CN1535941A - Selective hydrogenation catalyst carrier, its preparation method and catalyst containing said carrier - Google Patents
Selective hydrogenation catalyst carrier, its preparation method and catalyst containing said carrier Download PDFInfo
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- CN1535941A CN1535941A CNA031095275A CN03109527A CN1535941A CN 1535941 A CN1535941 A CN 1535941A CN A031095275 A CNA031095275 A CN A031095275A CN 03109527 A CN03109527 A CN 03109527A CN 1535941 A CN1535941 A CN 1535941A
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Abstract
The present invention relates to a carrier of ruthenium base ctalyst for preparing cycloolefine by aromatic selective hydrogenation, its preparation method and catalyst containing said carrier. The hydrogenation catalyst is formed from ruthenium and oxide carrier, and the carrier is composed of transition metal oxide and oxide of other main group and is prepared by using coprecipitation process. The adoption of said invented catalyst carrier can save dose of ruthenium, can reduce cost, can raise efficiency and life of catalyst, and said catalyst has high conversion rate and high selectivity for preparing cycloolefine by aromatic selective hydrogenation.
Description
Technical field
The present invention relates to the carrier and preparation method thereof that aromatic selective hydrogenation prepares the ruthenium-based catalyst of cycloolefin, described carrier is made up of the oxide compound of transition metal oxide and other main group element, is prepared by coprecipitation method.The invention still further relates to the hydrogenation catalyst that comprises described carrier and ruthenium.
Background technology
Cycloolefin such as tetrahydrobenzene are the important intermediates of petrochemical complex.Tetrahydrobenzene has highly active pair of key, can be used as the intermediate of fine chemicals such as medicine, food, chemistry of pesticide product, feed, polyester, nylon 6, nylon 66, and purposes is very extensive, particularly is applied in the nylon 66 polymeric amide industrial production.
Tetrahydrobenzene can pass through method preparations such as dehydration of cyclohexanol, cyclohexane halide dehydrohalogenation, cyclohexane dehydrogenation, but technical process complexity because of these methods, yield is low, cost is high, only be used for several preparations for many years with fine chemicals of high added value, as prepare Methionin (fodder additives) and cyclohexene oxide (perfume base), can not satisfy the demand that large-scale industrialization is produced tetrahydrobenzene and related products thereof.The benzene source is abundant, with low cost, by benzene selective hydrogenation one step preparation tetrahydrobenzene technical process shortening, efficient raising, facility investment is reduced, and for environmental protection positive effect is arranged also.So benzene selective hydrogenation prepares the development and application of tetrahydrobenzene technology, have great importance and wide application prospect.
The patent for preparing tetrahydrobenzene about benzene selective hydrogenation is existing a lot, and how hydrogenation catalyst prepares with methods such as the precipitator method, chemical reduction method, pickling processes.
Hertog makees catalyzer 1963 (J.Catal, 1963,2,79) with ruthenium black and prepares tetrahydrobenzene by benzene selective hydrogenation, and the yield of tetrahydrobenzene is reached about 2.2%.This method has been used ruthenium-based catalyst first.1972 (DE 2221139), RuCl such as the Drinkard of E.I.Du Pont Company
3For catalyzer carries out the reaction of benzene selective hydrogenation in autoclave, in reaction system, add entry simultaneously, the yield of tetrahydrobenzene is 32%.This method has improved the yield of tetrahydrobenzene in the presence of water.
Authorize the Ru-Zn bimetallic catalyst that discloses among the US 4665274 of industrial of Japanese Asahi Chemical Industry with precipitator method preparation, adopt this catalyzer to prepare tetrahydrobenzene by making benzene selective hydrogenation, the yield of tetrahydrobenzene can reach 50%.This catalyzer has the characteristics of high reactivity, highly selective, but insufficient is because Preparation of Catalyst efficient is low, the ruthenium utilization ratio that is unit mass is low, cause the catalyzer price very expensive, and this catalyzer is very responsive to elements such as S, Cl, Fe, As, Pb, these elements of denier just can cause catalyst deactivation, particularly sulfide, have a strong impact on the selectivity of reaction.
