CN104069858B - A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof - Google Patents
A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof Download PDFInfo
- Publication number
- CN104069858B CN104069858B CN201310101652.XA CN201310101652A CN104069858B CN 104069858 B CN104069858 B CN 104069858B CN 201310101652 A CN201310101652 A CN 201310101652A CN 104069858 B CN104069858 B CN 104069858B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- solution
- dimethyl carbonate
- mass concentration
- sio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
The invention discloses a kind of bifunctional catalyst and methods for making and using same thereof of Synthesis of dimethyl carbonate, in described catalyst, the mass content of each component is: Au is 0.1 ~ 10%, CeO
2be 1 ~ 30%, SiO
2be 60 ~ 98.9%; Described catalyst has catalysis CO concurrently
2with two kinds of functions of methanol-fueled CLC dimethyl carbonate and catalysis CO water gas shift reaction.The activity of described catalyst is high, and preparation process and using method simply, easily operate; And eliminate the adverse effect of byproduct water, substantially increase the stability of catalyst self, reaction condition is gentle, and product is easy to be separated.
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 Material synthesis dimethyl carbonate.
Background technology
Along with people are to the attention of environmental protection, green chemical industry oxide spinel dimethyl ester (DMC) environmentally friendly in Chemical Manufacture receives the concern of people day by day.Containing the reactive group such as methyl, methoxyl group, carbonyl in dimethyl carbonate molecule, make it have multiple reactivity worth, can with the reaction such as phenol, alcohol, amine, ester and amino alcohol, in these compound molecules, introduce methyl or carbonyl can produce multiple industrial chemicals.The toxicity of DMC is very low, also can substitute phosgene and make methylating reagent, severe toxicity can be substituted and carcinogenic dimethyl suflfate (DMS) for asking in body and the important fine chemical product such as antioxidant, plastic processing stabilizing agent in agricultural chemicals, medicine; Replace MTBE to make gasoline additive, can octane number be improved, increase the oxygen content of gasoline, reduce toxic emission; Also be widely used in this external lithium ion battery.
The production method of dimethyl carbonate mainly contains phosgene methyl alcohol method, ester-interchange method, oxidative carbonylation of methanol method, alcoholysis of urea, CO
25 kinds of methods are directly reacted with methyl alcohol.The raw material severe toxicity that phosgene methyl alcohol method uses, contaminated environment, is eliminated.Ester-interchange method is with oxirane or ethylene (third) alkene ester for raw material, and production cost is higher, lacks the market competitiveness; Oxidative carbonylation of methanol method is with the CH of cheapness
3oH, CO, O
2for raw material, production cost is low, and selectivity of product is high, but is raw material with carbon monoxide, and need add expensive gas maker, this reaction simultaneously also has potential explosion hazard.CO
2with the reaction of methyl alcohol Direct Synthesis of Dimethyl Carbonate, be that everybody studies many new technologies in recent years.Utilize CO
2with methanol-fueled CLC dimethyl carbonate, can be CO on the one hand
2energy-saving and emission-reduction provide favourable technical support; On the other hand, cost of material has sizable advantage.Once this technique realizes industrialization, impetus energetically can be produced to the development of C1 chemical industry, Coal Chemical Industry.
Chinese patent CN100531904 (a kind of catalyst by methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate and preparation and application thereof) is disclosed for methyl alcohol and CO
2the catalyst of direct catalytic synthesizing dimethyl carbonate is made up of the soluble salt of transition metal, auxiliary agent and carrier three part, and its weight ratio is 0.01 ~ 0.5: 0.01 ~ 0.1: 1.The preparation method of catalyst is: by carrier impregnation in the solution of the soluble salt containing transition metal, then add auxiliary agent, stirring at room temperature, ultrasonic disperse, room temperature leaves standstill, dry, after roast, restores activation and obtains catalyst.The abundant raw material source of this catalyst, with low cost.
The Chinese patent CN101632932 loaded catalyst of methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate (a kind of by) discloses a kind of for by methyl alcohol and CO
2the loaded catalyst of Synthesis of dimethyl carbonate, catalyst is using diatomite as carrier, using transition metal copper and mickel as the principal component of active component, with zinc, iron, cobalt etc. for auxiliary agent, wherein diatomite mass fraction is in the catalyst 60 ~ 95%, transition metal is 5 ~ 30%, and auxiliary agent is 0 ~ 15%.Catalyst is placed in 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 ~ 3.0MPa.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 shortcoming of catalytic performance instability.
