CN106268828B - Copper-based ester through hydrogenation carbon monoxide-olefin polymeric and its preparation method and application - Google Patents
Copper-based ester through hydrogenation carbon monoxide-olefin polymeric and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of copper-based ester through hydrogenation carbon monoxide-olefin polymerics and its preparation method and application, mainly solve the problems, such as that ester conversion rate in the prior art and alcohol are selectively lower.The copper-based ester through hydrogenation carbon monoxide-olefin polymeric that the present invention is prepared by using a kind of hydrogen plasma, including carrier and load active component on the carrier and auxiliary agent, the carrier is carbon material, the active component of load on the carrier is that the technical solution of copper and its preparation method and application preferably solves the above problem, be can be used in ester through hydrogenation.
Description
Technical field
The present invention relates to a kind of copper-based ester through hydrogenation carbon monoxide-olefin polymerics and its preparation method and application.
Background technique
Alcohol has important economic value, is widely used today as clean gasoline additive, liquid fuel, for oil product, change
Work raw materials for production etc..Wherein, higher alcohol serves not only as surfactant, anti emulsifier, dye dispersant, dehydrating agent, work
Industry detergent, but also as plasticizer, oil extraction agent, wetting agent, fragrance etc..The method of industrial production alcohol at present
Mainly there are alkene hydration method, carbonylation of olefin method and enester hydrogenation method.
The representative art of alkene hydration method is the cyclohexene hydration cyclohexanol technique of Japanese Asahi Kasei Corporation, the technology
It realizes and industrializes in nineteen ninety.When preparing alcohol using alkene hydration method, although having reaction selectivity high, three wastes discharge amount is low
Advantage, but that there are reaction pressures is high, reaction equilibrium conversion is very low, water alkene is than high, higher to cyclohexene purity requirement, phase
The deficiencies of equipment investment answered is big, separating energy consumption is high.For example, when using high silica ZSM-5 catalyst as catalyst for hydration of olefines,
When stopping 2h in two series connection slurry reactors, the conversion ratio of cyclohexene only has 12.5%.
The process of carbonylation of olefin method synthol includes homogeneous hydrogenation formylation aldehyde and aldehyde heterogeneous hydrogenation synthol
Two steps.Wherein, for homogeneous hydrogenation formylation aldehyde using noble metal as catalyst, reaction condition is more harsh, the conversion ratio of reaction
It is lower with selectivity.For example, in the method that carbonylation of olefin prepares aldehyde disclosed in the US5312996, using butadiene as raw material, rhodium
(Rh) catalyst, H are used as2Molar ratio with CO is 1:1, and reaction temperature is 95 DEG C, pressure 500psi, target product hexandial
Yield less than 20%, and in embodiment under optimal conditions, yield is still below 30%.It is made disclosed in CN1193954A
In the method for standby linear chain aldehyde, olefine, hydrogen and carbon monoxide are carried out to add hydrogen first in the organic solvent dissolved with catalyst
Acylation reaction produces linear chain aldehyde, and the catalyst contains the platinum compounds for being halogen-free anion, two tooth diaryl phosphins, abutment two
Luxuriant iron-based and acid assistant；Studies have shown that the conversion ratio of hexene is about when reaction pressure is 1000psi, temperature is 100 DEG C
30%, selectivity needs to add less than 90%, and in reaction process a large amount of solvent, therefore subsequent product separation process is complicated
And energy consumption is big, it is unfavorable to use industrialized production.
Enester hydrogenation method is divided into esterification and adds two step of hydrogen, and alkene and acid generate ester through esterification first, then to ester into
Row hydrogenation synthesis alcohol.The conversion ratio and selectivity that the reaction condition of this method is mild, reacts are high, and atom utilization is almost
100%, there is good industrial value.Wherein, the process of ester through hydrogenation synthol mostly uses Cu series catalysts, while addition helps
Agent increases its activity and stability.When being free of auxiliary agent in catalyst, catalytic activity is often lower, main reason is that catalyst
Preparation process needs to convert copper oxide for copper nitrate by high-temperature roasting, obtains the presoma of catalyst.It is high when without auxiliary agent
Temperature roasting easily leads to the active copper species sintering of catalyst, nanograin growth, to reduce catalytic activity.It is urged to improve
To change activity and needs to add auxiliary agent, for auxiliary agent based on Cr, Ba etc., the Cu-Cr such as by the exploitation of ARCO company, the U.S. is serial,
Poppehdof exploitation adds hydrogen to show preferable effect oxalate using Cu-Cr component as catalyst body.However,
These auxiliary agents have very big toxicity, and the preparation process of catalyst will cause serious environmental pollution.In view of environmental protection requirement,
The selection of auxiliary agent is of great significance.