Loaded catalyst becomes new research focus because of its unique character enjoys favor in benzene selective hydrogenation prepares the Catalytic processes of tetrahydrobenzene in recent years.Loaded catalyst is modified by surface-area, aperture and the pore volume of change carrier and to carrier, can control the activity and the selectivity of active ingredient effectively, and the efficient of catalyzer and life-span are improved.Especially infusive is that perhaps loaded catalyst will make benzene selective hydrogenation technology replace traditional batch reactor with fixed-bed reactor, thereby simplifies technical process greatly.
Most of oxide compound all has very high hardness and stable structure, does carrier with them and can avoid washing away broken because of gas and liquid-flow.They are again good stablizers simultaneously, can stop the clinkering than low melting material.Therefore people select various oxide compounds to do carrier in the benzene selective hydrogenation catalyst system.Single component oxide compound such as silica gel, aluminum oxide, rare earth element and various transition metal oxide are carrier commonly used.In US4503249, disclose and a kind ofly be carried on the method that there is lower section hydrogenation mononuclear aromatics in crystallite metal Ru on the alumina supporter, the yield of tetrahydrobenzene is only about 5%.This method prepares working load type catalyzer in the technology of tetrahydrobenzene at benzene selective hydrogenation first.In US4665274, disclose and a kind ofly be carried on the method that there is lower section hydrogenation mononuclear aromatics in crystallite metal Ru on the insoluble vitriol, the yield of tetrahydrobenzene is about 30%.Aforesaid method has used support of the catalyst, though improved activity, the yield of tetrahydrobenzene is not high.
Two component oxide compounds or more multi-component oxide because modulation surface-area and duct size more neatly, thereby be beneficial to the catalytic performance that improves loaded catalyst.The catalyzer that bi component oxide is done carrier is higher than the single component oxide compound to the selectivity of tetrahydrobenzene.In US6060243, disclose and a kind ofly be carried on the method that there is lower section hydrogenation mononuclear aromatics in crystallite metal Ru on the bimetallic oxide carrier of gallium oxide and zinc oxide, the yield of tetrahydrobenzene is about 40%.This method utilizes bimetallic oxide to do carrier first, has improved the yield of tetrahydrobenzene greatly, but the source of gallium is extensive inadequately, and cost is higher.
The present invention adopts the bi component oxide carrier of the oxide compound of wide material sources as the ruthenium base supported catalyst first, can high reactivity, highly selective prepares tetrahydrobenzene with the benzene shortening.
Summary of the invention
An object of the present invention is to provide the bi component oxide carrier that a kind of aromatic selective hydrogenation prepares the ruthenium-based catalyst of cycloolefin.
Another object of the present invention provides the preparation method of bi component oxide carrier that a kind of aromatic selective hydrogenation prepares the ruthenium-based catalyst of cycloolefin.
Another object of the present invention provides the ruthenium-based catalyst that a kind of aromatic selective hydrogenation that comprises carrier of the present invention prepares cycloolefin.
Another purpose of the present invention provides the application of ruthenium-based catalyst of the present invention.
One aspect of the present invention relates to the bi component oxide carrier that aromatic selective hydrogenation prepares the ruthenium-based catalyst of cycloolefin, wherein comprises ZnO and at least a transition metal oxide or main group metal or half-metal oxide except that ZnO.
ZnO is one of component of bi component oxide carrier of the present invention.Though do not wish to be subjected to the restriction of particular theory,, it is believed that because the ZnO possess hydrophilic property can be adsorbed on more water catalyst surface and form moisture film when the catalyzer aromatic selective hydrogenation is reacted.Water can promote the tetrahydrobenzene desorption, the tetrahydrobenzene deep hydrogenation that slows down, thus improve selectivity of catalyst.
Other oxide compound example in the bi component oxide carrier of the present invention includes but not limited to Al
2O
3, ZrO
2, La
2O
3, Fe
2O
3, Cr
2O
3, SiO
2, MgO, TiO
2Deng.Bi component oxide carrier of the present invention can comprise at least a in these oxide compounds, preferably comprises ZrO
2
Here the term of Shi Yonging " bi component oxide carrier " is meant the carrier that comprises ZnO and one or more other oxide compounds.So term " bi component oxide carrier " intention contains bi component oxide carrier and multi-component oxide carrier.