US Patent No. 20110196167 (Synthesisofdimethylcarbonatefromcarbondioxideandmethanol) 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 under normal pressure and lower temperature Synthesis of dimethyl carbonate.
US Patent No. 20070021297 (Catalystfordimethylcarbonatesynthesis) 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, there is higher dimethyl carbonate yield on the catalyst.
But, at CO
2with in the reaction of methanol-fueled CLC dimethyl carbonate, have the existence of water byproduct, dimethyl carbonate can be made to be hydrolyzed on the one hand, 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.The removal problem of byproduct of reaction water is not all mentioned in the patents such as above-mentioned CN100531904, CN101632932, US20110196167, US20070021297.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
2introduce acetonitrile hydration reaction with in the reaction of methanol-fueled CLC dimethyl carbonate, effectively improve the dewatering efficiency of reaction system, can under very gentle condition Synthesis of dimethyl carbonate.But the acetamide of the method meeting by-product molal quantity identical with dimethyl carbonate, needs the dehydration of extra increase acetamide to 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 methanol-fueled CLC dimethyl carbonate, its water byproduct makes dimethyl carbonate be hydrolyzed, and the shortcoming such as the equilibrium conversion of methyl alcohol is very low, and an object of the present invention is to provide one and has catalysis CO concurrently
2with the bifunctional catalyst of methanol-fueled CLC 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
2with two kinds of functions of methanol-fueled CLC dimethyl carbonate and catalysis CO water gas shift reaction.
CeO
2for catalysis CO
2with methanol-fueled CLC dimethyl carbonate.Au is used for catalysis CO water gas shift reaction, eliminates CO in time
2with the water of methanol-fueled CLC 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, and dimethyl carbonate is better selective.
As further improvement, the mass content of described Au is 2 ~ 5%, and conversion ratio and the dimethyl carbonate that can promote methyl alcohol in catalytic reaction are further selective.
As improving further 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, regulate its pH value to be 1 ~ 5, obtain solution 1; To HAuCl
4add NaOH solution in solution, regulate its pH value to be 3 ~ 10, obtain 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
2support impregnating solution 1, after 100 DEG C of dryings 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), spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dryings
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 ~ 3mm, and specific area is 300 ~ 600m
2/ g, pore volume is 0.5 ~ 1.5cm
3/ g, average pore size is 5 ~ 20nm.
The preparation method of above-mentioned bifunctional catalyst, the dipping described in step (2) is known by the art those of ordinary skill.Dipping temperature is room temperature ~ 100 DEG C, and dip time is 1 ~ 10h.
The preparation method of above-mentioned bifunctional catalyst, the drying described in step (2) is known by the art those of ordinary skill, and baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 10h.
The preparation method of above-mentioned bifunctional catalyst, the reduction described in step (3) is known by the art those of ordinary skill, and reduction temperature is room temperature ~ 100 DEG C, and the recovery time is 1 ~ 5h.
The preparation method of above-mentioned bifunctional catalyst, the drying described in step (3) is known by the art those of ordinary skill, and baking temperature is 50 ~ 150 DEG C, and drying time is 1 ~ 10h.
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, and reaction pressure is 0.1 ~ 10MPa, and air speed is 500 ~ 5000h
-1.
Above-mentioned bifunctional catalyst, described catalyst is used for methyl alcohol, CO and CO
2for the catalyst of Material synthesis dimethyl carbonate.
Bifunctional catalyst of the present invention, described SiO
2the specific area of carrier, pore volume and average pore size measure on U.S. Micromeritics company ASAP2010 physical adsorption appearance.In described catalyst, the content of each component is the standard test adopting RIPP128-90 on U.S. Jarrell-Ash company J-A1100 type ICP.
Bifunctional catalyst of the present invention, the activity rating of described catalyst carries out on continuous fixed bed reactors.Loaded catalyst 10ml, by methyl alcohol/CO/CO
2the ratio being 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 ~ 10MPa, and air speed is 500 ~ 5000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.The composition of described reactant liquor adopts 7890 chromatographic of Agilent company production, and adopt HP-5 (30m × 0.32mm × 0.25 μm) capillary chromatographic column, hydrogen fire defector, inner mark method ration, internal standard compound is n-butanol.According to chromatography result calculate methanol conversion and dimethyl carbonate selective.
