CN104549208B - A kind of catalyst of Synthesis of dimethyl carbonate and its preparation method and application - Google Patents
A kind of catalyst of Synthesis of dimethyl carbonate and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of urea of support type and the preparation method of methanol catalyst for preparing dimethyl carbonate, including following content：（1）Metallic salt or metal oxide are added into distilled water, and is stirred；（2）To step（1）Alcoholic solvent is added in solution and containing silicon precursor, after solution is stirred, regulation solution pH value is 2 ~ 5；（3）By step（2）Solution constant temperature is stirred to being converted into gel, aged at room temperature；（4）By step（3）In obtained gel drying to constant weight, grinding, obtain the urea and methanol catalyst for preparing dimethyl carbonate of final support type.Catalyst prepared by this method solves in existing urea and methanol preparing dimethyl carbonate technology the deficiencies such as equilibrium conversion is low, homogeneous catalyst is not readily separated, and the catalyst has high-activity stable.
Description
Technical field
The present invention relates to a kind of Synthesis of dimethyl carbonate catalyst and its preparation method and application, particularly urea and methanol
Catalyst of preparing dimethyl carbonate and its preparation method and application.
Background technology
Dimethyl carbonate（DMC）It is the environment-friendly type Organic Chemicals that one kind meets modern " cleaning procedure " requirement, is state
One of green chemical products that border society is unanimously assert.It can not only replace phosgene, dimethyl suflfate, chloromethane and chloro-carbonic acid
Methyl esters as being carbonylated, methylate, be esterified and ester exchange reagent, and be a kind of good green solvent and gasoline addition
Agent.
Methanol and the novelty that alcoholysis of urea catalytic synthesizing dimethyl carbonate (DMC) is replacement phosgene production DMC
Process route.Alcoholysis of urea makees base stock with wide material sources, cheap urea and methanol, inexpensive easily with raw material
Obtain, technique is simple and reacts the advantages of ammonia produced can be recycled, and the anhydrous generation of course of reaction, avoid first
The separation problem of alcohol-DMC- water complex systems, makes later separation purification simplification, reduces investment outlay, especially to existing chemical fertilizer factory
Develop downstream product attractive.
Patent WO9517369 uses Dibutyltin oxide, dimethoxide base tin, dibutyl methoxyl group NCO
Tin is reacted as catalyst with methyl carbamate or urea with methanol, while dimethyl carbonate is continuously steamed, such catalyst
Although higher product yield can be obtained, also can catalytic amino methyl formate decomposition.US5902894 uses height boiling point-like electron
Alms giver's oxycompound does solvent and co-catalyst, effectively inhibits the hair of the decomposition of methyl carbamate and the side reaction that methylates
It is raw.Its methyl carbamate conversion ratio is up to 98.3%, while dimethyl carbonate is selective up to 98.2%.Although organo-tin compound
With preferable catalytic effect, but their toxicity are big, price is high, homogeneous catalyst separated and recovered from product it is extremely difficult.
Patent CN1569809 proposes a kind of method by methanol and Synthesis of Dimethyl Carbonate from Urea.It is anti-in autoclave
Answer in device, at 130-180 DEG C, using amine salt type ionic liquid as catalyst, one-step synthesis dimethyl carbonate, its yield is
25-30%, selectivity is 100%.Although the catalyst effect is preferably, but still there is the problem of separating difficulty with product.
Therefore, it is that Synthesis of Dimethyl Carbonate from Urea technique is realized to develop the efficient, heterogeneous catalysis of non-environmental-pollution
Industrialized key.
The content of the invention
For equilibrium conversion in existing urea and methanol preparing dimethyl carbonate technology is low, homogeneous catalyst is not readily separated
Deficiency, the present invention provides a kind of for catalyst of urea and methanol preparing dimethyl carbonate and its preparation method and application.
A kind of urea of support type and the preparation method of methanol catalyst for preparing dimethyl carbonate, including following content：
（1）Metallic salt or metal oxide are added into distilled water, and is stirred；
（2）To step（1）Alcoholic solvent is added in solution and containing silicon precursor, after solution is stirred, adjust solution PH
It is worth for 2 ~ 5；
（3）By step（2）Solution constant temperature is stirred to being converted into gel, aged at room temperature；
（4）By step（3）In obtained gel drying to constant weight, grinding, obtain the urea and methanol system of final support type
Catalyst.
