CN106215943A - Ester through hydrogenation catalyst and its preparation method and application - Google Patents
Ester through hydrogenation catalyst and its preparation method and application Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The present invention relates to a kind of ester through hydrogenation catalyst and its preparation method and application, mainly solve the problem that ester conversion rate and alcohol selectivity in prior art are relatively low.The cuprio 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, described carrier is material with carbon element, load active component on the carrier is copper, the load technical scheme that auxiliary agent is zinc and its preparation method and application on the carrier preferably solves the problems referred to above, can be used in ester through hydrogenation.
Description
Technical field
The present invention relates to a kind of ester through hydrogenation catalyst and its preparation method and application.
Background technology
Alcohol has important economic worth, be 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, dehydrant, work
Industry detergent, but also can serve as plasticizer, oil extraction agent, wetting agent, spice etc..The method of current industrial production alcohol
Mainly there are alkene hydration method, carbonylation of olefin method and alkene esterification hydrogenation method.
The cyclohexene hydration Hexalin technique that representative art is Asahi Kasei Corporation of Japan of alkene hydration method, this technology
Industrialization is realized in nineteen ninety.When using alkene hydration method to prepare alcohol, although having reaction selectivity high, three wastes discharge amount is low
Advantage, but but have that reaction pressure is high, molecular balance conversion ratio is the lowest, water alkene than high, to cyclohexene purity requirement higher, phase
The equipment investment answered is big, the high deficiency of separating energy consumption.Such as, when employing high silica ZSM-5 catalyst is 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, homogeneous hydrogenation formylation aldehyde is with noble metal as catalyst, and reaction condition is the harshest, the conversion ratio of reaction
Relatively low with selectivity.Such as, in carbonylation of olefin disclosed in US5312996 prepares the method for aldehyde, with butadiene as raw material, rhodium
(Rh) as catalyst, H2Being 1:1 with the mol ratio of CO, reaction temperature is 95 DEG C, and pressure is 500psi, target product hexandial
Yield less than 20%, and in embodiment under optimal conditions, yield is still below 30%.Making disclosed in CN1193954A
In the method for standby linear chain aldehyde, carry out olefine, hydrogen and carbon monoxide in the organic solvent be dissolved with catalyst being hydrogenated with first
Acylation reaction produces linear chain aldehyde, and described catalyst contains the platinum compounds without halide anion, two tooth diaryl phosphines, abutment two
Cyclopentadienyl iron-based and acid assistant；Research shows, when reaction pressure be 1000psi, temperature be 100 DEG C time, the conversion ratio of hexene be about
30%, selectivity is less than needing to add substantial amounts of solvent in 90%, and course of reaction, follow-up product separation process is complicated
And energy expenditure is big, unfavorable industrialized production.
Alkene esterification hydrogenation method is divided into esterification and hydrogenation two steps, first alkene to generate ester with acid through esterification, then enters ester
Row hydrogenation synthesis alcohol.The reaction condition of the method is gentle, react conversion ratio and selectivity are high, and atom utilization is almost
100%, there is good industrial value.Wherein, process many employings Cu series catalysts of ester through hydrogenation synthol, adds simultaneously and helps
Agent increases its activity and stability.Time in catalyst without auxiliary agent, catalysis activity is the most relatively low, main reason is that catalyst
Preparation process needs, by high-temperature roasting, copper nitrate is converted into copper oxide, obtains the presoma of catalyst.Without high during auxiliary agent
Temperature roasting is easily caused the active copper species sintering of catalyst, nanograin growth, thus reduces catalysis activity.Urge to improve
Changing activity to need to add auxiliary agent, auxiliary agent is based on Cr, Ba etc., and the Cu-Cr as developed by ARCO company of the U.S. is serial,
What Poppehdof developed shows preferable effect as catalyst body to oxalate hydrogenation using Cu-Cr component.But,
These auxiliary agents have the biggest toxicity, and the preparation process of catalyst can cause serious environmental pollution.In view of the requirement of environmental protection,
The selection of auxiliary agent is significant.
Summary of the invention
One of the technical problem to be solved is ester conversion rate and the relatively low problem of alcohol selectivity in prior art,
A kind of new ester through hydrogenation catalyst is provided.Said composition has ester conversion rate and the higher advantage of alcohol selectivity.The present invention is wanted
Two solved the technical problem that are to provide the preparation method of a kind of ester through hydrogenation catalyst corresponding with solving one of technical problem.
