CN108722420A - A kind of preparation method of copper silicon systems catalyst - Google Patents
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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
- B01J23/78—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 alkali- or alkaline earth metals
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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Abstract
The invention belongs to catalyst manufacturing technology field, providing a kind of copper silicon systems method for preparing catalyst and application, catalyst has the characteristics that cyclohexanol high conversion rate and cyclohexanone selectivity are high.Catalyst provided by the invention is mainly organized as Cu2O/SiO2, and the acidic site of coagent improvement catalyst surface is added, effectively inhibit the generation of the side reactions such as cyclohexene.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of preparation method of copper silicon systems catalyst, which can
In being reacted for cyclohexanol gas-phase dehydrogenation preparing cyclohexanone.
Background technology
Cyclohexanone is a kind of important Organic Chemicals, is production caprolactam (raw material of nylon-6) and adipic acid (Buddhist nun
Dragon -66 raw material) main intermediate, in addition to this, cyclohexanone is also widely used in organic solvent, synthetic rubber and industrial coating
Equal industrial processes.The production method of cyclohexanone mainly has phenol hydrogenation method, cyclohexanol dehydrogenation method and cyclohexanol method etc..
Due to preparing phenol, the process is more complicated, and phenol is more toxic, so substantially no longer being used by phynol method preparing cyclohexanone.
It is divided into as oxidizing process and dehydriding by cyclohexanol preparing cyclohexanone, dehydriding is that hexamethylene is made in cyclohexanol dehydrogenation under the action of catalyst
Ketone, oxidizing process are that cyclohexanone is made by catalyst at 250 DEG C ~ 300 DEG C in cyclohexanol and air.Dehydriding is because of its by-product
Relatively fewer, easy to operate, high income is widely used in industrial production.
The cyclohexanol dehydrogenation catalyst of industrial early application is red iron oxide, is replaced later by zinc system catalyst,
Such as Ube ZnO-CaCO3, Romanian Sai Weineishidi is with Zn-Cr systems.In addition there are zinc oxide（Scientific
Design Co. and BASF）, the oxide of zinc calcium and the mixture of carbonate（Inventa）And the zinc that silica is carrier
The mixture of calcium potassium oxide（IFP）Deng zinc system catalyst is just succeeded in developing in China the 1960s, zinc system catalyst
Although conversion ratio is higher, reaction temperature is also higher (350~400 DEG C), causes selectivity poor, by-product is more, makes raw material ring
The utilization rate of hexanol is relatively low, and reaction temperature greater catalytic agent short life, is replaced substantially by other catalyst.
Since zinc cathode catalyst operation temperature is high, product cyclohexanone selectivity is poor, and energy consumption is big, and raw material availability is not
Height, and since by-product increases the burden of follow-up process more, the quality of caprolactam product is influenced, so from 20th century 70
Low temperature high-selectivity catalyst is competitively developed from age in the world, while some use the caprolactam of low form dehydrogenation
Production process is come out one after another.Such as patent CN02807661.3 describes a kind of urging based on copper oxide for cyclohexanol dehydrogenation
Agent, it is to additionally comprise the catalyst based on copper oxide-zinc oxide of very small amount of palladium and platinum or ruthenium or be based on oxygen
The catalyst for changing copper-silica can be used for producing hexamethylene under the reaction temperature of reduction compared with traditional catalyst
Ketone；CN200810234492.5 describes a kind of catalyst of preparing cyclohexanone by cyclohexanol dehydrogenation, is including content molar ratio mainly
