CN104069858A - Bifunctional catalyst for synthesis of dimethyl carbonate and preparation and application method thereof - Google Patents
Bifunctional catalyst for synthesis of dimethyl carbonate and preparation and application method thereof Download PDFInfo
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Abstract
The invention discloses a bifunctional catalyst for synthesis of dimethyl carbonate and preparation and an application method thereof. The catalyst comprises following components by weight: 0.1-10% of Au, 1-30% of CeO2, and 60-98.9% of SiO2. The catalyst has a function of catalyzing CO2 and methanol to synthesize the dimethyl carbonate and also has a function of catalyzing CO water gas shift reactions. The catalyst is high in activity, simple in preparation process and using method, and easy in operation. Bad influences of the byproduct water are eliminated. The stability of the catalyst is largely improved. Reaction conditions are mild. Reaction products are easy to separate.
Description
Technical field
The present invention relates to a kind of catalyst of Synthesis of dimethyl carbonate, be specifically related to a kind of with methyl alcohol, CO and CO
2for the bifunctional catalyst of raw material Synthesis of dimethyl carbonate.
Background technology
Along with the attention of people to environmental protection, in Chemical Manufacture, environmentally friendly green chemical industry material carbon dimethyl phthalate (DMC) receives people's concern day by day.In dimethyl carbonate molecule, contain the reactive groups such as methyl, methoxyl group, carbonyl, make it have multiple reactivity worth, can react with phenol, alcohol, amine, ester and amino alcohol etc., in these compound molecules, introduce methyl or carbonyl and can produce multiple industrial chemicals.The toxicity of DMC is very low, also can substitute phosgene and make methylating reagent, can substitute severe toxicity and carcinogenic dimethyl suflfate (DMS) and ask in the important fine chemical product such as body and antioxidant, plastic processing stabilizing agent for agricultural chemicals, medicine; Replace MTBE to make gasoline additive, can improve octane number, increase the oxygen content of gasoline, reduce toxic emission; In this external lithium ion battery, be also widely used.
The production method of dimethyl carbonate mainly contains phosgene methyl alcohol method, ester-interchange method, oxidative carbonylation of methanol method, alcoholysis of urea, CO
2directly react 5 kinds of methods with methyl alcohol.The raw material severe toxicity that phosgene methyl alcohol method is used, contaminated environment, is eliminated.Ester-interchange method is taking oxirane or ethylene (third) alkene ester as raw material, and production cost is higher, lacks the market competitiveness; Oxidative carbonylation of methanol method is with cheap CH
3oH, CO, O
2for raw material, production cost is low, and selectivity of product is high, but taking carbon monoxide as raw material, needs additional expensive gas maker, and this reaction simultaneously also has potential explosion hazard.CO
2with reacting of methyl alcohol Direct Synthesis of Dimethyl Carbonate, be that everybody studies many new technologies in recent years.Utilize CO
2with methyl alcohol Synthesis of dimethyl carbonate, can be on the one hand CO
2energy-saving and emission-reduction provide favourable technical support; On the other hand, on cost of material, there is sizable advantage.Once this technique realizes industrialization, can produce impetus energetically to the development of a carbonizer, Coal Chemical Industry.
Chinese patent CN100531904 (a kind of catalyst and preparation and application thereof by methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate) is disclosed for methyl alcohol and CO
2directly the catalyst of catalytic synthesizing dimethyl carbonate is made up of soluble salt, auxiliary agent and carrier three parts of transition metal, and its weight ratio is 0.01～0.5: 0.01～0.1: 1.The preparation method of catalyst is: carrier impregnation, in the solution containing the soluble salt of transition metal, then is added to auxiliary agent, and stirring at room temperature, ultrasonic dispersion, room temperature leaves standstill, dry, after roast, restores activation and obtains catalyst.The raw material sources of this catalyst are abundant, with low cost.