The three of the technical problem to be solved are to provide a kind of ester through hydrogenation catalyst corresponding with solving one of technical problem
Application.
For solving one of the problems referred to above, the technical solution used in the present invention is as follows: a kind of ester through hydrogenation catalyst, including carrier
And loading active component on the carrier and auxiliary agent, described carrier is material with carbon element, load activity on the carrier
Component is copper, and load auxiliary agent on the carrier is zinc；Wherein, described material with carbon element is multi-walled carbon nano-tubes, mesoporous carbon, activity
At least one in charcoal and carbon nano-fiber；Gross weight with cuprio ester through hydrogenation catalyst prepared by described hydrogen plasma
On the basis of amount, the mass content of active component is 5～30%, and the mass content of adjuvant component is 5～30%.
In technique scheme, it is preferable that described material with carbon element is multi-walled carbon nano-tubes.
For solving the two of the problems referred to above, the technical solution used in the present invention is as follows: the preparation side of a kind of ester through hydrogenation catalyst
Method, comprises the following steps:
(1) mantoquita crystal, zinc salt crystal and material with carbon element carrier are weighed according to catalyst composition and ratio, according to incipient impregnation
Zinc salt crystal is dissolved in deionized water by method, is uniformly mixed with material with carbon element carrier by zinc solution, carries out after standing 5～20 hours
It is dried；
(2) according to equi-volume impregnating, mantoquita crystal is dissolved in deionized water, copper salt solution is dried with step (1)
Powder uniformly mix, be dried after standing 5～20 hours；
(3) the dried powder sample obtained in step (2) is placed in the dielectric barrier plasma discharge of reactor
In region, being first passed through the air in inert gas replacement reactor, then pass to hydrogen/noble gas gaseous mixture, 0.5～2 is little
Between the electrode of plasma, apply high-tension electricity time after carry out discharge process 0.1～5 hours, obtaining catalyst solid powder；
(4) by the pressed powder molding of gained, carbon material supported cuprio ester through hydrogenation catalyst is obtained.
In technique scheme, it is preferable that in step (1), mantoquita is copper nitrate, and zinc salt is zinc nitrate；Zinc nitrate is molten
Liquid uniformly mixes with material with carbon element carrier, stands 5～20 hours at ambient temperature, puts in baking oven and is dried, and baking temperature is 30
～150 DEG C, drying time is 5～25 hours；Copper nitrate solution is uniformly mixed by step (2) with step (1) dried powder
Closing, stand 5～20 hours at ambient temperature, put in baking oven and be dried, described baking temperature is 30～150 DEG C, when being dried
Between be 5～25 hours；Material with carbon element carrier is dried after using front acid treatment, and described acid is nitric acid.
In technique scheme, it is preferable that described in step (2), noble gas is at least in nitrogen, helium, argon
Kind；In gaseous mixture, the volume fraction of hydrogen is 0.1～20%.
In technique scheme, it is preferable that described reactor material is quartz.
In technique scheme, it is preferable that nitric acid is 0.6～1.6:1 with the mass ratio of material with carbon element carrier；Described plasma
The discharge power of body is 20～200W.
For solving the three of the problems referred to above, the technical solution used in the present invention is as follows: the application of a kind of ester through hydrogenation catalyst, adopts
With described cuprio ester through hydrogenation carbon monoxide-olefin polymeric, ester type compound is carried out hydrogenation reaction and produces corresponding alcohol；Described esters
Compound is 1,4-cyclohexyl dicarboxylic acid dimethyl ester, sec-butyl acetate, cyclohexyl acetate, ethyl acetate, long-chain fatty acid first
At least one in ester, dimethyl oxalate., dimethyl adipate and terephthalate.
In technique scheme, it is preferable that the process conditions of ester through hydrogenation are: 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 (hydrogen and ester) mol ratio is 30-300:1.
In technique scheme, it is preferable that a length of C4-C6 of chain of long-chain fatty acid in described long-chain fatty acid methyl ester.
In the present invention, the content of described active component is in terms of the oxide of active metal.The present invention is to passing through equal-volume
Saline solution and the mixed uniformly concrete grammar of material with carbon element carrier are not had specific restriction by infusion process.For example, it is possible to saline solution is dripped
Add on material with carbon element carrier, it is possible to material with carbon element carrier is mixed in saline solution.Simultaneously to saline solution and the uniform mixed process of carrier
There is no specific restriction, uniformly can mix by the way of stirring, it is also possible to mixed by ultrasound wave.The present invention to saline solution with
The mixed dry run of material with carbon element carrier does not has specific restriction.It is, for example possible to use a conventional oven is dried, it is possible to use vacuum
Oven drying.