The aluminium oxide of the copper oxide of 25%-75%, the zinc oxide of 30%-65%, 1%-10%, structural promoter are content molar ratio
The mixture of 0.1%-5% scarce metallic compounds, coagent are the alkali metal compound of content molar ratio 0-1.0%；
CN200810234493.X describes a kind of preparation method of cyclohexanone catalyst by cyclohexanol dehydrogenation, with the method for co-precipitation into
It is prepared by row：The nitrate mixed solution of copper, zinc and aluminium and precipitating reagent are subjected to precipitation reaction, precipitating reagent can be K2CO3、
Na2CO3、NH4HCO3、(NH4)2CO3, one kind in NaOH, KOH or ammonium hydroxide, control precipitation temperature is 20 DEG C -90 DEG C, has been precipitated
Cheng Hou, be aged 25min-35min, be added auxiliary agent be filtered, wash, drying, calcining and compression molding and be made；
CN97196061.5 describes a kind of cyclohexanol dehydrogenation catalyst and its preparation method and application, is related to a kind of containing α-oxygen
Change aluminium and make the catalyst that carrier material copper makees active component, wherein the BET surface area of the aluminium oxide is (as DIN66131 is measured
) it is not less than 30m2/g；CN201110210438.9 describe it is a kind of for cyclohexanol dehydrogenation prepare cyclohexanone catalyst and
Preparation method, with CuO, ZnO and ZrO2For main active component, with MOAs catalyst modifier, wherein with weight hundred
Divide on the basis of ratio, each component content is：CuO 20 ~ 80%, ZnO 5 ~ 40%, ZrO21 ~ 40%, M2O0.5~10%.The system of the catalyst
Preparation Method is：The metal salt of the metal salt of copper, the metal salt of zinc and zirconium is miscible in deionized water, then, aqueous slkali is added
It is co-precipitated, precipitation finishes, and obtains precipitation mixture；By precipitation mixture after washing, drying, modifying agent is added or changes
Property agent raw material be uniformly mixed, roasting, compression molding；CN201110210414.3 describes one kind and preparing ring for cyclohexanol dehydrogenation
Catalyst of hexanone and preparation method thereof, with CuO, ZnO, ZrO2And SiO2For main active component, change using MO as catalyst
Property agent, wherein on the basis of weight percent, each component content is：CuO 20%-80%, ZnO5%-40%, ZrO21%-40%,
SiO20.1%-10%, MO0.5%-10%.CN201110418867.5 describes a kind of Cu2O/MgO catalyst and preparation method thereof,
The catalyst includes following weight percentage components：Nanometer Cu2O 1%~50%, MgO carrier surplus.The skill of the invention
The Cu that art scheme provides2Only include Cu on O/MgO catalyst2O and MgO carriers, Cu2O particles on the surface of the carrier dispersibility compared with
Good, grain size is nanoscale；CN00133278.3 describes a kind of cyclohexanone by dehydrogenating cyclohexanol catalyst and its preparation side
Method, it includes mainly the copper oxide, zinc oxide, aluminium oxide that content (m/m) is respectively 20%-70%, 28%-70%, 1%-10%,
The mixture of content (m/m) 0.1%-5% scarce metallic compounds and the alkali metal compound of content 0-1.0%, use are coprecipitated
Shallow lake method is made.CN90105453.4 describes a kind of multi component cyclohexanol dehydrogenation catalyst, group be divided into CuO, ZnO, MgO,
CaO and micro Na2O, weight percent 10%-50%, 10%-40%, 40%-60%, 6%-15%, 5PPM ~
30PPM.Although the research in relation to low temperature cyclohexanol dehydrogenation catalyst is more, current domestic industry device generally uses still
It is CuO/ZnO series catalysts, but the catalyst has the problems such as activity is low, selectivity is low compared with copper silicon systems catalyst.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of copper silicon systems catalyst, and it is de- to be especially used for cyclohexanol gas phase
The preparation method of hydrogen preparing cyclohexanone catalyst is added to modified additive its main feature is that the catalyst carrier has suitable pore structure,
So that there is high activity and selectivity using catalyst prepared by the carrier, the consumption of Cyclohexanone Production is greatly reduced.