Summary of the invention
The first technical problem to be solved by the present invention is ester conversion rate and the selectively lower problem of alcohol in the prior art,
A kind of new copper-based ester through hydrogenation carbon monoxide-olefin polymeric is provided.The composition has the advantages that ester conversion rate and alcohol are selectively higher.
The second technical problem to be solved by the present invention is to provide one kind and urges with the corresponding copper-based ester through hydrogenation of one of technical problem is solved
The preparation method of agent composition.The third technical problem to be solved by the present invention is to provide a kind of one of and solution technical problem
The application of corresponding copper-based ester through hydrogenation carbon monoxide-olefin polymeric.
One of in order to solve the above problem, The technical solution adopted by the invention is as follows: a kind of copper-based ester through hydrogenation catalyst combination
Object including carrier and loads active component on the carrier and auxiliary agent, and the carrier is carbon material, is supported on the load
Active component on body is copper, and the auxiliary agent is zinc；Wherein, the carbon material be multi-walled carbon nanotube, mesoporous carbon, active carbon with
And at least one of carbon nano-fiber；The total weight of the copper-based ester through hydrogenation catalyst prepared with the hydrogen plasma is
Benchmark, the mass content of active component are 5~30%, and the mass content of adjuvant component is 5~30%.
In above-mentioned technical proposal, it is preferable that the carbon material is multi-walled carbon nanotube.
In order to solve the above problem two, The technical solution adopted by the invention is as follows: a kind of copper-based ester through hydrogenation catalyst combination
The preparation method of object, comprising the following steps:
(1) mantoquita crystal, zinc salt crystal and processed carbon material carrier are weighed according to catalyst composition and ratio, according to etc.
Mantoquita crystal, zinc salt crystal are dissolved in deionized water by volume impregnation method, and obtained solution is uniformly mixed with carbon material carrier,
It is dried after standing 5~20 hours；
(2) powder sample after drying is placed in the dielectric barrier plasma discharge region of reactor, is first passed through lazy
Air in property gas displacement reactor, then passes to hydrogen/inert gas gaseous mixture, in plasma after 0.5~2 hour
Apply high-voltage electricity between electrode to carry out discharge treatment 0.1~5 hour, obtains catalyst solid powder；
(3) resulting solid powder is formed, obtains carbon material supported copper-based ester through hydrogenation catalyst.
In above-mentioned technical proposal, it is preferable that in step (1), mantoquita is copper nitrate, and zinc salt is zinc nitrate, by salting liquid with
Carbon material carrier uniformly mixes, and stands 5~20 hours at room temperature, is placed in oven and dried, and drying temperature is 30~150
DEG C, drying time is 5~25 hours；For carbon material carrier using drying after the preceding processing with acid, the acid is nitric acid.
In above-mentioned technical proposal, it is preferable that inert gas described in step (2) is nitrogen, helium, at least one in argon gas
Kind；The volume fraction of hydrogen is 0.1~20% in gaseous mixture.
In above-mentioned technical proposal, it is preferable that the reactor material is quartz.
In above-mentioned technical proposal, it is preferable that the mass ratio of nitric acid and carbon material carrier is 0.65~1.65:1；It is described it is equal from
The discharge power of daughter is 20~200W.
In order to solve the above problem three, The technical solution adopted by the invention is as follows: a kind of copper-based ester through hydrogenation catalyst combination
It is corresponding to be carried out hydrogenation reaction production using the copper-based ester through hydrogenation carbon monoxide-olefin polymeric by the application of object for ester type compound
Alcohol；The ester type compound is 1,4- cyclohexyl dicarboxylic acid dimethyl ester, sec-butyl acetate, cyclohexyl acetate, ethyl acetate, length
At least one of chain fatty acid methyl esters, dimethyl oxalate, dimethyl adipate and terephthalate.
In above-mentioned technical proposal, it is preferable that the process conditions of ester through hydrogenation are as follows: reaction temperature is 150-300 DEG C；Reaction pressure
For 3-9MPa；The mass space velocity of reaction raw materials is 0.2-0.8h-1；Hydrogen ester molar ratio is 30-300:1.
