CN109647497A - For epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate and preparation method and application - Google Patents
For epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate and preparation method and application Download PDFInfo
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- CN109647497A CN109647497A CN201811460299.3A CN201811460299A CN109647497A CN 109647497 A CN109647497 A CN 109647497A CN 201811460299 A CN201811460299 A CN 201811460299A CN 109647497 A CN109647497 A CN 109647497A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
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Abstract
A kind of catalyst group for epoxides, methanol and carbon dioxide preparation dimethyl carbonate becomes metal oxide and HZSM-5 molecular sieve, the weight percent of catalyst are as follows: metal oxide 0.005-20%, remaining is HZSM-5 molecular sieve.The present invention is directly implemented for CO2, methanol and epoxides one pot reaction preparing dimethyl carbonate, reaction step is simple, at low cost, the wider array of advantage of application prospect.
Description
Technical field
The present invention relates to a kind of catalyst and its system for epoxides, methanol and carbon dioxide preparation dimethyl carbonate
Preparation Method and application.
Background technique
Carbon dioxide is a kind of environmental-friendly one resource of carbon, rich reserves, nontoxic, non-combustible, cheap and easy to get and can
Circular regeneration.No matter from the point of view of environmental protection or renewable resource utilization, CO2Fixation and chemical conversion in terms of
Research is all of great significance.In organic synthesis, CO2The progress of the toxic compounds such as traditional CO and phosgene can partially be substituted
The synthesis of organic carbonate, polycarbonate and urea etc., these three compounds have achieved industrial production at present.
Organic carbonate is a kind of green chemical with characteristics such as higher boiling, low-steam pressure, low toxicities, has been widely used in
The multiple fields such as solvent, detergent, lithium battery electrolytes, fuel additive.Organic carbonate can be divided into linear carbonate
And cyclic carbonate.The linear carbonate for industrially having significant application value includes: dimethyl carbonate (dimethyl
Carbonate, DMC), diphenyl carbonate (diphenyl carbonatem, DPC), methyl ethyl carbonate etc.；Cyclic carbonate packet
It includes: ethylene carbonate (ethylene carbonate, EC) and propene carbonate (propylene carbonate, PC) etc..Its
Middle dimethyl carbonate (DCM) is colorless and transparent liquid at normal temperature, can with most of organic solvent, especially alcohol, ketone, ether,
Ester isopolarity solvent dissolves each other.DMC can replace freon, chloroform etc. to make solvent, make oil instead of methyl tertiary butyl ether(MTBE) (MTBE)
Product additive does methylating reagent instead of halide, dimethyl suflfate and makees carbonylation agent instead of phosgene.DMC pesticide,
The fields such as medicine, plastic fuel, coating and new material have wide application prospect.So the synthesis of dimethyl carbonate has
Very big practical application value and economic value.
The preparation method of domestic and international existing dimethyl carbonate mainly has: oxidative carbonylation of methanol method, ester-interchange method, urea alcohol
Solution, methanol and CO2Synthetic method, phosgenation.Carbonyl mainly is aoxidized with ester-interchange method, methanol in the actual industrial production of China
Change method and phosgenation.Since phosgene is toxic raw materials, and environment is caused seriously to pollute, phosgenation is gradually eliminated.
Method primarily now is ester-interchange method and methanol oxidation carbonyl process.Aoxidize that carbonyl process technical difficulty is big, the design to technique
Selection with equipment material requires stringent, investment height.Ester-interchange method dimethyl carbonate high income, reaction condition is mild, reacts
Journey is nontoxic, and by-product diol compound is also a kind of important industrial chemicals.This route is mainly proceeded in two phases at present, first
First carbon dioxide and epoxides cycloaddition reaction generate cyclic carbonate, and cyclic carbonate generates carbonic acid with methanol transesterification again
Dimethyl ester.The ester exchange reaction of cyclic carbonate and methanol can use bronsted lowry acids and bases bronsted lowry catalyst, but the effect of alkali is preferable.Industry at present
On be all made of homogeneous catalyst, such as the soluble bases of sodium methoxide is as catalyst for ester exchange reaction.The shortcomings that two-step method is high
It is energy consumption, with high investment.If this two-step reaction can be merged into a step, avoid cycloaddition, two step of transesterification production in
Separation process will substantially reduce production cost, be the production most promising method of dimethyl carbonate.Realize three component, one pot of height
The step of validity response most critical is to make reaction can be in temperature by active catalytic components while priming reaction substrate and carbon dioxide
It is quickly carried out under the conditions of.For carbon dioxide, the activation of epoxides and methanol is done following several strategies and is introduced.