The main technical schemes of the present invention：The preparation method of copper silicon systems catalyst, feature is in the catalyst using following
It is prepared by process：
（1）It is prepared by carrier
In the precipitation tank with stirring, in the case where temperature is 50 DEG C ~ 70 DEG C, sodium carbonate liquor or nitric acid are total to Ludox
Precipitation, precipitation endpoint pH are 6 ~ 10, and 10 min ~ 30min is aged at temperature 60 C ~ 80 DEG C, and washed, drying is granulated, pressure
Sheetmolding obtains semi-finished product carrier；
（2）Vehicle treated
Semi-finished product carrier is roasted 2 ~ 6 hours at 600 DEG C ~ 800 DEG C of temperature, by carrier at 160 DEG C ~ 200 DEG C after roasting
It is handled 2 ~ 4 hours in water, strong acid is then added wherein, adjust acid concentration weight percent 0.5% ~ 2%, at 70 DEG C ~ 90 DEG C
It is lower to impregnate 2 ~ 4 hours, it is washed, detach, be drying to obtain required carrier；
（3）Catalyst preparation
Catalyst preparation is carried out in closed reactor, is implemented by the following steps：1. preparing cuprammonia；2. impregnating：It will carry
Body is added in cupric ammine complex solution 1., and holding 4 hours is vacuumized under being stirred at 80 DEG C, and dipping is completed；3. detaching, washing
It washs, dry：Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, roasting；4. roasting it
Auxiliary agent dipping is carried out afterwards, and drying and roasting obtains catalyst prod.
The active constituent of the catalyst is Cu2O, Cu2O mass percentage are 18%~30%, coagent quality hundred
It is 1.0%~3.0% to divide content, remaining is carrier S iO2。
The catalyst is applied to preparing cyclohexanone by cyclohexanol dehydrogenation production process.
The specific surface area of the catalyst is 250.5m2/g~420 m2/ g, hole hold 0.35 ~ 0.87 ml/g, and average pore size is
3.0~8.0nm。
The strong acid added in the vehicle treated is nitric acid.
The coagent of the addition of the catalyst is alkalinous metal auxiliary agent.
The auxiliary agent is one or both of K, Na, Mg compound.
Catalyst prepared by the technology of the present invention method has the advantages that pore structure is reasonable, eliminates unwanted micro- in carrier
Hole provides suitable pore structure for cyclohexanol dehydrogenation reaction, and addition alkaline assistant effectively reduces the acid centre of catalyst,
Inhibit the generation of side reaction in reaction process so that reaction has the characteristics that cyclohexanol high conversion rate, cyclohexanone selectivity are high, energy
Enough energy consumption and material consumptions effectively reduced in process of cyclohexanone production.
Specific implementation mode
It is described in detail below by embodiment.The purpose for enumerating these examples is intended merely to explain the present invention, without
It is limitation of the present invention.
Embodiment 1
In the precipitation tank with stirring, the sodium carbonate liquor of 1M and JA-25 type Ludox are co-precipitated, are 50 in temperature
At DEG C, precipitation endpoint pH is 10, and 30min is aged under temperature 60 C, and washed, drying is granulated, and compression molding obtains semi-finished product load
Body roasts carrier 5 hours at 600 DEG C, then the carrier is handled 1 hour in 160 DEG C of water, is then added wherein strong
Acid adjusts acid concentration weight percent 0.5%, is impregnated 2.0 hours at 70 DEG C, washed, detach, be drying to obtain carrier A.
The carrier specific surface area is 250.5m2/ g, Kong Rongwei 0.32ml/g, average pore size 4.2nm.
Embodiment 2
In the precipitation tank with stirring, the sodium carbonate liquor of 1M and JA-25 type Ludox are co-precipitated, are 70 in temperature
At DEG C, precipitation endpoint pH is 9.0, and 20min is aged under temperature 70 C, and washed, drying is granulated, and compression molding obtains semi-finished product
Carrier is roasted 4 hours at 700 DEG C, then the carrier is handled 2 hours in 180 DEG C of water by carrier, is then added wherein
Strong acid adjusts acid concentration weight percent 1.2%, is impregnated 2 hours at 80 DEG C, washed, detach, be drying to obtain carrier B.
The carrier specific surface area is 350.2m2/ g, Kong Rongwei 0.45ml/g, average pore size 4.9nm.