The inventive method step（1）Described in metallic salt be zinc nitrate, zinc acetate, cerous nitrate or cerous nitrate in
One or more, preferably zinc nitrate/or cerous nitrate；Metal oxide is zinc oxide, cupric oxide, cerium oxide or aoxidized in sub- cerium
One or more, preferably aoxidize sub- cerium.Its load capacity is calculated as 3% ~ 20%, preferably 5% ~ 15% with active metal simple substance.
The inventive method step（2）Described in alcoholic solvent be absolute ethyl alcohol, n-butanol, isopropanol in one kind or several
Plant, preferably n-butanol.Described is tetraethyl orthosilicate containing silicon precursor.Solution reclaimed water and the mol ratio of the tetraethyl orthosilicate added
For 1~20, preferably 5~15；N-butanol is 0.1~5, preferably 0.5~3 with tetraethyl orthosilicate mol ratio.
The inventive method step（3）Described in thermostat temperature be 60~120 DEG C, preferably 70~100 DEG C, constant temperature time
For 1~5h, preferably 2~4h；Ageing time is 1~30h, preferably 5~26h.
The inventive method step（3）Middle aged at room temperature is carried out in the presence of phosphoric acid.It is described add phosphoric acid amount be
The 10% ~ 50% of active metal simple substance molal quantity, preferably 20% ~ 40%.The addition of phosphoric acid is carried significantly with gel rubber system collective effect
The stability and the yield of dimethyl carbonate of high catalyst.
The inventive method step（4）Described in drying temperature be 60~250 DEG C, preferably 70~230 DEG C, drying time is
6~28h, preferably 8~15h.
Support type urea and methanol catalyst for preparing dimethyl carbonate prepared by a kind of use above method, by the weight of catalyst
Content meter is measured, containing in terms of simple substance 3% ~ 20% active metal, remaining is carrier S iO2, preferably comprise 5% ~ 15% activity gold
Category.
Application of the above-mentioned loaded catalyst in urea and methanol preparing dimethyl carbonate, using urea and methanol as raw material,
Urea is 1 with methanol molar ratio:5~1:20, catalyst amount is the 5%~20% of reactant quality, and reaction temperature is 100-250
DEG C, preferably two sections temperature reactions at one section of 120~160 DEG C of reaction temperature, react 1~8h, 180~220 DEG C of second-stage reaction temperature
Under, react 2~10h.
Metallic salt or metal oxide catalyst that the present invention is prepared using sol-gal process, solve urea and methanol
The problems such as equilibrium conversion is low in Synthesis of dimethyl carbonate technology, homogeneous catalyst is difficult to separation and recovery, the catalyst preparation side
Method is simple, it is easy to reclaims separation, improves product quality.
Embodiment
The functions and effects of the present invention are further illustrated with reference to embodiment.
Example 1
（1）38g zinc nitrates are taken, are dissolved in 42ml distilled water, uniform stirring to zinc nitrate is completely dissolved；
（2）To step（1）N-butanol and tetraethyl orthosilicate, n-butanol and the tetraethyl orthosilicate mole of addition are added in solution
Than for 2.1；The mol ratio of tetraethyl orthosilicate of the solution reclaimed water with adding is 10, continues to stir, nitric acid is instilled into solution,
The pH value for adjusting solution is 3；
（3）By step（2）90 DEG C of constant temperature of solution stir 3h and are converted into gel to solution, then aged at room temperature 12h.
（4）By step（3）In obtained gel 10h is dried at a temperature of 100 DEG C, grinding obtains final supported catalyst
Agent.The amount of wherein active metal zinc be 15%, remaining is SiO2。
Evaluating catalyst, using urea and methanol as raw material, wherein urea 15g, methanol are carried out using autoclave reactor
136g, 27 grams of catalyst quality, one section of 150 DEG C of reaction temperature reacts 6h, and 215 DEG C of second-stage reaction temperature reacts 5h, carbonic acid two
Methyl esters yield reaches 20.3%, after catalyst is reclaimed, and using three times, dimethyl carbonate yield is 16.9%.
Example 2
（1）30g cerous nitrates are taken, are dissolved in 45ml distilled water, uniform stirring to cerous nitrate is completely dissolved；
（2）To step（1）N-butanol and tetraethyl orthosilicate, n-butanol and the tetraethyl orthosilicate mole of addition are added in solution
Than for 3；The mol ratio of tetraethyl orthosilicate of the solution reclaimed water with adding is 14, continues to stir, nitric acid is instilled into solution, adjust
The pH value for saving solution is 4；
（3）By step（2）80 DEG C of constant temperature stirring 2h solution of solution are converted into gel, then aged at room temperature 24h.