The mol ratio of ZnO and other one or more oxide compounds is 10 in bi component oxide carrier of the present invention: 1-1: 10, preferred 5: 1-1: 5.
Another aspect of the present invention relates to the method by the above-mentioned bi component oxide carrier of prepared by co-precipitation, and this method comprises:
(1) prepares a kind of aqueous mixture, wherein comprise zinc salt and at least a transition metal or main group metal or semimetallic salt or ester;
(2) add the precursor of precipitation agent with preparation bi component oxide carrier of the present invention; With
(3) precursor of the bi component oxide carrier that obtains of calcination steps (2) is to prepare bi component oxide carrier of the present invention.
Perhaps, the invention provides a kind of preparation method of bi component oxide carrier, comprising:
(1) prepare a kind of aqueous mixture, wherein comprise zinc salt and at least a transition metal or main group metal or semimetallic salt or ester, and precipitation agent;
(2) make the precursor of above-mentioned aqueous mixture generation precipitin reaction with preparation bi component oxide carrier of the present invention; With
(3) precursor of the bi component oxide carrier that obtains of calcination steps (2) is to prepare bi component oxide carrier of the present invention.
The zinc salt that can be used for the inventive method can be various water miscible zinc salts, includes but not limited to zinc nitrate, zinc sulfate, zinc chloride, zinc bromide, zinc acetate, zinc oxalate and hydrate thereof.
Precursor as another component of bi component oxide carrier of the present invention except that zinc oxide, the transition metal or main group metal or semimetallic salt or the ester that can be used for the inventive method are any transition metal or main group metal or the semimetallic salt or esters that can be dissolved or dispersed in Aquo System.The example includes but not limited to: as zirconium oxychloride, the zirconium tetrachloride of zirconium oxide precursor; As Al
2O
3The aluminum nitrate of precursor, sodium aluminate, potassium aluminate, aluminum chloride; As La
2O
3The lanthanum nitrate of precursor, lanthanum acetate, Lanthanum trichloride; As Fe
2O
3The iron trichloride of precursor, iron protochloride, ironic citrate, iron nitrate, ironic oxalate, ferrous sulfate, ferric sulfate; As Cr
2O
3The chromium acetate of precursor, chromic bromide, chromium chloride, chromium nitrate, chromium sulphate; As SiO
2The methyl orthosilicate of precursor, ethyl orthosilicate, methyl silicate, tetraethoxy, water glass, Starso; Magnesium chloride, sal epsom, magnesium nitrate as the MgO precursor.
The reaction medium that uses in the inventive method comprises water.In order to make described transition metal or main group metal or semimetallic salt or ester be dissolved or dispersed in the reaction medium better, described reaction medium is also optional to comprise polar organic solvent, such as but not limited to methyl alcohol, ethanol, Virahol, and ethylene glycol, propylene glycol, glycerine, acetone etc.If use polar organic solvent, then the ratio of water and polar organic solvent can be decided according to selected reactant species and consumption, but generally can be 10: 1～1: 10.
The precipitation agent that can be used in the inventive method comprises mineral alkali or salt such as oxyhydroxide, carbonate, supercarbonate, preferred Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, NaOH, KOH, Mg (OH)
2, NH
3H
2O etc.
Precipitation agent in the inventive method also can adopt organic bases, for example urea etc.
In the methods of the invention, the consumption of precipitation agent generally is that to make the pH value of reaction system be 7 or higher, is preferably 8 or higher, more preferably 9～13, most preferably be 10～11.
In the methods of the invention, the washing methods of carrier generally is to leave standstill an evening after precipitating fully, and behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, can obtain bi component oxide.
Behind the precursor that obtains the bi component oxide carrier, can adopt method well known in the art to carry out roasting.Roasting is for example carried out in air, oxygen-denuded air, oxygen-rich air or the oxygen generally at oxidizing atmosphere.The temperature of roasting can be 400～1000 ℃, is preferably 500 ℃-800 ℃.Roasting time can be 30 minutes～48 hours, is generally 1 hour～24 hours, is preferably 2h-10h.
After roasting obtains bi component oxide carrier of the present invention, generally can pulverize and sieve, to obtain the carrier of required granular size and distribution according to method well known in the art.The mean particle size of carrier of the present invention is generally 20～500 μ m, is preferably 30～300 μ m, more preferably 40～250 μ m, more more preferably 50-200 μ m.