CO2Oxygen there is faint lewis base property, nucleophilic site can be made, while carbonyl carbon has weak lewis acidity
It can make electrophilic site, easily be reacted with electron donor.Typical activation CO2Strategy be using nucleopilic reagent change CO2Linear type point
Minor structure assigns its higher reactivity, to further promote CO2Effective conversion.Representative activation system is for example organic
Highly basic, super base and alcohol bicomponent system, N-heterocyclic carbine and ammonium tungstate etc..Another effective activation CO2Method be using
Transistion metal compound adjusts its structure or distribution of charges, such as Raney nickel and d8-d10Late transition metal (Fe0,RhI,
Pd0,PdII) catalyst etc..
Through overactivation, oxygen atom cloud density reduces epoxides on ring, it is easier to ring-opening reaction occur.Therefore it activates
Reaction substrate is to CO2Chemical conversion reaction is of crucial importance, according to previous research report, epoxide-activation mode
Be broadly divided into three classes: 1) main group/transition metal is as Lewis acid active centre；2) proton carrier conduct
Acid active centre；3) organic molecule cationic (quaternary ammonium salt cationic, quaternary phosphine salt cation and ionic liquid etc.) is as activation
Center.Wherein, most economical effective system is quaternary ammonium salt as nucleopilic reagent, using transition metal species priming reaction substrate and
CO2, to realize that efficient catalytic converts under low pressure temperate condition.
Methanol is used as nucleopilic reagent in the reaction, and therefore, the nucleophilicity for improving methanol facilitates the activity of intensified response.
Such activating effect can be realized by such as organic alkali effect of strong supplied for electronic species.Nitrogen-atoms electron rich in organic base molecule
Property, by the way that hydrogen bond action occurs with methanol hydroxylethyl, to improve the charge density on methanol oxygen atom, and then improve its nucleophilic
Property.
ZSM-5 is the alumino-silicate mesopore zeolite molecular sieve with three-dimensional straight channels structure, it has fabulous heat steady
Qualitative, resistance to acid and alkali and lipophilic-hydrophobic property etc..Hydrogen HZSM-5 has lewis acid (Lewis acid) and bronsted simultaneously
Sour (Bronsted acid), and sour site and sour density are adjustable.In addition, passing through the letters such as carried metal or skeletal atom replacement
Just method can targetedly adjust the acid-base catalysis characteristic of HZSM-5.HZSM-5 molecular sieve is as high performance carrier materials or urges
Agent is got growing concern in organic synthesis field, they can be applied equally to CO2Catalytic conversion reaction, Er Qieyi
In recycling and reusing.
The present invention is by CO2, methanol, epoxides simultaneously reactor is added, directly synthesize carbon under suitable catalyst
Dimethyl phthalate.The technique requires catalyst to have catalysis to live cycloaddition reaction and cyclic carbonate alcoholysis reaction two-step reaction
Property, and optimal reaction condition is close.The catalyst of metal species and HZSM-5 molecular sieve composition is synthesized applied to three components
Dimethyl carbonate, all effective to cycloaddition reaction and alcoholysis reaction, there is presently no relevant research reports.
Summary of the invention
It is an object of the present invention to provide one kind to be used for CO2, methanol and epoxide reaction preparing dimethyl carbonate catalyst and
Preparation method and application.
The present invention is using a kind of new heterogeneous catalysis mode, and based on the building of HZSM-5 molecular sieve, multifunction is heterogeneous urges
Agent (M)/HZSM-5.Such catalyst has a variety of activation sites, to CO2Dual activation is carried out with reaction substrate, is mentioned significantly
High catalytic capability realizes the target that overactivity is mutually compatible with catalytic capability and simple recycling.
Functionalization (M)/HZSM-5 catalyst, which has, enriches adjustable soda acid site, to CO2It is carried out with organic reaction substrate
Dual activation, this synergistic effect make this heterogeneous catalysis system in low pressure CO2With realization efficient catalytic conversion under temperate condition.
Through the invention, the disadvantage of conventional catalyst system high pressure, high catalytic amount and reaction time length will be overcome, while provide one kind
The heterogeneous catalysis method of Cheap highly effective is convenient for large-scale application.
Catalyst composition of the invention includes metal oxide and HZSM-5 molecular sieve.
The weight percent of catalyst as described above are as follows: metal oxide 0.005-20%, remaining is HZSM-5 points
Son sieve.
Metal oxide as described above is one or more of Zn, Mg, Ce, Ca, Co, La, Ga, Zr oxide.
HZSM-5 molecular sieve silica alumina ratio Si/Al as described above is 10-130, specific surface area 200-
1000m2·g-1, partial size 20-10000nm, average pore size 0.5-20nm.
