CN102476052A - Supported ruthenium catalyst and preparation method thereof - Google Patents
Supported ruthenium catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a supported ruthenium catalyst and a preparation method thereof. The preparation method is characterized in that the preparation method comprises the following steps: 1, preprocessing a carrier with a soluble alkaline earth metal salt, wherein the mass of the soluble alkaline earth metal salt accounts for 0.1-20% of the mass of the carrier; and 2, dipping the alkaline earth metal salt processed carrier with a material which comprises a primary active component metallic ruthenium and an assisted catalytic component comprising one or several of Ni, Co, Pd and Pt, wherein the mass of the primary component metallic ruthenium accounts for 0.1-5% of the carrier, and the mass of the secondary component comprising one or several of Ni, Co, Pd and Pt accounts for 0.01-5% of the mass of the carrier. The catalyst of the invention is mainly applied to the selective hydrogenation process of an aromatic ring of an aromatic compound, wherein the aromatic ring of the aromatic compound has at least one alkyl group, one ester group, one hydroxyl group or an amino group and also has at least one C1-8 alkyl group. Compared with catalysts prepared with the prior art, the catalyst of the invention has the advantages of low cost, simple preparation method, high activity, good selectivity, high safety in the operation of the aromatic ring hydrogenation, realization of the operation of the aromatic ring hydrogenation under a low pressure, and good economy.
Description
Technical field
The present invention relates to metallic catalyst of support type and preparation method thereof; In particular to a kind of be first component with metal Ru; With any of metallic nickel, cobalt, palladium, platinum is second component, is load ruthenium catalyst of auxiliary agent and preparation method thereof with the alkaline earth oxide.
Background technology
Aromatic compound has become the important method of preparation compounds through phenyl ring being carried out selective hydrogenation.As of many uses by the alkyl cyclohexanol of the substituted phenol catalytic hydrogenation preparation of different alkyl; Cyclohexanol is a primary raw material of making nylon; Patchone is the important intermediate of spices, medicine and agricultural chemicals, and positive alkyl cyclohexanol, alkyl-cyclohexyl cyclohexanol are the important intermediate of preparation liquid crystal.Make 1 by dimethyl terephthalate (DMT) through benzene ring hydrogenation; The 4-dimethyl hexahydrophthalate; The latter is the important Organic Chemicals of producing mylar; The mylar that is substituted ethylene glycol or other polyalcohol production by it has good heat endurance and thermoplasticity, can under higher temperature, keep stable physical property and electrical property.
In the prior art, the active component that the phenyl ring selective hydrogenation of induced by alkyl hydroxybenzene prepares the alkyl cyclohexanol employing is Metal Palladium, rhodium, Pt Rh alloy, rhodium-ruthenium alloy or nickel.PL137526 has described the use Raney nickel, p-tert-butylphenol hydrogenation is obtained the method for right-tert-butyl group cyclohexanol.DE-A-3401343 and EP0141054 have described 2,4-tert-butyl phenol catalytic hydrogenation preparation 2, the method for 4-tert-butyl group cyclohexanol.Hydrogenation process divides two stages to carry out, and in first stage, uses with Al
2O
3Be the palladium catalyst of carrier, in second stage, use with Al
2O
3Be the ruthenium catalyst of carrier, tenor is 0.1～5% of a carrier, under the pressure of 300bar, reacts, and preferentially obtains forming 0.1～0.5% accessory substance simultaneously along tert-butyl group cyclohexanol kind.US2927127 discloses the method that is prepared right-tert-butyl group cyclohexanol by the p-tert-butylphenol catalytic hydrogenation, and catalyst system therefor is the ruthenium catalyst that loads on 5% on ruthenium catalyst and the active carbon of 5% on 5% rhodium catalyst on the active carbon, the brium carbonate.When the ruthenium catalyst of working load on active carbon, under 74～93 ℃ of reaction temperatures and pressure 70～120bar, react, can obtain 66% cis-isomer hydrogenated products.
