CN1850323A - Method for preparing load-type zirconium oxide and its using method - Google Patents
Method for preparing load-type zirconium oxide and its using method Download PDFInfo
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- CN1850323A CN1850323A CN 200610013758 CN200610013758A CN1850323A CN 1850323 A CN1850323 A CN 1850323A CN 200610013758 CN200610013758 CN 200610013758 CN 200610013758 A CN200610013758 A CN 200610013758A CN 1850323 A CN1850323 A CN 1850323A
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Abstract
The present invention relates to a preparation method of loaded type zirconium oxide catalyst and its application. Its preparation method is characterized by that it utilizes equivoluminal impregnation process or overimpregnation process; the weight percentage content of zirconium oxide in catalyst whole body is 0.1-50%; carrier can be silicon oxide, aluminium oxide, titanium oxide, magnesium oxide, molecular sieve, active carbon or montmorillonite; it uses zirconium oxychloride or zirconyl nitrate to prepare impregnation solution and makes impregnation, then makes drying and roasting processes so as to obtain the invented loaded type zirconium oxide catalyst. Said catalyst can be used in methylcarbonate amine decomposition process process to synthesize methyl carbanilate.
Description
Technical field
Technical scheme of the present invention relates to and comprises zirconic catalyst, specifically the preparation method of load-type zirconium oxide and application process 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 three 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 the synthetic DMC of oxidative carbonylation, therefore the development trend that meets the chemical industry greenization, cleans.
Be committed step with synthetic MPC 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 MPC.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 synthetic MPC of raw material 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, 120 ℃ of reactions 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 generation zinc oxide 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)=0.1 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%.
CN 03156419 " zirconia catalyst of synthesizing cyclohexyl methyl carbamate and its production and application " discloses and has utilized ZrO
2/ SiO
2Catalyst synthesizing cyclohexyl methyl carbamate does not relate to that to be used for this catalyst with dimethyl carbonate and aniline be the content of raw material synthesizing Amino-methye-formate, simultaneously this ZrO
2/ SiO
2Catalyst need carry out drying in the Supercritical Ethanol medium, this makes its preparation process complexity, and cost is higher relatively.
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 preparation method of load-type zirconium oxide and the application in synthesizing Amino-methye-formate thereof are provided, and the preparation method of load-type zirconium oxide of the present invention is simple, easy operating, and repeatability is high; This load-type zirconium oxide is the high heterogeneous catalysis of a kind of activity, be used for dimethyl carbonate amine-decomposing method synthesizing Amino-methye-formate, overcome homogeneous catalyst can not recycle, with the shortcoming of 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 preparation method of load-type zirconium oxide, select one of following two kinds of methods arbitrarily for use:
(1) equi-volume impregnating
I. the weight percent content of zirconia in catalyst integral body that selected zirconates resolves into is 0.1～50%;
II. take by weighing carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or the imvite of required weight, measure the volume of the required maceration extract of incipient impregnation with deionized water;
III. according to the weight of selecting the carrier that is taken by weighing with II of I, calculate the weight that takes by weighing requisite oxygen zirconium chloride or zirconyl nitrate, be dissolved in the volumetric deionized water of II step institute, be mixed with maceration extract;
IV. the maceration extract that III step is made dropwise is added drop-wise on the carrier of the II step weight that takes by weighing, incipient impregnation 24 hours, with soaked carrier in 40～70 ℃ of vacuum drying 1～10 hour;
V. again IV is gone on foot the dry carrier in prepared dipping back in air atmosphere in 200～700 ℃ of roastings 1～7 hour, make load-type zirconium oxide;
(2) excessive infusion process
I. the weight percent content of zirconia in catalyst integral body that selected zirconates resolves into is 0.1～50%;
II. take by weighing required weight carrier silica, aluminium oxide, titanium oxide, magnesia, divided sieve, active carbon or imvite, measure the volume of the required maceration extract of incipient impregnation with deionized water;
III. take by weighing the requisite oxygen zirconium chloride that 4～6 times the weight according to the selected and carrier that II takes by weighing of I calculates or the weight of zirconyl nitrate, be dissolved in 4～6 times to the II step in the volumetric deionized water, be mixed with maceration extract;
IV. II being gone on foot alleged carrier and place the maceration extract that III step makes, is 30～100 ℃ of excessive dippings 10～48 hours down in temperature, can obtain soaked carrier through vacuum filtration, with soaked carrier in 40～70 ℃ of vacuum drying 1～10 hour;
V. again IV is gone on foot the dry carrier in prepared dipping back in air atmosphere in 200～700 ℃ of roastings 1～7 hour, make load-type zirconium oxide.