Another aspect of the present invention relates to the ruthenium-based catalyst that a kind of aromatic selective hydrogenation that comprises bi component oxide carrier of the present invention prepares cycloolefin.According to an embodiment, can adopt pickling process that the ruthenium component is loaded on the described bi component oxide carrier.
Be carried on suitable ruthenium compound on the described bi component oxide carrier including, but not limited to ruthenium trichloride as the active ingredient source in the inventive method.
In the ruthenium-based catalyst of the present invention, in the quality percentage composition of ruthenium metal in catalyzer, the charge capacity of ruthenium is 0.1-50%, is preferably 2-10%.
Of the present inventionly relate in one aspect to the application of described ruthenium-based catalyst aspect the corresponding cycloolefin of selection hydrogenation preparing of the many rings of catalysis or mononuclear aromatics such as benzene, naphthalene, biphenyl and alkylbenzene again.
Technology by the corresponding cycloolefin of selection hydrogenation preparing of many rings and mononuclear aromatics such as benzene, naphthalene, biphenyl and alkylbenzene is well known in the art.The general batch reactor that adopts, temperature of reaction 100-200 ℃, hydrogen pressure is 3-7Mpa, rotating speed is greater than 1000rpm.
The raw material sources of bi component oxide carrier of the present invention are extensive, and are cheap, and can easily obtain.The active ingredient ruthenium is carried on the catalyzer that this preparing carriers obtains, many rings and mononuclear aromatics especially the selection hydrogenation of benzene are had high activity and selectivity.
Specific embodiments
Further describe the present invention below in conjunction with embodiment.Be noted that these embodiment only are in order to demonstrate the invention, in office where face does not constitute limitation of the scope of the invention.In the following example and comparing embodiment, transformation efficiency and selectivity are defined by following formula.
It is Agilent 4890D gas chromatograph that the analytical reaction product is formed employed analytical instrument.
Embodiment 1
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash into mass percentage concentration under the vigorous stirring and be 30% sodium hydroxide solution, pH is warming up to 70 ℃ behind the 10-11, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration with the distilled water wash throw out to there not being Cl
-After, throw out is put in the baking oven in 120 ℃ of dried overnight.This throw out is put into retort furnace be warming up to 700 ℃, roasting 5 hours.To obtain getting less than 200 orders after bi component oxide grinds stand-by.
Preparation of Catalyst
With conventional immersion process for preparing catalyzer 2%Ru/ZrO
2-ZnO.To contain 0.06gRuCl
3Solution splash in the 3g carrier, stir into a paste.Keep 10h under the room temperature, put it in the baking oven 100 ℃ then and spend the night.Reaction is preceding to place the following 300 ℃ of reduction 5h of nitrogen atmosphere with dried catalyzer.Evaluating catalyst
At volume is to add 60ml water, 11g Zinc vitriol, the catalyzer of the above-mentioned preparation of 3g and 40ml benzene in 500ml and the stainless steel autoclave crossed with hydrogen exchange in advance.160 ℃, 5MPa hydrogen reacts under the rotating speed 1000rpm condition.The results are shown in Table 1.
Embodiment 2
Preparing carriers
20.833g tetraethoxy is dissolved in the 40ml ethanol, the 29.75g zinc nitrate is added in the 20ml water, after under the room temperature two kinds of solution stirring being mixed, splashes into 30% sodium hydroxide solution under the vigorous stirring, and pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, throw out is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The throw out that drying is crossed is put into retort furnace, 700 ℃ of roastings 5 hours.Grind to form below 200 orders bi component oxide carrier that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The results are shown in Table 1.
Embodiment 3
Preparing carriers
37.51g ANN aluminium nitrate nonahydrate and 29.75g zinc nitrate are added in the 500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the sodium hydroxide solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, throw out is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The throw out that filtration cakes torrefaction is crossed is put into retort furnace, 700 ℃ of roastings 5 hours.Grind to form below 200 orders bi component oxide carrier that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 1.
Embodiment 4
Preparing carriers
43.302g lanthanum nitrate and 29.75g zinc nitrate are added in the 500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the sodium hydroxide solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, throw out is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant throw out is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Obtaining the bi component oxide carrier grinds to form below 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The results are shown in Table 1.