There is comparatively significant disadvantages in the method for the described catalytic hydrogenation aromatic ring of above patent, and promptly pressure the bullion content very high or load of catalyst institute is too high, obviously is uneconomic for commercial Application.
Described among the US3334149 with dimethyl terephthalate (DMT) and made feedstock production 1, the method for 4-dimethyl hexahydrophthalate.This method generates 1 with the dimethyl terephthalate (DMT) hydrogenation; Need to use high pressure in the process of 4-dimethyl hexahydrophthalate; For example greater than the absolute pressure (34600KPa) of 346bar; And used palladium/aluminium oxide catalyst, this specific palladium/aluminium oxide catalyst contains the palladium that is deposited on 0.5% on the aluminium oxide, and the crystalline phase of aluminium oxide is the mixture of bayerite and boehmite.
Chinese patent CN1099382 discloses improving one's methods by dimethyl terephthalate (DMT) hydrogenation preparing cyclohexane dimethyl ester equally.Similar palladium/the aluminium oxide catalyst that used of this method and US3334149 patent; Use this palladium/aluminium oxide catalyst to contain the palladium that is deposited on 0.5～1% on the aluminium oxide; The crystalline phase of aluminium oxide is the mixing phase of θ, α, the palladium that is deposited on alumina surface apart from the degree of depth of alumina surface less than 100 μ m.This method is generating 1 with the dimethyl terephthalate (DMT) hydrogenation, also needs higher pressure in the process of 4-dimethyl hexahydrophthalate, for example uses the absolute pressure greater than 60bar (6000KPa).Using higher hydroprocessing pressure obviously, is uneconomic on producing, because increased the expense of operating cost and required high pressure reaction assembly, its shortcoming and US3334149 are similar.
Summary of the invention
Phenyl ring selective hydrogenation to aromatic compound of the prior art prepares reaction pressure height in the compounds process; The shortcomings such as bullion content height of catalyst institute load; The preparation method who the purpose of this invention is to provide a kind of highly active load ruthenium catalyst of the aromatic ring hydrogenation that is used for aromatic compound; Except that having an alkyl or ester group or hydroxyl or amino at least, also can have at least one C on the aromatic ring of described aromatic compound
1～C
8Alkyl.
One of the object of the invention provides a kind of load ruthenium catalyst:
A kind of load ruthenium catalyst is characterized in that: load first component is a ruthenium on carrier, and second component is any in nickel, cobalt, palladium, the platinum; In the carrier quality; First constituent content is that 0.1～5%, second constituent content is 0.01～5%, and surplus is a carrier.
Described carrier is any in aluminium oxide, silica, diatomite, silica gel, alum clay, zeolite or the zirconia, is preferably aluminium oxide;
Two of the object of the invention provides a kind of preparation method of load ruthenium catalyst, may further comprise the steps:
(1) uses the alkali salt impregnated carrier, and 200～900 ℃ alkali salt is converted into alkaline earth oxide in temperature;
(2) with infusion process or spraying process, the soluble compounds of any metal of the first component ruthenium and the second component nickel, cobalt, palladium, platinum is carried on the carrier that step (1) handled gets catalyst precarsor, the specific area of described carrier is 5～500m
2/ g;
(3) dried catalyst precursor;
(4) with catalyst precarsor with reducing agent reduce load ruthenium catalyst.
Above-mentioned Preparation of catalysts method, described carrier is any in aluminium oxide, silica, diatomite, silica gel, alum clay, zeolite or the zirconia, is preferably aluminium oxide.
The scope of the BET surface area of described alumina support is at 5～300m
2/ g.
Above-mentioned Preparation of catalysts method, the alkali salt of described solubility are the nitrate or the chloride of magnesium, calcium, barium.
Above-mentioned Preparation of catalysts method, the quality of described alkali salt are 0.1～20% of carrier quality.
Above-mentioned Preparation of catalysts method, described alkali salt adopt the method for spraying, equivalent or excessive dipping to impregnated in carrier, and described carrier through the alkaline-earth metal dipping is dry under 50～200 ℃, 200～900 ℃ of following roastings.