（4）By step（3）In obtained gel 12h is dried at a temperature of 100 DEG C, grinding obtains final supported catalyst
Agent.The amount of wherein active metal cerium be 11%, remaining is SiO2。
Evaluating catalyst, using urea and methanol as raw material, wherein urea 18g, methanol are carried out using autoclave reactor
116g, 17 grams of catalyst quality, one section of 120 DEG C of reaction temperature reacts 7h, and 190 DEG C of second-stage reaction temperature reacts 4h, carbonic acid two
Methyl esters yield reaches 22.8%, after catalyst is reclaimed, and using three times, dimethyl carbonate yield is 19.6%.
Example 3
（1）32g cerous nitrates are taken, are dissolved in 40ml distilled water, uniform stirring to cerous nitrate is completely dissolved；
（2）To step（1）N-butanol and tetraethyl orthosilicate, n-butanol and the tetraethyl orthosilicate mole of addition are added in solution
Than for 1.0；The mol ratio of tetraethyl orthosilicate of the solution reclaimed water with adding is 9, continues to stir, nitric acid is instilled into solution,
The pH value for adjusting solution is 4；
（3）By step（2）80 DEG C of constant temperature stirring 2.5h solution of solution are converted into gel, then aged at room temperature 16h.
（4）By step（3）In obtained gel 14h is dried at a temperature of 70 DEG C, grinding obtains final supported catalyst
Agent.The amount of wherein active metal cerium be 8%, remaining is SiO2。
Evaluating catalyst, using urea and methanol as raw material, wherein urea 15g, methanol are carried out using autoclave reactor
95g, 17 grams of catalyst quality, one section of 120 DEG C of reaction temperature reacts 4h, and 180 DEG C of second-stage reaction temperature reacts 8h, carbonic acid diformazan
Ester yield reaches 21.7%, after catalyst is reclaimed, and using three times, dimethyl carbonate yield is 18.6%.
Example 4
（1）33g zinc nitrates are taken, are dissolved in 35ml distilled water, uniform stirring to zinc nitrate is completely dissolved；
（2）To step（1）N-butanol and tetraethyl orthosilicate, n-butanol and the tetraethyl orthosilicate mole of addition are added in solution
Than for 1.8；The mol ratio of tetraethyl orthosilicate of the solution reclaimed water with adding is 12, continues to stir, nitric acid is instilled into solution,
The pH value for adjusting solution is 5；
（3）By step（2）80 DEG C of constant temperature of solution stir 2h and are converted into gel to solution, then add after 8g phosphoric acid, room temperature
Aging 20h.
（4）By step（3）In obtained gel 9h is dried at a temperature of 120 DEG C, grinding obtains final supported catalyst
Agent.The amount of wherein active metal zinc be 13%, remaining is SiO2。
Evaluating catalyst, using urea and methanol as raw material, wherein urea 12g, methanol are carried out using autoclave reactor
70g, 6 grams of catalyst quality, one section of 140 DEG C of reaction temperature reacts 5h, and 200 DEG C of second-stage reaction temperature reacts 7h, carbonic acid diformazan
Ester yield reaches 28.7%, after catalyst is reclaimed, and using three times, dimethyl carbonate yield is 27.2%.
Example 5
（1）20g zinc nitrates are taken, are dissolved in 30ml distilled water, uniform stirring to zinc nitrate is completely dissolved；
（2）To step（1）N-butanol and tetraethyl orthosilicate, n-butanol and the tetraethyl orthosilicate mole of addition are added in solution
Than for 0.8；The mol ratio of tetraethyl orthosilicate of the solution reclaimed water with adding is 6, continues to stir, nitric acid is instilled into solution,
The pH value for adjusting solution is 4；
（3）By step（2）70 DEG C of constant temperature of solution stir 3.5h and are converted into gel to solution, then add after 6g phosphoric acid, room
Warm aging 8h.
（4）By step（3）In obtained gel 12h is dried at a temperature of 70 DEG C, grinding obtains final supported catalyst
Agent.The amount of wherein active metal zinc be 11%, remaining is SiO2。
Evaluating catalyst, using urea and methanol as raw material, wherein urea 18g, methanol are carried out using autoclave reactor
135g, 15 grams of catalyst quality, one section of 130 DEG C of reaction temperature reacts 3h, and 170 DEG C of second-stage reaction temperature reacts 3h, carbonic acid two
Methyl esters yield reaches 25.6%, after catalyst is reclaimed, and using three times, dimethyl carbonate yield is 24.3%.