Ester through hydrogenation catalyst is typically traded with the form of precursor and stores, although ester through hydrogenation catalyst precarsor can not be straight
Connect catalytic reaction, but traditionally ester through hydrogenation catalyst precarsor is being known as " catalyst ".Ester through hydrogenation catalyst precarsor passes through
Just having catalysis activity after reduction, this is generally completed by the operator of commercial plant, and those skilled in the art know should be also
Former process, therefore not to repeat here.Ester through hydrogenation catalyst precarsor can make the shape of various needs, example according to the demand of user
As, can be spherical, the lamellar etc. through molding, it is also possible to for the shape before molding, such as powder.Ester through hydrogenation catalyst precarsor warp
Just there is after crossing reduction catalysis activity.Therefore, before carrying out hydrogenation reaction, it usually needs by described hydrogenation catalyst at 150-
Reduce in the hydrogen gas stream 12-24 hour at 250 DEG C.
The present inventor finds after further investigation, and hydrogen plasma is applied to cuprio ester through hydrogenation catalyst
Preparation, can make to be loaded with active component, the catalyst precursor of auxiliary agent is decomposed into copper oxide under cryogenic, is prevented effectively from
The sintering of catalyst that high-temperature roasting causes.Obtaining catalyst and have less nano, active component dispersibility is more uniformly distributed,
There is higher catalysis activity.Based on above-mentioned discovery, inventor completes the present invention.When the cuprio ester through hydrogenation that the present invention is provided
Catalyst is when the hydrogenation reaction of ester type compound, it is possible to obtain higher ester conversion rate and alcohol selectivity, and great industry should
By prospect, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
Embodiment 1
Weigh, by the composition and ratio of catalyst, many walls carbon that nitrate trihydrate copper, zinc nitrate hexahydrate and nitric acid treatment cross respectively to receive
Mitron, in CNT preprocessing process, nitric acid is 0.6:1 with the mass ratio of CNT, and the external diameter of CNT is 25
～35nm, internal diameter 10～20nm, use equi-volume impregnating to be dissolved in deionized water by zinc nitrate respectively, be subsequently adding many walls carbon
Nano-tube support, puts in ultrasound wave and processes 1 hour, is subsequently placed in drying baker and is dried 15 hours, obtains pressed powder.Use
Copper nitrate is dissolved in deionized water by equi-volume impregnating, then mixs homogeneously with dried pressed powder, is put subsequently
Enter in drying baker and be dried 20 hours.Use the plasma emission source of power 100W, with hydrogen helium mix gas as discharge medium,
Hydrogen volume mark is 10%, processes 1 hour in plasma reactor, and the mass fraction obtaining copper oxide is 24%, oxygen
Change the loaded catalyst that mass fraction is 22% of zinc.After cooling, pressed powder is carried out tabletting, broken after filter out 45～
The granule of 55 mesh.
(1) catalyst of preparation is used for the hydrogenation reaction of ethyl acetate.Specifically, 9g ester through hydrogenation catalyst is loaded admittedly
In fixed bed reactor, then temperature be 215 DEG C, hydrogen stream be 115mL/min under conditions of reduce 16 hours.Then vinegar it is passed through
Acetoacetic ester, hydrogenation temperature 235 DEG C, hydrogenation pressure 5.5MPa, the mass space velocity 0.45h of reaction raw materials-1, hydrogen/ester mol ratio 55:
Carry out hydrogenation reaction under conditions of 1, obtain the product containing ethanol, wherein, the conversion ratio of ethyl acetate and the selection of ethanol
Property is shown in Table 1 along with the reaction result in response time.
Table 1
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 77.3 | 83.5 | 96.5 | 94.8 | 96.6 | 97.5 | 97.2 |
| Selectivity (%) | 93.2 | 97.1 | 97.2 | 97.3 | 98.3 | 96.5 | 97.3 |
(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 temperature be 235 DEG C, hydrogen stream be 110mL/min under conditions of reductase 12 4 hours.Then lead to
Enter cyclohexyl acetate, and at hydrogenation temperature 235 DEG C, hydrogenation pressure 5.5MPa, the mass space velocity 0.48h of reaction raw materials-1, hydrogen/
Carry out hydrogenation reaction under conditions of ester mol ratio 60:1, obtain the product containing ethanol and Hexalin, wherein, cyclohexyl acetate
The overall selectivity of conversion ratio and ethanol and Hexalin is shown in Table 2 along with the reaction result in response time.