In above-mentioned two kinds of methods, the preferred V step is: again IV is gone on foot the dry carrier in prepared dipping back in air atmosphere in 300～500 ℃ of roastings 2～5 hours, make load-type zirconium oxide.
In above-mentioned two kinds of methods, the preferred I step is: the weight percent content of the zirconia that selected zirconates resolves in catalyst integral body is 5～20%.
The application process of the load-type zirconium oxide that said method makes, use it for synthesizing Amino-methye-formate, concrete technology is: with load-type zirconium oxide, aniline and dimethyl carbonate join in the autoclave, the mol ratio of aniline and dimethyl carbonate is 1: 1～30, the mass ratio of aniline and catalyst is 1: 0.01～0.5, temperature rises to 90～200 ℃, reacted 1～20 hour, load-type zirconium oxide and reactant liquor are separated the reactant liquor filtration under diminished pressure, with the reactant liquor decompression distillation, remove unreacted DMC and can make the products benzene methyl carbamate again.
In the application process of above-mentioned load-type zirconium oxide, the mol ratio of preferred aniline and dimethyl carbonate is 1: 5～20, and the mass ratio of aniline and catalyst is 1: 0.05～0.3, and temperature rises to 120～180 ℃, reacts 5～10 hours.
In the application process of above-mentioned load-type zirconium oxide, utilize the isolated load-type zirconium oxide of filtration under diminished pressure to clean with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours,, reuse again 500 ℃ of following roastings 5 hours.
The invention has the beneficial effects as follows: compare with prior art, the present invention has following advantage:
1. load-type zirconium oxide preparation method of the present invention need not carry out the drying process of catalyst in the Supercritical Ethanol medium, and only needs general conventional drying technology, and entire method is simple, easy operating, and repeatability is high, sees embodiment 18 for details.
2. the load-type zirconium oxide that makes of the inventive method is after use, drying and roasting, and it is active to descend not obviously, so its good stability is easily regenerated and is reused.
3. the load-type zirconium oxide that makes of the inventive method is a solid-phase catalyst, very easily separates with product, and very easily self reclaims, and does not in use pollute the environment, and is environmentally friendly.
4. in the application with aniline and dimethyl carbonate synthesizing Amino-methye-formate, the performance of the load-type zirconium oxide that the inventive method makes is better than the performance of the similar catalyst of additive method preparation, sees embodiment 17 for details.
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) the selected weight percent content of zirconia in catalyst integral body is 5%;
(2) take by weighing 5 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 10 milliliters;
(3) weighing 0.69 gram ZrOCl
28H
2O is dissolved in 10 ml deionized water, is mixed with maceration extract;
(4) maceration extract that (3) step is made dropwise is added drop-wise to the 5 gram SiO that (2) take by weighing
2On, incipient impregnation 24 hours is with soaked carrier vacuum drying 2 hours in 60 ℃ of waters bath with thermostatic control;
(5) again that prepared dipping back of (4) step is dry carrier 500 ℃ of roastings 5 hours in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 2
(1) the selected weight percent content of zirconia in catalyst integral body is 3%;
(2) get 5 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 10 milliliters;
(3) weighing 2 gram ZrOCl
28H
2O is dissolved in 50 ml deionized water, is mixed with maceration extract;
(4) (2) are gone on foot 5 alleged gram SiO
2Place the maceration extract that makes of (3) step, be heated to 90 ℃, excessive dipping 24 hours obtains soaked carrier through vacuum filtration, with soaked carrier in 60 ℃ of vacuum drying 3 hours;
(5) again that prepared dipping back of (4) step is dry carrier 500 ℃ of roastings 5 hours in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 3-5
Identical with the preparation method of embodiment 1, just change the middle sintering temperature of step (5) and be respectively 400 ℃, 600 ℃, 700 ℃, make required separately load-type zirconium oxide of the present invention respectively.