Chinese patent CN101632932 (a kind of loaded catalyst by methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate) discloses a kind of for by methyl alcohol and CO
2the loaded catalyst of Synthesis of dimethyl carbonate, catalyst is using diatomite as carrier, principal component using transition metal copper and mickel as active component, taking zinc, iron, cobalt etc. as auxiliary agent, wherein the mass fraction of diatomite in catalyst is 60～95%, transition metal is 5～30%, and auxiliary agent is 0～15%.Catalyst is placed in to reaction unit, regulates gas-phase methanol and CO
2mol ratio be 2: 1～3: 1, in 110～140 DEG C of reactions, reaction pressure is 0.6～3.0 MPa.This catalyst preparation step is simple, good stability, and catalytic efficiency is high; Overcome existing catalyst used carrier and need pass through complicated step pretreatment, expensive, the unsettled shortcoming of catalytic performance.
US Patent No. 20110196167 (Synthesis of dimethyl carbonate from carbon dioxide and methanol) discloses for methyl alcohol and CO
2a series of heterogeneous catalysis of Synthesis of dimethyl carbonate, comprise 5%Rh/Al
2o
3, 5%Rh/ZSM-5,5%Rh-20%K/Al
2o
3, 52%Ni/Al
2o
3-SiO
2, 5%Mo
2c/Al
2o
3deng.These catalyst can provide acidic site and basic sites simultaneously, make this reaction can be at normal pressure and lower temperature Synthesis of dimethyl carbonate.
US Patent No. 20070021297 (Catalyst for dimethyl carbonate synthesis) discloses a kind of at supercritical CO
2the catalyst of Synthesis of dimethyl carbonate under condition, this catalyst is by acid carrier ZrO
2, Al
2o
3, TiO
2upper load SO
4 2-, PO
4 3-method preparation and obtain, on this catalyst, there is higher dimethyl carbonate yield.
But, at CO
2in the reaction of methyl alcohol Synthesis of dimethyl carbonate, have the existence of water byproduct, can make on the one hand dimethyl carbonate hydrolysis, molecular balance moves to left, and the equilibrium conversion of reaction equilibrium constant and methyl alcohol is all very low; On the other hand, water also can cause the inactivation of catalyst.In the patents such as above-mentioned CN100531904, CN101632932, US20110196167, US20070021297, all do not mention the removal problem of byproduct of reaction water.Therefore, the removal of byproduct of reaction water is very important in whole synthetic reaction.
Recently, rich heavy Gui first-class (low pressure CO
2with methyl alcohol at CeO
2direct Synthesis of Dimethyl Carbonate on solid catalyst. methanol production and application, 2011 (1): 28-32) at CO
2with in the reaction of methyl alcohol Synthesis of dimethyl carbonate, introduced acetonitrile hydration reaction, effectively improved the dewatering efficiency of reaction system, can be under very gentle condition Synthesis of dimethyl carbonate.But the method can by-product and the acetamide of the identical molal quantity of dimethyl carbonate, need the extra acetamide that increases to dewater and be reduced into the technique of acetonitrile.In addition, this technique is by-product methyl acetate also, causes acetamide loss.
Summary of the invention
For CO of the prior art
2with the reaction of methyl alcohol Synthesis of dimethyl carbonate, its water byproduct makes dimethyl carbonate hydrolysis, and the shortcoming such as the equilibrium conversion of methyl alcohol is very low, and one of object of the present invention is to provide one and has catalysis CO concurrently
2bifunctional catalyst with methyl alcohol Synthesis of dimethyl carbonate and catalysis CO water gas shift reaction.Two of object of the present invention is to provide the preparation method of described bifunctional catalyst.
Technical scheme of the present invention is as follows:
A bifunctional catalyst for Synthesis of dimethyl carbonate, comprises following component, and its mass content is:
Au is 0.1～10%,
CeO
2be 1～30%,
SiO
2be 60～98.9%,
Described catalyst has catalysis CO concurrently
2two kinds of functions with methyl alcohol Synthesis of dimethyl carbonate and catalysis CO water gas shift reaction.
CeO
2for catalysis CO
2with methyl alcohol Synthesis of dimethyl carbonate.Au, for catalysis CO water gas shift reaction, eliminates CO in time
2with the water of methyl alcohol Synthesis of dimethyl carbonate byproduct in process, significantly improve methanol conversion and dimethyl carbonate is selective.SiO
2for supported active center Au and activated centre CeO
2carrier.
As improvement, described CeO
2mass content be 8～20%, in catalytic reaction, methanol conversion is higher, dimethyl carbonate is selectively better.
