CN1850325A - Load-type catalyst for synthesizing Amino-methye-formate, its preparing and applicating method - Google Patents
Load-type catalyst for synthesizing Amino-methye-formate, its preparing and applicating method Download PDFInfo
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- CN1850325A CN1850325A CN 200610013757 CN200610013757A CN1850325A CN 1850325 A CN1850325 A CN 1850325A CN 200610013757 CN200610013757 CN 200610013757 CN 200610013757 A CN200610013757 A CN 200610013757A CN 1850325 A CN1850325 A CN 1850325A
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Abstract
The present invention relates to a loaded type catalyst for synthesizing methyl carbanilate, its preparation and application method. Said catalyst is formed from TiO2, ZnO and carrier silicon oxide, aluminium oxide, titanium oxide, magnesium oxide, molecular sieve, active carbon or montmorillonite, in which the mole ratio of ZnO;TiO2 is 1:0.2-5. Said catalyst, phenylamine and methyl caronate are added into a high-pressure kettle, heated to make reaction, then decompressed, filtered and separated to remove catalyst so as to obtain the invented product methyl carbanilate. Besides, said invention also provides the concrete steps of said catalyst preparation method.
Description
Technical field
Technical scheme of the present invention relates to the catalyst that comprises titanium dioxide and zinc oxide, specifically a kind of supported titanium
2-ZnO catalyst and methods for making and using same thereof.
Technical background
Methyl phenyl carbamate (being called for short MPC) is the synthesizing diphenyl methane vulcabond intermediate of (being called for short MDI), and MDI is one of important source material of synthesis of polyurethane, and its polyurethane product is widely used in the industries such as electromechanics, boats and ships, aviation, civil construction, light industry.The synthetic method of MDI mainly is divided into phosgenation and non-phosgene, and phosgenation is present industrialized main method.Because there are shortcomings such as raw material severe toxicity, by-product hydrochloric acid etching apparatus in phosgenation, people more pay attention to the exploitation of non-phosgene in recent years.Wherein adopting " green chemical " dimethyl carbonate (being called for short DMC) to replace phosgene, can react under temperate condition, is to produce one of up-and-coming method of MDI.It was two steps that this technology is divided into, and its reaction equation is as follows:
As can be seen, this technology is by-product first alcohol and water only, and wherein methyl alcohol is again the raw material of oxidative carbonylation Synthesis of dimethyl carbonate, therefore the development trend that meets the chemical industry greenization, cleans.
Be committed step with the synthesizing Amino-methye-formate in this route, be divided into the alcoholysis method of oxidation carbonization, reduction carbonyl process, dimethyl carbonate amine-decomposing method and urea at present about the synthetic method of methyl phenyl carbamate.Wherein oxidation carbonization and reduction carbonyl process need react under high temperature and high pressure, and use noble metal as catalyst more, and production cost is higher, and not seeing has industrialized report.To disclose a kind of be the method for raw material synthesizing amino methyl formate with phenylurea and methyl alcohol to CN 1528741A in addition, will phenylurea, solvent, methyl alcohol and catalyst add in the reactor and react.This method need use benzene and toluene to be solvent, and is unfriendly to environment.And be the raw material synthesizing Amino-methye-formate with dimethyl carbonate and aniline, not using solvent, the methyl alcohol of by-product is again the raw material of the synthetic DMC of oxidative carbonylation, is to a kind of environment amenable technology.
With aniline and dimethyl carbonate is that the synthetic used catalyst of MPC of raw material comprises homogeneous catalyst and heterogeneous catalysis two classes.