In above-mentioned technical proposal, it is preferable that a length of C4-C6 of chain of long chain fatty acids in the long chain fatty acids methyl esters.
In the present invention, the content of the active component is in terms of the oxide of active metal.The present invention is to by isometric
Salting liquid and the mixed uniformly specific method of carbon material carrier are not had specific limitation by infusion process.For example, salting liquid can be dripped
It adds on carbon material carrier, carbon material carrier can also be mixed into salting liquid.Simultaneously to salting liquid and the uniform mixed process of carrier
There is no specific limitation, can uniformly be mixed by way of stirring, can also be mixed by ultrasonic wave.The present invention to salting liquid with
The mixed drying process of carbon material carrier does not have specific limitation.It is dry that it is, for example, possible to use a conventional ovens, it is possible to use vacuum
Oven drying.
Ester through hydrogenation catalyst is generally traded and is stored in the form of precursor, although ester through hydrogenation catalyst precarsor cannot be straight
Catalysis reaction is connect, however ester through hydrogenation catalyst precarsor is traditionally being known as " catalyst ".Ester through hydrogenation catalyst precarsor passes through
Just there is catalytic activity, this is usually completed by the operator of commercial plant, and those skilled in the art are known should be also after reduction
Former process, therefore not to repeat here.The shape of various needs, example can be made in ester through hydrogenation catalyst precarsor according to the demand of user
It such as, can be for by molding spherical, sheet etc., or the shape before molding, such as powder.Ester through hydrogenation catalyst precarsor warp
Crossing just has catalytic activity after reduction.Therefore, before carrying out hydrogenation reaction, it usually needs by the hydrogenation catalyst in 150-
It is restored in the hydrogen gas stream at 250 DEG C 12-24 hours.
The present inventor has found that hydrogen plasma is applied to copper-based ester through hydrogenation catalyst after further investigation
Preparation, can make to load active component, the catalyst precursor of auxiliary agent is decomposed into copper oxide under cryogenic, effectively avoid
Sintering of catalyst caused by high-temperature roasting.Catalyst is obtained with smaller nano, active component dispersibility is more uniform,
With higher catalytic activity.Based on above-mentioned discovery, inventor completes the present invention.When by copper-based ester through hydrogenation provided by the invention
When catalyst is used for the hydrogenation reaction of ester type compound, higher ester conversion rate and alcohol selectivity can be obtained, great industry is answered
With prospect, preferable technical effect is achieved.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
Embodiment 1
The multi wall carbon that nitrate trihydrate copper, zinc nitrate hexahydrate and nitric acid treatment are crossed is weighed respectively by the composition and ratio of catalyst to receive
Mitron, in carbon nanotube preprocessing process, the mass ratio of nitric acid and carbon nanotube is 0.65:1, and the outer diameter of carbon nanotube is 25
Copper nitrate and zinc nitrate are dissolved in deionized water by~35nm, 10~20nm of internal diameter using equi-volume impregnating, are then added more
Wall carbon nano tube carrier is put into ultrasonic wave and handles 1 hour, is subsequently placed into drying box 15 hours dry.Using power 100W
Plasma emission source, using hydrogen helium mix gas as discharge medium, hydrogen volume score be 10%, in plasma reaction
It is handled 1 hour in device, obtains CuO-ZnO/ carbon nanotube precursor, wherein the mass fraction of copper oxide is 25%, zinc oxide
Mass fraction is 20%.Solid powder is subjected to tabletting after cooling, the particle of 40~50 mesh is filtered out after broken.
(1) catalyst of preparation is used for the hydrogenation reaction of ethyl acetate.Specifically, 10g ester through hydrogenation catalyst is packed into
In fixed bed reactors, then restored 11 hours under conditions of temperature is 220 DEG C, hydrogen stream is 110mL/min.Then it is passed through
Ethyl acetate, 230 DEG C of hydrogenation temperature, hydrogenation pressure 4.5MPa, reaction raw materials mass space velocity 0.45h-1, hydrogen/ester molar ratio
Hydrogenation reaction is carried out under conditions of 45:1, obtains the product containing ethyl alcohol, wherein the choosing of the conversion ratio and ethyl alcohol of ethyl acetate
Selecting property is shown in Table 1 with the reaction result in reaction time.
