CN110479236A - A kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst and preparation method - Google Patents
A kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst and preparation method Download PDFInfo
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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Abstract
The invention discloses a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst and preparation method thereof, wherein catalyst is using one of Elements C e, La, Zr, two or three as active component；The active component is present in catalyst with the oxide form of the element, and the mass percent of the active component in the catalyst is 10-100% in terms of element oxide form.The beneficial effects of the present invention are: the present invention is specific to carbon dioxide (CO2) and methanol (CH3OH) Direct Synthesis of Dimethyl Carbonate method provides a kind of catalyst, active high, the high advantage of selectivity.
Description
Technical field
The present invention relates to catalyst technical field, in particular to a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate are with urging
Agent and preparation method.
Background technique
With the continuous development of human civilization and social economy, people increasingly increase the demand of coal, petroleum, natural gas
Add, extensive industrial model causes the problem of environmental pollution being on the rise, Carbon Dioxide in Air (CO2) content sharply increase
Cause serious greenhouse effects.According to statistics, nearly two over 100 years the burning and exhausting of global fossil fuel total carbon dioxide capacity
It is more than the summation pass by the mankind over the past 3000 years and discharge carbon dioxide.Global warming issue caused by the excess emissions of greenhouse gases
The survival and development that numerous biologies include the mankind are affected, international community increasingly payes attention to environmental problem, and every country is in order to change
Kind environment, develops low-carbon economy, has promulgated a series of law treaties, and such as United Nations Framework Convention on Climate Change, " capital of a country is agreed
Book " and " Paris agreement ".It is simple to will affect economy by carbon emission reduction but from the angle of sustainable development view
Normal development, therefore, how effectively using carbon dioxide convert it into it is useful and with added value chemical substance by
People pay close attention to more and more widely.
The chemical formula of dimethyl carbonate (DMC) is (CH3O)2CO, relative molecular mass 90.08g/mol are one under room temperature
Kind is colorless and transparent, slightly has the slightly sweet liquid of smell, taste.From molecular structure, DMC is considered as the dimethyl of carbonic acid
Ester, so researcher thinks that it is a kind of important organic synthesis intermediate.Why with many kinds of substance chemistry can occur for DMC
Reaction is that there are many functional groups because containing in its molecular structure, such as carbonyl (- C=O-), methyl (- CH3) and methoxyl group (CH3O-)
Deng.Therefore, in organic chemical industry's synthesis, dimethyl carbonate is referred to as following " new foundation stone ", and belonging to especially has development prospect
Chemical products.
The molecular structure of DMC is very unique, because containing there are many functional groups, it is possible to many chemical substances
Reaction is learned, methylation, carbonylation, transesterification etc. can mainly occur and react, DMC can be carbonylated, methylating reagent；And because
For no toxicity, it is possible to be used as low poison solvent.DMC molecular structure CH3O-CO-OCH3The content of middle oxygen atom is up to 53%,
The octane number of gasoline can preferably be improved.Under similarity condition, when gasoline combustion being made to reach equal oxygen content, methyl tertiary butyl ether(MTBE)
(MTBE) 4.5 times more than the usage amount of usage amount ratio DMC.Use DMC as gasoline additive, moreover it is possible to reduce nytron
The discharge amount of object, carbon monoxide；In addition, common gasoline additive MTBE be highly soluble in water and can polluted underground water source, but
DMC does not have these disadvantages, therefore DMC will become a kind of most potential gasoline additive.
The method of traditional production dimethyl carbonate has phosgenation, ester-interchange method, alcoholysis of urea, methanol in chemical industry synthesis
Oxidation carbonylation method.Traditional phosgenation process route is more mature, DMC high income, but phosgene has a severe toxicity in the method, and
A large amount of HCl is generated in reaction process to carry out serious corrosion to equipment belt.Ester-interchange method synthesis DMC has been carried out industrial metaplasia
It produces, this synthetic method craft is many and diverse, and economic cost is high, and reaction raw materials need ethylene oxide or propylene oxide, both substances
Source limited by petrochemical industry, and by-product propylene glycol market capacity has reached saturation, so ester-interchange method is not to close
At the ideal way of dimethyl carbonate.Alcoholysis of urea is that urea with methanol two-step reaction synthesizes DMC, although the conversion ratio of reaction
It is higher, but selectivity is lower, and the separation of in-between product methyl carbamate and dimethyl carbonate is to prevent alcoholysis of urea work
The a great problem of industryization application.The advantages of this synthetic route of oxidative carbonylation of methanol method is that raw material is easy to get, but there are biggish
Security risk, and the selectivity of used catalyst is poor, and there are etching problems to equipment for catalyst.