The existing report of relevant application homogeneous catalysis agent method has: US 4395565 has reported and has utilized sodium methoxide to be the synthetic MPC of catalyst, 12O ℃ of reaction 5 hours, the conversion ratio of aniline is 40%, the selectivity of MPC is 77.8%, the shortcoming of using this catalyst is to reuse, after reaction finishes, need with in the acid and sodium methoxide to reach separated product and catalyst gets purpose; (T Baba such as Toshihide Baba, A Kobayashi, H Tanaka, et al.Catalysis Letter, 2002,82 (3-4): 193) studied the synthetic of on zinc acetate catalyst toluene diamino-methyl formate and diphenyl methane diamino acid methyl ester, yield is respectively 96% and 98%.Though zinc acetate has catalytic activity preferably for such reaction, its shortcoming is an easily inactivation of reaction back, and catalyst can not be recycled.
Relevant this synthetic reaction uses the research of heterogeneous catalysis then to focus mostly in leaded compound.Plumbous poisonous, unfriendly to environment.Zihua Fu etc. (Z Fu, Y Ono.Journal of Molecular Catalysis, 1994,91:399) with Pb (OAc)
2Pb (OH)
2Be the catalyst synthesizing Amino-methye-formate, reacted 1 hour down at 180 ℃ that the conversion ratio of aniline is 97%, the yield of MPC is 95%; Kang Wukui etc. (princes and dukes should wait for Kang Wukui, Yao Jie. Journal of Molecular Catalysis, 2003,17 (2): 136) with Pb
3O
4The composite oxides of-ZnO are the synthetic MPC of catalyst, n (aniline): n (DMC)=0.2, and n (catalyst): n (aniline)=O.1 reacted 4 hours down at 170 ℃, and the conversion ratio of aniline is 63.28%, but does not provide the yield of MPC; Li Qifeng etc. (Li Qifeng, Wang Junwei, Dong Wensheng etc. catalysis journal, 2003,24 (8): 639-642) with In
2O
3/ SiO
2Be the synthetic MPC of catalyst, its yield only is 59.45%.
From above-mentioned prior art, be in the production technology of raw material synthesizing Amino-methye-formate with dimethyl carbonate and aniline, homogeneous catalyst can not recycle, with the product separation difficulty; And unfriendly to environment, the active low shortcoming of existing heterogeneous catalysis existence.
Summary of the invention
Technical problem to be solved by this invention is: the supported titanium that a kind of synthesizing phenyl-methyl-formater is provided
2-ZnO catalyst and methods for making and using same thereof, this catalyst is the high heterogeneous catalysis of a kind of activity, be used for dimethyl carbonate amine-decomposing method synthesizing Amino-methye-formate, having overcome homogeneous catalyst can not recycle, with the product separation difficulty, and there is unfriendly to environment, active low shortcoming in existing heterogeneous catalysis.
The present invention solves this technical problem the technical scheme that is adopted:
The loaded catalyst of synthesizing phenyl-methyl-formater of the present invention is by TiO
2, ZnO and carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or imvite form, wherein the mol ratio of two kinds of active components is ZnO: TiO
2=1: 0.2～5, active component TiO
2With the load capacity of ZnO be 1～50%, load capacity is meant active component TiO
2With the weight percent content of ZnO in loaded catalyst integral body.
In the loaded catalyst of above-mentioned synthesizing phenyl-methyl-formater, the mol ratio of two kinds of active components is preferably ZnO: TiO
2=1: 1～2.
In the loaded catalyst of above-mentioned synthesizing phenyl-methyl-formater, active component TiO
2Be preferably 10～30% with the load capacity of ZnO.
The preparation method of the loaded catalyst of above-mentioned synthesizing phenyl-methyl-formater, its step is as follows:
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 1～50%;
(2) take by weighing carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or the imvite of aequum, measure the volume of the required absolute methanol of incipient impregnation with absolute methanol;
(3) according to selected active component TiO of (1) step
2With the load capacity of ZnO is 1～50% to determine required ZnO and TiO
2Total amount, again according to ZnO and TiO
2Mol ratio be 1: 0.2～5 to calculate and take by weighing required butyl titanate and organic acid zinc salt, they are dissolved in (2) step in the absolute methanol of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80～120 ℃ of vacuum drying 5～15 hours;
(5) behind the dipping that (4) are made dry catalyst in air atmosphere in 300～800 ℃ of roastings 2～10 hours, make the loaded catalyst of required synthesizing phenyl-methyl-formater.