The present invention is by CO
2be coupled with methanol-fueled CLC 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 methanol-fueled CLC dimethyl carbonate and catalysis CO water gas shift reaction, at activated centre CeO
2upper generation 2CH
3oH+CO
2→ (CH
3o)
2cO+H
2the reaction of O, there is CO+H in activated centre Au
2o → CO
2+ H
2reaction, the CO water gas shift reaction of coupling eliminates CO in time
2with the water of methanol-fueled CLC dimethyl carbonate byproduct in process, significantly improve methanol conversion and dimethyl carbonate is selective.
Relative to prior art, advantage of the present invention is: one, and the activity of catalyst is high, and preparation process and using method simply, easily operate.Its two, bifunctional catalyst eliminates the adverse effect of byproduct water, substantially increases the stability of catalyst self.Its three, the reaction condition of catalyst is gentle, and product is easy to be separated.
Accompanying drawing explanation
Accompanying drawing 1 is Au/CeO
2/ SiO
2with methyl alcohol, CO and CO on bifunctional catalyst
2for the reaction mechanism of Material synthesis dimethyl carbonate (dimethylcarbonate, DMC).
Detailed description of the invention
Embodiment 1
The preparation of catalyst:
(1) to mass concentration be 1% cerous nitrate solution in add the citric acid solution that mass concentration is 1%, regulate its pH value to be 3, obtain solution 1; Be the HAuCl of 0.5% to mass concentration
4add the NaOH solution that mass concentration is 0.5% in solution, regulate its pH value to be 8, obtain solution 2;
(2) be 2mm by diameter, specific area is 500m
2/ g, pore volume is 1.0cm
3/ g, average pore size is the spherical SiO of 10nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 400 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 1% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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:
10ml catalyst is loaded, by methyl alcohol/CO/CO in continuous fixed bed reactors
2the ratio being 2/0.05/1 according to mol ratio passes into reactor, is 150 DEG C in reaction temperature, and reaction pressure is 2MPa, and air speed is 1000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts chromatographic, and methanol conversion is 14.6%, and dimethyl carbonate is selective is 93.5%.
Embodiment 2
The preparation of catalyst:
(1) to mass concentration be 0.1% cerous nitrate solution in add the citric acid solution that mass concentration is 0.1%, regulate its pH value to be 1, obtain solution 1; Be the HAuCl of 0.1% to mass concentration
4add the NaOH solution that mass concentration is 0.1% in solution, regulate its pH value to be 3, obtain solution 2;
(2) be 0.5mm by diameter, specific area is 600m
2/ g, pore volume is 0.5cm
3/ g, average pore size is the spherical SiO of 5nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 200 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 0.1% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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:
10ml catalyst is loaded, by methyl alcohol/CO/CO in continuous fixed bed reactors
2the ratio being 0.1/0.01/1 according to mol ratio passes into reactor, is 50 DEG C in reaction temperature, and reaction pressure is 0.1MPa, and air speed is 500h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts chromatographic, and methanol conversion is 4.8%, and dimethyl carbonate is selective is 80.2%.
Embodiment 3
The preparation of catalyst:
(1) to mass concentration be 10% cerous nitrate solution in add the citric acid solution that mass concentration is 10%, regulate its pH value to be 5, obtain solution 1; Be the HAuCl of 10% to mass concentration
4add the NaOH solution that mass concentration is 5% in solution, regulate its pH value to be 10, obtain solution 2;
(2) be 3mm by diameter, specific area is 300m
2/ g, pore volume is 1.5cm
3/ g, average pore size is the spherical SiO of 20nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 600 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 5% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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:
10ml catalyst is loaded, by methyl alcohol/CO/CO in continuous fixed bed reactors
2the ratio being 10/0.5/1 according to mol ratio passes into reactor, is 300 DEG C in reaction temperature, and reaction pressure is 10MPa, and air speed is 5000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts chromatographic, and methanol conversion is 6.5%, and dimethyl carbonate is selective is 82.2%.