Embodiment 6-8
Identical with the preparation method of embodiment 1, just change and select the weight percent content of zirconia in catalyst in the step (1) for being respectively 10%, 20%, 30%, promptly change ZrOCl in the step (3)
28H
2The weighing of O is respectively 1.5 grams, 3.3 grams, 5.6 load-type zirconium oxides of the present invention of restraining requiredly separately.
Embodiment 9-14
Identical with the preparation method of embodiment 1, just change the used carrier of catalyst and be respectively aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or imvite, make required separately load-type zirconium oxide of the present invention.
Embodiment 15
The load-type zirconium oxide that embodiment 1-13 is made 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.
Load-type zirconium oxide of the present invention is applied to synthesizing Amino-methye-formate: load-type zirconium oxide of the present invention 1.8 grams, 7 milliliters of aniline, the dimethyl carbonate with embodiment 1-13 preparation joins in the autoclave for 130 milliliters respectively, be heated to 150 ℃, reacted 5 hours, load-type zirconium oxide and reactant liquor are separated the reactant liquor filtration under diminished pressure, reactant liquor is with efficient liquid phase chromatographic analysis and calculate the productive rate of methyl phenyl carbamate.
The load-type zirconium oxide evaluation result of embodiment 1,2 sees Table 1.
The different preparation methods of table 1 are to the load-type zirconium oxide Effect on Performance
| The embodiment sequence number | 1 | 2 |
| Productive rate (%) | 74 | 80 |
The load-type zirconium oxide evaluation result of embodiment 1,3,4,5 sees Table 2.
Table 2 sintering temperature is to the load-type zirconium oxide Effect on Performance
| The embodiment sequence number | 1 | 3 | 4 | 5 |
| Sintering temperature (℃) | 500 | 400 | 600 | 700 |
| Productive rate (%) | 74 | 79.8 | 70 | 55.5 |
The load-type zirconium oxide evaluation result of embodiment 1,6,7,8 sees Table 3.
Table 3 zirconia load capacity is to the influence of load-type zirconium oxide
| The embodiment sequence number | 1 | 6 | 7 | 8 |
| Load capacity (%) | 5 | 10 | 20 | 30 |
| Productive rate (%) | 74 | 78 | 65.3 | 57.1 |
The load-type zirconium oxide evaluation result of embodiment 1,9,10,11,12,13,14 sees Table 4.
Table 4 different carriers is to the influence of load-type zirconium oxide
| The embodiment sequence number | 1 | 9 | 10 | 11 | 12 | 13 | 14 |
| Carrier | Silica | Aluminium oxide | Titanium oxide | Magnesia | Molecular sieve | Active carbon | Imvite |
| Productive rate (%) | 74 | 35.2 | 62.5 | 32.8 | 35.1 | 60 | 42 |
Embodiment 16
The load-type zirconium oxide that embodiment 1 is made is applied to dimethyl carbonate and aniline is in the reaction of raw material synthesizing Amino-methye-formate, select for use under the differential responses condition, carry out the evaluation of reaction condition to the load-type zirconium oxide performance impact, test method is identical with embodiment 15, the results are shown in table 5.
Table 5 reaction condition is to the load-type zirconium oxide Effect on Performance
| The mol ratio of benzene and dimethyl carbonate | The mass ratio of catalyst and aniline | Reaction temperature (℃) | Reaction time (hour) | Productive rate (%) |
| 1∶5 | 0.08∶1 | 110 | 5 | 50.4 |
| 1∶5 | 0.25∶1 | 110 | 5 | 63 |
| 1∶5 | 0.5∶1 | 110 | 5 | 64.6 |
| 1∶10 | 0.25∶1 | 110 | 5 | 68.9 |
| 1∶20 | 0.25∶1 | 110 | 5 | 70.6 |
| 1∶20 | 0.25∶1 | 150 | 5 | 74 |
| 1∶20 | 0.25∶1 | 170 | 5 | 63.5 |
| 1∶5 | 0.05∶1 | 180 | 5 | 59.8 |
| 1∶30 | 0.01∶1 | 200 | 1 | 43.6 |
| 1∶1 | 0.5∶1 | 90 | 20 | 29.8 |
By above data as can be seen, improve the consumption of load-type zirconium oxide, reaction yield increases thereupon, continues to increase catalyst amount, and productive rate is almost constant; 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.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 170 ℃, and byproduct of reaction increases, and reaction yield reduces on the contrary.