In the preparation method of the loaded catalyst of above-mentioned synthesizing phenyl-methyl-formater, employed organic acid zinc salt is zinc formate, zinc acetate, zinc propionate, zinc butyrate, zinc valerate, zinc octoate or zinc stearate.
The application process of the loaded catalyst of above-mentioned synthesizing phenyl-methyl-formater is, with dimethyl carbonate and aniline is being application in the raw material synthesizing Amino-methye-formate, and the mol ratio of selected aniline and dimethyl carbonate is 1: 1～30, aniline and supported titanium
2The weight ratio of-ZnO catalyst is 1: 0.01～0.5, with supported titanium
2-ZnO catalyst, aniline and dimethyl carbonate join in the autoclave, and temperature rises to 90～200 ℃, react 1～20 hour, and the reactant liquor filtration under diminished pressure is made supported titanium
2-ZnO catalyst and reactant liquor are separated, and again with the reactant liquor decompression distillation, remove unreacted DMC and can make the products benzene methyl carbamate.
In the Application of Catalyst method of above-mentioned synthesizing phenyl-methyl-formater, the mol ratio of described aniline and dimethyl carbonate is 1: 5～20, aniline and TiO
2The mass ratio of-ZnO catalyst is 1: 0.05～0.3, and temperature rises to 100～180 ℃, reacts 5～10 hours.
In the Application of Catalyst method of above-mentioned synthesizing phenyl-methyl-formater, the supported titanium of utilizing isolated by vacuum filtration or filtration under diminished pressure to go out
2-ZnO catalyst cleans with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours, 500 ℃ of following roastings 5 hours, reuses again.
The invention has the beneficial effects as follows: the supported titanium of synthesizing phenyl-methyl-formater of the present invention
2-ZnO catalyst is a solid-phase catalyst, its catalytic activity height, good stability, easily regenerates, is easy to separate to reclaim (seeing embodiment 18), TiO
2-ZnO is environmentally friendly, in preparation and use, do not pollute the environment, thereby overcome and in prior art, have the catalyst separation difficulty, product quality is caused adverse influence, catalyst is difficult for recycling, and the shortcoming that in use pollutes the environment.In addition, Preparation of catalysts method easy operating of the present invention, repeatability is high.
The specific embodiment
The invention will be further described with specific embodiment below, but do not limit protection scope of the present invention.
Embodiment 1
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 10%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 10% determine required ZnO and TiO
2Total amount be 0.56 the gram, again according to ZnO and TiO
2Mol ratio be to calculate at 1: 1 to take by weighing required butyl titanate 0.0035mol and Zn (OOCCH
3)
22H
2O 0.0035mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80 ℃ of vacuum drying 8 hours;
(5) behind the dipping that (4) are made dry catalyst in air atmosphere in 500 ℃ of roastings 8 hours, make required synthesizing phenyl-methyl-formater load capacity and be 10% supported titanium 2-ZnO catalyst.
Embodiment 2-6
Identical with the preparation method of embodiment 1, just change the used carrier of catalyst and be respectively aluminium oxide, titanium oxide, magnesia, active carbon or imvite, make required separately synthesizing phenyl-methyl-formater load capacity and be 10% supported titanium
2-ZnO catalyst.
Embodiment 7
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 5%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 5% determine required ZnO and TiO
2Total amount be 0.26 the gram, again according to ZnO and TiO
2Mol ratio be to calculate and take by weighing required butyl titanate 0.0016mol and Zn (OOCCH at 1: 1
3)
22H
2O 0.0016mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 100 ℃ of vacuum drying 10 hours;
(5) catalyst behind the dipping that (4) are made in 500 ℃ of roastings 8 hours, makes required synthesizing phenyl-methyl-formater load capacity and is 5% supported titanium in air atmosphere
2-ZnO catalyst.