Embodiment 4
The preparation of catalyst:
(1) to mass concentration be 1% cerous nitrate solution in add the citric acid solution that mass concentration is 0.5%, regulate its pH value to be 2, obtain solution 1; Be the HAuCl of 0.3% to mass concentration
4add the NaOH solution that mass concentration is 0.5% in solution, regulate its pH value to be 5, obtain solution 2;
(2) be 1.5mm by diameter, specific area is 400m
2/ g, pore volume is 1.2cm
3/ g, average pore size is the spherical SiO of 16nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 300 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 0.5% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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:
10ml catalyst is loaded, by methyl alcohol/CO/CO in continuous fixed bed reactors
2the ratio being 0.1/0.5/1 according to mol ratio passes into reactor, is 100 DEG C in reaction temperature, and reaction pressure is 0.5MPa, and air speed is 1000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts chromatographic, and methanol conversion is 6.9%, and dimethyl carbonate is selective is 85.6%.
Embodiment 5
The preparation of catalyst:
(1) to mass concentration be 7% cerous nitrate solution in add the citric acid solution that mass concentration is 8%, regulate its pH value to be 4, obtain solution 1; Be the HAuCl of 7% to mass concentration
4add the NaOH solution that mass concentration is 3% in solution, regulate its pH value to be 7, obtain solution 2;
(2) be 2mm by diameter, specific area is 550m
2/ g, pore volume is 0.7cm
3/ g, average pore size is the spherical SiO of 6nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 500 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 4% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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:
10ml catalyst is loaded, by methyl alcohol/CO/CO in continuous fixed bed reactors
2the ratio being 10/0.01/1 according to mol ratio passes into reactor, is 250 DEG C in reaction temperature, and reaction pressure is 8MPa, and air speed is 4000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that the present embodiment obtains adopts chromatographic, and methanol conversion is 6.0%, and dimethyl carbonate is selective is 81.5%.
Embodiment 6
The preparation of catalyst:
(1) to mass concentration be 2% cerous nitrate solution in add the citric acid solution that mass concentration is 0.3%, regulate its pH value to be 2.5, obtain solution 1; Be the HAuCl of 1% to mass concentration
4add the NaOH solution that mass concentration is 0.4% in solution, regulate its pH value to be 4, obtain solution 2;
(2) be 2mm by diameter, specific area is 550m
2/ g, pore volume is 0.7cm
3/ g, average pore size is the spherical SiO of 6nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 400 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 0.2% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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 obtained adopts chromatographic, and methanol conversion is 12.8%, and dimethyl carbonate is selective is 92.6%.
Embodiment 7
The preparation of catalyst:
(1) to mass concentration be 5% cerous nitrate solution in add the citric acid solution that mass concentration is 7%, regulate its pH value to be 4.5, obtain solution 1; Be the HAuCl of 2% to mass concentration
4add the NaOH solution that mass concentration is 3.5% in solution, regulate its pH value to be 9, obtain solution 2;
(2) be 1.5mm by diameter, specific area is 400m
2/ g, pore volume is 1.2cm
3/ g, average pore size is the spherical SiO of 16nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 400 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 4% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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 obtained adopts chromatographic, and methanol conversion is 16.2%, and dimethyl carbonate is selective is 95.7%.
Embodiment 8
The preparation of catalyst:
(1) to mass concentration be 2% cerous nitrate solution in add the citric acid solution that mass concentration is 1%, regulate its pH value to be 3.5, obtain solution 1; Be the HAuCl of 0.8% to mass concentration
4add the NaOH solution that mass concentration is 0.3% in solution, regulate its pH value to be 9, obtain solution 2;
(2) be 2mm by diameter, specific area is 500m
2/ g, pore volume is 1.0cm
3/ g, average pore size is the spherical SiO of 10nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, after 100 DEG C of dry 5h and 400 DEG C roasting 4h, continue the solution 2 of at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 2% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dry 5h
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 obtained adopts chromatographic, and methanol conversion is 17.0%, and dimethyl carbonate is selective is 98.2%.
Comparative example 1
This comparison example is compared with embodiment 1, and catalyst only has catalysis CO
2with the function of methanol-fueled CLC dimethyl carbonate.