Using carbon dioxide (CO2) and methanol (CH3OH) Direct Synthesis of Dimethyl Carbonate, a large amount of of CO2 are advantageously reduced
Discharge, converts the methanol of excess capacity, this process route has very big development prospect, but not yet due to industrializeding catalyst
It develops, therefore the synthetic method is at present still in the laboratory research stage.
Summary of the invention
Goal of the invention of the invention is to provide a kind of long service life, raw material is easy to get, the simple titanium dioxide of preparation process
Carbon (CO2) and methanol (CH3OH) the catalyst of Direct Synthesis of Dimethyl Carbonate.
In order to achieve the above-mentioned object of the invention, the present invention provides a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonates with urging
Agent, the catalyst are using one of Elements C e, La, Zr, two or three as active component；Preferably, described to urge
Agent is using Elements C e or La or Zr as active component.
When element combinations in the active component in use, the mass ratio of each element (in terms of each element oxide form)
Are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0-7)；That is:
When active component is Elements C e and La, the mass ratio of each element is (with each element oxide in the active component
Form meter) are as follows: CeO2:La2O3Mass ratio be (2-6): (1-4)；
When active component is Elements C e, La, Zr, the mass ratio of each element (is aoxidized in the active component with each element
Object form meter) are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0.1-7).
In order to preferably realize foregoing invention purpose, the present invention also provides the preparation methods of the catalyst, specific to wrap
Include following steps:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2One of O, two or three,
It is dissolved in distilled water and is configured to solution, alkaline solution precipitating is slowly added in the case where being stirred continuously, control pH value is >=8
(pH value is preferably 10-12)；Stirring 1h is then proceeded to, is aged 12h, filtering and washing, dry 12h, crushes under the conditions of being placed in 100 DEG C
Obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, then is dried, roasts
Obtain finished catalyst；Wherein, the shaping assistant is CMC, and the peptizing agent is citric acid, the shaping assistant and the glue
The additional amount of solvent is respectively as follows: CMC 0.1-3.0%；Citric acid 0.1-5.0%；The additional amount of water is comminuting matter, forms and help
The 15-40% of agent and peptizing agent gross mass.
Wherein, in the step (1), alkaline solution KOH, NaOH, K2CO3And NH3·H2One of O solution, two kinds
Or it is a variety of；The concentration of the alkaline solution is 2mol/L；In the step (2), drying temperature is 30-150 DEG C, drying time is
2-24h, maturing temperature is 480-680 DEG C, calcining time 2-8h.
It is described the present invention also provides the preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst
Preparation method the following steps are included:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2One of O, two or three,
It is dissolved in distilled water and is configured to solution, alkaline solution precipitating is slowly added in the case where being stirred continuously, control pH value is >=8；
Stirring 1h is then proceeded to, is aged 12h, filtering and washing, dry 12h, crushes to obtain comminuting matter under the conditions of being placed in 100 DEG C；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, then is dried, roasts
Obtain finished catalyst.Wherein, the shaping assistant is CMC, and the peptizing agent is citric acid, the shaping assistant and the glue
The additional amount of solvent is respectively as follows: CMC 0.1-3.0%；Citric acid 0.1-5.0%；The additional amount of water is comminuting matter, forms and help
The 15-40% of agent and peptizing agent gross mass.
In the step (1), alkaline solution KOH, NaOH, K2CO3And NH3·H2One of O solution, two kinds or more
Kind；The concentration of the alkaline solution is 2mol/L.
In the step (2), drying temperature is 30-150 DEG C, drying time 2-24h, maturing temperature is 480-680 DEG C,
Calcining time is 2-8h.
The catalyst that the preparation method obtains, be using one of Elements C e, La, Zr, two or three as activity
Component, and the element is present in catalyst in the form of an oxide；The active component is in institute in terms of element oxide form
Stating the mass percent in catalyst is 10-100%, preferably 30-60%；The mass ratio of each element in the active component
(in terms of each element oxide form) are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0-7), it may be assumed that
When active component is Elements C e and La, the mass ratio of each element is (with each element oxide in the active component
Form meter) are as follows: CeO2:La2O3Mass ratio be (2-6): (1-4)；
When active component is Elements C e, La, Zr, the mass ratio of each element (is aoxidized in the active component with each element
Object form meter) are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0.1-7).
The beneficial effects of the present invention are: the present invention is specific to carbon dioxide (CO2) and methanol (CH3OH it) directly synthesizes
Dimethyl carbonate method provides a kind of catalyst, active high, the high advantage of selectivity；Pass through determination of activity result table
Bright: the catalyst prepared by the application specified conditions is to carbon dioxide (CO2) and methanol (CH3OH) direct carbonate synthesis diformazan
Ester all has activity, and CeO2、La2O3、ZrO2Composite oxides activity be better than single oxide, titanium dioxide of the invention
Carbon (CO2) and methanol (CH3OH) selectivity of Direct Synthesis of Dimethyl Carbonate catalyst is very high (100%).
Detailed description of the invention
Fig. 1 is the structural schematic diagram of minisize reaction kettle in comparative test of the present invention.
Specific embodiment
In order to clarify the technical characteristics of the invention, being illustrated below by specific embodiment to this programme.
Embodiment 1
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O is simultaneously dissolved in distilled water, is configured to the cerous nitrate solution of 0.288mol/L；Not
It is 12 that KOH solution to the pH value that concentration is 2mol/L, which is slowly added dropwise, in the case where disconnected stirring；Continue stirring 1 hour, it is then static
Ageing 10 hours, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 1.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 1.7% of comminuting matter, 2.7%；
The additional amount of water is the 23% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 2
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) La (NO is weighed3)3·6H2O is simultaneously dissolved in distilled water, is configured to the lanthanum nitrate hexahydrate of 0.288mol/L；Not
It is 12 that KOH solution to the pH value that concentration is 2mol/L, which is slowly added dropwise, in the case where disconnected stirring；Continue stirring 1 hour, it is then static
Ageing 10 hours, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 2.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 0.9% of comminuting matter, 2.1%；
The additional amount of water is the 28% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 3
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Zr (NO is weighed3)4·5H2O is simultaneously dissolved in distilled water, is configured to the zirconium nitrate solution of 0.288mol/L；Not
It is 12 that KOH solution to the pH value that concentration is 2mol/L, which is slowly added dropwise, in the case where disconnected stirring；Continue stirring 1 hour, it is then static
Ageing 10 hours, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 3.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 1.3% of comminuting matter, 1.6%；
The additional amount of water is the 32% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 4
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O is simultaneously dissolved in distilled water, is configured to 0.288mol/L nitric acid
The mixed solution of zirconium and 0.288mol/L lanthanum nitrate；It is molten that the KOH that concentration is 2mol/L is slowly added dropwise in the case where being stirred continuously
Liquid to pH value is 12；Continue stirring 1 hour, then static ageing 10 hours, filtering and washing, dry 12 under the conditions of being placed in 100 DEG C
Hour, crush to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 3.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 0.5% of comminuting matter, 1.2%；
The additional amount of water is the 21% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 5
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to 0.288mol/L nitric acid
The mixed solution of cerium and 0.288mol/L zirconium nitrate；It is molten that the KOH that concentration is 2mol/L is slowly added dropwise in the case where being stirred continuously
Liquid to pH value is 12；Continue stirring 1 hour, then static ageing 10 hours, filtering and washing, dry 12 under the conditions of being placed in 100 DEG C
Hour, crush to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 5.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 1.9% of comminuting matter, 0.8%；
The additional amount of water is the 20% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 6
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) La (NO is weighed3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to 0.288mol/L nitric acid
The mixed solution of lanthanum and 0.288mol/L zirconium nitrate；It is molten that the KOH that concentration is 2mol/L is slowly added dropwise in the case where being stirred continuously
Liquid to pH value is 12；Continue stirring 1 hour, then static ageing 10 hours, filtering and washing, dry 12 under the conditions of being placed in 100 DEG C
Hour, crush to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 6.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 2.1% of comminuting matter, 0.1%；
The additional amount of water is the 17% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 7
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to
The mixed solution of the cerous nitrate of 0.288mol/L, 0.288mol/L lanthanum nitrate and 0.288mol/L zirconium nitrate；What is be stirred continuously
In the case of KOH solution to the pH value that concentration is 2mol/L is slowly added dropwise is 12；Continue stirring 1 hour, then static ageing 10 is small
When, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 7.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 2.5% of comminuting matter, 3.5%；
The additional amount of water is the 15% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 8
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to
The mixed solution of the cerous nitrate of 0.288mol/L, 0.288mol/L lanthanum nitrate and 0.288mol/L zirconium nitrate；What is be stirred continuously
In the case of KOH solution to the pH value that concentration is 2mol/L is slowly added dropwise is 14；Continue stirring 1 hour, then static ageing 10 is small
When, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 8.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 2.8% of comminuting matter, 4.0%；
The additional amount of water is the 35% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 9
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to
The mixed solution of the cerous nitrate of 0.288mol/L, 0.288mol/L lanthanum nitrate and 0.288mol/L zirconium nitrate；What is be stirred continuously
In the case of KOH solution to the pH value that concentration is 2mol/L is slowly added dropwise is 10；Continue stirring 1 hour, then static ageing 10 is small
When, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 9.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 3.0% of comminuting matter, 4.5%；
The additional amount of water is the 37% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 10
The preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst is present embodiments provided, specifically
Step are as follows:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2O is simultaneously dissolved in distilled water, is configured to
The mixed solution of the cerous nitrate of 0.288mol/L, 0.288mol/L lanthanum nitrate and 0.288mol/L zirconium nitrate；What is be stirred continuously
In the case of KOH solution to the pH value that concentration is 2mol/L is slowly added dropwise is 8；Continue stirring 1 hour, then static ageing 10 is small
When, filtering and washing is 12 hours dry under the conditions of being placed in 100 DEG C, crushes to obtain comminuting matter；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, is done under the conditions of 100 DEG C
Then dry 10h roasts 6h under the conditions of 550 DEG C again, obtains finished catalyst 10.
Wherein, shaping assistant CMC, peptizing agent are citric acid, and additional amount is respectively the 0.1% of comminuting matter, 5.0%；
The additional amount of water is the 40% of comminuting matter, shaping assistant and peptizing agent gross mass.
Embodiment 11
In embodiment 1-10, in step (2), drying temperature, drying time respectively can be with are as follows: 30 DEG C-for 24 hours, 45 DEG C of -18h,
65 DEG C of -17h, 78 DEG C of -16h, 95 DEG C of -15h, 115 DEG C of -14h, 125 DEG C of -10h, 135 DEG C of -8h, 150 DEG C of -2h, maturing temperature, roasting
Burning the time respectively can be with are as follows: 480 DEG C of -8h, 500 DEG C of -7.5h, 520 DEG C of -6h, 560 DEG C of -5h, 610 DEG C of -4h, 640 DEG C of -3h, 680
℃-2h。
Embodiment 12
In embodiment 1-11, the alkaline solution being slowly added dropwise in the case where being stirred continuously can also be NaOH, K2CO3Or
NH3·H2O solution, or both or three mixed solution.
Comparative test
It is used for the obtained 10 kinds of catalyst samples (each sample constituent content is as shown in table 1) of embodiment 1-10 miniature anti-
Kettle is answered to carry out Catalyst Evaluation Test, the structure of the minisize reaction kettle is as shown in Figure 1, in which: 1, pressure gauge；2, explosive valve；3,
Intake valve (or exhaust valve)；4, sampling valve；5, temperature sensor；6, insulation shell；7, reaction kettle body；8, control panel；This examination
In testing, the design parameter of the minisize reaction kettle are as follows: volume 250mL, design pressure 10MPa, design temperature 300oC, mixing speed
0-1000r/min。
The methanol of the catalyst sample and certain mass that weigh embodiment 1-10 certain mass respectively is fitted into reaction kettle；With
CO2 gas inflates the air deflated in displacement kettle repeatedly, and finally rushes CO2Gas is to specified pressure.Controller switches are opened, if
Set reaction temperature, reaction time, reflection revolving speed, when temperature is raised to set temperature, beginning timing；After reaction, it is cooled to