Embodiment 8
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 20%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 20% determine required ZnO and TiO
2Total amount be 1.25 the gram, again according to ZnO and TiO
2Mol ratio be to calculate and take by weighing required butyl titanate 0.0078mol and Zn (OOCCH at 1: 1
3)
22H
2O 0.0078mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 100 ℃ of vacuum drying 10 hours;
(5) catalyst behind the dipping that (4) are made in 500 ℃ of roastings 8 hours, makes required synthesizing phenyl-methyl-formater load capacity and is 20% supported titanium 2-ZnO catalyst in air atmosphere.
Embodiment 9
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 30%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 30% determine required ZnO and TiO
2Total amount be 2.14 the gram, again according to ZnO and TiO
2Mol ratio be to calculate and take by weighing required butyl titanate 0.0134mol and Zn (OOCCH at 1: 1
3)
22H
2O 0.0134mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 100 ℃ of vacuum drying 10 hours;
(5) catalyst behind the dipping that (4) are made in 500 ℃ of roastings 8 hours, makes required synthesizing phenyl-methyl-formater load capacity and is 30% supported titanium in air atmosphere
2-ZnO catalyst.
Embodiment 10
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 10%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 10% determine required ZnO and TiO
2Total amount be 0.56 the gram, again according to ZnO and TiO
2Mol ratio be to calculate and take by weighing required butyl titanate 0.0046mol and Zn (OOCCH at 1: 2
3)
22H
2O 0.0023mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80 ℃ of vacuum drying 8 hours;
(5) catalyst behind the dipping that (4) are made in 600 ℃ of roastings 5 hours, makes required synthesizing phenyl-methyl-formater load capacity and is 10% supported titanium in air atmosphere
2-ZnO catalyst.
Embodiment 11
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 10%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 10% determine required ZnO and TiO
2Total amount be 0.56 the gram, again according to ZnO and TiO
2Mol ratio be to calculate and take by weighing required butyl titanate 0.0023mol and Zn (OOCCH at 1: 0.5
3)
22H
2O 0.0046mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80 ℃ of vacuum drying 8 hours;
(5) catalyst behind the dipping that (4) are made in 600 ℃ of roastings 5 hours, makes required synthesizing phenyl-methyl-formater load capacity and is 10% supported titanium in air atmosphere
2-ZnO catalyst.
Embodiment 12-14
Identical with the preparation method of embodiment 1, change just that sintering temperature is 400 ℃, 600 ℃, 700 ℃ in the step (5), make required separately synthesizing phenyl-methyl-formater load capacity and be 10% supported titanium
2-ZnO catalyst.
Embodiment 15
Identical with the preparation method of embodiment 1, change just that roasting condition is 600 ℃ of following roastings 5 hours in the step (5), make required synthesizing phenyl-methyl-formater load capacity and be 10% supported titanium
2-ZnO catalyst.
Embodiment 16
The supported titanium that embodiment 1-15 is made
2-ZnO catalyst is applied to dimethyl carbonate and aniline is in the reaction of raw material synthesizing Amino-methye-formate, and reaction result is compared, in order to the performance of the catalyst of estimating each embodiment preparation.
The supported titanium that the foregoing description 1-15 is made respectively
2-ZnO catalyst 1.8 restrains, joins in the autoclave with aniline 7ml, dimethyl carbonate 130ml, is heated to 150 ℃, reacts 5 hours, and the reactant liquor filtration under diminished pressure is made supported titanium
2-ZnO catalyst and product are separated, and reactant liquor is with efficient liquid phase chromatographic analysis and calculate the productive rate of methyl phenyl carbamate.
In embodiment 1,7,8,9, active component TiO
2With the load capacity of ZnO to supported titanium
2-ZnO catalyst Effect on Performance evaluation result sees Table 1.