Example 6
Be the same as Example 4, is simply added without phosphoric acid, and dimethyl carbonate yield reaches 22.4%, after catalyst is reclaimed, uses three
Secondary, dimethyl carbonate yield is 17.5%.
Example 7
Be the same as Example 4, is simply added without phosphoric acid, and dimethyl carbonate yield reaches 21.7%, after catalyst is reclaimed, uses three
Secondary, dimethyl carbonate yield is 18.2%.
Comparative example 1
SiO after being handled with 40 mesh phosphoric acid modifications2As carrier, zinc nitrate is loaded using conventional impregnation method, zinc is obtained
Load capacity is 13% catalyst, and appreciation condition be the same as Example 1 obtains dimethyl carbonate yield for 10.5%, after catalyst is reclaimed
Yield is down to 3.2% again.
Claims (14)
1. a kind of urea of support type and the preparation method of methanol catalyst for preparing dimethyl carbonate, it is characterised in that：Including as follows
Content：
（1）Metallic salt or metal oxide are added into distilled water, and is stirred；
（2）To step（1）Alcoholic solvent is added in solution and containing silicon precursor, after solution is stirred, regulation solution pH value is 2
~5；
（3）By step（2）Solution constant temperature is stirred to being converted into gel, aged at room temperature；
（4）By step（3）In obtained gel drying to constant weight, grinding, obtain the urea and methanol carbonic acid of final support type
Diformazan ester catalyst；
Wherein, step（1）Described in metallic salt be zinc nitrate, zinc acetate, cerous nitrate or cerous nitrate in one kind or several
Kind；Metal oxide is the one or more in zinc oxide, cupric oxide, cerium oxide or the sub- cerium of oxidation, and its load capacity is with active gold
Category simple substance is calculated as 3wt% ~ 20wt%.
2. according to the method described in claim 1, it is characterised in that：Step（1）Described in metallic salt be zinc nitrate or nitre
Sour Asia cerium；Metal oxide is the sub- cerium of oxidation, and its load capacity is calculated as 5wt% ~ 15wt% with active metal simple substance.
3. according to the method described in claim 1, it is characterised in that：Step（2）Described in alcoholic solvent be absolute ethyl alcohol, positive fourth
One or more in alcohol, isopropanol, described is tetraethyl orthosilicate containing silicon precursor.
4. method according to claim 3, it is characterised in that：Step（2）Solution reclaimed water is with adding containing silicon precursor
Mol ratio is 1~20；Alcoholic solvent is 0.1~5 with tetraethyl orthosilicate mol ratio, and described alcoholic solvent is n-butanol.
5. method according to claim 4, it is characterised in that：Step（2）Solution reclaimed water is with adding containing silicon precursor
Mol ratio is 5~15；Alcoholic solvent is 0.5~3 with tetraethyl orthosilicate mol ratio.
6. according to the method described in claim 1, it is characterised in that：Step（3）Described in thermostat temperature be 60~120 DEG C,
Constant temperature time is 1~5h, and ageing time is 1~30h.
7. method according to claim 6, it is characterised in that：Step（3）Described in thermostat temperature be 70~100 DEG C,
Constant temperature time is 2~4h；Ageing time is 5~26h.
8. according to the method described in claim 1, it is characterised in that：Step（3）Middle aged at room temperature is entered in the presence of phosphoric acid
Capable.
9. method according to claim 8, it is characterised in that：The amount for adding phosphoric acid is active metal simple substance molal quantity
10% ~ 50%.
10. according to the method described in claim 1, it is characterised in that：Step（4）Described in drying temperature be 60~250 DEG C,
Drying time is 6~28h.
11. method according to claim 10, it is characterised in that：Step（4）Described in drying temperature be 70~230
DEG C, drying time is 8~15h.
12. support type urea and methanol catalyst for preparing dimethyl carbonate prepared by a kind of use claim 1-11 either method,
It is characterized in that：Based on the weight content of catalyst, the metallic salt or metal oxide of load are calculated as with active metal simple substance
3% ~ 20%, remaining is carrier S iO2。
13. the application of support type urea and methanol catalyst for preparing dimethyl carbonate described in claim 12, it is characterised in that：To urinate
Element and methanol are raw material, and urea is 1 with methanol molar ratio:5~1:20, catalyst amount is the 5%~20% of reactant quality, instead
It is 100-250 DEG C to answer temperature.
14. application according to claim 13, it is characterised in that：Using two sections of temperature reactions, one section of reaction temperature 120~
At 160 DEG C, react at 1~8h, 180~220 DEG C of second-stage reaction temperature, react 2~10h.
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