Table 2
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 |
| Conversion ratio (%) | 85.4 | 93.7 | 94.5 | 96.8 | 95.8 | 97.6 | 95.9 |
| Overall selectivity (%) | 94.8 | 97.6 | 98.1 | 98.1 | 95.2 | 97.2 | 98.5 |
(3) catalyst of preparation is used for the hydrogenation reaction containing dimethyl oxalate..Specifically, by 10g ester through hydrogenation catalyst
Load in fixed bed reactors, then temperature be 200 DEG C, hydrogen stream be 90mL/min under conditions of reduce 14 hours.Then
It is passed through dimethyl oxalate., and at hydrogenation temperature 200 DEG C, hydrogenation pressure 6MPa, the mass space velocity 0.5h of reaction raw materials-1, hydrogen/ester
Carry out hydrogenation reaction under conditions of mol ratio 55:1, obtain the product containing ethylene glycol and methanol, wherein, turning of dimethyl oxalate.
The overall selectivity of rate and ethylene glycol and methanol is shown in Table 3 along with the reaction result in response time.
Table 3
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 90 | 120 |
| Conversion ratio (%) | 76.4 | 88.3 | 91.2 | 94.9 | 94.1 | 95.1 | 93.9 |
| Overall selectivity (%) | 92.6 | 95.5 | 94.1 | 95.3 | 94.2 | 96.3 | 97.4 |
Embodiment 2
Employing cocoanut active charcoal is carrier, weighs nitrate trihydrate copper, zinc nitrate hexahydrate respectively according to catalyst proportion of composing
The activated carbon crossed with nitric acid treatment, during Activated Carbon Pretreatment, nitric acid is 1.6:1 with the mass ratio of activated carbon, employing etc.
Zinc nitrate crystal is dissolved in deionized water by volume impregnation method, drops to solution, in carrier, stir after being completely dissolved, mixed
Close liquid and stand 6 hours at ambient temperature, put in baking oven and be dried 12 hours, obtain pressed powder.Use equi-volume impregnating
Copper nitrate crystal is dissolved in deionized water, solution is dropped in dried pressed powder after being completely dissolved, stir,
Mixed liquor stands 5 hours at ambient temperature, puts in baking oven and is dried 13 hours.Using power is the plasma emission of 135W
Device, with the hydrogen argon gaseous mixture of 105ml as discharge medium, hydrogen volume mark is 12%, sends out at tubular type discharge plasma
Raw device processes 3.5 hours, obtain copper oxide mass content be 27%, zinc oxide mass content be the supported catalyst of 13%
Agent.Compression molding after cooling, filters out the granule of 40～60 mesh after crushing.
(1) catalyst is used for the hydrogenation reaction of ethyl acetate.Specifically, 15g ester through hydrogenation catalyst is loaded fixed bed
In reactor, then temperature be 210 DEG C, hydrogen stream be 100mL/min under conditions of reduce 18 hours.Then acetic acid second it is passed through
Ester, hydrogenation temperature 215 DEG C, hydrogenation pressure 5.5MPa, the mass space velocity 0.6h of reaction raw materials-1, the bar of hydrogen/ester mol ratio 45:1
Carry out hydrogenation reaction under part, obtain the product containing ethanol, wherein, the conversion ratio of ethyl acetate and the selectivity of ethanol along with
The reaction result in response time is shown in Table 4.
Table 4
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 87.1 | 89.2 | 91.3 | 90.2 | 94.4 | 93.5 | 94.3 | 92.2 |
| Selectivity (%) | 93.2 | 95.4 | 95.8 | 96.1 | 94.3 | 96.4 | 97.1 | 97.4 |
(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, then temperature be 250 DEG C, hydrogen stream be 100mL/min under conditions of reduce 12 hours.Then lead to
Enter cyclohexyl acetate, hydrogenation temperature 245 DEG C, hydrogenation pressure 5MPa, the mass space velocity 0.5h of reaction raw materials-1, hydrogen/ester mol ratio
Carry out hydrogenation reaction under conditions of 55:1, obtain the product containing ethanol and Hexalin, wherein, the conversion ratio of cyclohexyl acetate with
And the overall selectivity of ethanol and Hexalin is shown in Table 5 along with the reaction result in response time.