Table 1 load capacity is to supported titanium
2-ZnO catalyst Effect on Performance
| The embodiment sequence number | 1 | 7 | 8 | 9 |
| Load capacity | 10 | 5 | 20 | 30 |
| Productive rate (%) | 67 | 60.5 | 56.2 | 25.8 |
In embodiment 1-6, carrier is to supported titanium
2-ZnO catalyst Effect on Performance evaluation result sees Table 2.
Table 2 carrier is to supported titanium
2-ZnO catalyst Effect on Performance
| The embodiment sequence number | 1 | 2 | 3 | 4 | 5 | 6 |
| Carrier | Silica | Aluminium oxide | Titanium oxide | Magnesia | Active carbon | Imvite |
| Productive rate (%) | 67 | 54.2 | 31.2 | 19.8 | 15.3 | 39.4 |
In embodiment 1,12,13,14, sintering temperature is to supported titanium
2-ZnO catalyst Effect on Performance evaluation result sees Table 3.
Table 3 sintering temperature is to supported titanium
2-ZnO catalyst Effect on Performance
| The embodiment sequence number | 1 | 12 | 13 | 14 |
| Sintering temperature | 500℃ | 400℃ | 600℃ | 700℃ |
| Productive rate (%) | 67 | 42.3 | 48.6 | 32.1 |
In embodiment 10,11,15, ZnO and TiO
2Mol ratio to supported titanium
2-ZnO catalyst Effect on Performance evaluation result sees Table 4.
Table 4 ZnO and TiO
2Mol ratio to supported titanium
2-ZnO catalyst Effect on Performance
| The embodiment sequence number | 10 | 11 | 15 |
| ZnO and TiO 2Mol ratio | 1∶2 | 1∶0.5 | 1∶1 |
| Productive rate (%) | 58.9 | 45.7 | 70.2 |
Embodiment 17
The supported titanium that embodiment 1 is made
2-ZnO catalyst is applied to dimethyl carbonate and aniline is in the reaction of raw material synthesizing Amino-methye-formate, selects for use under the differential responses condition, carries out reaction condition to supported titanium
2The evaluation of-ZnO catalyst performance impact, test method is identical with embodiment 16, the results are shown in table 5.
Table 5 reaction condition is to supported titanium
2-ZnO catalyst Effect on Performance
| The mol ratio of benzene and dimethyl carbonate | The mass ratio of catalyst and aniline | Reaction temperature (℃) | Reaction time (h) | Productive rate (%) |
| 1∶5 | 0.08∶1 | 90 | 5 | 22.8 |
| 1∶5 | 0.1∶1 | 110 | 5 | 40.7 |
| 1∶5 | 0.3∶1 | 150 | 5 | 58.9 |
| 1∶20 | 0.25∶1 | 150 | 5 | 78 |
| 1∶1 | 0.01∶1 | 200 | 20 | 11.2 |
| 1∶30 | 0.5∶1 | 90 | 1 | 15.7 |
The data declaration of table 5, the fixing consumption of aniline, along with the consumption that improves dimethyl carbonate, reaction yield increases thereupon, but continues to increase the consumption of dimethyl carbonate, and productive rate is almost constant; Improve catalyst consumption, reaction yield increases thereupon, continues to increase catalyst amount, and productive rate reduces on the contrary to some extent.In synthetic reaction, along with the raising of reaction temperature, the reaction time can shorten, and reaction yield increases.But reaction temperature is higher than 190 ℃, and byproduct of reaction increases, and reaction yield reduces on the contrary; Reaction temperature is lower than 120 ℃, and reaction yield is lower, is unfavorable for suitability for industrialized production.
Embodiment 18
The supported titanium that embodiment 1 is made
2React under the reaction condition of-ZnO catalyst in embodiment 16, after reaction finishes, the supported titanium of utilizing isolated by vacuum filtration to go out
2-ZnO catalyst cleans with absolute ethyl alcohol, 60 ℃ of following vacuum drying 21 hours, and again 500 ℃ of following roastings 5 hours, after measured, supported titanium
2-ZnO catalyst activity does not almost change, and reuses.