Table 1
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 78.3 | 95.3 | 98.1 | 96.5 | 98.4 | 98.3 | 97.8 |
| Selectivity (%) | 97.8 | 97.9 | 98.9 | 97.9 | 98.2 | 98.1 | 97.9 |
(2) catalyst of preparation is used for the hydrogenation reaction of cyclohexyl acetate.Specifically, 10g ester through hydrogenation catalyst is filled
Enter in fixed bed reactors, then reductase 12 4 hours under conditions of temperature is 235 DEG C, hydrogen stream is 110mL/min.Then lead to
Enter cyclohexyl acetate, and 235 DEG C of hydrogenation temperature, hydrogenation pressure 5.5MPa, reaction raw materials mass space velocity 0.48h-1, hydrogen/
Hydrogenation reaction is carried out under conditions of ester molar ratio 60:1, obtains the product containing ethyl alcohol and cyclohexanol, wherein cyclohexyl acetate
The overall selectivity of conversion ratio and ethyl alcohol and cyclohexanol is shown in Table 2 with the reaction result in reaction time.
Table 2
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 87.3 | 94.7 | 98.2 | 98.5 | 98.9 | 98.1 | 99.2 |
| Overall selectivity (%) | 97.5 | 97.1 | 98.9 | 98.8 | 98.8 | 97.9 | 98.1 |
(3) catalyst of preparation is used for the hydrogenation reaction containing dimethyl oxalate.Specifically, by 10g ester through hydrogenation catalyst
It is fitted into fixed bed reactors, is then restored 14 hours under conditions of temperature is 200 DEG C, hydrogen stream is 90mL/min.Then
Be passed through dimethyl oxalate, and 200 DEG C of hydrogenation temperature, hydrogenation pressure 6MPa, reaction raw materials mass space velocity 0.5h-1, hydrogen/ester
Hydrogenation reaction is carried out under conditions of molar ratio 55:1, obtains the product containing ethylene glycol and methanol, wherein dimethyl oxalate turns
Rate and the overall selectivity of ethylene glycol and methanol are shown in Table 3 with the reaction result in reaction time.
Table 3
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 90 | 120 |
| Conversion ratio (%) | 72.5 | 83.2 | 92.9 | 95.8 | 94.7 | 95.7 | 94.4 |
| Overall selectivity (%) | 93.1 | 95.4 | 94.8 | 96 | 95.5 | 96.1 | 96.2 |
Embodiment 2
It uses cocoanut active charcoal for carrier, weighs nitrate trihydrate copper, zinc nitrate hexahydrate respectively according to catalyst composition ratio
The active carbon crossed with nitric acid treatment, during Activated Carbon Pretreatment, the mass ratio of nitric acid and active carbon is 1.5:1, using etc.
Nitric acid copper crystal, zinc nitrate crystal are dissolved in deionized water by volume impregnation method, and solution is added dropwise in carrier after being completely dissolved,
It stirs evenly, mixed liquor stands 6 hours at room temperature, is placed in oven and dried 12 hours.Use power for 120W etc.
Gas ions transmitter, using the hydrogen argon gas gaseous mixture of 110ml as discharge medium, hydrogen volume score is 15%, is discharged in tubular type
It is handled 2 hours in plasma generator, obtains the load that copper oxide mass content is 25%, zinc oxide mass content is 15%
Type catalyst.Compression molding after cooling filters out the particle of 40~60 mesh after broken.
(1) catalyst is used for the hydrogenation reaction of ethyl acetate.Specifically, 15g ester through hydrogenation catalyst is packed into fixed bed
In reactor, then restored 18 hours under conditions of temperature is 200 DEG C, hydrogen stream is 100mL/min.Then it is passed through acetic acid second
Ester, 245 DEG C of hydrogenation temperature, hydrogenation pressure 5.5MPa, reaction raw materials mass space velocity 0.45h-1, hydrogen/ester molar ratio 40:1
Under the conditions of carry out hydrogenation reaction, obtain the product containing ethyl alcohol, wherein the selectivity of the conversion ratio of ethyl acetate and ethyl alcohol with
The reaction result in reaction time be shown in Table 4.
