CN105013501A - Preparation method of aldehyde gas phase hydrogenation catalyst - Google Patents
Preparation method of aldehyde gas phase hydrogenation catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of an aldehyde gas phase hydrogenation catalyst. The method comprises the following steps: 1, mixing certain proportions of a copper-containing compound, a zinc-containing compound, a manganese-containing compound and/or a zirconium-containing compound with certain amounts of water and alcohol to prepare a mixed solution 1, carrying out cocurrent flow titration on the mixed solution 1 and an aqueous precipitation agent solution 1, and ageing to obtain a slurry 1; 2, mixing certain proportions of an aluminum-containing compound and a magnesium-containing compound with certain amounts of water and alcohol to prepare a mixed solution 2, adding a surfactant to the mixed solution 2, carrying out cocurrent flow titration on the mixed solution 2 and an aqueous precipitation agent solution 2, and ageing to obtain a slurry 2;and 3, mixing the slurry 1 with the slurry 2, filtering, washing, drying, roasting, and carrying out tabletting molding to obtain the catalyst. The aldehyde gas phase hydrogenation catalyst prepared through the method has the advantages of uniform distribution of active components, high copper dispersion, and excellent activity and selectivity.
Description
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of preparation method of aldehyde gas phase hydrogenation catalyst.
Background technology
Butanols is a kind of important Organic Chemicals, is the solvent of multiple coating, can be used for manufacturing dibutyl phthalate, butyl acrylate, butyl acetate, butyl glycol ether etc., also can be used for manufacturing surfactant, is widely used.
The method of current industrial production butanols mainly contains: fermentation method, oxo synthesis, Reppe method and aldol condensation of acetaldehyde method.Propenecarbonyl synthetic method due to raw material be easy to get, carbonylating process pressure reduces relatively, product n-butanol improves with the ratio of isobutanol and can coproduction simultaneously or producing the advantages such as 2-Ethylhexyl Alcohol has become the most important production method of butanols specially.
Butyraldehyde hydrogenation process is the critical process producing butanols, and catalyst is the core of butyraldehyde hydrogenation reaction.Butyraldehyde hydrogenation catalyst mainly contains noble metal catalyst, nickel catalyst and Cu-series catalyst.Noble metal catalyst hydrogenation activity is high, but it is expensive, affects the economy of device, is eliminated at present.Nickel catalyst hydrogenation activity temperature is low, operation energy consumption is few, for liquid phase method aldehyde hydrogenation technique.Cu-series catalyst is mainly used in vapor phase method aldehyde hydrogenation process.Vapor phase method because of reaction pressure low, process equipment is simple and be widely used, and most domestic butanols device adopts vapor phase method, the copper-zinc system catalyst that catalyst adopts the precipitation method to prepare.
Aldehyde gas phase hydrogenation catalyst has report in numerous patents.Disclosed in US5550302, aldehyde hydrogenating catalyst consists of Cu-Cr-Zn-Mn-Ba-Zr/Ti, containing environmentally harmful heavy metal Cr in this catalyst.Catalyst copper removal zinc disclosed in DE3737277 is outward also containing alkali metal and/or transition metal.DE4244273 discloses a kind of Na
2o modification CuZnAl catalyst is used for butyraldehyde gas phase hydrogenation process.CN1050994A adds a small amount of alkali metal and the auxiliary agent such as nickel, cobalt to improve catalyst choice in copper zinc catalyst, but increases with additive dosage, and catalyst activity can decline.Patent disclosed in CN1695802A adopts multiple step coprecipitation method, and adopt aluminium and auxiliary agent co-precipitation and the co-precipitation of copper zinc, the catalyst choice of preparation is good.CN1087971C adopts organic acid to do precipitating reagent, without the need to washing, but catalyst activity and poor stability.CN100398202C discloses a kind of aldehyde hydrogenating catalyst preparation method, and the method adopts continuous print multiple step coprecipitation method to prepare CuZnAl catalyst.Catalyst disclosed in CN1251796C, except containing except copper zinc-aluminium, also contains alkali metal or alkaline-earth metal isoreactivity auxiliary agent.The vapor hydroformylation catalyst of above-mentioned open report is copper-zinc system catalyst prepared by the precipitation method, and in report, not mentioned preparation process is on the performance of catalyst under the impact of catalyst composition homogeneity and copper grain size and high-speed.
In industrial production, improve device disposal ability, device economic benefit can be improved, reduce production cost.Because adding hydrogen to aldehyde in gas phase generation alcohol is strong exothermal reaction, improves unit capacity, reaction bed temperature will inevitably be caused to raise, high temperature easily causes the side reactions such as polymerization, condensation to occur, and can reduce quality and the yield of product alcohol.