Embodiment 17
Load-type zirconium oxide that embodiment 1 is made and commercially available ZrO
2And SiO
2Carry out the reaction of synthesizing Amino-methye-formate under the reaction condition in embodiment 15, and carry out specific activity, the results are shown in Table shown in 6:
The ZrO that table 6 is commercially available
2, SiO
2With load-type zirconium oxide ZrO of the present invention
2/ SiO
2Performance relatively
| Catalyst type | ZrO 2/SiO 2 | ZrO 2 | SiO 2 |
| Productive rate (%) | 74 | 4.0 | 1.8 |
As can be seen, with ZrO
2Load on SiO
2Go up its activity and be higher than single ZrO far away
2Or SiO
2
Embodiment 18
According to preparing ZrO among the patent CN 03156419.4
2/ SiO
2Method prepare catalyst, and carry out the reaction of synthesizing Amino-methye-formate under the reaction condition of load-type zirconium oxide of the present invention in embodiment 15 that makes with embodiment 1, carry out specific activity, productive rate is respectively 72.5% and 74%, this shows, the preparation method of load-type zirconium oxide of the present invention is simple, and active better.
Embodiment 19
React under the reaction condition of load-type zirconium oxide in embodiment 15 that embodiment 1 is made, after reaction finishes, utilize the isolated catalyst of filtration under diminished pressure to clean with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours, again 500 ℃ of following roastings 5 hours, after measured, catalyst activity does not change, and reuses.
Embodiment 20
(1) the selected weight percent content of zirconia in catalyst integral body is 0.1%;
(2) take by weighing 50 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 100 milliliters;
(3) weighing 0.11 gram ZrO (NO
3)
22H
2O is dissolved in 100 ml deionized water, is mixed with maceration extract;
(4) maceration extract that (3) step is made dropwise is added drop-wise to the 50 gram SiO that (2) take by weighing
2On, incipient impregnation 24 hours is with soaked carrier vacuum drying 1 hour in 70 ℃ of waters bath with thermostatic control;
(5) again that prepared dipping back of (4) step is dry carrier 700 ℃ of roastings 1 hour in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 21
(1) the selected weight percent content of zirconia in catalyst integral body is 50%;
(2) take by weighing 5 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 10 milliliters;
(3) weighing 11 gram ZrO (NO
3)
22H
2O is dissolved in 10 ml deionized water, is mixed with maceration extract;
(4) maceration extract that (3) step is made dropwise is added drop-wise to the 5 gram SiO that (2) take by weighing
2On, incipient impregnation 24 hours is with soaked carrier vacuum drying 10 hours in 40 ℃ of waters bath with thermostatic control;
(5) again that prepared dipping back of (4) step is dry carrier 200 ℃ of roastings 7 hours in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 22
(1) the selected weight percent content of zirconia in catalyst integral body is 0.1%;
(2) get 50 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 100 milliliters;
(3) weighing 0.52 gram ZrOCl
28H
2O is dissolved in 400 ml deionized water, is mixed with maceration extract;
(4) (2) are gone on foot 50 alleged gram SiO
2Place the maceration extract that makes of (3) step, be heated to 50 ℃, excessive dipping 10 hours can obtain soaked carrier through filtration under diminished pressure, with soaked carrier in 40 ℃ of vacuum drying 10 hours;
(5) again that prepared dipping back of (4) step is dry carrier 700 ℃ of roastings 1 hour in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 23
(1) the selected weight percent content of zirconia in catalyst integral body is 50%;
(2) get 5 gram SiO
2, measuring the required liquor capacity of incipient impregnation with deionized water is 10 milliliters;
(3) weighing 78 gram ZrOCl
28H
2O is dissolved in 60 ml deionized water, is mixed with maceration extract;
(4) (2) are gone on foot 5 alleged gram SiO
2Place the maceration extract that makes of (3) step, be heated to 50 ℃, excessive dipping 10 hours can obtain soaked carrier through filtration under diminished pressure, with soaked carrier in 70 ℃ of vacuum drying 1 hour;
(5) again that prepared dipping back of (4) step is dry carrier 200 ℃ of roastings 7 hours in Muffle furnace in air atmosphere make required load-type zirconium oxide of the present invention.