Table 4
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 78.3 | 88.2 | 84.8 | 89.1 | 85.4 | 84.7 | 84.4 | 87.8 |
| Selectivity (%) | 96.8 | 95.2 | 95.7 | 96.1 | 95.2 | 97.3 | 97.1 | 97.2 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Specifically, 10g ester through hydrogenation catalyst is filled
Enter in fixed bed reactors, is then restored 12 hours under conditions of temperature is 255 DEG C, hydrogen stream is 100mL/min.Then lead to
Enter cyclohexyl acetate, 225 DEG C of hydrogenation temperature, hydrogenation pressure 5MPa, reaction raw materials mass space velocity 0.45h-1, hydrogen/ester mole
Than carrying out hydrogenation reaction under conditions of 45:1, the product containing ethyl alcohol and cyclohexanol is obtained, wherein the conversion ratio of cyclohexyl acetate
And the overall selectivity of ethyl alcohol and cyclohexanol is shown in Table 5 with the reaction result in reaction time.
Table 5
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 84.9 | 94.7 | 95.1 | 94.2 | 93.5 | 94.7 | 93.8 | 93.7 |
| Overall selectivity (%) | 95.4 | 95.6 | 95.2 | 95.9 | 95.5 | 98.3 | 95.8 | 97.7 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction of dimethyl oxalate.Specifically, 10g ester through hydrogenation catalyst is filled
Enter in fixed bed reactors, is then restored 13 hours under conditions of temperature is 225 DEG C, hydrogen stream is 75mL/min.Then lead to
Enter dimethyl oxalate, and 230 DEG C of hydrogenation temperature, hydrogenation pressure 5.5MPa, reaction raw materials mass space velocity 0.45h-1, hydrogen/
Hydrogenation reaction is carried out under conditions of ester molar ratio 60:1, obtains the product containing ethylene glycol and methanol, wherein dimethyl oxalate
The overall selectivity of conversion ratio and ethylene glycol and methanol is shown in Table 6 with the reaction result in reaction time.
Table 6
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 70.4 | 84.3 | 86.8 | 87.5 | 87.1 | 88.4 | 86.5 | 87.2 |
| Overall selectivity (%) | 95.5 | 96 | 96.7 | 96.1 | 95.1 | 95.2 | 95.3 | 96.1 |
Embodiment 3
The multi wall carbon that nitrate trihydrate copper, zinc nitrate hexahydrate and nitric acid treatment are crossed is weighed respectively by the composition and ratio of catalyst to receive
Mitron, in carbon nanotube preprocessing process, the mass ratio of nitric acid and carbon nanotube is 1.65:1, and the outer diameter of carbon nanotube is 40
Copper nitrate is dissolved in deionized water using equi-volume impregnating, multi-wall carbon nano-tube is then added by~50nm, 20~35nm of internal diameter
Pipe carrier is put into ultrasonic wave and handles 2.5 hours, is subsequently placed into baking oven 10 hours dry.Using the plasma of power 120W
Body emission source, using hydrogen argon gas gaseous mixture as discharge medium, hydrogen volume score is 10%, is handled in plasma reactor
1 hour, obtaining oxidation copper content was 15%, the catalyst precursor that zinc oxide content is 20%.After cooling by solid powder into
Row tabletting filters out the particle of 40~50 mesh after broken.
(1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Specific steps are same as Example 1, acetic acid second
The selectivity of the conversion ratio of ester and ethyl alcohol is shown in Table 7 with the reaction result in reaction time.
Table 7
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 74.4 | 92.3 | 94.5 | 92.4 | 93.4 | 94.1 | 95.3 | 93.8 |
| Selectivity (%) | 96.7 | 95.7 | 98.5 | 97.8 | 97.2 | 98.3 | 98.5 | 97.8 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Specific steps are same as Example 1, acetic acid
The overall selectivity of the conversion ratio and acetic acid of cyclohexyl and cyclohexanol is shown in Table 8 with the reaction result in reaction time.
Table 8
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 71.2 | 89.5 | 94.5 | 98 | 98.1 | 97.8 | 97.5 | 95.8 |
| Overall selectivity (%) | 98.1 | 96.2 | 96.5 | 96.2 | 97.5 | 97.5 | 98.5 | 98.2 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction containing dimethyl oxalate.Specific steps are same as Example 1, grass
The overall selectivity of the conversion ratio and ethylene glycol of dimethyl phthalate and methanol is shown in Table 9 with the reaction result in reaction time.