Above-mentioned Preparation of catalysts method, the soluble compounds of described ruthenium and nickel, cobalt, palladium, platinum are chloride, nitrate, acetate or the amine complex of metal, preferably nitrate or chloride.
Above-mentioned Preparation of catalysts method, described amine complex are to contain the amino compound of coordination, such as dichloro four ammonia palladiums, dichloro diamino palladium, dichloro four ammino platinum.
Above-mentioned Preparation of catalysts method, the quality of the described first component metals ruthenium are that 0.1～5%, the second component metals nickel, cobalt, the palladium of carrier, the quality of platinum are 0.01～5% of carrier.
Above-mentioned Preparation of catalysts method, the shape of described carrier is multiple, such as being shapes such as powder, spherical, sheet, cylindric, clover, bunge bedstraw herb, honeycomb.
Above-mentioned Preparation of catalysts method, in described ruthenium and nickel, cobalt, palladium, the platinum soluble compounds of any metal can be synchronously or substep adopt the method for spraying, equivalent or excessive dipping to be carried on through the pretreated carrier of alkaline-earth metal.
Above-mentioned Preparation of catalysts method, described reducing agent are any or its combination in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate, the sodium borohydride.
Above-mentioned Preparation of catalysts method, described catalyst are used for the aromatic ring hydrogenation process of aromatic compound.Except that having an alkyl or ester group or hydroxyl or amino at least, also can have at least one C on the aromatic ring of described aromatic compound
1～C
8Alkyl.
The particle of catalyst of the present invention is as the criterion can not cause reaction mass in reactor, to form channel, and preferred granular size is in 0.5～5mm scope.
The method of the benzene ring hydrogenation with aromatic compound of the present invention; Preferred mode of operation is to carry out continuously; Wherein with aromatic compound material or aromatic compound material and solvent thereof with the drip mode through a fixed beds; Can the unreacted aromatic compound material of part be recycled to the charging aperture of reactor, and can be used as the partial solvent of reaction mass.In the trickle bed operating process, the liquid hourly space velocity (LHSV) of reaction mass (LHSV) is about 0.05～5.0h
-1, be preferably 0.1～2h
-1, will feed reactor and from this reaction system, flow out routinely above stoichiometric hydrogen, the mol ratio of hydrogen and reaction mass is about 1～500 scope, preferred 3～50 scope.
Activity of such catalysts evaluation of the present invention is carried out in the trickle bed reaction system.The air path part of this system comprises the high pressure hydrogen source of the gas; Be adjusted to required reaction pressure through pressure-regulating valve; Get into reactor assembly and contact with reaction mass, get into high die pressing product knockout drum through tail gas and hydrogenation material after the hydrogenation reaction, the hydrogen after the separation is through metering emptying.The reaction tube of this system is 316 stainless steel tubes that one section 1.3m is long, internal diameter is about 14mm, and hypomere is filled with the inert filler of φ 1～2 on reaction tube, and catalyst is seated in the middle part of reaction tube, through the temperature of the thermocouple measurement bed in the reaction tube.
With respect to prior art, advantage of the present invention is: load ruthenium catalyst with low cost, and the preparation method is simple, and prepared catalyst activity is high, and selectivity is good, and stable chemical performance has the industrialization practical value.Safe during the operation of aromatic ring hydrogenation, can under lower pressure, move good economy performance.
The technical characterictic that the invention is further illustrated by the following examples, but be not limited to embodiment.
The specific embodiment
Embodiment 1
Take by weighing spherical alumina (the surface area 260m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in alumina support behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 3.0%, nickel content is 0.4% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the alumina support through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% formalin reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst A.
Embodiment 2
Take by weighing spherical alumina (the surface area 5m of 20g diameter 1.5～2.5mm
2/ g), take by weighing 0.020g calcium nitrate and be dissolved in the 20g deionized water, be sprayed on the alumina support, behind 50 ℃ of dry 6h,, naturally cool to room temperature again in 200 ℃ of roasting 5h.Get the 20g ruthenium content and be 0.1%, nickel content is 0.01% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the alumina support through the alkaline earth modification; Through 100 ℃ of dry 10h, again under room temperature with 15% formalin reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst B.