Embodiment 5
Preparing carriers
27.03g Iron(III) chloride hexahydrate and 29.75g zinc nitrate are added in the 500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the sodium hydroxide solution, pH is 10-11.Be warming up to 70 ℃, 1 hour postcooling of stirring reaction is to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, throw out is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.It is following stand-by that the bi component oxide carrier that obtains grinds to form 200 orders.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 1.
Comparing embodiment 1
Except without the zinc nitrate, other same procedure by embodiment 1 is carried out.The results are shown in Table 1.
Comparing embodiment 2
Except without the zinc nitrate, other same procedure by embodiment 2 is carried out.The results are shown in Table 1.
Comparing embodiment 3
Except without the zinc nitrate, other same procedure by embodiment 3 is carried out.The results are shown in Table 1.
Comparing embodiment 4
Except without the zinc nitrate, other same procedure by embodiment 4 is carried out.The results are shown in Table 1.
Comparing embodiment 5
Except without the zirconium oxychloride, other same procedure by embodiment 1 is carried out.The results are shown in Table 1.
The catalytic performance of the catalyzer of table 1 different components oxide compound and bi component oxide carrier
Carrier catalysis component reaction time transformation efficiency/% selectivity/%
/min
Embodiment 1 ZrO
2/ ZnO 2%Ru 10 25.30 60.14
Embodiment 2 SiO
2/ ZnO 2%Ru 60 12.47 47.68
Embodiment 3 Al
2O
3/ ZnO 2%Ru 62 16.16 74.12
Embodiment 4 La
2O
3/ ZnO 2%Ru 30 17.15 73.06
Embodiment 5 Fe
2O
3/ ZnO 2%Ru 24 18.66 67.62
Comparing embodiment 1 ZrO
22%Ru 100 19.69 39.04
Comparing embodiment 2 SiO
22%Ru 45 21.81 41.26
Comparing embodiment 3 Al
2O
32%Ru 4 23.46 32.20
Comparing embodiment 4 La
2O
32%Ru 30 39.11 3.85
Comparing embodiment 5 ZnO 2%Ru 15 12.10 15.23
Embodiment 6
Preparing carriers
Zirconium oxychloride and zinc nitrate that mol ratio was respectively 5: 1,1: 1,1: 5 are added in the 1500ml water, after mixing under the room temperature, under the vigorous stirring 30% NaOH are splashed in this solution, and the control rate of addition made pH reach 10-11 with 15 minutes.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, throw out is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 7 hours.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 2.
The catalytic performance of catalyzer under the different Zr/Zn mol ratio of table 2
| ????Zr/Zn | Catalyst component | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| ????5/1 | ????4％Ru | ????32 | ????21.58 | ????47.40 |
| ????1/1 | ????4％Ru | ????8 | ????23.01 | ????70.79 |
| ????1/5 | ????4％Ru | ????8 | ????20.72 | ????67.70 |
Embodiment 7
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the sodium hydroxide solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 3.
Embodiment 8
Preparing carriers
64.4g zirconium oxychloride, 59.5g zinc nitrate and 275.52g urea are added in the 1500ml water, after mixing under the room temperature, are warming up to 110 ℃ and maintain this temperature under the vigorous stirring, occur white gelatinous precipitate after 1 hour.Reduce to room temperature after continuing to stir 1h, leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 3.
Embodiment 9
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the KOH solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 3.
Embodiment 10
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash into 30% Na under the vigorous stirring
2CO
3In the solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 3.
Embodiment 11
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash into 30% NH under the vigorous stirring
3H
2In the O solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration filter cake with the distilled water wash throw out to there not being Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Obtaining bi component oxide grinds to form below 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 3.
The different precipitation agents of table 3 make the catalytic performance of the catalyzer of carrier
Precipitation agent carrier catalysis reaction times transformation efficiency/% selectivity/%
Component/min
Embodiment 7 NaOH ZrO
2/ ZnO 4%Ru 15 19.80 80.26
Embodiment 8 (NH
2)
2CO ZrO
2/ ZnO 4%Ru 12 17.14 57.99
Embodiment 9 KOH ZrO
2/ ZnO 4%Ru 9 24.77 48.63
Embodiment 10 Na
2CO
3ZrO
2/ ZnO 4%Ru 5 17.84 50.04
Embodiment 11 NH
3H
2O ZrO
2/ ZnO 4%Ru 5 18.56 53.12
Embodiment 12
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, splash under the vigorous stirring in 30% the NaOH solution, pH is 10-11.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace differing temps roasting 5-7 hour.Temperature is from 500 ℃-900 ℃.Grind to form below 200 orders bi component oxide that obtains stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 4.