Table 9
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 84.2 | 84.3 | 96.1 | 98.5 | 98.2 | 98.6 | 97.3 | 98.5 |
| Overall selectivity (%) | 95.2 | 95.7 | 96.7 | 96.8 | 98 | 95.5 | 96.7 | 97.2 |
Embodiment 4
It uses cocoanut active charcoal for carrier, weighs nitrate trihydrate copper, sulfonitric zinc respectively according to catalyst composition ratio
The active carbon crossed with nitric acid treatment, in activated carbon tube preprocessing process, the mass ratio of nitric acid and active carbon is 1.05:1, is used
Nitric acid copper crystal, zinc nitrate crystal are dissolved in deionized water by equi-volume impregnating, and solution is added dropwise to carrier after being completely dissolved
In, it stirs evenly, mixed liquor is handled 5 hours in ultrasonic cleaner, is placed in oven and dried 15 hours.Use power for
The plasma emitters of 90W, using the hydrogen argon gas gaseous mixture of 500ml as discharge medium, hydrogen volume score is 20%, in pipe
It is handled 3 hours in formula discharge plasma generator, obtaining copper oxide mass content is 25%, and zinc oxide mass content is 15%
Loaded catalyst.Compression molding after cooling filters out the particle of 50~60 mesh after broken.
(1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Specific steps are same as Example 1, acetic acid second
The selectivity of the conversion ratio of ester and ethyl alcohol is shown in Table 10 with the reaction result in reaction time.
Table 10
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 84.1 | 91.6 | 94.3 | 95.4 | 94.2 | 95.1 | 96.1 | 95.2 |
| Selectivity (%) | 95.7 | 95.8 | 95.6 | 95.9 | 97.1 | 97.4 | 96.8 | 97.2 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Specific steps are same as Example 1, acetic acid
The overall selectivity of the conversion ratio and acetic acid of cyclohexyl and cyclohexanol is shown in Table 11 with the reaction result in reaction time.
Table 11
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 55.8 | 72.2 | 84.4 | 95.7 | 98.1 | 96.5 | 98.1 | 97.9 |
| Overall selectivity (%) | 98.5 | 98.1 | 97.3 | 95.9 | 98.1 | 97.3 | 98.1 | 97.5 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction containing dimethyl oxalate.Specific steps are same as Example 1, grass
The overall selectivity of the conversion ratio and ethylene glycol of dimethyl phthalate and methanol is shown in Table 12 with the reaction result in reaction time.
Table 12
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 74.3 | 78.1 | 97.2 | 96.8 | 98.2 | 98.3 | 97.6 | 98.1 |
| Overall selectivity (%) | 95.5 | 97 | 96.7 | 97.8 | 97.2 | 97.3 | 97.1 | 98.2 |
Comparative example 1
The multi wall carbon that nitrate trihydrate copper, zinc nitrate hexahydrate and nitric acid treatment are crossed is weighed respectively by the composition and ratio of catalyst to receive
Mitron, in carbon nanotube preprocessing process, the mass ratio of nitric acid and carbon nanotube is 0.95:1, and the outer diameter of carbon nanotube is 25
Copper nitrate is dissolved in deionized water using equi-volume impregnating, multi-wall carbon nano-tube is then added by~35nm, 10~20nm of internal diameter
Pipe carrier is put into ultrasonic wave and handles 1 hour, is subsequently placed into drying 15 hours in baking oven, desciccate is from 25 DEG C of room temperature with 10
DEG C/rate of min rises to 450 DEG C, it then roasts 6 hours at 350 DEG C again, obtains the CuO/ carbon nanotube forerunner of 25 weight %
Body.Solid powder is subjected to tabletting after cooling, the particle of 40~50 mesh is filtered out after broken.
(1) catalyst of preparation is used for the hydrogenation reaction of ethyl acetate.Specifically, 10g ester through hydrogenation catalyst is packed into
In fixed bed reactors, then restored 12 hours under conditions of temperature is 230 DEG C, hydrogen stream is 120mL/min.Then it is passed through
Ethyl acetate, 240 DEG C of hydrogenation temperature, hydrogenation pressure 4.5MPa, reaction raw materials mass space velocity 0.45h-1, hydrogen/ester molar ratio
Hydrogenation reaction is carried out under conditions of 40:1, obtains the product containing ethyl alcohol, wherein the choosing of the conversion ratio and ethyl alcohol of ethyl acetate
Selecting property is shown in Table 13 with the reaction result in reaction time.