Embodiment 19
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 50%;
(2) take by weighing carrier silica 5 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 20ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 50% determine required ZnO and TiO
2Total amount be 1.7 the gram, again according to ZnO and TiO
2Mol ratio be to calculate at 1: 0.2 to take by weighing required butyl titanate 0.01mol and Zn (OOCCH
3)
22H
2O 0.05mol, they are dissolved in (2) step among the absolute methanol 20ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 120 ℃ of vacuum drying 5 hours;
(5) behind the dipping that (4) are made dry catalyst in air atmosphere in 800 ℃ of roastings 2 hours, make required synthesizing phenyl-methyl-formater load capacity and be 50% supported titanium
2-ZnO catalyst.
Embodiment 20
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 1%;
(2) take by weighing carrier silica 16.8 grams, the volume of measuring the required methyl alcohol of incipient impregnation with absolute methanol is 68ml;
(3) according to selected active component TiO of (1) step
2Be weight percentage with the load capacity of ZnO and 50% determine required ZnO and TiO
2Total amount be 5 the gram, again according to ZnO and TiO
2Mol ratio be to calculate at 1: 0.2 to take by weighing required butyl titanate 0.00035mol and Zn (OOCCH
3)
22H
2O 0.00175mol, they are dissolved in (2) step among the absolute methanol 68ml of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80 ℃ of vacuum drying 15 hours;
(5) behind the dipping that (4) are made dry catalyst in air atmosphere in 300 ℃ of roastings 10 hours, make required synthesizing phenyl-methyl-formater load capacity and be 1% supported titanium
2-ZnO catalyst.
Embodiment 21
Get the supported titanium that embodiment 1 makes
2-ZnO catalyst 1.8 restrains, presses aniline and TiO
2The mass ratio of-ZnO catalyst is that the mol ratio of 1: 0.05 and aniline and dimethyl carbonate is to calculate get amount and aniline and dimethyl carbonate at 1: 5, and they are joined in the autoclave, is heated to 100 ℃, reacts 10 hours, and the reactant liquor filtration under diminished pressure is made supported titanium
2-ZnO catalyst and reactant liquor are separated, and again with the reactant liquor decompression distillation, remove unreacted DMC and can make the products benzene methyl carbamate, utilize the isolated supported titanium of filtration under diminished pressure
2-ZnO catalyst cleans with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours, 500 ℃ of following roastings 5 hours, reuses again.
Embodiment 22
Get the supported titanium that embodiment 1 makes
2-ZnO catalyst 1.8 restrains, presses aniline and TiO
2The mass ratio of-ZnO catalyst is that the mol ratio of 1: 0.05 and aniline and dimethyl carbonate is to calculate get amount and aniline and dimethyl carbonate at 1: 5, and they are joined in the autoclave, is heated to 180 ℃, reacts 5 hours, and the reactant liquor filtration under diminished pressure is made supported titanium
2-ZnO catalyst and reactant liquor are separated, and again with the reactant liquor decompression distillation, remove unreacted DMC and can make the products benzene methyl carbamate, utilize the isolated supported titanium of filtration under diminished pressure
2-ZnO catalyst cleans with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours, 500 ℃ of following roastings 5 hours, reuses again.
Claims (8)
1. the loaded catalyst of synthesizing phenyl-methyl-formater, it is characterized in that: it is by TiO
2, ZnO and carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or imvite form, wherein the mol ratio of two kinds of active components is ZnO :/TiO
2=1: 0.2～5, active component TiO
2With the load capacity of ZnO be 1～50%, load capacity is meant active component TiO
2With the weight percent content of ZnO in loaded catalyst integral body.
2. according to the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 1, it is characterized in that: the mol ratio of two kinds of active components is ZnO: TiO
2=1: 1～2.