Embodiment 3
In the precipitation tank with stirring, the salpeter solution of 1M and JN-30 type Ludox are co-precipitated, are 60 DEG C in temperature
Under, precipitation endpoint pH is 6.0, and 10min is aged at 90 DEG C of temperature, and washed, drying is granulated, and compression molding obtains semi-finished product load
Body roasts carrier 2 hours at 800 DEG C, then the carrier is handled 4 hours in 200 DEG C of water, is then added wherein strong
Acid adjusts acid concentration weight percent 2%, is impregnated 2 hours at 80 DEG C, washed, detach, be drying to obtain support C.The load
Surface area per unit volume product is 456.1m2/ g, Kong Rongwei 0.85ml/g, average pore size 5.2nm.
Embodiment 4
In the precipitation tank with stirring, the salpeter solution of 1M and JN-25 type Ludox are co-precipitated, are 70 DEG C in temperature
Under, precipitation endpoint pH is 7.0, and 20min is aged under temperature 70 C, and washed, drying is granulated, and compression molding obtains semi-finished product load
Carrier is roasted 3 hours at 750 DEG C, then the carrier is handled 1.5 hours in 190 DEG C of water by body, is then added wherein
Strong acid adjusts acid concentration weight percent 0.9%, is impregnated 2 hours at 80 DEG C, washed, detach, be drying to obtain carrier D.
The carrier specific surface area is 421.1m2/ g, Kong Rongwei 0.76ml/g, average pore size 5.4nm.
Embodiment 5
In the precipitation tank with stirring, the sodium carbonate liquor of 1M and JN-25 type Ludox are co-precipitated, are 50 in temperature
At DEG C, precipitation endpoint pH is 10, and 20min is aged at 85 DEG C of temperature, and washed, drying is granulated, and compression molding obtains semi-finished product load
Body roasts carrier 4 hours at 690 DEG C, then the carrier is handled 1 hour in 160 DEG C of water, is then added wherein strong
Acid adjusts acid concentration weight percent 0.5%, is impregnated 2 hours at 90 DEG C, washed, detach, be drying to obtain carrier E.It should
Carrier specific surface area is 280.9m2/ g, Kong Rongwei 0.58ml/g, average pore size 4.8nm.
Embodiment 6
1. configuration cuprammonia processed：It takes the ammonium hydroxide of 200ml 10M to be added in the copper nitrate solution of 1000ml 0.5M, is configured to clear
Clear cupric ammine complex solution, then add the stirring of 600 ml ionized waters.2. impregnating：160g carriers A is taken to be added to copper ammonia complexation 1.
In object solution, holding 4 hours is vacuumized under agitation at 80 DEG C, dipping is completed.3. separation, washing, drying：Will dipping material into
Row is separated by solid-liquid separation, and solid material is washed to neutral, then is dried, and 450 DEG C roast 3 hours, take 3 grams of magnesium nitrate, are configured to
10% aqueous solution sprays on a catalyst, then 400 DEG C of roastings obtain catalyst in 2 hours.Catalyst Cu2O content is 18.3%,
Specific surface area is 280.3m2/ g, Kong Rongwei 0.35ml/g, average pore size 3.7nm.
Embodiment 7
1. configuration cuprammonia processed：The ammonium hydroxide of 200ml 10M is taken to be added in the copper nitrate solution of 800ml 0.8M, 5ml 0.5M nitre
Sour sodium is configured to clear cupric ammine complex solution, then adds the stirring of 600 ml ionized waters.2. impregnating：160g carrier Bs are taken to be added to
1. cupric ammine complex solution in, 80 DEG C under agitation vacuumize holding 4 hours, dipping complete.3. separation, washing, drying：
Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, and 450 DEG C roast 2 hours, take nitric acid
2.8 grams of potassium, the aqueous solution for being configured to 10% spray on a catalyst, then 400 DEG C of roastings obtain catalyst prod in 2 hours.The catalysis
Agent Cu2O content is 22.2%, specific surface area 380.7m2/ g, Kong Rongwei 0.68ml/g, average pore size 6.8nm.