Table 13
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 67.3 | 75.3 | 78.1 | 76.5 | 78.4 | 79.2 | 77.3 |
| Selectivity (%) | 95.1 | 94.3 | 92.1 | 91.7 | 91.2 | 921 | 91.3 |
(2) catalyst of preparation is used for the hydrogenation reaction of cyclohexyl acetate.Specifically, 10g ester through hydrogenation is catalyzed
Agent is fitted into fixed bed reactors, then reductase 12 5 hours under conditions of temperature is 245 DEG C, hydrogen stream is 120mL/min.It connects
Be passed through cyclohexyl acetate, and 245 DEG C of hydrogenation temperature, hydrogenation pressure 5.5MPa, reaction raw materials mass space velocity 0.55h-1, hydrogen
Hydrogenation reaction is carried out under conditions of gas/ester molar ratio 65:1, obtains the product containing ethyl alcohol and cyclohexanol, wherein acetic acid hexamethylene
The overall selectivity of the conversion ratio and ethyl alcohol of ester and cyclohexanol is shown in Table 14 with the reaction result in reaction time.
Table 14
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 67.3 | 64.7 | 72.2 | 78.5 | 72.2 | 68.1 | 69.2 |
| Overall selectivity (%) | 87.5 | 87.1 | 90.2 | 92.1 | 91.8 | 91.7 | 90.2 |
(3) catalyst of preparation is used for the hydrogenation reaction of dimethyl oxalate.Specifically, 10g acid resistant form ester is added
Hydrogen catalyst is fitted into fixed bed reactors, and then reduction 14 is small under conditions of temperature is 210 DEG C, hydrogen stream is 90mL/min
When.Then be passed through dimethyl oxalate, and 200 DEG C of hydrogenation temperature, hydrogenation pressure 6MPa, reaction raw materials mass space velocity 0.5h-1、
Hydrogenation reaction is carried out under conditions of hydrogen/ester molar ratio 50:1, obtains the product containing ethylene glycol and methanol, wherein oxalic acid two
The overall selectivity of the conversion ratio and ethylene glycol of methyl esters and methanol is shown in Table 15 with the reaction result in reaction time.
Table 15
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 90 | 120 |
| Conversion ratio (%) | 52.5 | 65..2 | 72.2 | 75.4 | 74.4 | 72.5 | 70.1 |
| Overall selectivity (%) | 90.1 | 90.2 | 88.4 | 86.6 | 90.2 | 90.1 | 89.4 |
Comparative example 2
It uses cocoanut active charcoal for carrier, weighs nitrate trihydrate copper and nitric acid treatment mistake respectively according to catalyst composition ratio
Active carbon, during Activated Carbon Pretreatment, the mass ratio of nitric acid and active carbon is 1.35:1, will using equi-volume impregnating
Nitric acid copper crystal is dissolved in deionized water, and solution is added dropwise in carrier after being completely dissolved, and is stirred evenly, and mixed liquor is in ultrasonic wave
It handles 5 hours, is placed in oven and dried 24 hours in washer, then by desciccate from 25 DEG C of the room temperature rates with 5 DEG C/min
350 DEG C are risen to, is then roasted 8 hours at 350 DEG C, is gradually cooling to room temperature, obtains ester through hydrogenation catalyst.It obtains aoxidizing copper
Measure the loaded catalyst that content is 25%.Compression molding after catalyst is cooling filters out the particle of 40~50 mesh after broken.
1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Specific steps are same as Example 1, ethyl acetate
Conversion ratio and the selectivity of ethyl alcohol be shown in Table 16 with the reaction result in reaction time.
Table 16
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 54.1 | 61.6 | 64.3 | 65.4 | 64.3 | 62.5 | 63.4 | 61.2 |
| Selectivity (%) | 85.7 | 85.8 | 85.6 | 86 | 84.7 | 83.2 | 86.1 | 87.1 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Specific steps are same as Example 1, acetic acid
The overall selectivity of the conversion ratio and acetic acid of cyclohexyl and cyclohexanol is shown in Table 17 with the reaction result in reaction time.
Table 17
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 55.2 | 52.2 | 54.4 | 65.7 | 58.1 | 59.5 | 64.1 | 67.2 |
| Overall selectivity (%) | 88.5 | 87.1 | 87.3 | 85.9 | 87.1 | 88.3 | 87.2 | 87.6 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction containing dimethyl oxalate.Specific steps are same as Example 1, grass
The overall selectivity of the conversion ratio and ethylene glycol of dimethyl phthalate and methanol is shown in Table 18 with the reaction result in reaction time.