Table 5
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 86.3 | 91.2 | 93.5 | 93.8 | 93.7 | 94.1 | 94.2 | 94.2 |
| Overall selectivity (%) | 92.3 | 94.2 | 95.1 | 96.2 | 96.2 | 97.3 | 94.5 | 95.1 |
(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, then temperature be 190 DEG C, hydrogen stream be 75mL/min under conditions of reductase 12 2 hours.Then lead to
Enter dimethyl oxalate., and at hydrogenation temperature 230 DEG C, hydrogenation pressure 5.5MPa, the mass space velocity 0.53h of reaction raw materials-1, hydrogen/
Carry out hydrogenation reaction under conditions of ester mol ratio 65:1, obtain 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 along with the reaction result in response time.
Table 6
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 73.4 | 86.3 | 87.5 | 87.1 | 86.2 | 86.1 | 85.8 | 87.9 |
| Overall selectivity (%) | 95.4 | 96.2 | 96.1 | 96.5 | 95.4 | 94.2 | 95.5 | 94.5 |
Embodiment 3
Weigh, by the composition and ratio of catalyst, many walls carbon that nitrate trihydrate copper, zinc nitrate hexahydrate and nitric acid treatment cross respectively to receive
Mitron, in CNT preprocessing process, nitric acid is 0.95:1 with the mass ratio of CNT, and the external diameter of CNT is 40
～50nm, internal diameter 25～35nm, use equi-volume impregnating to be dissolved in deionized water by zinc nitrate, be subsequently adding multi-wall carbon nano-tube
Pipe carrier, puts in ultrasound wave and processes 2.5 hours, is subsequently placed in baking oven and is dried 12 hours, obtains pressed powder.The bodies such as employing
Copper nitrate is dissolved in deionized water by long-pending infusion process, is subsequently adding dried pressed powder, puts into process 2.5 in ultrasound wave little
Time, it is subsequently placed in baking oven and is dried 10 hours.Use the plasma emission source of power 125W, with hydrogen argon gaseous mixture for putting
Electrolyte, hydrogen volume mark is 9%, processes 2.5 hours, obtain copper oxide mass content in plasma reactor
15%, zinc oxide mass content is the catalyst precursor of 25%.After cooling, pressed powder is carried out tabletting, filter out after crushing
The granule of 40～50 mesh.
(1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Concrete steps are same as in Example 1, acetic acid second
The conversion ratio of ester and the selectivity of ethanol are shown in Table 7 along with the reaction result in response time.
Table 7
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 72.1 | 93.5 | 94.2 | 92.5 | 92.7 | 93.5 | 94.8 | 94.1 |
| Selectivity (%) | 95.2 | 95.1 | 97.3 | 95.5 | 95.9 | 96.4 | 97.1 | 97.3 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Concrete steps are same as in Example 1, acetic acid
The overall selectivity of the conversion ratio of cyclohexyl and acetic acid and Hexalin is shown in Table 8 along with the reaction result in response time.
Table 8
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 77.2 | 90.3 | 91.2 | 93.5 | 95.2 | 94.1 | 95.9 | 94.9 |
| Overall selectivity (%) | 98.1 | 96.2 | 94.9 | 97.1 | 96.5 | 97.3 | 98.2 | 97.1 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction containing dimethyl oxalate..Concrete steps are same as in Example 1, grass
The overall selectivity of the conversion ratio of dimethyl phthalate and ethylene glycol and methanol is shown in Table 9 along with the reaction result in response time.
Table 9
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 84.2 | 89.3 | 93.2 | 95.5 | 95.9 | 97.2 | 97.4 | 97.8 |
| Overall selectivity (%) | 95.3 | 95.6 | 96.1 | 96.3 | 98.3 | 95.8 | 96.2 | 98 |
Embodiment 4
Employing cocoanut active charcoal is carrier, weighs nitrate trihydrate copper, zinc nitrate hexahydrate respectively according to catalyst proportion of composing
The activated carbon crossed with nitric acid treatment, during Activated Carbon Pretreatment, nitric acid is 0.65:1 with the mass ratio of activated carbon, employing etc.