Embodiment 3
Take by weighing spherical alumina (the surface area 300m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 4.0g calcium nitrate and be dissolved in the 20g deionized water, the excessive alumina support that impregnated in again in 900 ℃ of roasting 5h, naturally cools to room temperature behind 200 ℃ of dry 6h.Get the 20g ruthenium content and be 5.0%, nickel content is 5.0% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the alumina support through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 80 ℃ temperature with 15% formalin reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst C.
Embodiment 4
Take by weighing spherical silicon dioxide (the surface area 150m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing the 1.00g magnesium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in silica supports behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, cobalt content is 0.4% hydrate ruthenium trichloride and the mixed solution of cabaltous nitrate hexahydrate; Be sprayed on the silica supports through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% formic acid solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst D.
Embodiment 5
Take by weighing spherical diatomite (the surface area 105m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in diatomite support behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, nickel content is 0.4% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the diatomite support through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% hydrazine hydrate solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst E.
Embodiment 6
Take by weighing spherical silica-gel (the surface area 370m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing the 1.00g barium chloride and be dissolved in the 20g deionized water, equivalent impregnation again in 500 ℃ of roasting 5h, naturally cools to room temperature in silica-gel carrier behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, palladium content is 0.5% hydrate ruthenium trichloride and the mixed solution of palladium bichloride; Equivalent impregnation is in the silica-gel carrier through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% paraformaldehyde solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst F.
Embodiment 7
Take by weighing spherical alum clay (the surface area 160m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in the alum clay carrier behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, platinum content is 0.2% hydrate ruthenium trichloride and the mixed solution of platinum chloride; Equivalent impregnation is in the alum clay carrier through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% glucose solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst G.
Embodiment 8
Take by weighing spherical zeolite (the surface area 500m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in Zeolite support behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, nickel content is 0.4% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the Zeolite support through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% sodium formate solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst H.
Embodiment 9
Take by weighing Zirconia ball (the surface area 110m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 550 ℃ of roasting 5h, naturally cools to room temperature in Zirconia carrier behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be 1.0%, nickel content is 0.4% hydrate ruthenium trichloride and the mixed solution of Nickelous nitrate hexahydrate; Equivalent impregnation is in the Zirconia carrier through the alkaline earth modification; Through 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% sodium borohydride solution reductase 12 h, after fully washing with deionized water; Dry 10h under 100 ℃ gets catalyst I.
Embodiment 10
Take by weighing spherical alumina (the surface area 260m of 20g diameter 1.5～2.5mm
2/ g), taking by weighing 1.00g calcium nitrate and be dissolved in the 20g deionized water, equivalent impregnation again in 650 ℃ of roasting 5h, naturally cools to room temperature in alumina support behind 100 ℃ of dry 6h.Get the 20g ruthenium content and be the solution of 1.0% hydrate ruthenium trichloride, be sprayed on the alumina support through the alkaline earth modification, after the drying again equivalent impregnation 20g nickel content be the solution of 0.4% Nickelous nitrate hexahydrate.Behind 100 ℃ of dry 10h, again under 50 ℃ temperature with 15% formalin reductase 12 h, after fully washing with deionized water, at 100 ℃ of dry 10h down, catalyst J.
Gained catalyst A～J is carried out activity rating on hydrogenation plant, used hydrogenating materials is the cyclohexane solution of 5% dimethyl terephthalate (DMT).The liquid hourly space velocity (LHSV) 0.25h of raw material
-1, the mol ratio of hydrogen and raw material is 5: 1, reaction pressure 4.0MPa, and 150 ℃ of reaction temperatures, the conversion ratio of dimethyl terephthalate (DMT) and 1, the yield of 4-dimethyl hexahydrophthalate is seen table 1.