1. embodiment 8 configures cuprammonia processed：The ammonium hydroxide of 100ml 10M is taken to be added to the copper nitrate solution of 800ml 1.0M
In, 5ml 0.5M sodium nitrate is configured to clear cupric ammine complex solution, then adds the stirring of 600 ml ionized waters.2. impregnating：It takes
160g support Cs are added in cupric ammine complex solution 1., vacuumize holding 4 hours under agitation at 80 DEG C, and dipping is completed.③
Separation, washing, drying：Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, 450 DEG C of roastings
It burns 2 hours, takes 2.8 grams of potassium nitrate, the aqueous solution for being configured to 10% sprays on a catalyst, then 400 DEG C of roastings are urged for 2 hours
Agent product.Catalyst Cu2O content is 26.1%, specific surface area 465.7m2/ g, Kong Rongwei 0.87ml/g, average pore size are
6.5nm。
Embodiment 9
1. configuration cuprammonia processed：The ammonium hydroxide of 100ml 10M is taken to be added in the copper nitrate solution of 900ml 1.0M, 5ml 0.5M nitre
Sour sodium is configured to clear cupric ammine complex solution, then adds the stirring of 600 ml ionized waters.2. impregnating：160g carriers D is taken to be added to
1. cupric ammine complex solution in, 80 DEG C under agitation vacuumize holding 4 hours, dipping complete.3. separation, washing, drying：
Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, and 450 DEG C roast 2 hours, take nitric acid
1.0 grams of sodium, the aqueous solution for being configured to 10% spray on a catalyst, then 420 DEG C of roastings obtain catalyst prod in 3 hours.The catalysis
Agent Cu2O content is 28.7%, specific surface area 432.4m2/ g, Kong Rongwei 0.77ml/g, average pore size 5.9nm.
Embodiment 10
5 configuration cuprammonias processed：The ammonium hydroxide of 100ml 10M is taken to be added in the copper nitrate solution of 950ml 1.0M, 5ml 0.5M nitre
Sour sodium is configured to clear cupric ammine complex solution, then adds the stirring of 600 ml ionized waters.2. impregnating：160g carriers E is taken to be added to
1. cupric ammine complex solution in, 80 DEG C under agitation vacuumize holding 4 hours, dipping complete.3. separation, washing, drying：
Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, and 450 DEG C roast 2 hours, take nitric acid
1.0 grams of sodium is configured to water-soluble the 29.8% of 10%, specific surface area 276.5m2/ g, Kong Rongwei 0.45ml/g, average pore size are
4.8nm。
Comparative example 1
Take 1.0M copper nitrate solution 1200ml solution, 1.0M zinc nitrate solution 2400ml solution and 3.0M aluminum nitrate solutions 100ml
Mixing, mixed solution is added drop-wise to while stirring under conditions of 30 DEG C ~ 80 DEG C（10%~15%）Sodium carbonate liquor in, then
It is aged 20min ~ 30min in 30 DEG C ~ 80 DEG C of conditions, auxiliary agent is added after washing, refilters, dry, be granulated, 280 DEG C ~ 400
DEG C roasting 4 ~ 6 hours, last compression molding is to get available catalyst.
Activity rating
Catalyst sample prepared by embodiment 6 ~ 10 and comparative example 1 is lived in specification ￠ 32 × 2mm fixed bed reactors
Property evaluation, raw material cyclohexanol air speed be 0.60h-1, 230 DEG C of controlling reaction temperature, carry out under conditions of catalyst loading 50ml
As a result activity rating sees attached list 1.
