CN102553598A - Catalyst for synthetizing benzyl carbamate, preparation method and application - Google Patents
Catalyst for synthetizing benzyl carbamate, preparation method and application Download PDFInfo
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- CN102553598A CN102553598A CN2010106099811A CN201010609981A CN102553598A CN 102553598 A CN102553598 A CN 102553598A CN 2010106099811 A CN2010106099811 A CN 2010106099811A CN 201010609981 A CN201010609981 A CN 201010609981A CN 102553598 A CN102553598 A CN 102553598A
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Abstract
The invention discloses a catalyst for synthetizing benzyl carbamate, a preparation method and application. Active components of the catalyst are formed by combining any two of iron oxide, titanium oxide and nickel oxide, and aluminum oxide serves as a carrier. Urea and benzyl alcohol serve as reactant and are synthetized into benzyl carbamate through pressure reduction catalysis reaction at 140-180 DEG C. Urea conversion and selectivity of benzyl carbamate are high, and separation yield of benzyl carbamate can reach more than 90%.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application of synthesizing amino benzyl formate.
Background technology
Benzyq carbamate is one type of important medicine intermediate, has very high added value, the about 360,000/ton of market price.Can be used for the synthetic bioactive phosphorous dipeptides such as sterilization, weeding and coordinate plant growth that have.
Prior synthesizing method is mainly following two kinds of methods (I): by carbobenzoxy chloride and ammonia effect and get.Carbobenzoxy chloride is slowly added under vigorous stirring in the cold ammoniacal liquor (relative density 0.90) of 5 times of volumes, reactant mixture is at room temperature placed 30min, leach deposition, washing, the dry finished product that gets.Prior synthesizing method (II): with urethanes and benzylalcohol in toluene under the aluminium propoxide catalysis reaction make.The former shortcoming is that cost is higher, and the latter's shortcoming has been to use the price of organic solvent and urethanes also relatively costly.Therefore be necessary to develop the relatively low and method of efficient synthesizing amino benzyl formate with an organic solvent not of a kind of cost from the angle of commercial Application.
Summary of the invention
The object of the present invention is to provide a kind of catalyst of synthesizing amino benzyl formate.
Another purpose of the present invention is to provide a kind of Preparation of catalysts method of synthesizing amino benzyl formate.
A further object of the present invention is to provide a kind of method of synthesizing amino benzyl formate.
A kind of catalyst of synthesizing amino benzyl formate is characterized in that catalyst supports the composition metal composite oxides by alumina support and forms, and the activity of such catalysts component is by any two kinds of combinations in iron oxide, titanium oxide and the nickel oxide, and carrier is an aluminium oxide; Wherein the amount of catalyst activity composition is 5-15wt.%, in the gross weight of catalyst by 100%.
A kind of Preparation of catalysts method of synthesizing amino benzyl formate; It is characterized in that the Preparation of catalysts method is an infusion process, the pH value of maceration extract is smaller or equal to 5, and dip time is 2-10 hour; The sintering temperature of catalyst precarsor is 300-700 ℃; Roasting time is 3-8 hour, and the environment of roasting is air or nitrogen, and the used compound of catalyst precarsor is selected from any two kinds of combinations in ferric nitrate, nickel nitrate and the butyl titanate.
We find; In the presence of catalyst of the present invention, be raw material with lower-cost urea, adopt the method for urea alcoholysis; Under the reaction condition of gentleness; Can the synthesizing amino benzyl formate, if unique accessory substance ammonia and the urea production that will react connect the Atom economy 100% of this reaction.
A kind of method of synthesizing amino benzyl formate is characterized in that this method is a reactant with urea and Bian alcohol, in 140-180 ℃ of decompression catalytic reaction synthesizing amino benzyl formate; Catalyst supports the composition metal composite oxides by alumina support to be formed, and the activity of such catalysts component is by any two kinds of combinations in iron oxide, titanium oxide and the nickel oxide, and carrier is an aluminium oxide; Wherein the amount of catalyst activity composition is 5-15wt.%, in the gross weight of catalyst by 100%.
In the method for synthesizing amino benzyl formate, the vacuum that decompression is adopted is 0.8-0.2 atmospheric pressure.
In the method for synthesizing amino benzyl formate, Bian alcohol is 3/1-8/1 with urea mol ratio.
In the method for synthesizing amino benzyl formate, the mass ratio of catalyst and urea is 0.05/1-0.2/1.