In prior art, precipitation is uneven, copper grain dispersion degree is poor, prepare poor repeatability to adopt the copper zinc-aluminium butanols catalyst prepared of the precipitation method to exist, butyraldehyde low conversion rate under high-speed, the problem such as hot(test)-spot temperature is high, butanol selectivity is poor.By improving the uniformity of precipitation process and the decentralization of copper, the pore passage structure of optimization of catalysts and then improve catalyst heat and mass transfer performance, for preparing high activity, high selectivity butyraldehyde gas phase hydrogenation catalyst is most important.
Summary of the invention
The invention provides the preparation method that a kind of aldehyde gas phase hydrogenation prepares the catalyst of alcohol, the catalyst activity uniform component distribution, the copper grain dispersion degree that adopt the method to prepare be high, specific area and pore volume large, catalyst activity is high, selective good.
For achieving the above object, the technical solution used in the present invention is:
Aldehyde gas phase hydrogenation prepares a preparation method for the catalyst of alcohol, comprises the following steps:
(1) by a certain proportion of copper-containing compound, zinc compound, be mixed with the aqueous solution containing manganese compound and/or zirconium-containing compound, in the aqueous solution, add alcohol be again mixed with mixed solution 1, by mixed solution 1 and the precipitating reagent aqueous solution 1 and drip is fixed, agingly obtain slurries 1;
(2) a certain proportion of aluminum contained compound, magnesium-containing compound are mixed with the aqueous solution, in the aqueous solution, add alcohol be again mixed with mixed solution 2, and surfactant is added in mixed solution 2, by mixed solution 2 and the precipitating reagent aqueous solution 2 and drip is fixed, agingly obtain slurries 2;
(3) slurry 1 and slurry 2 are mixed, then filter, wash, drying, roasting, compression molding, obtain catalyst.
In the inventive method, copper-containing compound in step (1), zinc compound and the concentration of metal ions containing the aqueous solution of manganese compound and/or zirconium-containing compound are 0.5-3.0mol/L, wherein copper and zinc mol ratio are 1:2 to 3:2, and copper and manganese and/or zirconium mol ratio are 9:1 to 150:1; In step (2), the concentration of metal ions of the aqueous solution of aluminum contained compound and magnesium-containing compound is 0.5-3.0mol/L, and wherein magnalium mol ratio is 1:1 to 5:1, preferred 2:1 to 4:1, more preferably 2:1 to 3:1.
In the inventive method, in step (1), control precipitation process pH within the scope of 6.5-8.0, and drip fixed temperature controls at 50-80 DEG C, aging temperature is 50-80 DEG C, and ageing time is 0.5-2h.
In the inventive method, in step (2), control precipitation process pH within the scope of 6.5-9.5, and drip fixed temperature controls at 60-90 DEG C, aging temperature is 60-90 DEG C, and ageing time is 1-4h.
In the inventive method, in step (3), described baking temperature is 90-120 DEG C, and drying time is 6-18h, and sintering temperature is 300-400 DEG C, roasting time 2-8h.
Alcohol of the present invention is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, and described in step (1) and step (2), the consumption of alcohol is respectively the 1-20% of water quality, preferred 1-10%, more preferably 5-10%.In preparation process, add small molecular alcohol, alcohol add the solubility reducing precipitation, also reduce the Hyarogen-bonding of original aqueous systems, improve the uniformity of catalyst microcosmic composition, alleviate agglomeration, improve the decentralization of copper, and then improve the activity and selectivity of catalyst.
The surfactant of step of the present invention (2) is one or more and anion surfactant in non-ionic surface active agent: OP-10, Tween 80, Tx-100, AEO AEO-9: one or more in neopelex, lauryl sodium sulfate, methyl sodiosul foaliphatate, by mass, non-ionic surface active agent and anion surfactant compound proportion are 1:1 to 5:1, preferred 1:1 to 4:1, more preferably 2:1 to 4:1.The addition of described surfactant is the 0.1-10% of aqueous solvent and alcohol quality summation, preferred 0.5-5%, more preferably 0.5-3%.Surfactant is non-ionic surface active agent and anion surfactant is composite forms, and compound surfactant good stability, CMC point is low, more effectively can play a role while reduction surfactant addition.
The precipitating reagent of step of the present invention (1) is one or more in sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH, potassium hydroxide, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor; The precipitating reagent of described step (2) is the compound precipitants that sodium carbonate and/or potash form with NaOH and/or potassium hydroxide.In precipitating reagent, sodium carbonate and/or potash and NaOH and/or potassium hydroxide mass ratio are 1:1 to 1:10, preferred 2:5 to 4:5, more preferably 2:5 to 3:5.