As further improvement, the mass content of described Au is 2～5%, and conversion ratio and the dimethyl carbonate that can further promote methyl alcohol in catalytic reaction are selective.
As further improving again, described SiO
2mass content be 75～90%, make activated centre Au and activated centre CeO
2that disperses is better.
The preparation method of above-mentioned bifunctional catalyst, is characterized in that comprising the following steps:
(1) in cerous nitrate solution, add citric acid solution, regulating its pH value is 1～5, obtains solution 1; To HAuCl
4in solution, add NaOH solution, regulating its pH value is 3～10, obtains solution 2;
The mass concentration of described cerous nitrate solution is 0.1～10%, and the mass concentration of described citric acid solution is 0.1～10%, described HAuCl
4the mass concentration of solution is 0.1～10%, and the mass concentration of described NaOH solution is 0.1～5%;
(2) by SiO
2carrier impregnation solution 1, after 100 DEG C of dry and 200～600 DEG C of roasting 4h, continues dipping solution 2, obtains catalyst precarsor;
(3) adopt sodium formate solution to reduce the catalyst precarsor of step (2),, be dried and obtain Au/CeO through 100 DEG C to neutral with deionized water washing
2/ SiO
2catalyst; The mass concentration of described sodium formate solution is 0.1～5%.
Above-mentioned bifunctional catalyst, described SiO
2carrier is the spheric granules of diameter 0.5～3 mm, and specific area is 300～600 m
2/ g, pore volume is 0.5～1.5 cm
3/ g, average pore size is 5～20 nm.
The preparation method of above-mentioned bifunctional catalyst, the described dipping of step (2) is that the art those of ordinary skill is known.Dipping temperature is room temperature～100 DEG C, and dip time is 1～10 h.
The preparation method of above-mentioned bifunctional catalyst, described dry of step (2) is that the art those of ordinary skill is known, and baking temperature is 50～150 DEG C, and be 1～10 h drying time.
The preparation method of above-mentioned bifunctional catalyst, the described reduction of step (3) is that the art those of ordinary skill is known, and reduction temperature is room temperature～100 DEG C, and the recovery time is 1～5 h.
The preparation method of above-mentioned bifunctional catalyst, described dry of step (3) is that the art those of ordinary skill is known, and baking temperature is 50～150 DEG C, and be 1～10 h drying time.
Above-mentioned bifunctional catalyst, the catalytic reaction condition of described catalyst is: methyl alcohol/CO/CO in reaction raw materials
2mol ratio be 0.1～10/0.01～0.5/1, reaction temperature is 50～300 DEG C, reaction pressure is 0.1～10 MPa, air speed is 500～5000 h
-1.
Above-mentioned bifunctional catalyst, described catalyst is used for methyl alcohol, CO and CO
2for the catalyst of raw material Synthesis of dimethyl carbonate.
Bifunctional catalyst of the present invention, described SiO
2specific area, pore volume and the average pore size of carrier is to measure on the U.S. ASAP2010 of Micromeritics company physical adsorption appearance.In described catalyst, the content of each component is the standard test that adopts RIPP128-90 on the U.S. J-A1100 of Jarrell-Ash company type ICP.
Bifunctional catalyst of the present invention, the activity rating of described catalyst is carrying out on fixed bed reactors continuously.Loaded catalyst 10 ml, by methyl alcohol/CO/CO
2the ratio that is 0.1～10/0.01～0.5/1 according to mol ratio passes into reactor, is 50～300 DEG C in reaction temperature, and reaction pressure is 0.1～10 MPa, and air speed is 500～5000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.The 7890 gas chromatograph analyses that the composition of described reactant liquor adopts Agilent company to produce, and employing HP-5 (m) capillary chromatographic column of 30 mm × 0.25, m × 0.32 μ, hydrogen flame detects, inner mark method ration, internal standard compound is n-butanol.Selective according to chromatography result calculating methanol conversion and dimethyl carbonate.