3. according to the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 1, it is characterized in that: active component TiO
2With the load capacity of ZnO be 10～30%.
4. the preparation method of the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 1, it is characterized in that: step is as follows:
(1) active component TiO in the loaded catalyst of selected synthesizing phenyl-methyl-formater
2With the load capacity of ZnO be 1～50%;
(2) take by weighing carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or the imvite of aequum, measure the volume of the required absolute methanol of incipient impregnation with absolute methanol;
(3) according to selected active component TiO of (1) step
2With the load capacity of ZnO is 1～50% to determine required ZnO and TiO
2Total amount, again according to ZnO and TiO
2Mol ratio be 1: 0.2～5 to calculate and take by weighing required butyl titanate and organic acid zinc salt, they are dissolved in (2) step in the absolute methanol of definite volume, be mixed with maceration extract;
(4) maceration extract that is mixed with of (3) step dropwise is added drop-wise on the carrier that (2) step taken by weighing, incipient impregnation 24 hours, with the catalyst behind the dipping in 80～120 ℃ of vacuum drying 5～15 hours;
(5) behind the dipping that (4) are made dry catalyst in air atmosphere in 300～800 ℃ of roastings 2～10 hours, make the loaded catalyst of required synthesizing phenyl-methyl-formater.
5. according to the preparation method of the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 4, it is characterized in that: employed organic acid zinc salt is zinc formate, zinc acetate, zinc propionate, zinc butyrate, zinc valerate, zinc octoate or zinc stearate.
6. the application process of the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 1, it is characterized in that: with dimethyl carbonate and aniline be application in the raw material synthesizing Amino-methye-formate, the mol ratio of selected aniline and dimethyl carbonate is 1: 1～30, aniline and supported titanium
2The weight ratio of-ZnO catalyst is 1: 0.01～0.5, with supported titanium
2-ZnO catalyst, aniline and dimethyl carbonate join in the autoclave, and temperature rises to 90～200 ℃, react 1～20 hour, and the reactant liquor filtration under diminished pressure is made supported titanium
2-ZnO catalyst and reactant liquor are separated, and again with the reactant liquor decompression distillation, remove unreacted DMC and can make the products benzene methyl carbamate.
7. according to the application process of the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 6, it is characterized in that: the mol ratio of described aniline and dimethyl carbonate is 1: 5～20, aniline and TiO
2The mass ratio of-ZnO catalyst is 1: 0.05～0.3, and temperature rises to 100～180 ℃, reacts 5～10 hours.
8. according to the application process of the loaded catalyst of the described synthesizing phenyl-methyl-formater of claim 6, it is characterized in that: utilize the isolated supported titanium of filtration under diminished pressure
2-ZnO catalyst cleans with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours, 500 ℃ of following roastings 5 hours, reuses again.
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| CN101829554A (en) * | 2010-03-26 | 2010-09-15 | 中国科学院化学研究所 | Repeatedly used catalyst for synthesizing dimethyl carbonate |
| CN101891651A (en) * | 2009-05-19 | 2010-11-24 | 拜耳材料科技(中国)有限公司 | Catalyst used in preparation of N-substituted carbamate and preparation method and application thereof |
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| CN102872912A (en) * | 2012-09-18 | 2013-01-16 | 哈尔滨理工大学 | Catalyst for synthesizing methyl phenyl carbamate and preparation and application methods thereof |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1141960B (en) * | 1981-01-28 | 1986-10-08 | Anic Spa | PROCEDURE FOR THE PREPARATION OF AROMATIC URETANS |
| US5773643A (en) * | 1987-01-13 | 1998-06-30 | Daicel Chemical Industries, Ltd. | Process for preparation of isocyanate compounds |
| JP2001316115A (en) * | 2000-03-28 | 2001-11-13 | Degussa Ag | Doping-processed titanium dioxide |
| GB0312703D0 (en) * | 2003-06-03 | 2003-07-09 | Oxonica Ltd | Agricultural compositions |
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