The different maturing temperatures of table 4 make the catalytic performance of the catalyzer of carrier
Maturing temperature ℃ catalyst component reaction times/min transformation efficiency/% selectivity/%
500????????????4％Ru??????????3.5???????????24.71??????????47.28
600????????????4％Ru??????????5?????????????23.3???????????56.98
700????????????4％Ru??????????5?????????????20.34??????????58.48
800????????????4％Ru??????????8?????????????27.80??????????65.37
900????????????4％Ru??????????30????????????12.05??????????51.08
Embodiment 13
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, under the vigorous stirring 30% NaOH are splashed in this solution, the control rate of addition made pH reach 10-11 with 15 minutes.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Obtaining bi component oxide grinds to form below 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 5.
Embodiment 14
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, under the vigorous stirring 30% NaOH are splashed in this solution, the control rate of addition made pH reach 10-11 with 15 minutes.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration throw out put into 120 ℃ of dried overnight in the baking oven.The exsiccant filter cake is put into distilled water wash, to checking no Cl with Silver Nitrate
-After put into retort furnace and be warming up to 700 ℃, roasting 5 hours.Obtain bi component oxide, grind to form below 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 5.
Embodiment 15
Preparing carriers
64.4g zirconium oxychloride and 59.5g zinc nitrate are added in the 1500ml water, after mixing under the room temperature, under the vigorous stirring 30% NaOH are splashed in this solution, the control rate of addition made pH reach 10-11 with 15 minutes.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration throw out put into 120 ℃ of dried overnight in the baking oven.Put into retort furnace and be warming up to 700 ℃, roasting 5 hours.Then carrier is put into distilled water and wash, to checking no Cl with Silver Nitrate
-After, drying obtains bi component oxide, grinds to form below 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 5.
The catalytic performance of catalyzer under the different carrier washing methods of table 5
| The carrier washing methods | Reaction times/min | Transformation efficiency/% | Selectivity/% | |
| Embodiment 13 | Directly the filter wash cake is stand-by to there not being the roasting of ClU after drying | 12 | ?22.52 | ?74.44 |
| Embodiment 14 | Wash Cl behind the filtration cakes torrefaction -, roasting then | 13 | ?23.70 | ?69.33 |
| Embodiment 15 | Wash Cl after the carrier roasting -, dry then | 13 | ?21.92 | ?64.62 |
Embodiment 16
Preparing carriers
64.4g zirconium oxychloride and 59.5 zinc nitrates are added in the 1500ml water, after mixing under the room temperature, under the vigorous stirring 30% NaOH are splashed in this solution, the control rate of addition made pH reach 10-11 with 15 minutes.Be warming up to 70 ℃, continue 1 hour postcooling of stirring reaction to room temperature.Leave standstill an evening after stopping to stir, behind the suction filtration, filter cake is washed with distilled water to no Cl
-After put into dried overnight in the baking oven.The exsiccant filter cake is put into retort furnace be warming up to 700 ℃, roasting 5 hours.Obtain bi component oxide, grind to form below 80-100 order and 200 orders stand-by.
Preparation of Catalyst is identical with embodiment 1 with appreciation condition.The result is as shown in table 6.
The catalytic performance of catalyzer under the table 6 different carriers granularity
| The order number | Catalyst component | Reaction times/min | Transformation efficiency/% | Selectivity/% |
| The 80-100 order | ????6％Ru | ????11 | ????21.64 | ????53.44 |
| Below 200 orders | ????6％Ru | ????11 | ????24.79 | ????68.07 |
Claims (11)
1. an aromatic selective hydrogenation prepares the bi component oxide carrier of the ruthenium-based catalyst of cycloolefin, wherein comprises ZnO and at least a transition metal oxide or main group metal or half-metal oxide except that ZnO.