The present invention is by CO
2be coupled with methyl alcohol Synthesis of dimethyl carbonate and these the two kinds of reactions of CO hydrosphere transformation, the Au/CeO of preparation
2/ SiO
2catalyst has catalysis CO concurrently
2with two kinds of functions of methyl alcohol Synthesis of dimethyl carbonate and catalysis CO water gas shift reaction, at activated centre CeO
2upper generation 2CH
3oH+CO
2→ (CH
3o)
2cO+H
2, on the Au of activated centre, there is CO+H in the reaction of O
2o → CO
2+ H
2reaction, the CO water gas shift reaction of coupling has been eliminated CO in time
2with the water of methyl alcohol Synthesis of dimethyl carbonate byproduct in process, significantly improve methanol conversion and dimethyl carbonate is selective.
With respect to prior art, advantage of the present invention is: one, and the activity of catalyst is high, and preparation process and using method are simple, easily operation.Its two, bifunctional catalyst has been eliminated the adverse effect of by-product water, has greatly improved the stability of catalyst self.Its three, the reaction condition gentleness of catalyst, product be easy to separate.
Brief description of the drawings
Accompanying drawing 1 is Au/CeO
2/ SiO
2on bifunctional catalyst with methyl alcohol, CO and CO
2for the reaction mechanism of raw material Synthesis of dimethyl carbonate (dimethyl carbonate, DMC).
Detailed description of the invention
Embodiment 1
The preparation of catalyst:
(1) in the cerous nitrate solution that is 1% to mass concentration, add mass concentration and be 1% citric acid solution, regulating its pH value is 3, obtains solution 1; The HAuCl that is 0.5% to mass concentration
4in solution, add mass concentration and be 0.5% NaOH solution, regulating its pH value is 8, obtains solution 2;
(2) be 2 mm by diameter, specific area is 500 m
2/ g, pore volume is 1.0 cm
3/ g, average pore size is the spherical SiO of 10 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 400 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 1% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 3%, CeO
2be 10%, SiO
2be 87%.
The activity rating of catalyst:
Loading 10 ml catalyst in fixed bed reactors continuously, by methyl alcohol/CO/CO
2the ratio that is 2/0.05/1 according to mol ratio passes into reactor, is 150 DEG C in reaction temperature, and reaction pressure is 2 MPa, and air speed is 1000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts gas chromatograph analysis, and methanol conversion is 14.6%, and dimethyl carbonate is selectively 93.5%.
Embodiment 2
The preparation of catalyst:
(1) in the cerous nitrate solution that is 0.1% to mass concentration, add mass concentration and be 0.1% citric acid solution, regulating its pH value is 1, obtains solution 1; The HAuCl that is 0.1% to mass concentration
4in solution, add mass concentration and be 0.1% NaOH solution, regulating its pH value is 3, obtains solution 2;
(2) be 0.5 mm by diameter, specific area is 600 m
2/ g, pore volume is 0.5 cm
3/ g, average pore size is the spherical SiO of 5 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 200 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 0.1% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 0.1%, CeO
2be 1%, SiO
2be 98.9%.
The activity rating of catalyst:
Loading 10 ml catalyst in fixed bed reactors continuously, by methyl alcohol/CO/CO
2the ratio that is 0.1/0.01/1 according to mol ratio passes into reactor, is 50 DEG C in reaction temperature, and reaction pressure is 0.1 MPa, and air speed is 500 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts gas chromatograph analysis, and methanol conversion is 4.8%, and dimethyl carbonate is selectively 80.2%.
Embodiment 3
The preparation of catalyst:
(1) in the cerous nitrate solution that is 10% to mass concentration, add mass concentration and be 10% citric acid solution, regulating its pH value is 5, obtains solution 1; The HAuCl that is 10% to mass concentration
4in solution, add mass concentration and be 5% NaOH solution, regulating its pH value is 10, obtains solution 2;
(2) be 3 mm by diameter, specific area is 300 m
2/ g, pore volume is 1.5 cm
3/ g, average pore size is the spherical SiO of 20 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 600 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 5% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 10%, CeO
2be 30%, SiO
2be 60%.
The activity rating of catalyst:
Loading 10 ml catalyst in fixed bed reactors continuously, by methyl alcohol/CO/CO
2the ratio that is 10/0.5/1 according to mol ratio passes into reactor, is 300 DEG C in reaction temperature, and reaction pressure is 10 MPa, and air speed is 5000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts gas chromatograph analysis, and methanol conversion is 6.5%, and dimethyl carbonate is selectively 82.2%.