Embodiment 24
Get load-type zirconium oxide 1.8 grams that embodiment 1 makes, by the mass ratio of aniline and zirconia catalyst is that the mol ratio of 1: 0.05 and aniline and dimethyl carbonate is to calculate the amount of getting and aniline and dimethyl carbonate at 1: 5, they are joined in the autoclave, be heated to 100 ℃, reacted 10 hours, load-type zirconium oxide and reactant liquor are separated the reactant liquor filtration under diminished pressure, again with the reactant liquor decompression distillation, remove unreacted DMC and can make the product methyl phenyl carbamate, utilize the isolated load-type zirconium oxide of filtration under diminished pressure to clean with absolute ethyl alcohol, 60 ℃ of following vacuum drying 21 hours, 500 ℃ of following roastings 5 hours, reuse again.
Embodiment 25
Get load-type zirconium oxide 1.8 grams that embodiment 1 makes, by the mass ratio of aniline and zirconia catalyst is that the mol ratio of 1: 0.05 and aniline and dimethyl carbonate is to calculate the amount of getting and aniline and dimethyl carbonate at 1: 5, they are joined in the autoclave, be heated to 180 ℃, reacted 5 hours, load-type zirconium oxide and reactant liquor are separated the reactant liquor filtration under diminished pressure, again with the reactant liquor decompression distillation, remove unreacted DMC and can make the product methyl phenyl carbamate, utilize the isolated load-type zirconium oxide of filtration under diminished pressure to clean with absolute ethyl alcohol, 60 ℃ of following vacuum drying 21 hours, 500 ℃ of following roastings 5 hours, reuse again.
In the foregoing description, the material consumption in the equi-volume impregnating calculates as follows:
A. establishing the weight percent content of zirconia in catalyst is a=zirconia/zirconia+carrier=0.1～50%;
B. the amount that takes by weighing carrier is b;
C. then zirconic amount is m=a * b/ (1-a);
D. establish and to take by weighing ZrOCl
28H
2The amount of O is X, establishes to take by weighing ZrO (NO
3) 2H
2The amount of O is Y;
ZrOCl
28H
2The molecular weight of O=321, ZrO (NO
3) 2H
2The molecular weight of O=267,
ZrO
2Molecular weight=123;
Have
X＝m×321/123 Y＝m×267/123
In the foregoing description, the material consumption in the excessive infusion process calculates as follows:
A. establishing the weight percent content of zirconia in catalyst is a=zirconia/zirconia+carrier=0.1～50%;
B. the amount that takes by weighing carrier is b;
C. then zirconic amount is m=a * b/ (1-a);
D. the volume of establishing the used deionized water of excessive dipping be the used deionized water of incipient impregnation volume n doubly;
If need ZrOCl
28H
2The amount of O is X, and establishing needs ZrO (NO
3) 2H
2The amount of O is Y;
ZrOCl
28H
2The molecular weight of O=321, ZrO (NO
3) 2H
2The molecular weight of O=267, ZrO
2Molecular weight=123;
The volume of the maceration extract that adsorbs in the maceration extract that carrier adsorbs in excessive dipping and the incipient impregnation is identical, therefore has
X＝n×m×321/123 Y＝n×m×267/123
Claims (6)
1. the preparation method of load-type zirconium oxide is characterized in that selecting for use arbitrarily one of following two kinds of methods:
(1) equi-volume impregnating
I. the weight percent content of zirconia in catalyst integral body that selected zirconates resolves into is 0.1～50%;
II. take by weighing carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or the imvite of required weight, measure the volume of the required maceration extract of incipient impregnation with deionized water;
III. according to the weight of selecting the carrier that is taken by weighing with II of I, calculate the weight that takes by weighing requisite oxygen zirconium chloride or zirconyl nitrate, be dissolved in the volumetric deionized water of II step institute, be mixed with maceration extract;
IV. the maceration extract that III step is made dropwise is added drop-wise on the carrier of the II step weight that takes by weighing, incipient impregnation 24 hours, with soaked carrier in 40～70 ℃ of vacuum drying 1～10 hour;
V. again IV is gone on foot the dry carrier in prepared dipping back in air atmosphere in 200～700 ℃ of roastings 1～7 hour, make load-type zirconium oxide;
(2) excessive infusion process
I. the weight percent content of zirconia in catalyst integral body that selected zirconates resolves into is 0.1～50%;
II. take by weighing carrier silica, aluminium oxide, titanium oxide, magnesia, molecular sieve, active carbon or the imvite of required weight, measure the volume of the required maceration extract of incipient impregnation with deionized water;
III. take by weighing the requisite oxygen zirconium chloride that 4～6 times the weight according to the selected and carrier that II takes by weighing of I calculates or the weight of zirconyl nitrate, be dissolved in 4～6 times to the II step in the volumetric deionized water, be mixed with maceration extract;
IV. II being gone on foot alleged carrier and place the maceration extract that III step makes, is 30～100 ℃ of excessive dippings 10～48 hours down in temperature, can obtain soaked carrier through vacuum filtration, with soaked carrier in 40～70 ℃ of vacuum drying 1～10 hour;
V. again IV is gone on foot the dry carrier in prepared dipping back in air atmosphere in 200～700 ℃ of roastings 1～7 hour, make load-type zirconium oxide.