Table 18
| Reaction time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 64.3 | 68.1 | 67.2 | 65.8 | 68.4 | 66.5 | 64.3 | 67.2 |
| Overall selectivity (%) | 75.5 | 77 | 76.7 | 75.7 | 77.2 | 77.3 | 78.1 | 78.4 |
Embodiment 1-4 the result shows that, when ester through hydrogenation catalyst provided by the invention is reacted for ester through hydrogenation, longer anti-
At once interior to obtain higher ester conversion rate and alcohol selectivity, and must be urged in comparative example using conventional hot high-temperature roasting
The performance of agent is far below catalyst provided by the invention.
Above embodiments describe the prefered embodiments of the present invention in detail, and still, the present invention is not limited to above-mentioned implementations
Detail in mode can carry out technical solution of the present invention a variety of simple within the scope of the technical concept of the present invention
Modification, these simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (2)
1. a kind of copper-based ester through hydrogenation carbon monoxide-olefin polymeric including carrier and loads active component on the carrier and helps
Agent, the carrier are carbon material, and the active component loaded on the carrier is copper, and the auxiliary agent is zinc；Wherein, the carbon materials
Material is at least one of multi-walled carbon nanotube, mesoporous carbon, active carbon and carbon nano-fiber；With hydrogen plasma preparation
On the basis of the total weight of copper-based ester through hydrogenation catalyst, the mass content of active component is 5~30%, the mass content of adjuvant component
It is 15~30%；The preparation method of the copper-based ester through hydrogenation carbon monoxide-olefin polymeric, comprising the following steps:
(1) mantoquita crystal, zinc salt crystal and carbon material carrier are weighed according to catalyst composition and ratio, it will according to equi-volume impregnating
Mantoquita crystal, zinc salt crystal are dissolved in deionized water, and obtained solution is uniformly mixed with carbon material carrier, and it is small to stand 5~20
When after be dried；
(2) powder sample after drying is placed in the dielectric barrier plasma discharge region of reactor, is first passed through indifferent gas
Air in body metathesis reactor then passes to hydrogen/inert gas gaseous mixture, in the electrode of plasma after 0.5~2 hour
Between apply high-voltage electricity carry out discharge treatment 0.1~5 hour, obtain catalyst solid powder；
(3) resulting solid powder is formed, obtains carbon material supported copper-based ester through hydrogenation catalyst；
The copper-based ester through hydrogenation carbon monoxide-olefin polymeric produces corresponding alcohol for ester type compound to be carried out hydrogenation reaction；Institute
Stating ester type compound is 1,4- cyclohexyl dicarboxylic acid dimethyl ester, sec-butyl acetate, cyclohexyl acetate, ethyl acetate, long-chain rouge
At least one of fatty acid methyl esters, dimethyl oxalate, dimethyl adipate and terephthalate；In step (1), mantoquita is nitre
Sour copper, zinc salt are zinc nitrate, and salting liquid is uniformly mixed with carbon material carrier, stand 5~20 hours at room temperature, are put into
Dry in baking oven, drying temperature is 30~150 DEG C, and drying time is 5~25 hours；After carbon material carrier is using the preceding processing with acid
Dry, the acid is nitric acid；Inert gas described in step (2) is at least one of nitrogen, helium, argon gas；In gaseous mixture
The volume fraction of hydrogen is 0.1~20%；The reactor material is quartz；The mass ratio of nitric acid and carbon material carrier is 0.65
~1.65:1；The discharge power of the plasma is 20~200W；The process conditions of ester through hydrogenation are as follows: reaction temperature 150-
300℃；Reaction pressure is 3-9MPa；The mass space velocity of reaction raw materials is 0.2-0.8h-1；Hydrogen ester molar ratio is 30-300:1；Institute
State a length of C4-C6 of chain of long chain fatty acids in long chain fatty acids methyl esters.
2. copper-based ester through hydrogenation carbon monoxide-olefin polymeric according to claim 1, it is characterised in that the carbon material is that multi wall carbon is received
Mitron.
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| CN103480374A (en) * | 2013-09-25 | 2014-01-01 | 神华集团有限责任公司 | Method for preparing acetic ester hydrogenation catalyst |
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| CN103480374A (en) * | 2013-09-25 | 2014-01-01 | 神华集团有限责任公司 | Method for preparing acetic ester hydrogenation catalyst |
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