2. carrier according to claim 1, it is selected from Al
2O
3-ZnO, ZrO
2-ZnO, La
2O
3-ZnO, Fe
2O
3-ZnO, Cr
2O
3-ZnO, SiO
2-ZnO and MgO-ZnO.
3. carrier according to claim 1, the mol ratio of wherein said two kinds of component oxide are 10: 1-1: 10.
4. carrier according to claim 3, the mol ratio of wherein said two kinds of component oxide are 5: 1-1: 5.
5. carrier according to claim 1, wherein the mean particle size of carrier is 20～500 μ m.
6. the preparation method of carrier according to claim 1 comprises:
(1) prepares a kind of aqueous mixture, wherein comprise zinc salt and at least a transition metal or main group metal or semimetallic salt or ester;
(2) add the precursor of precipitation agent with preparation bi component oxide carrier of the present invention; With
(3) precursor of the bi component oxide carrier that obtains of calcination steps (2) is to prepare bi component oxide carrier of the present invention.
7. the preparation method of carrier according to claim 1 comprises:
(1) prepare a kind of aqueous mixture, wherein comprise zinc salt and at least a transition metal or main group metal or semimetallic salt or ester, and precipitation agent;
(2) make the precursor of above-mentioned aqueous mixture generation precipitin reaction with preparation bi component oxide carrier of the present invention; With
(3) precursor of the bi component oxide carrier that obtains of calcination steps (2) is to prepare bi component oxide carrier of the present invention.
8. according to claim 6 or 7 described methods, wherein precipitation agent is selected from Na
2CO
3, NaHCO
3, K
2CO
3, KHCO
3, NaOH, KOH, NH
3H
2O and urea.
9. according to claim 6 or 7 described methods, wherein the maturing temperature of carrier is 400 ℃-1000 ℃, and roasting time is 3h-10h.
10. the described method of claim 9, wherein the maturing temperature of carrier is 500 ℃-800 ℃, roasting time is 4h-8h.
11. an aromatic selective hydrogenation prepares the catalyzer of cycloolefin, comprises among the claim 1-5 carrier and the load ruthenium compound active ingredient thereon of any one, in the quality percentage composition of ruthenium metal in catalyzer, the charge capacity of ruthenium is 0.1-50%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744085A (en) * | 2012-07-23 | 2012-10-24 | 郑州大学 | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation |
| CN102921415A (en) * | 2012-10-31 | 2013-02-13 | 江苏清泉化学有限公司 | Hydrogenation catalyst, preparation method of hydrogenation catalyst and application of hydrogenation catalyst to 2-methyltetrahydrofuran synthesis |
| CN104391010A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cr2O3-ZnO composite nano material as well as preparation method and application thereof |
| CN110961100A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
| CN115888707A (en) * | 2022-11-25 | 2023-04-04 | 南京工业大学 | Transition metal loaded monatomic catalyst and preparation method and application thereof |
-
2003
- 2003-04-09 CN CN 03109527 patent/CN1234665C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744085A (en) * | 2012-07-23 | 2012-10-24 | 郑州大学 | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation |
| CN102744085B (en) * | 2012-07-23 | 2013-10-09 | 郑州大学 | Catalytic system containing nanometer Ru catalyst and alkali zinc sulfate salt and method for preparing cyclohexene through catalytic benzene selective hydrogenation |
| CN102921415A (en) * | 2012-10-31 | 2013-02-13 | 江苏清泉化学有限公司 | Hydrogenation catalyst, preparation method of hydrogenation catalyst and application of hydrogenation catalyst to 2-methyltetrahydrofuran synthesis |
| CN104391010A (en) * | 2014-11-19 | 2015-03-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Cr2O3-ZnO composite nano material as well as preparation method and application thereof |
| CN110961100A (en) * | 2018-09-30 | 2020-04-07 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
| CN110961100B (en) * | 2018-09-30 | 2022-12-20 | 中国石油化工股份有限公司 | Catalyst for preparing cyclohexene by cyclohexane dehydrogenation and preparation method thereof |
| CN115888707A (en) * | 2022-11-25 | 2023-04-04 | 南京工业大学 | Transition metal loaded monatomic catalyst and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1234665C (en) | 2006-01-04 |
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