Zinc nitrate crystal is dissolved in deionized water by volume impregnation method, drops to solution, in carrier, stir after being completely dissolved, mixed
Close liquid to process in ultrasonic cleaner 1.5 hours, put in baking oven and be dried 24 hours, obtain pressed powder；Use equal-volume
Copper nitrate crystal is dissolved in deionized water by infusion process, is dropped to by solution in above-mentioned pressed powder after being completely dissolved, and stirring is all
Even, mixed liquor processes 5.5 hours in ultrasonic cleaner, puts in baking oven and is dried 24 hours.Use power be 150W etc.
Gas ions emitter, with the hydrogen argon gaseous mixture of 500ml as discharge medium, hydrogen volume mark is 15%, discharges in tubular type
Plasma generator processes 3.5 hours, obtain copper oxide mass content be 35%, zinc oxide mass content be 15% negative
Supported catalyst.Compression molding after cooling, filters out the granule of 50～60 mesh after crushing.
(1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Concrete steps are same as in Example 1, acetic acid second
The conversion ratio of ester and the selectivity of ethanol are shown in Table 10 along with the reaction result in response time.
Table 10
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 76.3 | 88.2 | 92.3 | 95.2 | 94.8 | 94.5 | 94.8 | 95.7 |
| Selectivity (%) | 95.6 | 95.3 | 94 | 95.2 | 97.3 | 96.8 | 96.5 | 97.2 |
(2) ester through hydrogenation catalyst is used for the hydrogenation reaction of cyclohexyl acetate.Concrete steps are same as in Example 1, acetic acid
The overall selectivity of the conversion ratio of cyclohexyl and acetic acid and Hexalin is shown in Table 11 along with the reaction result in response time.
Table 11
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 75.2 | 84.2 | 89.8 | 92.3 | 98.5 | 97.9 | 96.5 | 96.9 |
| Overall selectivity (%) | 97.5 | 98.4 | 97.1 | 95.5 | 97.2 | 95.8 | 98.4 | 96.2 |
(3) ester through hydrogenation catalyst is used for the hydrogenation reaction containing dimethyl oxalate..Concrete steps are same as in Example 1, grass
The overall selectivity of the conversion ratio of dimethyl phthalate and ethylene glycol and methanol is shown in Table 12 along with the reaction result in response time.
Table 12
| Response time (h) | 5 | 10 | 20 | 35 | 50 | 70 | 90 | 120 |
| Conversion ratio (%) | 58.2 | 78.9 | 94.2 | 95.9 | 98.1 | 98.3 | 95.9 | 97.2 |
| Overall selectivity (%) | 92.8 | 94.1 | 98 | 96.2 | 96.5 | 97.1 | 96.2 | 98 |
Comparative example 1
Weigh nitrate trihydrate copper respectively by the composition and ratio of catalyst and multi-walled carbon nano-tubes that nitric acid treatment is crossed, receive at carbon
In mitron preprocessing process, nitric acid is 1.3:1 with the mass ratio of CNT, and the external diameter of CNT is 25～35nm, internal diameter
10～20nm, use equi-volume impregnating to be dissolved in deionized water by copper nitrate, be subsequently adding multi-walled carbon nano-tubes carrier, put into
Ultrasound wave processes 1 hour, is subsequently placed in baking oven and is dried 15 hours, desciccate from room temperature 25 DEG C with the speed of 10 DEG C/min
Rising to 450 DEG C, roasting 6 hours at 350 DEG C, obtain the CuO/ carbon nanotube precursor of 25 weight % the most again.Will be solid after cooling
Body powder carries out tabletting, filters out the granule of 40～50 mesh after crushing.
(1) catalyst of preparation is used for the hydrogenation reaction of ethyl acetate.Specifically, 10g ester through hydrogenation catalyst is loaded
In fixed bed reactors, then temperature be 230 DEG C, hydrogen stream be 120mL/min under conditions of reduce 12 hours.Then it is passed through
Ethyl acetate, hydrogenation temperature 240 DEG C, hydrogenation pressure 4.5MPa, the mass space velocity 0.45h of reaction raw materials-1, hydrogen/ester mol ratio
Carry out hydrogenation reaction under conditions of 40:1, obtain the product containing ethanol, wherein, the conversion ratio of ethyl acetate and the choosing of ethanol
Selecting property is shown in Table 13 along with the reaction result in response time.