Table 1
| Catalyst | Conversion ratio/% | Yield/% |
| A | 99.5 | 99.0 |
| B | 90.7 | 82.6 |
| C | 99.8 | 98.1 |
| D | 96.3 | 90.8 |
| E | 96.8 | 91.9 |
| F | 92.7 | 89.7 |
| G | 93.3 | 91.4 |
| H | 97.7 | 92.8 |
| I | 92.6 | 89.6 |
| J | 91.5 | 85.1 |
Embodiment 11
The benzene ring hydrogenation that instance 1 prepared catalyst A is used for xylenes, phenol, aniline, paracresol, p-t-butyl phenol, dibutyl phthalate, right-tert-octylphenol; Used hydrogenating materials is respectively the cyclohexane solution of 5% xylenes, phenol, aniline, paracresol, p-t-butyl phenol, dibutyl phthalate, right-tert-octylphenol, and the liquid hourly space velocity (LHSV) of raw material is 0.25h
-1, the mol ratio of hydrogen and raw material is 5: 1, the hydrogenation result sees table 2.
Table 2
| Raw material | Temperature/℃ | Pressure/MPa | Conversion ratio/% | Yield/% |
| Xylenes | 170 | 4.0 | 97.5 | 95.5 |
| Phenol | 150 | 4.0 | 94.8 | 88.6 |
| Aniline | 160 | 5.5 | 93.7 | 78.6 |
| Paracresol | 155 | 5.5 | 92.9 | 85.1 |
| P-t-butyl phenol | 160 | 6.0 | 94.2 | 86.7 |
| Dibutyl phthalate (DBP) | 155 | 5.0 | 98.4 | 95.5 |
| Right-tert-octylphenol | 165 | 5.5 | 95.3 | 91.7 |
Embodiment 12
Basic identical with embodiment 1, but following change is arranged:
Reducing agent is 15% the sodium formate and the mixed solution (mass ratio of sodium formate and sodium borohydride is 1/1) of sodium borohydride.
Embodiment 13
Basic identical with embodiment 1, but being shaped as of aluminium oxide is Powdered.
Embodiment 14
Basic identical with embodiment 1, but aluminium oxide be shaped as sheet.
Embodiment 15
Basic identical with embodiment 1, but being shaped as of aluminium oxide is cylindric.
Embodiment 16
Basic identical with embodiment 1, but aluminium oxide be shaped as clover.
Embodiment 17
Basic identical with embodiment 1, but aluminium oxide be shaped as bunge bedstraw herb.
Embodiment 18
Basic identical with embodiment 1, but being shaped as of aluminium oxide is cellular.
Embodiment 19
Basic identical with embodiment 4, but the soluble compounds of cobalt is a cobalt acetate.
Embodiment 20
Basic identical with embodiment 6, but the soluble compounds of palladium is dichloro four ammonia palladiums.
Embodiment 21
Basic identical with embodiment 6, but the soluble compounds of palladium is a dichloro diamino palladium.
Embodiment 22
Basic identical with embodiment 7, but the soluble compounds of platinum is dichloro four ammino platinum.
Comparative example 1
This comparison example is to prepare load ruthenium catalyst by the method that CN1915962 describes.
With 2g RuCl
3Be dissolved in the 325mL deionized water and be mixed with maceration extract, be heated with stirring to 60 ℃, add 20% sodium hydroxide solution maceration extract pH value is adjusted to 8.The spherical γ type aluminium oxide that adds 14.3g diameter 1.5～2.5mm continues to stir 10min.Be cooled to room temperature and leave standstill 0.5h, drip the formalin of 9.2g 36%, stirring reaction 1h leaves standstill 0.5h, filters, and spends deionised water 4 times, promptly gets the catalyst of this comparative example.