Embodiment 4
The preparation of catalyst:
(1) in the cerous nitrate solution that is 1% to mass concentration, add mass concentration and be 0.5% citric acid solution, regulating its pH value is 2, obtains solution 1; The HAuCl that is 0.3% to mass concentration
4in solution, add mass concentration and be 0.5% NaOH solution, regulating its pH value is 5, obtains solution 2;
(2) be 1.5 mm by diameter, specific area is 400 m
2/ g, pore volume is 1.2 cm
3/ g, average pore size is the spherical SiO of 16 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 300 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 0.5% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 0.1%, CeO
2be 30%, SiO
2be 69.9%.
The activity rating of catalyst:
Loading 10 ml catalyst in fixed bed reactors continuously, by methyl alcohol/CO/CO
2the ratio that is 0.1/0.5/1 according to mol ratio passes into reactor, is 100 DEG C in reaction temperature, and reaction pressure is 0.5 MPa, and air speed is 1000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts gas chromatograph analysis, and methanol conversion is 6.9%, and dimethyl carbonate is selectively 85.6%.
Embodiment 5
The preparation of catalyst:
(1) in the cerous nitrate solution that is 7% to mass concentration, add mass concentration and be 8% citric acid solution, regulating its pH value is 4, obtains solution 1; The HAuCl that is 7% to mass concentration
4in solution, add mass concentration and be 3% NaOH solution, regulating its pH value is 7, obtains solution 2;
(2) be 2 mm by diameter, specific area is 550 m
2/ g, pore volume is 0.7 cm
3/ g, average pore size is the spherical SiO of 6 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 500 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 4% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 10%, CeO
2be 1%, SiO
2be 89%.
The activity rating of catalyst:
Loading 10 ml catalyst in fixed bed reactors continuously, by methyl alcohol/CO/CO
2the ratio that is 10/0.01/1 according to mol ratio passes into reactor, is 250 DEG C in reaction temperature, and reaction pressure is 8 MPa, and air speed is 4000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts gas chromatograph analysis, and methanol conversion is 6.0%, and dimethyl carbonate is selectively 81.5%.
Embodiment 6
The preparation of catalyst:
(1) in the cerous nitrate solution that is 2% to mass concentration, add mass concentration and be 0.3% citric acid solution, regulating its pH value is 2.5, obtains solution 1; The HAuCl that is 1% to mass concentration
4in solution, add mass concentration and be 0.4% NaOH solution, regulating its pH value is 4, obtains solution 2;
(2) be 2 mm by diameter, specific area is 550 m
2/ g, pore volume is 0.7 cm
3/ g, average pore size is the spherical SiO of 6 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 400 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 0.2% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 2%, CeO
2be 8%, SiO
2be 90%.
The activity rating of catalyst:
The reaction condition of the present embodiment catalyst is substantially the same manner as Example 1, and the reactant liquor obtaining adopts gas chromatograph analysis, and methanol conversion is 12.8%, and dimethyl carbonate is selectively 92.6%.
Embodiment 7
The preparation of catalyst:
(1) in the cerous nitrate solution that is 5% to mass concentration, add mass concentration and be 7% citric acid solution, regulating its pH value is 4.5, obtains solution 1; The HAuCl that is 2% to mass concentration
4in solution, add mass concentration and be 3.5% NaOH solution, regulating its pH value is 9, obtains solution 2;
(2) be 1.5 mm by diameter, specific area is 400 m
2/ g, pore volume is 1.2 cm
3/ g, average pore size is the spherical SiO of 16 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 400 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 4% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 5%, CeO
2be 20%, SiO
2be 75%.
The activity rating of catalyst:
The reaction condition of the present embodiment catalyst is substantially the same manner as Example 1, and the reactant liquor obtaining adopts gas chromatograph analysis, and methanol conversion is 16.2%, and dimethyl carbonate is selectively 95.7%.