In the method for synthesizing amino benzyl formate, the reaction time is 3-8 hour.
In the method for synthesizing amino benzyl formate; Breadboard implementation process is: with urea, Bian alcohol; Catalyst is incorporated in the 10L agitated reactor that contains the condensing reflux post successively; Be warming up to 140-180 ℃, (0.8-0.2 atmospheric pressure) reacts and extracts the ammonia that produces in the course of reaction simultaneously out under the reduced pressure then.The question response device is chilled to room temperature, and catalyst filtration is separated, and catalyst need not pass through any processing and just can reuse.Obtain containing the mixed solution (205 ℃ of Bian alcohol boiling points, about 270 ℃ of the boiling points of benzyq carbamate) of the pure and mild benzyq carbamate of Bian,, after Bian alcohol steamed, obtain white solid (purity is 98%) through the method for decompression distillation.Best reaction result, urea transformation rate are 100%, and the selectivity of benzyq carbamate is greater than 99%, and the separation yield of benzyq carbamate can reach more than 90%.
Analysis condition: the quantitative analysis of benzyq carbamate, available Agilent 6820GC accomplishes, and this Agilent6820GC has the capillary (fid detector) of 30m * 0.25mm * 0.33 μ m.The analysis of benzyq carbamate yield can be through drawing the calibration curve of dipropyl carbonate, and then on curve, look for a little and obtaining, and promptly utilizes the external standard method acquisition.The quantitative analysis of said urea can utilize Agilent 1200HPLC to accomplish, and this Agilent1200HPLC has UV, visible light detector and the Agilent C18 chromatographic column that contains 40% methyl alcohol flowing phase.The qualitative analysis of the byproduct that other of said reaction is possible can utilize HP 6890/5973GC-MS to accomplish, and this HP 6890/5973GC-MS has the capillary of 30m * 0.25mm * 0.33 μ m and has the chemstation of NIST spectra database.
Compare with existing synthesizing amino benzyl formate technology, the present invention has the following advantages:
Catalyst is mainly supported catalyst, and the preparation process is simple relatively, and the catalyst price is relatively low.
Gentleness, catalytic activity and reaction selectivity are high relatively, the reaction time is shorter relatively for reaction condition.
Catalyst is convenient to separate with reaction system, can reuse.
The specific embodiment
Embodiment 1:
HNO with 50ml 26-27wt.%
3The aqueous solution dropwise is added drop-wise to and contains 10ml C
16H
34O
4In the beaker of the 100ml of Ti, the pH value of regulator solution is to 1-2.Add 15g six water ferric nitrates then, constantly shake, clarify until solution; Add the 50g aluminium oxide, at room temperature flooded 4 hours, it is transferred in the baking oven dried by the fire 4 hours under 110 ℃; Obtain catalyst precursor,, obtain catalyst A catalyst precursor 500 ℃ of roastings 4 hours in air
Embodiment 2:
HNO with 50ml 26-27wt.%
3The aqueous solution dropwise is added drop-wise to and contains 10ml C
16H
34O
4In the beaker of the 100ml of Ti, the pH value of regulator solution is to 1-2.Add 15g six water nickel nitrates then, constantly shake, clarify until solution; Add the 50g aluminium oxide, at room temperature flooded 4 hours, it is transferred in the baking oven dried by the fire 4 hours under 110 ℃; Obtain catalyst precursor,, obtain catalyst B catalyst precursor 600 ℃ of roastings 3 hours in air
Embodiment 3:
With 15g six water ferric nitrates and 30ml H
2O joins in the beaker of 100ml.Then, add 15g Ni (NO again
3)
26H
2O.After waiting to dissolve, the pH value of regulator solution is to 3-3.5.Add the 50g aluminium oxide again, at room temperature flooded 5 hours, it is transferred in the baking oven 100 ℃ of bakings 5 hours down, obtain catalyst precursor,, obtain catalyst C catalyst precursor 550 ℃ of roastings 4 hours in air
Embodiment 4:
With 600g urea, 6000ml Bian alcohol, the 60g catalyst A joins successively that to contain 1.2m long, and internal diameter is that sealing rises to 170 ℃ with temperature in the 10L agitated reactor of condensing reflux post of 38mm, and being decompressed to vacuum is 0.4 atmospheric pressure, reacts 6 hours.Recording the urea transformation rate is 100%, and the selectivity of benzyq carbamate is 95%.