1 catalyst activity evaluation result of subordinate list
| Sample | Hexamethylene alcohol conversion % | Cyclohexanone selectivity % | Cyclohexene ppm |
| Embodiment 6 | 56.68 | 99.51 | 26 |
| Embodiment 7 | 61.78 | 99.27 | 38 |
| Embodiment 8 | 59.66 | 99.26 | 21 |
| Embodiment 9 | 60.82 | 99.41 | 24 |
| Embodiment 10 | 59.27 | 99.39 | 29 |
| Comparative example 1 | 53.25 | 98.65 | 87 |
Claims (7)
1. a kind of preparation method of copper silicon systems catalyst, feature are prepared in the catalyst using following procedure：
（1）It is prepared by carrier
In the precipitation tank with stirring, in the case where temperature is 50 DEG C ~ 70 DEG C, sodium carbonate liquor or nitric acid are total to Ludox
Precipitation, precipitation endpoint pH are 6 ~ 10, and 10 min ~ 30min is aged at temperature 60 C ~ 80 DEG C, and washed, drying is granulated, pressure
Sheetmolding obtains semi-finished product carrier；
（2）Vehicle treated
Semi-finished product carrier is roasted 2 ~ 6 hours at 600 DEG C ~ 800 DEG C of temperature, by carrier at 160 DEG C ~ 200 DEG C after roasting
It is handled 2 ~ 4 hours in water, strong acid is then added wherein, adjust acid concentration weight percent 0.5% ~ 2%, at 70 DEG C ~ 90 DEG C
It is lower to impregnate 2 ~ 4 hours, it is washed, detach, be drying to obtain required carrier；
（3）Catalyst preparation
Catalyst preparation is carried out in closed reactor, is implemented by the following steps：1. preparing cuprammonia；2. impregnating：It will carry
Body is added in cupric ammine complex solution 1., and holding 4 hours is vacuumized under being stirred at 80 DEG C, and dipping is completed；3. detaching, washing
It washs, dry：Dipping material is separated by solid-liquid separation, solid material is washed to neutral, then is dried, roasting；4. roasting it
Auxiliary agent dipping is carried out afterwards, and drying and roasting obtains catalyst prod.
2. the preparation method of catalyst according to claim 1, it is characterised in that the active constituent of catalyst is Cu2O,
Cu2O mass percentages are 18%~30%, and coagent mass percentage is 1.0%~3.0%, remaining is carrier S iO2。
3. the preparation method of catalyst according to claim 1 or 2, it is characterised in that the catalyst is applied to cyclohexanol
Preparing cyclohexanone by dehydrogenating production process.
4. the preparation method of catalyst according to claim 1 or 2, it is characterised in that the specific surface area of the catalyst is
250.5m2/g~420 m2/ g, hole hold 0.35 ~ 0.87 ml/g, and average pore size is 3.0 ~ 8.0nm.
5. the preparation method of catalyst according to claim 1, it is characterised in that the strong acid added in vehicle treated is nitre
Acid.
6. the preparation method of catalyst according to claim 2, it is characterised in that the coagent of the addition of catalyst is
Alkalinous metal auxiliary agent.
7. the preparation method of catalyst according to claim 6, it is characterised in that one in auxiliary agent K, Na, Mg compound
Kind or two kinds.
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| CN111087276A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Green production process of cyclohexane and cyclohexanone |
| CN111359619A (en) * | 2020-04-23 | 2020-07-03 | 上海亚铂化工科技有限公司 | Catalyst with function of catalyzing alcohol dehydrogenation reaction, preparation method and application thereof, and method for catalyzing alcohol dehydrogenation reaction |
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| CN114570366A (en) * | 2020-12-02 | 2022-06-03 | 上海迅凯新材料科技有限公司 | Dehydrogenation catalyst, preparation method and application of dehydrogenation catalyst in preparation of gamma-butyrolactone through dehydrogenation |
| CN114570373A (en) * | 2020-12-02 | 2022-06-03 | 上海迅凯新材料科技有限公司 | Copper-silicon catalyst, preparation method and application in preparing cyclohexanone by dehydrogenation |
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| CN114570366A (en) * | 2020-12-02 | 2022-06-03 | 上海迅凯新材料科技有限公司 | Dehydrogenation catalyst, preparation method and application of dehydrogenation catalyst in preparation of gamma-butyrolactone through dehydrogenation |
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| CN114570373B (en) * | 2020-12-02 | 2024-05-14 | 上海迅凯新材料科技有限公司 | Copper-silicon catalyst, preparation method and application thereof in preparing cyclohexanone by dehydrogenation |
| CN112473675A (en) * | 2020-12-17 | 2021-03-12 | 常州大学 | Catalyst for preparing p-dioxanone and method for preparing p-dioxanone |
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| CN116116410A (en) * | 2023-02-24 | 2023-05-16 | 湘潭大学 | Copper-based catalyst and preparation method and application thereof |
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