Embodiment 8
The preparation of catalyst:
(1) in the cerous nitrate solution that is 2% to mass concentration, add mass concentration and be 1% citric acid solution, regulating its pH value is 3.5, obtains solution 1; The HAuCl that is 0.8% to mass concentration
4in solution, add mass concentration and be 0.3% NaOH solution, regulating its pH value is 9, obtains solution 2;
(2) be 2 mm by diameter, specific area is 500 m
2/ g, pore volume is 1.0 cm
3/ g, average pore size is the spherical SiO of 10 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, after 100 DEG C of dry 5 h and 400 DEG C of roasting 4 h, continue the at room temperature solution 2 of impregnation steps (1), and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 2% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/CeO through 100 DEG C of dry 5 h with deionized water washing
2/ SiO
2catalyst.
In the catalyst that the present embodiment obtains, the mass content of each component is: Au is 3%, CeO
2be 15%, SiO
2be 82%.
The activity rating of catalyst:
The reaction condition of the present embodiment catalyst is substantially the same manner as Example 1, and the reactant liquor obtaining adopts gas chromatograph analysis, and methanol conversion is 17.0%, and dimethyl carbonate is selectively 98.2%.
Comparative example 1
This comparison example is compared with embodiment 1, and catalyst only has catalysis CO
2function with methyl alcohol Synthesis of dimethyl carbonate.
The preparation of catalyst:
(1) in the cerous nitrate solution that is 1% to mass concentration, add mass concentration and be 1% citric acid solution, regulating its pH value is 3, obtains solution 1;
(2) be 2 mm by diameter, specific area is 500 m
2/ g, pore volume is 1.0 cm
3/ g, average pore size is the spherical SiO of 10 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, through 100 DEG C of dry 5 h and 400 DEG C of roasting 4 h, obtain CeO
2/ SiO
2catalyst.
In the catalyst that this comparative example obtains, the mass content of each component is: CeO
2be 10%, SiO
2be 90%.
The activity rating of catalyst:
The reaction condition of this comparative example catalyst is substantially the same manner as Example 1, and the reactant liquor obtaining adopts gas chromatograph analysis, and methanol conversion is 3.7%, and dimethyl carbonate is selectively 80.5%.
Comparative example 2
This comparison example is compared with embodiment 1, and catalyst only has the function of catalysis CO hydrosphere transformation.
The preparation of catalyst:
(1) HAuCl that is 0.5% to mass concentration
4in solution, add mass concentration and be 0.5% NaOH solution, regulating its pH value is 8, obtains solution 1;
(2) be 2 mm by diameter, specific area is 500 m
2/ g, pore volume is 1.0 cm
3/ g, average pore size is the spherical SiO of 10 nm
2particulate vector is the solution 1 of impregnation steps (1) at room temperature, and dip time 2 h, obtain catalyst precarsor;
(3) sodium formate solution that is 1% by the catalyst precarsor employing mass concentration of step (2), at 50 DEG C of reductase 12 h, to neutral, obtains Au/SiO through 100 DEG C of dry 5 h with deionized water washing
2catalyst.
In the catalyst that this comparative example obtains, the mass content of each component is: Au is 3%, SiO
2be 97%.
The activity rating of catalyst:
The reaction condition of this comparative example catalyst is substantially the same manner as Example 1, and the reactant liquor obtaining adopts gas chromatograph analysis, and methanol conversion is 0.5%, and dimethyl carbonate is selectively 0.
Comparative example 3
This comparison example is compared with embodiment 1, the method Synthesis of dimethyl carbonate of describing according to Chinese patent CN101632932 (a kind of loaded catalyst by methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate).
30 g diatomite supports are immersed in 5% watery hydrochloric acid, agitator treating 24 h, then with deionized water washing to neutral, in 120 DEG C of dry 10 h.By the diatomite support of above-mentioned processing, 1.866 g Ni (NO
3) .6H
2o, 3.099 g Cu (NO
3) .3H
2the ammoniacal liquor of O and 180 ml 25% reacts 24 h in stirring at room temperature, and then ultrasonic dispersion 3 h, then in 70 DEG C of rotary evaporated to dryness, calcine 3 h in 350 DEG C after 100 DEG C of dry 12 h in Muffle furnace, in tubular reduction furnace in 5%H
2/ 95%N
2lower 600 DEG C of reduction activation 1 h obtain for CO
2catalyst with methyl alcohol Synthesis of dimethyl carbonate.