Embodiment 5:
With 600g urea, 6000ml Bian alcohol, the 60g catalyst A joins successively that to contain 1.2m long, and internal diameter is that sealing rises to 180 ℃ with temperature in the 10L agitated reactor of condensing reflux post of 38mm, and being decompressed to vacuum is 0.2 atmospheric pressure, reacts 5 hours.Recording the urea transformation rate is 100%, and the chromatogram selectivity of benzyq carbamate is 94%.
Embodiment 6:
With 600g urea, 6000ml Bian alcohol, the 60g catalyst A joins successively that to contain 1.2m long, and internal diameter is that sealing rises to 170 ℃ with temperature in the 10L agitated reactor of condensing reflux post of 38mm, and being decompressed to vacuum is 0.6 atmospheric pressure, reacts 6 hours.Recording the urea transformation rate is 96%, and the chromatogram selectivity of benzyq carbamate is 95%.
Embodiment 7:
With 600g urea, 6000ml Bian alcohol, the 60g catalyst B joins successively that to contain 1.2m long, and internal diameter is that sealing rises to 150 ℃ with temperature in the 10L agitated reactor of condensing reflux post of 38mm, and being decompressed to vacuum is 0.4 atmospheric pressure, reacts 6 hours.Recording the urea transformation rate is 100%, and the selectivity of benzyq carbamate is 90%.
Embodiment 8:
With 600g urea, 6000ml Bian alcohol, 60g catalyst C join successively that to contain 1.2m long, and internal diameter is that sealing rises to 150 ℃ with temperature in the 10L agitated reactor of condensing reflux post of 38mm, and being decompressed to vacuum is 0.4 atmospheric pressure, reacts 6 hours.Recording the urea transformation rate is 100%, and the selectivity of benzyq carbamate is 93%.
Claims (7)
1. the catalyst of a synthesizing amino benzyl formate is characterized in that catalyst supports the composition metal composite oxides by alumina support and forms, and the activity of such catalysts component is by any two kinds of combinations in iron oxide, titanium oxide and the nickel oxide, and carrier is an aluminium oxide; Wherein the amount of catalyst activity composition is 5-15wt.%, in the gross weight of catalyst by 100%.
2. Preparation of catalysts method according to claim 1; It is characterized in that the Preparation of catalysts method is an infusion process, the pH value of maceration extract is smaller or equal to 5, and dip time is 2-10 hour; The sintering temperature of catalyst precarsor is 300-700 ℃; Roasting time is 3-8 hour, and the environment of roasting is air or nitrogen, and the used compound of catalyst precarsor is selected from any two kinds of combinations in ferric nitrate, nickel nitrate and the butyl titanate.
3. the method for a synthesizing amino benzyl formate is characterized in that this method is a reactant with urea and Bian alcohol, in 140-180 ℃ of decompression catalytic reaction synthesizing amino benzyl formate; Catalyst supports the composition metal composite oxides by alumina support to be formed, and the activity of such catalysts component is by any two kinds of combinations in iron oxide, titanium oxide and the nickel oxide, and carrier is an aluminium oxide; Wherein the amount of catalyst activity composition is 5-15wt.%, in the gross weight of catalyst by 100%.
4. method as claimed in claim 3, the vacuum that is adopted that it is characterized in that reducing pressure is 0.8-0.2 atmospheric pressure.
5. method as claimed in claim 3 is characterized in that Bian alcohol is 3/1-8/1 with urea mol ratio.
6. method as claimed in claim 3, the mass ratio that it is characterized in that catalyst and urea is 0.05/1-0.2/1.
7. method as claimed in claim 3 is characterized in that the reaction time is 3-8 hour.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
| CN101518729A (en) * | 2008-02-26 | 2009-09-02 | 拜耳材料科技贸易(上海)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
| CN101596452A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of catalyst for preparing dimethyl carbonate by using urea alcoholysis and preparation method thereof |
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2010
- 2010-12-23 CN CN2010106099811A patent/CN102553598A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
| CN101518729A (en) * | 2008-02-26 | 2009-09-02 | 拜耳材料科技贸易(上海)有限公司 | Catalyst used for synthesizing alkyl carbamate and preparing method and application thereof |
| CN101596452A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of catalyst for preparing dimethyl carbonate by using urea alcoholysis and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662215A (en) * | 2020-07-27 | 2020-09-15 | 重庆化工职业学院 | Process for preparing carbamates |
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Application publication date: 20120711 |