In order to achieve the above object, the present invention prepares Modified HZSM-5 Zeolite Catalyst by the method impregnated, it is specific to prepare
Method includes the following steps:
Preparing metal cation concn is 0.01~0.50gml-1Metal-nitrate solutions, be added HZSM-5 molecule
Sieve impregnates 1-24h, then in 60-150 DEG C of drying 2-24h, the solid abrasive that will be obtained, 200-450 DEG C of roasting 3-
12h。
Metal nitrate as described above is the nitrate of Zn, Mg, Ce, Ca, Co, La, Ga, Zr.
The application of catalyst preparation dimethyl carbonate of the invention, reaction condition are as follows:
It is 10-50% that epoxides and methanol, which account for reactor volume ratio, adds quaternary ammonium salt and catalysis in reaction system
Agent is 60-180 DEG C in reaction temperature, fills CO2To 0.1-6MPa, reactant residence time in reaction bed is controlled
It makes at 1-8 hours, wherein epoxides and methanol molar ratio 1:1-1:30, the molar ratio of quaternary ammonium salt and epoxides is
0.05-0.2, in terms of tenor in metal oxide, the molal quantity and catalyst quality ratio of epoxides are 0.05-
0.2mmol/gcat,
Epoxides as described above is ethylene oxide or propylene oxide.
Quaternary ammonium salt as described above is 4-propyl bromide, tetraethylammonium bromide, etamon chloride, tetrapropyl chlorination
One of ammonium, tetrabutylammonium chloride, tetrabutylammonium bromide.
Technical advantage of the invention is as follows:
The present invention discloses a kind of HZSM-5 molecular sieve catalyst modified by infusion process.With existing industrial catalyst phase
Than the substantive distinguishing features and progress that the present invention has are:
(1) industrial substep catalyst is operated under higher reaction pressure, for the design system of reactor
It makes and service condition proposes more harsh requirement, this work HZSM-5 molecular sieve is convenient for changing by straightforward procedure progress metal
Property, reaction pressure is low, has important meaning to the manufacturing cost for reducing product；
(2) HZSM-5 molecular sieve has both lewis acid and bronsted acid, can with Activation Activation multiclass substrate, (M)/
HZSM-5 molecular sieve has not been reported as efficient functionalization catalyst for three component reaction preparing dimethyl carbonates；
(3) HZSM-5 molecular sieve have oleophilic drainage characteristic, relative to species such as metal oxides, surface be easier to
Reaction substrate is contacted and is interacted, and is conducive to react efficient progress；
(4) functional molecular sieve is used as catalyst, is directly realized by three component one pot reaction preparing dimethyl carbonates, reaction step letter
Single, at low cost, application prospect is wider.
(5) catalytic efficiency of catalyst: conversion ratio >=99%, carbonic ester yield >=99%, catalyst are at least recycled 6
More than secondary, activity is not reduced.
Specific embodiment
A specific embodiment of the invention is further described in detail below by specific embodiment.
Embodiment 1
Preparation zinc ion concentration is 0.2gml-1Zinc nitrate solution, be added HZSM-5 molecular sieve impregnate 12h, wherein
The silica alumina ratio of ZSM-5 molecular sieve is 70, specific surface area 700m2·g-1, partial size 10000nm, average pore size 0.5nm.With
Afterwards in 80 DEG C of drying 2h, the solid abrasive that will be obtained, 250 DEG C of roasting 9h are to get arriving required modified molecular sieve catalyst.It is made
ZSM-5 Type Zeolites agent in zinc oxide mass percentage be 0.5%.
Catalyst is used for the reaction of preparing dimethyl carbonate.Reaction raw materials are propylene oxide and methanol, account for reactor and always hold
Long-pending 30%, epoxides and methanol molar ratio 5 add etamon chloride in reaction system, the substance and propylene oxide
Molar ratio is 0.2.Metal component molal quantity and propylene oxide in (the M)/HZSM-5 molecular sieve catalyst added in reaction system
Molar ratio be 0.2, in reaction temperature be 100 DEG C, CO in reactor2It is pressurized under the conditions of 1MPa, reactant is in reaction bed
Middle residence time control is in 4h.
Embodiment 2-11
On the basis of embodiment 1, embodiment 2-11 carries out catalyst composition and preparation process and reaction condition
Adjustment, specific data see attached list 1 and subordinate list 2.Reaction condition and result see attached list 3.
Comparative example 1
Reaction raw materials are propylene oxide and methanol, account for the 30% of reactor total measurement (volume), epoxides and methanol molar ratio 1:
5, etamon chloride is added in reaction system, and the molar ratio of the substance and propylene oxide is 0.07.It is not added in reaction system
Catalyst, in reaction temperature be 100 DEG C, CO in reactor2It is pressurized under the conditions of 1MPa, when reactant stops in reaction bed
Between control in 4h.Specific data see attached list 3.