In fixed bed reactors, load the above-mentioned catalyst of 10 ml, by methyl alcohol, CO
2the ratio that is 2:1 according to mol ratio passes into fixed bed reactors, is 150 DEG C in reaction temperature, and reaction pressure is 2 MPa, and air speed is 1000 h
-1condition under react, product is through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that this comparative example obtains adopts gas chromatograph analysis, and methanol conversion is 5.7%, and dimethyl carbonate is selectively 83.6%.
Claims (7)
1. a bifunctional catalyst for Synthesis of dimethyl carbonate, comprises following component, and its mass content is:
Au is 0.1～10%,
CeO
2be 1～30%,
SiO
2be 60～98.9%.
2. the bifunctional catalyst of Synthesis of dimethyl carbonate according to claim 1, the mass content that it is characterized in that described Au is 2～5%.
3. the bifunctional catalyst of Synthesis of dimethyl carbonate according to claim 1, is characterized in that described CeO
2mass content be 8～20%.
4. the bifunctional catalyst of Synthesis of dimethyl carbonate according to claim 1, is characterized in that described SiO
2mass content be 75～90%.
5. the preparation method of the bifunctional catalyst described in claim 1 or 4, is characterized in that comprising the following steps:
(1) in cerous nitrate solution, add citric acid solution, regulating its pH value is 1～5, obtains solution 1; To HAuCl
4in solution, add NaOH solution, regulating its pH value is 3～10, obtains solution 2; The mass concentration of described cerous nitrate solution is 0.1～10%, and the mass concentration of described citric acid solution is 0.1～10%, described HAuCl
4the mass concentration of solution is 0.1～10%, and the mass concentration of described NaOH solution is 0.1～5%;
(2) by SiO
2the solution 1 of carrier impregnation step (1), after 100 DEG C of dry and 200～600 DEG C of roasting 4 h, continues the solution 2 of impregnation steps (1), obtains catalyst precarsor;
(3) adopt sodium formate solution to reduce the catalyst precarsor of step (2),, be dried and obtain Au/CeO through 100 DEG C to neutral with deionized water washing
2/ SiO
2catalyst, the mass concentration of described sodium formate solution is 0.1～5%.
6. bifunctional catalyst according to claim 1, is characterized in that: described SiO
2carrier is the spheric granules of diameter 0.5～3 mm, and specific area is 300～600 m
2/ g, pore volume is 0.5～1.5 cm
3/ g, average pore size is 5～20 nm.
7. the application of bifunctional catalyst claimed in claim 1, is characterized in that: the catalytic reaction condition of described catalyst is: methyl alcohol/CO/CO in reaction raw materials
2mol ratio be 0.1～10/0.01～0.5/1, reaction temperature is 50～300 DEG C, reaction pressure is 0.1～10 MPa, air speed is 500～5000 h
-1.
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Cited By (4)
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| CN104841414A (en) * | 2015-04-17 | 2015-08-19 | 太原理工大学 | Nanometer cerium dioxide catalyst preparation method |
| CN109438244A (en) * | 2018-10-18 | 2019-03-08 | 清华大学 | A method of glycerol carbonate is manufactured from glycerine and carbon dioxide |
| 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 |
| EP4011857A1 (en) * | 2020-12-09 | 2022-06-15 | Blueplasma Power, S.L. | Apparatus and process for producing dimethyl carbonate |
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| JP2013013864A (en) * | 2011-07-05 | 2013-01-24 | Toyota Motor Corp | Method for manufacturing metal cluster supported catalyst |
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| JP2013013864A (en) * | 2011-07-05 | 2013-01-24 | Toyota Motor Corp | Method for manufacturing metal cluster supported catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841414A (en) * | 2015-04-17 | 2015-08-19 | 太原理工大学 | Nanometer cerium dioxide catalyst preparation method |
| CN109438244A (en) * | 2018-10-18 | 2019-03-08 | 清华大学 | A method of glycerol carbonate is manufactured from glycerine and carbon dioxide |
| 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 |
| EP4011857A1 (en) * | 2020-12-09 | 2022-06-15 | Blueplasma Power, S.L. | Apparatus and process for producing dimethyl carbonate |
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| CN104069858B (en) | 2016-04-13 |
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