The preparation of catalyst:
(1) to mass concentration be 1% cerous nitrate solution in add the citric acid solution that mass concentration is 1%, regulate its pH value to be 3, obtain solution 1;
(2) be 2mm by diameter, specific area is 500m
2/ g, pore volume is 1.0cm
3/ g, average pore size is the spherical SiO of 10nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, through 100 DEG C of dry 5h and 400 DEG C roasting 4h, obtains 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 obtained adopts chromatographic, and methanol conversion is 3.7%, and dimethyl carbonate is selective is 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) to mass concentration be the HAuCl of 0.5%
4add the NaOH solution that mass concentration is 0.5% in solution, regulate its pH value to be 8, obtain solution 1;
(2) be 2mm by diameter, specific area is 500m
2/ g, pore volume is 1.0cm
3/ g, average pore size is the spherical SiO of 10nm
2the solution 1 of particulate vector at room temperature impregnation steps (1), dip time 2h, obtains catalyst precarsor;
(3) catalyst precarsor of step (2) is adopted mass concentration be the sodium formate solution of 1% at 50 DEG C of reductase 12 h, spend deionized water to neutral, obtain Au/SiO through 100 DEG C of dry 5h
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 obtained adopts chromatographic, and methanol conversion is 0.5%, and dimethyl carbonate is selective is 0.
Comparative example 3
This comparison example compared with embodiment 1, the method Synthesis of dimethyl carbonate described according to the Chinese patent CN101632932 loaded catalyst of methyl alcohol and carbon dioxide Direct Synthesis of Dimethyl Carbonate (a kind of by).
30g diatomite support is immersed in the watery hydrochloric acid of 5%, agitator treating 24h, then spends deionized water to neutral, in 120 DEG C of dry 10h.By the diatomite support of above-mentioned process, 1.866gNi (NO
3) .6H
2o, 3.099gCu (NO
3) .3H
2the ammoniacal liquor of O and 180ml25% reacts 24h in stirring at room temperature, then ultrasonic disperse 3h, then in 70 DEG C of rotary evaporated to dryness, calcines 3h, in 5%H in tubular reduction furnace after 100 DEG C of dry 12h in 350 DEG C in Muffle furnace
2/ 95%N
2lower 600 DEG C of reduction activation 1h obtain for CO
2with the catalyst of methanol-fueled CLC dimethyl carbonate.
The above-mentioned catalyst of 10ml is loaded, by methyl alcohol, CO in fixed bed reactors
2the ratio being 2:1 according to mol ratio passes into fixed bed reactors, is 150 DEG C in reaction temperature, and reaction pressure is 2MPa, and air speed is 1000h
-1condition under react, product, through cooling, obtains the reactant liquor containing dimethyl carbonate.
The reactant liquor that this comparative example obtains adopts chromatographic, and methanol conversion is 5.7%, and dimethyl carbonate is selective is 83.6%.
Claims (3)
1. a bifunctional catalyst for Synthesis of dimethyl carbonate, comprises following component, and its mass content is:
Au is 2 ~ 5%,
CeO
2be 8 ~ 20%,
SiO
2be 75 ~ 90%,
The preparation method of described bifunctional catalyst, comprises the following steps:
(1) in cerous nitrate solution, add citric acid solution, regulate its pH value to be 1 ~ 5, obtain solution 1; To HAuCl
4add NaOH solution in solution, regulate its pH value to be 3 ~ 10, obtain 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 dryings and 200 ~ 600 DEG C of roasting 4h, continues the solution 2 of impregnation steps (1), obtains catalyst precarsor;
(3) adopt sodium formate solution to reduce the catalyst precarsor of step (2), spend deionized water to neutral, obtain Au/CeO through 100 DEG C of dryings
2/ SiO
2catalyst, the mass concentration of described sodium formate solution is 0.1 ~ 5%.
2. bifunctional catalyst according to claim 1, is characterized in that: described SiO
2carrier is the spheric granules of diameter 0.5 ~ 3mm, and specific area is 300 ~ 600m
2/ g, pore volume is 0.5 ~ 1.5cm
3/ g, average pore size is 5 ~ 20nm.