40 DEG C hereinafter, sampling carries out chromatography.
The calculation of yield formula of dimethyl carbonate (DMC) is as follows:
The composition content of 1 embodiment 1-10 catalyst of table
| Catalyst | CeO2(%) | La2O3(%) | ZrO2(%) | Remarks |
| Catalyst 1 | 100 | PH=12 | ||
| Catalyst 2 | 100 | PH=12 | ||
| Catalyst 3 | 100 | PH=12 | ||
| Catalyst 4 | 50 | 50 | PH=12 | |
| Catalyst 5 | 50 | 50 | PH=12 | |
| Catalyst 6 | 50 | 50 | PH=12 | |
| Catalyst 7 | 33.3 | 33.3 | 33.3 | PH=12 |
| Catalyst 8 | 33.3 | 33.3 | 33.3 | PH=14 |
| Catalyst 9 | 33.3 | 33.3 | 33.3 | PH=10 |
| Catalyst 10 | 33.3 | 33.3 | 33.3 | PH=8 |
The determination of activity experimental result of 2 embodiment 1-10 catalyst of table
By table 2, it can be seen that on the activity rating device in laboratory, to the carbon dioxide (CO of sample2) and methanol
(CH3OH) Direct Synthesis of Dimethyl Carbonate catalyst activity is evaluated, by determination of activity the result shows that: pass through the application
The catalyst of specified conditions preparation is to carbon dioxide (CO2) and methanol (CH3OH) Direct Synthesis of Dimethyl Carbonate all has activity,
And CeO2、La2O3、ZrO2Composite oxides activity be better than single oxide, carbon dioxide (CO of the invention2) and methanol
(CH3OH) selectivity of Direct Synthesis of Dimethyl Carbonate catalyst is very high (100%).
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst, which is characterized in that the catalyst is with element
One of Ce, La, Zr, it is used as active component two or three.
2. catalyst according to claim 1, which is characterized in that the active component is with the oxide form of the element
It is present in catalyst, the mass percent of the active component in the catalyst is 10- in terms of element oxide form
100%。
3. catalyst according to claim 1 or 2, which is characterized in that in the active component each element mass ratio (with
Each element oxide form meter) are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0-7)；Or,
When active component is Elements C e and La, the mass ratio of each element is (with each element oxide form in the active component
Meter) are as follows: CeO2:La2O3Mass ratio be (2-6): (1-4)；
When active component is Elements C e, La, Zr, the mass ratio of each element is (with each element oxide shape in the active component
Formula meter) are as follows: CeO2:La2O3:ZrO2Mass ratio be (2-6): (1-4): (0.1-7).
4. catalyst according to claim 1-3, which is characterized in that the preparation method of the catalyst include with
Lower step:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2One of O, two or three, are dissolved in
It is configured to solution in distilled water, alkaline solution precipitating is slowly added in the case where being stirred continuously, control pH value is >=8；Then
Continue to stir 1h, is aged 12h, filtering and washing, dry 12h, crushes to obtain comminuting matter under the conditions of being placed in 100 DEG C；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, then is dried, roasts and obtain
Finished catalyst.
5. catalyst according to claim 4, which is characterized in that in the step (1), alkaline solution KOH, NaOH,
K2CO3And NH3·H2One of O solution, two or more；The concentration of the alkaline solution is 2mol/L.
6. catalyst according to claim 4 or 5, which is characterized in that in the step (2), drying temperature 30-150
DEG C, drying time 2-24h, maturing temperature is 480-680 DEG C, calcining time 2-8h.
7. the preparation method of a kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst, which is characterized in that the preparation
Method the following steps are included:
(1) Ce (NO is weighed3)3·6H2O、La(NO3)3·6H2O、Zr(NO3)4·5H2One of O, two or three, are dissolved in
It is configured to solution in distilled water, alkaline solution precipitating is slowly added in the case where being stirred continuously, control pH value is >=8；Then
Continue to stir 1h, is aged 12h, filtering and washing, dry 12h, crushes to obtain comminuting matter under the conditions of being placed in 100 DEG C；
(2) shaping assistant, peptizing agent and water are added into comminuting matter, after being uniformly mixed molding, then is dried, roasts and obtain
Finished catalyst.
8. preparation method according to claim 7, which is characterized in that in the step (1), alkaline solution KOH,
NaOH、K2CO3And NH3·H2One of O solution, two or more；The concentration of the alkaline solution is 2mol/L.
9. preparation method according to claim 7 or 8, which is characterized in that in the step (2), drying temperature 30-