Table 13
| Response 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 catalyst is filled
Enter in fixed bed reactors, then temperature be 245 DEG C, hydrogen stream be 120mL/min under conditions of reductase 12 5 hours.Then lead to
Enter cyclohexyl acetate, and at hydrogenation temperature 245 DEG C, hydrogenation pressure 5.5MPa, the mass space velocity 0.55h of reaction raw materials-1, hydrogen/
Carry out hydrogenation reaction under conditions of ester mol ratio 65:1, obtain the product containing ethanol and Hexalin, wherein, cyclohexyl acetate
The overall selectivity of conversion ratio and ethanol and Hexalin is shown in Table 14 along with the reaction result in response time.
Table 14
| Response 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 through hydrogenation is urged
Agent loads in fixed bed reactors, then temperature be 210 DEG C, hydrogen stream be 90mL/min under conditions of reduce 14 hours.
Then dimethyl oxalate. it is passed through, and at hydrogenation temperature 200 DEG C, hydrogenation pressure 6MPa, the mass space velocity 0.5h of reaction raw materials-1, hydrogen
Carry out hydrogenation reaction under conditions of gas/ester mol ratio 50:1, obtain the product containing ethylene glycol and methanol, wherein, oxalic acid diformazan
The overall selectivity of the conversion ratio of ester and ethylene glycol and methanol is shown in Table 15 along with the reaction result in response time.
Table 15
| Response 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
Employing cocoanut active charcoal is carrier, weighs nitrate trihydrate copper and nitric acid treatment mistake respectively according to catalyst proportion of composing
Activated carbon, during Activated Carbon Pretreatment, the mass ratio of nitric acid and activated carbon is 1.5:1, uses the equi-volume impregnating will
Copper nitrate crystal is dissolved in deionized water, drops to solution, in carrier, stir after being completely dissolved, and mixed liquor is at ultrasound wave
Washer processes 5 hours, puts in baking oven and be dried 24 hours, then by desciccate from room temperature 25 DEG C with the speed of 5 DEG C/min
Rising to 350 DEG C, then roasting 8 hours at 350 DEG C, are gradually cooling to room temperature, obtain ester through hydrogenation catalyst.Obtain aoxidizing copper
Amount content is the loaded catalyst of 25%.Compression molding after catalyst cooling, filters out the granule of 40～50 mesh after crushing.
1) ester through hydrogenation catalyst is used for the hydrogenation reaction of ethyl acetate.Concrete steps are same as in Example 1, ethyl acetate
Conversion ratio and the selectivity of ethanol be shown in Table 16 along with the reaction result in response time.
Table 16
| Response 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.Concrete steps are same as in Example 1, acetic acid
The overall selectivity of the conversion ratio of cyclohexyl and acetic acid and Hexalin is shown in Table 17 along with the reaction result in response time.
Table 17
| Response 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..Concrete steps are same as in Example 1, grass
The overall selectivity of the conversion ratio of dimethyl phthalate and ethylene glycol and methanol is shown in Table 18 along with the reaction result in response time.
Table 18
| Response 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 result shows, the ester through hydrogenation catalyst that the present invention provides is when ester through hydrogenation reacts, longer anti-
All it is obtained in that higher ester conversion rate and alcohol selectivity in Ying Shi, and comparative example uses the hot high-temperature roasting of routine must urge
The catalyst that the performance of agent provides far below the present invention.
Above example describes the preferred embodiment of the present invention in detail, but, the present invention is not limited to above-mentioned enforcement
Detail in mode, in the technology concept of the present invention, technical scheme can be carried out multiple simply
Modification, these simple variant belong to protection scope of the present invention.
It is further to note that each the concrete technical characteristic described in above-mentioned detailed description of the invention, at not lance
In the case of shield, can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy illustrates the most separately.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. an ester through hydrogenation catalyst, including carrier and load active component on the carrier and auxiliary agent, described carrier
For material with carbon element, load active component on the carrier is copper, and load auxiliary agent on the carrier is zinc；Wherein, described
Material with carbon element is at least one in multi-walled carbon nano-tubes, mesoporous carbon, activated carbon and carbon nano-fiber；With described hydrogen plasma
On the basis of the gross weight of cuprio ester through hydrogenation catalyst prepared by body method, the mass content of active component is 5～30%, adjuvant component
Mass content be 5～30%.
Ester through hydrogenation catalyst the most according to claim 1, it is characterised in that described material with carbon element is multi-walled carbon nano-tubes.
3. the preparation method of ester through hydrogenation catalyst described in claim 1, comprises the following steps:
(1) mantoquita crystal, zinc salt crystal and material with carbon element carrier are weighed according to catalyst composition and ratio, will according to equi-volume impregnating
Zinc salt crystal is dissolved in deionized water, is uniformly mixed with material with carbon element carrier by zinc solution, does after standing 5～20 hours
Dry；
(2) according to equi-volume impregnating, mantoquita crystal is dissolved in deionized water, by copper salt solution and step (1) dried powder
End uniformly mixing, is dried after standing 5～20 hours；
(3) the dried powder sample obtained in step (2) is placed in the dielectric barrier plasma discharge region of reactor
In, first it is passed through the air in inert gas replacement reactor, then passes to hydrogen/noble gas gaseous mixture, after 0.5～2 hour
Between the electrode of plasma, apply high-tension electricity carry out discharge process 0.1～5 hours, obtaining catalyst solid powder；
(4) by the pressed powder molding of gained, carbon material supported cuprio ester through hydrogenation catalyst is obtained.
The most according to claim 3, the preparation method of ester through hydrogenation catalyst, it is characterised in that in step (1), mantoquita is nitric acid
Copper, zinc salt is zinc nitrate；Zinc nitrate solution is uniformly mixed with material with carbon element carrier, stands 5～20 hours at ambient temperature, put
Entering in baking oven and be dried, baking temperature is 30～150 DEG C, and drying time is 5～25 hours；In step (2) by copper nitrate solution with
Step (1) dried powder uniformly mixes, and stands 5～20 hours at ambient temperature, puts in baking oven and is dried, and described is dry
Dry temperature is 30～150 DEG C, and drying time is 5～25 hours；Material with carbon element carrier is dried after using front acid treatment, and described acid is
Nitric acid.
The preparation method of ester through hydrogenation catalyst the most according to claim 3, it is characterised in that noble gas described in step (2)
For at least one in nitrogen, helium, argon；In gaseous mixture, the volume fraction of hydrogen is 0.1～20%.
The preparation method of ester through hydrogenation catalyst the most according to claim 3, it is characterised in that described reactor material is quartz.
7. according to the preparation method of ester through hydrogenation catalyst described in claim 3 and 4, it is characterised in that nitric acid and material with carbon element carrier
Mass ratio is 0.6～1.6:1；The discharge power of described plasma is 20～200W.
8. an application for ester through hydrogenation catalyst, uses the ester through hydrogenation carbon monoxide-olefin polymeric described in claim 1, by esters chemical combination
Thing carries out hydrogenation reaction and produces corresponding alcohol；Described ester type compound is 1,4-cyclohexyl dicarboxylic acid dimethyl ester, acetic acid Zhong Ding
In ester, cyclohexyl acetate, ethyl acetate, long-chain fatty acid methyl ester, dimethyl oxalate., dimethyl adipate and terephthalate
At least one.
The application of ester through hydrogenation catalyst the most according to claim 8, it is characterised in that the process conditions of ester through hydrogenation are: reaction temperature
Degree is for 150-300 DEG C；Reaction pressure is 3-9MPa；The mass space velocity of reaction raw materials is 0.2-0.8h-1；Hydrogen ester mol ratio is 30-
300:1.
The application of ester through hydrogenation catalyst the most according to claim 8, it is characterised in that long-chain in described long-chain fatty acid methyl ester
The a length of C4-C6 of chain of fatty acid.
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| CN110841705A (en) * | 2019-11-29 | 2020-02-28 | 万华化学集团股份有限公司 | Porous material loaded high-dispersion nano-copper catalyst and preparation method and application thereof |
| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
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| US6464779B1 (en) * | 2001-01-19 | 2002-10-15 | Novellus Systems, Inc. | Copper atomic layer chemical vapor desposition |
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| CN110871071A (en) * | 2018-09-04 | 2020-03-10 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN110871071B (en) * | 2018-09-04 | 2022-02-01 | 中国科学院大连化学物理研究所 | Copper-based catalyst for preparing methyl glycolate and preparation and application thereof |
| CN110841705A (en) * | 2019-11-29 | 2020-02-28 | 万华化学集团股份有限公司 | Porous material loaded high-dispersion nano-copper catalyst and preparation method and application thereof |
| CN110841705B (en) * | 2019-11-29 | 2022-09-16 | 万华化学集团股份有限公司 | Porous material loaded high-dispersion nano-copper catalyst and preparation method and application thereof |
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