2. according to the preparation method of the described load-type zirconium oxide of claim 1, it is characterized in that: in above-mentioned two kinds of methods, the sintering temperature in V step is 300～500 ℃, and roasting time is 2～5 hours.
3. according to the preparation method of the described load-type zirconium oxide of claim 1, it is characterized in that: in above-mentioned two kinds of methods, the weight percent content of zirconia in catalyst integral body that the selected zirconates in I step resolves into is 5～20%.
4. the application process of load-type zirconium oxide, it is characterized in that: load-type zirconium oxide, aniline and dimethyl carbonate are joined in the autoclave, the mol ratio of aniline and dimethyl carbonate is 1: 1～30, the mass ratio of aniline and catalyst is 1: 0.01～0.5, temperature rises to 90～200 ℃, reacted 1～20 hour, load-type zirconium oxide and reactant liquor are separated the reactant liquor filtration under diminished pressure, with the reactant liquor decompression distillation, remove unreacted dimethyl carbonate and can make the products benzene methyl carbamate again.
5. according to the application process of the described load-type zirconium oxide of claim 4, it is characterized in that: the mol ratio of aniline and dimethyl carbonate is 1: 5～20, the mass ratio of aniline and catalyst is 1: 0.05～0.3, and temperature rises to 120～180 ℃, reacts 5～10 hours.
6. according to the application process of the described load-type zirconium oxide of claim 4, it is characterized in that: utilize the isolated load-type zirconium oxide of filtration under diminished pressure to clean with absolute ethyl alcohol, 60 ℃ of following vacuum drying 5 hours,, reuse again 500 ℃ of following roastings 5 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100137584A CN100393413C (en) | 2006-05-19 | 2006-05-19 | Method for preparing load-type zirconium oxide and its using method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105189407B (en) * | 2013-01-30 | 2017-04-19 | 杰特科夫·彼德 | Method for doping an aluminium oxide ceramic |
| CN111377443A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1065026A (en) * | 1990-06-02 | 1992-10-07 | 中国科学院兰州化学物理研究所 | Preparation of ethylene by use of synthetic gas |
| CN1101271C (en) * | 2000-12-15 | 2003-02-12 | 南开大学 | Loading nanometer zirconia composite carrier and its preparation |
| CN1137082C (en) * | 2002-09-03 | 2004-02-04 | 南开大学 | Catalyst for synthesizing N,N-dimethylphenylamine |
| CN1214861C (en) * | 2003-08-26 | 2005-08-17 | 河北工业大学 | Zirconium oxide catalyst for synthesizing cyclohexyl menthyl formate, and preparing method and use thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101829554B (en) * | 2010-03-26 | 2012-12-05 | 中国科学院化学研究所 | Repeatedly used catalyst for synthesizing dimethyl carbonate |
| CN105189407B (en) * | 2013-01-30 | 2017-04-19 | 杰特科夫·彼德 | Method for doping an aluminium oxide ceramic |
| CN111377443A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
| CN111377443B (en) * | 2018-12-29 | 2022-06-07 | 中国石油化工股份有限公司 | Copper-doped activated carbon composite material and preparation method thereof |
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