene aromatization reaction and preparation and application thereof |
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