Comparative example 2
On the basis of embodiment 1, comparative example 2 forms catalyst and reaction condition is adjusted, reaction raw materials
For propylene oxide and methanol, the 30% of reactor total measurement (volume), epoxides and methanol molar ratio 1:5 are accounted for, is added in anti-reaction system
Add etamon chloride, the molar ratio of the substance and propylene oxide is 0.07.It is added in reaction system and does not add modified HZSM-5
Molecular sieve catalyst, epoxides and unmodified HZSM-5 molecular sieve catalyst mass ratio are 10.0, in reaction temperature be 100
DEG C, CO in reactor2It is pressurized under the conditions of 1MPa, reactant residence time in reaction bed controls in 4h.Specific data are shown in
Subordinate list 3.
1 catalyst preparation conditions of subordinate list
2 catalyst of subordinate list composition
| Embodiment | Metal oxide composition and its proportion/wt% in catalyst |
| 1 | Zinc oxide, 0.5 |
| 2 | Magnesia, 15 |
| 3 | Cerium oxide, 10 |
| 4 | Calcium oxide, 10 |
| 5 | Cobalt oxide, 5 |
| 6 | Lanthana, 10 |
| 7 | Gallium oxide, 2 |
| 8 | Zirconium oxide, 5 |
| 9 | Zinc oxide, 5；Magnesia, 5 |
| 10 | Calcium oxide, 5；Lanthana, 5 |
| 11 | Magnesia, 8；Cerium oxide, 7 |
3 reaction condition of subordinate list and result
。
Claims (9)
1. a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate, it is characterised in that catalyst
Group becomes metal oxide and HZSM-5 molecular sieve, the weight percent of catalyst are as follows: metal oxide 0.005-20%,
Remaining is HZSM-5 molecular sieve.
2. it is as described in claim 1 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate,
It is characterized in that the metal oxide is one or more of Zn, Mg, Ce, Ca, Co, La, Ga, Zr oxide.
3. it is as described in claim 1 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate,
It is characterized in that the HZSM-5 molecular sieve silica alumina ratio Si/Al is 10-130, specific surface area is 200-1000 m2·g-1, partial size is 20-10000 nm, and average pore size is 0.5-20 nm.
4. as described in any one of claims 1-3 a kind of for epoxides, methanol and carbon dioxide preparation dimethyl carbonate
Catalyst preparation method, it is characterised in that catalyst is prepared by dipping method.
5. as claimed in claim 4 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate
Preparation method, it is characterised in that dipping method of modifying it is as follows:
Preparing metal cation concn is 0.01~0.50 gml-1Metal-nitrate solutions, be added HZSM-5 molecular sieve, leaching
Stain 1-24 h, then in 60-150 DEG C of drying 2-24 h, the solid abrasive that will be obtained, 200-450 DEG C of roasting 3-12 h.
6. as claimed in claim 4 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate
Preparation method, it is characterised in that the metal nitrate be Zn, Mg, Ce, Ca, Co, La, Ga, Zr nitrate.
7. as described in any one of claims 1-3 a kind of for epoxides, methanol and carbon dioxide preparation dimethyl carbonate
Catalyst application, it is characterised in that include the following steps:
It is 10-50% that epoxides and methanol, which account for reactor volume ratio, quaternary ammonium salt and catalyst is added in reaction system, in anti-
Answering temperature is 60-180 DEG C, fills CO2To 0.1-6 MPa, reactant residence time in reaction bed is controlled in 1-
8 hours, wherein epoxides and methanol molar ratio 1:1-1:30, the molar ratio of quaternary ammonium salt and epoxides was 0.05-0.2,
In terms of tenor in metal oxide, the molal quantity and catalyst quality ratio of epoxides are 0.05-0.2 mmol/gcat。
8. as claimed in claim 7 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate
Application, it is characterised in that the epoxides be ethylene oxide or propylene oxide.
9. as claimed in claim 7 a kind of for epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate
Application, it is characterised in that the quaternary ammonium salt be 4-propyl bromide, tetraethylammonium bromide, etamon chloride, tetrapropyl
One of ammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112439405A (en) * | 2020-12-21 | 2021-03-05 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing dimethyl carbonate from methanol, carbon dioxide and 2-cyanopyridine and preparation method and application thereof |
| WO2021125989A1 (en) * | 2019-12-17 | 2021-06-24 | Qatar Foundation For Education, Science And Community Development | Methods of producing dimethyl carbonate |
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