3. the application of bifunctional catalyst according to 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, and reaction pressure is 0.1 ~ 10MPa, and air speed is 500 ~ 5000h
-1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101652.XA CN104069858B (en) | 2013-03-27 | 2013-03-27 | A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310101652.XA CN104069858B (en) | 2013-03-27 | 2013-03-27 | A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104069858A CN104069858A (en) | 2014-10-01 |
| CN104069858B true CN104069858B (en) | 2016-04-13 |
Family
ID=51591696
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310101652.XA Active CN104069858B (en) | 2013-03-27 | 2013-03-27 | A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104069858B (en) |
Families Citing this family (4)
| 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 |
| CN109438244B (en) * | 2018-10-18 | 2021-03-05 | 清华大学 | Method for preparing glycerol carbonate from glycerol and carbon dioxide |
| 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 |
| ES2914350B2 (en) * | 2020-12-09 | 2023-01-30 | Blueplasma Power S L | DEVICE AND PROCESS TO PRODUCE DIMETHYL CARBONATE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407160A (en) * | 2011-10-14 | 2012-04-11 | 湖南大学 | Preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5655723B2 (en) * | 2011-07-05 | 2015-01-21 | トヨタ自動車株式会社 | Method for producing metal cluster supported catalyst |
-
2013
- 2013-03-27 CN CN201310101652.XA patent/CN104069858B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407160A (en) * | 2011-10-14 | 2012-04-11 | 湖南大学 | Preparation method of core-shell structure CeO2@SiO2 load metalloporphyrin catalyst prepared by double wrapping method |
Non-Patent Citations (2)
| Title |
|---|
| Influences of CeO2 microstructures on the structure and activity of Au/CeO2/SiO2 catalysts in CO oxidation;Kun Qian等;《Journal of Molecular Catalysis A: Chemical》;20090221;第306卷;第40-47页 * |
| 还原性氧化物及其复合物在金催化CO中的作用;张慧丽;《中国优秀硕士论文全文数据库工程科技Ⅰ辑》;20100915(第09期);正文第1-88页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104069858A (en) | 2014-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103172517B (en) | Methyl methoxyacetate preparation method | |
| Liu et al. | Squaramide-derived framework modified periodic mesoporous organosilica: A robust bifunctional platform for CO2 adsorption and cooperative conversion | |
| CN104069858B (en) | A kind of bifunctional catalyst of Synthesis of dimethyl carbonate and methods for making and using same thereof | |
| CN108126704B (en) | Cerium-iron-zirconium composite oxide catalyst, preparation method and application thereof | |
| CN103084178B (en) | Copper-contained hydrotalcite-based catalyst for preparing mixed alcohol by using synthesis gas as well as preparation method and application thereof | |
| Peng et al. | Recent progress in phosgene-free methods for synthesis of dimethyl carbonate | |
| CN103230810A (en) | Fischer-Tropsch synthetic catalyst for preparing low-carbon olefin by utilizing synthetic gas, modified molecular sieve carrier and preparation method | |
| TW200904524A (en) | A reactor system and process for reacting a feed | |
| JP5820818B2 (en) | Olefin production catalyst and olefin production method | |
| CN101279257B (en) | Catalyst for synthesizing oxalic ester and preparation method and application thereof | |
| CN107376954B (en) | Catalyst for CO gas phase coupling synthesis of dimethyl carbonate, preparation method and application thereof | |
| CN104588011A (en) | Alkane dehydrogenation catalyst and preparation method thereof | |
| CN102863335B (en) | Preparation method of diethyl succinate | |
| CN104072376B (en) | A kind of by CO 2with the method for methanol-fueled CLC methylcarbonate | |
| Ahmad et al. | Synthesis of oxymethylene dimethyl ethers (OMEn) via methanol mediated COx hydrogenation over Ru/BEA catalysts | |
| CN103933978A (en) | Supported nanocatalyst for catalytic conversion of carbon dioxide as well as preparation method and application thereof | |
| EP2301663A1 (en) | Catalyst for fischer-tropsch synthesis, and process for production of hydrocarbon | |
| Kojčinović et al. | Heterogeneous catalytic materials for carboxylation reactions with CO2 as reactant | |
| CN105435768A (en) | Process method for synthesizing propylene carbonate by urea alcoholysis | |
| CN101722001A (en) | Composite catalyst for dimethyl ether synthesis and preparation method and application thereof | |
| CN103551154B (en) | Preparation methods and catalysis method of dimethyl maleate hydrogenation catalyst | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN106890670B (en) | A kind of Dimethyl ether carbonylation produces catalyst and its application of methyl acetate | |
| Bai et al. | Influence of acid–base properties of the support on copper-based catalysts for catalytic dehydrogenation of 2-butanol | |
| Chang et al. | Sustainable synthesis of epoxides from halohydrin cyclization by composite solid-based catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |