CN1504259A - Regenerable hydrogenation catalyst and method for producing the same - Google Patents
Regenerable hydrogenation catalyst and method for producing the same Download PDFInfo
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Abstract
A regenerative hydrogenation catalyst and method for preparing the same, which comprises SiO2 carrier and one or more active component loads of Cu, Fe, Co, Ni, Cr, Mn, Mo, wherein the weight percentage of the active component is 10-40%, the rest are carrying agents, and the weight percentage of Cu in the catalyst is 10-26%, the catalyst is prepared by one of the methods of precipitation process, co-settling method and maceration.
Description
Technical field
The invention belongs to hydrogenation catalyst and preparation method thereof in the technical field of chemistry and chemical engineering, particularly be useful for the hydrogenation preparing arylamine of aromatic hydrocarbon nitro compound, the course of reaction of aldehyde hydrogenation system alcohol, specifically, be exactly that nitrobenzene and ortho-methylnitrobenzene and the aromatic hydrocarbon nitro compound that can adopt gas-solid phase reaction prepare arylamine and furfural hydrogenation prepares the required Preparation of catalysts method of furfuryl alcohol.
Technical background
In chemical industry, the hydrogenation reaction of nitro compound is very common reaction, adopts following method usually:
Earlier raw material is handled, remove dinitro thing and sulfur-containing compound in the nitro compound, to guarantee that impurities in raw materials is not to catalyst poisoning, raw material is carried out preheating, send into reactor, control hydrogen-oil ratio and temperature, prevent that catalyst from burning, if the content of nitro thing 〉=0.2% in the amine that hydrogenation obtains, catalyst just need regeneration, catalyst is absolutely necessary in this process.
The hydrogenation catalyst that present industrial nitro compound uses generally speaking has two types, and a kind of is noble metal such as ruthenium, rhodium, platinum, palladium catalyst, and this type of catalyst activity is higher, costs an arm and a leg, and need add catalyst recovery devices; Another kind of is loaded catalyst based on single copper, cheap, and sufficient raw is therefore domesticly furtherd investigate a kind of catalyst in back.
U.S. Pat 4265834 provides a kind of precious metal that uses to be active component, is prepared the catalyst of aniline by hydrogenation of chloronitrobenzene.Its active component is elements such as palladium and vanadium, niobium, tantalum, chromium, molybdenum, tungsten, titanium, and carrier is IIB, IVB, VB subgroup element and oxide, and catalyst can not be regenerated.
U.S. Pat 5304525 provides a kind of and has used palladium to load on graphite or petroleum coke is supported catalyst, wherein also contain account for palladium 0.001～0.5% iridium and (or) catalyst of 0.001～0.3% rhodium, the occupation mode of this catalyst is a gas phase hydrogenation, with graphite or petroleum coke as carrier, the intensity of itself is just not high, and easy to wear, heat conduction rate variance, the processing of can not regenerating.
Introduced a kind of catalyst of Ni on aluminium oxide in the U.S. Pat 4191664 with the coprecipitation preparation, adopt the technology of high-temperature roasting carrier, reduced the interaction of active component and aluminium oxide, increased the aperture of catalyst simultaneously, therefore activity of such catalysts increases, but catalyst adopts high-temperature roasting, high temperature reduction in preparation process, cause the nickel crystallite of catalyst surface to assemble easily, and make catalyst activity reduction; In addition if contain sulfate radical in the carrier (in the aluminium hydroxide product with aluminum sulfate-sodium metaaluminate method production, generally contain sulfate radical), reduction hydrogen is easy to the sulfate radical generation chemical reaction in the aluminium oxide during high temperature reduction, and the nickel generation sulfide in the catalyst is poisoned.
Introduced a kind of 5～30%Ni that contains among the Chinese patent CN95107484,1～10%Mo, 0～15%SiO
2Reaching surplus is Al
2O
3Hydrogenization catalyst preparation method, be earlier to make MoO with infusion process or kneading method
3Content be 6～13% contain the molybdenum carrier, then with the ammonia spirit dipping of Ni-Mo mixture, again through roasting, reduction.This catalyst is applicable to various distillates and edible oil and the hydrogenation aromatics-removing and the decolouring that contain the high viscosity white oil of heavy aromatics.
Introduced a kind of among the Chinese patent CN91108646 with γ-Al
2O
3Precursor elder generation's moulding roasting more then is the precursor of nickel and molybdenum and soaks molybdenum earlier and soak nickel and technology such as low-temperature bake, low-temperature reduction again after roasting with the ammonia spirit that contains molybdenum and nickel compound.This method also exists nickel poisons easily, and the shortcoming that nickel is not easy to be reduced during low-temperature reduction.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of more reproducible Catalysts and its preparation method of high catalytic activity and advantages of excellent stability that has is provided.
Technical scheme of the present invention is:
One or more metals on carrier among loaded Cu, Fe, Co, Ni, Cr, Mn, the Mo or its oxide, carrier shared percentage by weight in catalyst is 60～90%, all the other are active component, Cu is 10～26% at the percentage by weight of catalyst, the rest activity component is respectively the atomic ratio of Cu respectively: Cu: Fe=1: 0.01～0.2, Cu: Co=1: 0.02～0.2, Cu: Ni=1: 0.01～0.2, Cu: Cr=1: 0.01～0.5, Cu: Mn=1: 0.01～0.2, Cu: Mo=1: 0.01～0.2;
Used carrier is prepared by following method:
(1) with sodium silicate solution and the sulfuric acid solution reaction of 3～30wt%, reaction temperature is controlled at 5～80 ℃, and pH is controlled at 2.5～10;
(2) with the solution forming oil column of step (1) gained, aging 3～6 hours, the dilute sulfuric acid with 2～3% soaked 1～2 hour, with 40～50 ℃ water washing;
(3) solution of step (2) gained soaks through ammoniacal liquor again, dewaters in drier to water content≤80%, and drying places 500～550 ℃ of activation to moisture≤10%, obtains used carrier through screening.
The carrier of catalyst also can be selected commercially available gross porosity microsphere silica gel for use among the present invention.
The atomic ratio of above-mentioned activity of such catalysts component is preferably: Cu: Fe=1: 0.04～0.1, Cu: Co=1: 0.04～0.15, Cu: Ni=1: 0.01～0.2, Cu: Cr=1: 0.02～0.3, Cu: Mn=1: 0.02～0.1, Cu: Mo=1: 0.02～0.1.
Above-mentioned Preparation of catalysts method is: active component is any with the aqueous solution of its corresponding salt or ammonia solution, and any by the precipitation method or co-precipitation or infusion process loads on the above-mentioned described carrier, through washing, dry catalyst finished product.
Wherein the precipitation method or coprecipitation are to take by weighing salt such as a certain amount of copper, iron, cobalt, nickel, chromium, manganese, molybdenum, be preferably nitrate, be made into the solution of 2～60wt%, join in the above-mentioned carrier, the alkaline solution that drips concentration 0.5～10% when stirring is as precipitating reagent, and its alkaline solution can be Na
2CO
3, NH
3H
2O, NaOH, KOH a kind of or their mixture, precipitation fully after, static 8 hours, spend deionised water for several times, dry down at 105～280 ℃.
In addition, the load of active component also can adopt the mode of infusion process respectively or common infusion process to carry out, and dipping solution can be any of the aqueous solution of the corresponding salt of active component or ammonia solution.
During with the compound solution impregnated carrier of cupric, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=2～6: 1.
During with the compound solution impregnated carrier of iron content, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～2: 1.
When containing the compound solution impregnated carrier of cobalt, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～3: 1.
During with nickeliferous compound solution impregnated carrier, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～3: 1.
When containing the compound solution impregnated carrier of chromium, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～4: 1.
When containing the compound solution impregnated carrier of manganese, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～3: 1.
When containing the compound solution impregnated carrier of molybdenum, normally adopt the method (weight ratio) of excessive dipping, liquid: Gu=1.5～3: 1.
Zhi Bei catalyst content (is benchmark with the catalyst weight) is according to the method described above: copper 10～26%, iron 0.1～4.5%, cobalt 0.1～4.5%, nickel 0.1～4.5%, chromium 0.1～11%, manganese 0.1～4.5%, molybdenum 0.1～4.5%.
The specific surface area of catalyst of above-mentioned preparation is: 250～550m
2/ g, bulk density is: 0.48～0.70kg/L, pore volume is: 0.55～0.80ml/g.
Zhi Bei catalyst should through 150～350 ℃, preferably reduce 4～48 hours for 220～300 ℃ times under hydrogen before use according to the method described above.
The content that above-mentioned catalyst is applicable to sulphur in the raw material (or compound of sulfur-bearing) and dinitro compound is all less than the hydrogenation process of the nitro compound of 5ppm.
The method that catalyst of the present invention is used to prepare arylamine is: at normal pressure or add and depress, under 190～330 ℃ of the temperature, aromatic hydrocarbon nitro compound and hydrogen are joined in fixed bed (or fluid bed) reactor continuously, the ratio of control hydrogen and aromatic hydrocarbon nitro compound is 12～6: 1, keeping the charging air speed is 0.05～1.0LHSV, the conversion ratio of aromatic hydrocarbon nitro compound 〉=99.9%, the selectivity of aromatic hydrocarbon nitro compound 〉=98%.
Catalyst of the present invention is compared, is had the following advantages with present widely used copper-silica (being also referred to as modification copper catalyst or single copper catalyst) catalyst:
(1) catalyst of the present invention is existing at present catalyst (single copper catalyst) more than a times service life, and only this item just can bring enormous benefits to Aniline Production factory;
(2) catalyst of the present invention has nontoxic, harmless, nonflammable, non-explosive and etching apparatus not;
(3) do not contain precious metal;
(4) regeneration easily, method is simple.
The specific embodiment
The specific embodiment 1
1, the preparation of carrier
With sodium silicate solution and the sulfuric acid solution reaction of 3～30wt%, reaction temperature is controlled at 5～80 ℃, and pH is controlled at 2.5～10; With the solution forming oil column of gained, aging 3～6 hours, the dilute sulfuric acid with 2～3% soaked 1～2 hour, with 40～50 ℃ water washing; The solution of gained is soaked through ammoniacal liquor again, dewater in drier to water content≤80%, drying as for 500～550 ℃ of activation, through sieving, obtains 40～100 purpose catalyst used carriers to moisture≤10%.
2, Preparation of catalysts
In beaker with iron, cobalt, nickel, chromium, manganese, the molybdenum salt such as (being preferably nitrate) of 35g copper nitrate and respective amount, be dissolved in the 100ml water, add certain amount of ammonia water and make it generate cupric ammine complex (compound that can not generate complex compound adopts the precipitation method), add the 40g carrier, stir, add 30～100 ℃ of thermal control temperature, be preferably 50～80 ℃, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings.
Catalyst composed as follows:
Copper 10～26%, iron 0.1～4.5%, cobalt 0.1～4.5%, nickel 0.1～4.5%, chromium 0.1～11%, manganese 0.1～4.5%, molybdenum 0.1～4.5%.
3, evaluating catalyst test:
Get 10.0 gram catalyst and join in fixed bed (or fluid bed) reactor, reaction condition is as follows:
190～300 ℃ of reaction temperatures, at normal pressure or add and depress, nitrobenzene and hydrogen are joined in fixed bed (or fluid bed) reactor continuously, the ratio of control hydrogen and nitrobenzene is 12～6: 1, keeping the charging air speed of nitrobenzene is 0.05～1.0LHSV, the conversion ratio of nitrobenzene 〉=99.9%, the selectivity of nitrobenzene 〉=98%.
The life of catalyst contrast test, be to adopt the modification copper catalyst and the catalyst of the present invention of Jilin Chemical Industry Company (being called for short Jiization) catalyst plant production to compare, the reactor that the evaluation test of catalyst is adopted is Φ 16 * 500mm, material is a stainless steel, on the reactor, in, portable thermocouple measurement is adopted in following temperature survey, hydrogen is controlled with mass flow controller, nitrobenzene adopts reciprocating pump control charging, mix earlier, back preheating, every day timing sampling, sample is analyzed with liquid chromatogram, when nitrobenzene in the product 〉=0.2%, think catalysqt deactivation, it the results are shown in Table 1:
Table 1
| Catalyst of the present invention | The catalyst of Jiization production | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 ????28 ????29 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6240 ????6720 ????7160 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3476 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
4, the renovation process of catalyst
The catalyst of above-mentioned inactivation is stopped charging, blow out with the hydrogen of nitrogen with reactor, at 220～330 ℃ of following bubbling air 8～48h, blow out with the air of nitrogen with reactor again, feed hydrogen 8～48h down at 220～330 ℃, regeneration finishes.
Evaluating catalyst after the regeneration
Evaluating catalyst condition after the regeneration is identical with above-mentioned evaluating catalyst condition, the results are shown in Table 1.1:
Table 1.1
| Regenerated catalyst of the present invention | The regenerated catalyst of Jiization | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 ????28 ????29 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6240 ????6720 ????7090 | ????1.0 ????1.0 ????1.0 ????2.0 ????2.0 ????1.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????2.0 ????1.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3430 | ????1.0 ????1.0 ????1.0 ????1.0 ????2.0 ????2.0 ????1.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
The specific embodiment 2
1, the preparation of carrier:
With the specific embodiment 1.
2, Preparation of catalysts:
In beaker with nickel, the chromium salt such as (being preferably nitrate) of 35g copper nitrate and respective amount, be dissolved in the 100ml water, add certain amount of ammonia water and make it generate cupric ammine complex (compound that can not generate complex compound adopts the precipitation method), add the 40g carrier, stir, add 30～100 ℃ of thermal control temperature, be preferably 50～80 ℃, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings.
Catalyst composed as follows:
Copper 10～22%, nickel 0.1～4.5%, chromium 0.1～11%.
3, the evaluation test of catalyst:
Reaction condition is with the specific embodiment 1, and evaluation result sees Table 2:
Table 2
| Catalyst of the present invention | The catalyst of Jiization production | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 ????27 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6240 ????6430 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3430 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
4, the regeneration of catalyst
The renovation process of catalyst is identical with the specific embodiment 1.
The specific embodiment 3
1, the preparation of carrier
With the specific embodiment 1.
2, Preparation of catalysts
In beaker with iron, nickel, the chromium salt such as (being preferably nitrate) of 35g copper nitrate and respective amount, be dissolved in the 100ml water, add certain amount of ammonia water and make it generate cupric ammine complex (compound that can not generate complex compound adopts the precipitation method), add the 40g carrier, stir, add 30～100 ℃ of thermal control temperature, be preferably 50～80 ℃, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings.
Catalyst composed as follows:
Copper 10～22%, iron 0.1～4.5%, nickel 0.1～4.5%, chromium 0.1～11%.
3, the evaluation test of catalyst:
Reaction condition is with the specific embodiment 1, and evaluation result sees Table 3:
4, the regeneration of catalyst
The renovation process of catalyst is identical with the specific embodiment 1.
Table 3
| Catalyst of the present invention | The catalyst of Jiization production | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 ????28 ????30 ????31 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6240 ????6720 ????7200 ????7350 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.8 ????0.6 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 ????99.8 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3280 ????3390 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
The specific embodiment 4
1, the preparation of carrier
With the specific embodiment 1.
2, Preparation of catalysts
In beaker with iron, the chromium salt such as (being preferably nitrate) of 35g copper nitrate and respective amount, be dissolved in the 100ml water, add certain amount of ammonia water and make it generate cupric ammine complex (compound that can not generate complex compound adopts the precipitation method), add the 40g carrier, stir, add 30～100 ℃ of thermal control temperature, be preferably 50～80 ℃, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings.
Catalyst composed as follows:
Copper 10～22%, iron 0.1～4.5%, chromium 0.1～11%.
3, the evaluation test of catalyst:
Reaction condition is with the specific embodiment 1, and evaluation result sees Table 4:
4, the regeneration of catalyst
The renovation process of catalyst is identical with the specific embodiment 1.
Table 4
| Catalyst of the present invention | The catalyst of Jiization production | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6190 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3280 ????3580 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
The specific embodiment 5
1, the preparation of carrier
With the specific embodiment 1.
2, Preparation of catalysts
In beaker with iron, the molybdenum salt such as (being preferably nitrate) of 35g copper nitrate and respective amount, be dissolved in the 100ml water, add certain amount of ammonia water and make it generate cupric ammine complex (compound that can not generate complex compound adopts the precipitation method), add the 40g carrier, stir, add 30～100 ℃ of thermal control temperature, be preferably 50～80 ℃, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings.
Catalyst composed as follows:
Copper 10～22%, iron 0.1～4.5%, molybdenum 0.1～4.5%.
3, the evaluation test of catalyst:
Reaction condition is with the specific embodiment 1, and evaluation result sees Table 5:
4, the regeneration of catalyst
The renovation process of catalyst is identical with the specific embodiment 1.
Table 5
| Catalyst of the present invention | The catalyst of Jiization production | |||||
| Test period (d) | Inlet amount (L) | Air speed (LSHV) | Conversion ratio (%) | Inlet amount (L) | Air speed (LHSV) | Conversion ratio (%) |
| ????2 ????4 ????6 ????8 ????10 ????12 ????14 ????16 ????18 ????20 ????22 ????24 ????26 ????27 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3360 ????3840 ????4320 ????4800 ????5280 ????5760 ????6240 ????6510 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 ????99.8 | ????480 ????960 ????1440 ????1920 ????2400 ????2880 ????3280 ????3390 | ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????1.0 ????0.8 ????0.6 | ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.9 ????99.8 |
Claims (4)
1, a kind of reproducible hydrogenation catalyst and preparation method thereof is characterized in that, at SiO
2One or more metals on the carrier among loaded Cu, Fe, Co, Ni, Cr, Mn, the Mo or its oxide, carrier shared weight ratio in catalyst is 60～90%, all the other are active component, Cu is 10～26% at the percentage by weight of catalyst, each active component is respectively the atomic ratio of Cu respectively: Cu: Fe=1: 0.01～0.2, Cu: Co=1: 0.02～0.2, Cu: Ni=1: 0.0～0.2, Cu: Cr=1: 0.0～0.5, Cu: Mn=1: 0.01～0.2, Cu: Mo=1: 0.01～0.2;
The Preparation of catalysts method is
Iron, cobalt, nickel, chromium, manganese, the molybdenum of getting a certain amount of active ingredient copper and respective amount are preferably salt such as nitrate, soluble in water, can adopt any of the precipitation method or co-precipitation or infusion process, carry out in the mode of dipping or common dipping respectively, dipping solution can be any of the aqueous solution of the corresponding salt of active component or ammonia solution, add carrier, stir, add 30～100 ℃ of thermal control temperature, dipping 5～10h, static, cooling is filtered, washing, obtain the catalyst finished product 200 ℃ of following dryings, catalyst composed as follows:
Copper 10～26%, iron 0.1～4.5%, cobalt 0.1～4.5%, nickel 0.1～4.5%, chromium 0.1～11%, manganese 0.1～4.5%, molybdenum 0.1～4.5%;
The specific area of catalyst is: 250～550m
2/ g, bulk density is: 0.48～0.70kg/L, pore volume is: 0.55～0.80ml/g.
2, reproducible hydrogenation catalyst according to claim 1 and preparation method thereof is characterized in that, the effective active component loads on SiO
2Carrier on, the carrier specific area of described catalyst is 300～600m
2/ g, bulk density is 350～450g/L, granularity is 125～825um.
3, reproducible hydrogenation catalyst according to claim 1 and preparation method thereof, it is characterized in that, active principle can adopt any of the precipitation method or co-precipitation or infusion process, carry out in the mode of dipping or common dipping respectively, dipping solution can be any of the aqueous solution of the corresponding salt of active component or ammonia solution.
4, a kind of reproducible hydrogenation catalyst and preparation method thereof is characterized in that: at SiO
2One or more metals on the carrier among loaded Cu, Fe, Co, Ni, Cr, Mn, the Mo or its oxide, carrier shared weight ratio in catalyst is 60～90%, all the other are active component, Cu is 10～26% at the percentage by weight of catalyst, each active component is respectively the atomic ratio of Cu respectively: Cu: Fe=1: 0.01～0.2, Cu: Co=1: 0.02～0.2, Cu: Ni=1: 0.0～0.2, Cu: Cr=1: 0.0～0.5, Cu: Mn=1: 0.01～0.2, Cu: Mo=1: 0.01～0.2; Make in order to the below method: the iron of getting a certain amount of active ingredient copper and respective amount, cobalt, nickel, chromium, manganese, molybdenum is preferably salt such as nitrate, soluble in water, can adopt any of the precipitation method or co-precipitation or infusion process, carry out in the mode of dipping or common dipping respectively, dipping solution can be any of the aqueous solution of the corresponding salt of active component or ammonia solution, adds carrier, stirs, add 30～100 ℃ of thermal control temperature, dipping 5～10h, static, cooling, filter, washing obtains the catalyst finished product 200 ℃ of following dryings, catalyst composed as follows: copper 10～26%, iron 0.1～4.5%, cobalt 0.1～4.5%, nickel 0.1～4.5%, chromium 0.1～11%, manganese 0.1～4.5%, molybdenum 0.1～4.5%; Specific area is: 250～550m
2/ g, bulk density is: 0.48～0.70kg/L, pore volume is: 0.55～0.80ml/g.
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| CNB021446520A CN1301154C (en) | 2002-11-29 | 2002-11-29 | Regenerable hydrogenation catalyst and method for producing the same |
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| CNB021446520A CN1301154C (en) | 2002-11-29 | 2002-11-29 | Regenerable hydrogenation catalyst and method for producing the same |
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| CN105032424A (en) * | 2015-06-05 | 2015-11-11 | 中国科学院化学研究所 | Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4191664A (en) * | 1975-06-16 | 1980-03-04 | Union Oil Company Of California | Thermally stable nickel-alumina catalysts useful for methanation and other reactions |
| DE2849002A1 (en) * | 1978-11-11 | 1980-05-22 | Bayer Ag | METHOD FOR THE CATALYTIC HYDRATION OF NITROBENZOL |
| CN1034439A (en) * | 1988-11-18 | 1989-08-02 | 石啸生 | Word root index based on pronunciation and writing trace |
| DE4039026A1 (en) * | 1990-12-07 | 1992-06-11 | Bayer Ag | METHOD FOR PRODUCING ANILINE |
| DE4326692A1 (en) * | 1993-08-10 | 1995-02-16 | Akzo Nobel Nv | Process for the production of gamma-butyrolactone |
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2002
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