150 DEG C, drying time 2-24h, maturing temperature is 480-680 DEG C, calcining time 2-8h.
10. according to the described in any item preparation methods of claim 7-9, which is characterized in that the catalysis that the preparation method obtains
Agent is using one of Elements C e, La, Zr, two or three as active component, and the element exists in the form of an oxide
In catalyst, the mass percent of the active component in the catalyst is 10-100% in terms of element oxide form；
The mass ratio of each element in the active component (in terms of each element oxide form) are as follows: CeO2:La2O3:ZrO2Mass ratio be
(2-6): (1-4): (0-7).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786875A (en) * | 2018-04-11 | 2018-11-13 | 天津大学 | A kind of preparation method of Zn-Zr bimetallics dimerization body catalyst |
| CN110563585A (en) * | 2019-10-11 | 2019-12-13 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
| CN110882686A (en) * | 2019-12-18 | 2020-03-17 | 西南石油大学 | Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate |
| CN113620806A (en) * | 2021-07-02 | 2021-11-09 | 湘南学院 | Preparation method of dimethyl carbonate |
| CN115382534A (en) * | 2022-08-30 | 2022-11-25 | 福建中盛宏业新材科技股份公司 | Method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07224011A (en) * | 1994-02-15 | 1995-08-22 | Showa Denko Kk | Production of carbonic acid ester |
| JP2009034659A (en) * | 2007-07-11 | 2009-02-19 | Gunma Industry Support Organization | Catalyst for synthesizing hydrocarbons, method for manufacturing the same and method for producing hydrocarbons by using the same |
| CN101596452A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalyst for preparing dimethyl carbonate by urea alcoholysis and preparation method thereof |
| CN104892423A (en) * | 2015-05-18 | 2015-09-09 | 太原理工大学 | A process of preparing dimethyl carbonate by oxidative carbonylation of methanol |
| US9518003B1 (en) * | 2013-07-30 | 2016-12-13 | E3Tec Service, Llc | Method of producing high-concentration alkyl carbonates using carbon dioxide as feedstock |
| CN106336358A (en) * | 2015-08-10 | 2017-01-18 | 中国石油化工股份有限公司 | Method for direct catalytic synthesis of dimethyl carbonate from carbon dioxide and methanol |
-
2019
- 2019-09-06 CN CN201910843960.7A patent/CN110479236A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07224011A (en) * | 1994-02-15 | 1995-08-22 | Showa Denko Kk | Production of carbonic acid ester |
| JP2009034659A (en) * | 2007-07-11 | 2009-02-19 | Gunma Industry Support Organization | Catalyst for synthesizing hydrocarbons, method for manufacturing the same and method for producing hydrocarbons by using the same |
| CN101596452A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalyst for preparing dimethyl carbonate by urea alcoholysis and preparation method thereof |
| US9518003B1 (en) * | 2013-07-30 | 2016-12-13 | E3Tec Service, Llc | Method of producing high-concentration alkyl carbonates using carbon dioxide as feedstock |
| CN104892423A (en) * | 2015-05-18 | 2015-09-09 | 太原理工大学 | A process of preparing dimethyl carbonate by oxidative carbonylation of methanol |
| CN106336358A (en) * | 2015-08-10 | 2017-01-18 | 中国石油化工股份有限公司 | Method for direct catalytic synthesis of dimethyl carbonate from carbon dioxide and methanol |
Non-Patent Citations (4)
| Title |
|---|
| RIM SAADA: "Catalytic conversion of carbon dioxide (CO2) into value added chemicals", 《LONDON SOUTH BANK UNIVERSITY PHD THESIS》 * |
| 朱洪法编: "《催化剂成型》", 31 January 1992 * |
| 赵丽芳: "二氧化碳与甲醇直接合成碳酸二甲酯的CeO2及Ce1-xLaxO催化剂的研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
| 邢鑫等: "纳米CeO2催化CO2与甲醇反应合成碳酸二甲酯的研究", 《化学工程师》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786875A (en) * | 2018-04-11 | 2018-11-13 | 天津大学 | A kind of preparation method of Zn-Zr bimetallics dimerization body catalyst |
| CN108786875B (en) * | 2018-04-11 | 2021-04-20 | 天津大学 | Preparation method of Zn-Zr bimetal dimer catalyst |
| CN110563585A (en) * | 2019-10-11 | 2019-12-13 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
| CN110563585B (en) * | 2019-10-11 | 2021-02-09 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
| CN110882686A (en) * | 2019-12-18 | 2020-03-17 | 西南石油大学 | Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate |
| CN110882686B (en) * | 2019-12-18 | 2023-01-10 | 西南石油大学 | Monolithic catalyst for preparing dimethyl carbonate by direct synthesis method, preparation method and direct synthesis method of dimethyl carbonate |
| CN113620806A (en) * | 2021-07-02 | 2021-11-09 | 湘南学院 | Preparation method of dimethyl carbonate |
| CN113620806B (en) * | 2021-07-02 | 2023-07-25 | 湘南学院 | Preparation method of dimethyl carbonate |
| CN115382534A (en) * | 2022-08-30 | 2022-11-25 | 福建中盛宏业新材科技股份公司 | Method for preparing dimethyl carbonate by catalyzing methanol with cerium-based oxide |
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