Activity of such catalysts appreciation condition and embodiment 1 are basic identical, and used hydrogenating materials is the cyclohexane solution of 5% dimethyl terephthalate (DMT).The liquid hourly space velocity (LHSV) of raw material is 0.25h
-1, the mol ratio of hydrogen and raw material is 5: 1, reaction pressure 4.0MPa, 150 ℃ of reaction temperatures.The conversion ratio of the dimethyl terephthalate (DMT) of this comparative example is 81.2%, 1, and the yield of 4-dimethyl hexahydrophthalate is 65.4%.
Claims (14)
1. load ruthenium catalyst; It is characterized in that: load first component is a ruthenium on carrier, and second component is any in nickel, cobalt, palladium, the platinum, and said carrier is any in aluminium oxide, silica, diatomite, silica gel, alum clay, zeolite or the zirconia; In the carrier quality; First constituent content is that 0.1～5%, second constituent content is 0.01～5%, and surplus is a carrier.
2. catalyst according to claim 1 is characterized in that: said carrier is an aluminium oxide.
3. the preparation method of a load ruthenium catalyst may further comprise the steps:
(1) use the alkali salt impregnated carrier, and 200～900 ℃ alkali salt is converted into alkaline earth oxide in temperature, described carrier is any in aluminium oxide, silica, diatomite, silica gel, alum clay, zeolite or the zirconia;
(2) with infusion process or spraying process, the soluble compounds of any metal in the first component ruthenium and the second component nickel, cobalt, palladium, the platinum is carried on the carrier that step (1) handled gets catalyst precarsor, the specific area of described carrier is 5～500m
2/ g;
(3) dried catalyst precursor;
(4) with catalyst precarsor with reducing agent reduce load ruthenium catalyst.
4. Preparation of catalysts method according to claim 3 is characterized in that: said carrier is an aluminium oxide.
5. Preparation of catalysts method according to claim 4 is characterized in that: the scope of the BET surface area of described alumina support is at 5～300m
2/ g.
6. Preparation of catalysts method according to claim 3 is characterized in that: described alkali salt is the nitrate or the chloride of magnesium, calcium, barium.
7. Preparation of catalysts method according to claim 3 is characterized in that: the quality of described alkali salt is 0.1～20% of a carrier quality.
8. Preparation of catalysts method according to claim 3; It is characterized in that: described alkali salt adopts the method for spraying, equivalent or excessive dipping to be carried on carrier; Described carrier through the alkaline-earth metal dipping is dry under 50～200 ℃, 200～900 ℃ of following roastings.
9. Preparation of catalysts method according to claim 3 is characterized in that: the compound of the described first component ruthenium and the second component nickel, cobalt, palladium, platinum is chloride, nitrate, acetate or the amine complex of metal.
10. Preparation of catalysts method according to claim 3 is characterized in that: the compound of the described first component ruthenium and the second component nickel, cobalt, palladium, platinum is corresponding nitrate or chloride.
11. Preparation of catalysts method according to claim 3 is characterized in that: the quality of described first component is that the quality of 0.1～5%, second component of carrier is 0.01～5% of a carrier.
12. Preparation of catalysts method according to claim 3 is characterized in that: in the described ruthenium and the second component nickel, cobalt, palladium, the platinum soluble compounds of any metal can be synchronously or substep adopt the method for spraying, equivalent or excessive dipping to be carried on through the pretreated carrier of alkaline-earth metal.
13. Preparation of catalysts method according to claim 3 is characterized in that: described reducing agent is any or its combination in formaldehyde, formic acid, hydrazine hydrate, paraformaldehyde, glucose, sodium formate, the sodium borohydride.
14. Preparation of catalysts method according to claim 3 is characterized in that: described catalyst is used for the aromatic ring hydrogenation process of aromatic compound.
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| CN110090647A (en) * | 2019-03-19 | 2019-08-06 | 凯凌化工(张家港)有限公司 | A kind of catalyst and preparation method preparing 1,4- cyclohexane dicarboxylic acid di-isooctyl |
| CN110433823A (en) * | 2019-07-30 | 2019-11-12 | 万华化学集团股份有限公司 | It is a kind of for synthesizing the catalyst and its preparation method and application of diaminomethyl hexamethylene |
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