In the inventive method, add surfactant in aluminium and the magnesium aqueous solution, and adopt sodium carbonate and/or potash and NaOH and/or potassium hydroxide to do precipitating reagent, co-precipitation obtains the magnalium hydrotalcite precursor of even particle size distribution.Surfactant add the uniformity that improve precipitation process, magnalium hydrotalcite and the copper zinc of particle fine uniform play the effect splitting, isolate copper zinc after precipitating and mixing, and are conducive to the heat endurance improving copper zinc particles in catalyst.
Copper-containing compound of the present invention is one or more of copper nitrate, copper chloride and copper acetate; Aluminum contained compound is one or more of aluminum nitrate, aluminium chloride and aluminium acetate; Zinc compound is one or more of zinc nitrate, zinc chloride and zinc acetate; Magnesium-containing compound is one or more in magnesium nitrate, magnesium chloride and magnesium acetate; One or more in manganese nitrate, manganese chloride and manganese acetate are selected from containing manganese compound; Zirconium-containing compound be selected from zirconyl nitrate or zirconium oxychloride one or both.
The catalyst composition adopting method of the present invention to prepare comprises: cupric oxide 30-55wt%, aluminium oxide 1-10wt%, zinc oxide 40-65wt%, one or both 0.1-5wt% in manganese oxide and zirconia, magnesia 0.1-5wt%, by overall catalyst weight.
Preferably, catalyst of the present invention composition comprises: cupric oxide 31-50wt%, aluminium oxide 1-8wt%, zinc oxide 45-64wt%, and one or both 0.2-3wt% in manganese oxide and zirconia, magnesia 0.2-5wt%, by overall catalyst weight.In catalytic component, manganese and zirconium adds the decentralization that improve copper in catalyst.
More preferably, catalyst of the present invention composition comprises: cupric oxide 35-55wt%, aluminium oxide 1-5wt%, zinc oxide 45-60wt%, and one or both 0.5-3wt% in manganese oxide and zirconia, magnesia 0.5-5wt%, by overall catalyst weight.
Catalyst of the present invention just possesses corresponding catalytic activity after need carrying out reduction activation, prepares alcohol for aldehyde gas phase hydrogenation, especially prepares butanols for butyraldehyde gas phase hydrogenation.
The method of the reduction activation of catalyst of the present invention comprises: the mist volume space velocity 300-1000h keeping hydrogen and nitrogen
-1, first temperature of reactor is risen to 160-180 DEG C, the mechanical water of constant temperature 1-2h Removal of catalyst absorption, then passes into containing volume fraction 5v%H
2hydrogen and the gaseous mixture of nitrogen carry out prereduction 1h, progressively improve the ratio of hydrogen in hydrogen and nitrogen mixture afterwards to 10v%, 20v%, 50v%, 100%, control this process catalyst bed hot(test)-spot temperature and be no more than 220 DEG C, finally be warming up to 220 DEG C of reductase 12-5h under pure hydrogen atmosphere, obtain the catalyst of reduction-state.
The catalyst of reduction-state of the present invention is used for butyraldehyde gas phase hydrogenation and prepares butanols, reaction pressure 0.4-0.6MPa, and reaction temperature is 110-140 DEG C, H
2/ aldehyde mol ratio 10-30:1, Feed space velocities 0.3-0.9ml
iBAml
-1 cath
-1.
Pressure of the present invention is relative pressure.
Catalyst of the present invention is used for butyraldehyde gas phase hydrogenation and prepares butanols process, catalyst activity uniform component distribution, copper decentralization is high, catalyst has larger specific surface and pore volume, the catalyst of preparation has excellent activity and selectivity, be applied to the reaction that butyraldehyde gas phase hydrogenation prepares butanols, butyraldehyde conversion ratio is greater than 99.5%, is selectively greater than 99.7%.
Detailed description of the invention
Below in conjunction with embodiment, the inventive method is described in detail, but the present invention is not limited to embodiment.
Adopt powder x-ray diffraction to carry out material phase analysis to catalyst, and apply Scherrer method calculating copper crystallite dimension.
The physical adsorption appearance that the pore structure parameter of catalyst adopts Merck & Co., Inc of the U.S. to produce measures.Specific area adopts BET equation by N
2adsorption isotherm is tried to achieve, and the aperture of application BJH model calculation sample, average pore size obtains according to Langmuir desorption Solving Equations.
Embodiment 1
By 274.8g copper nitrate (Cu (NO
3)
23H
2o), 570.2g zinc nitrate (Zn (NO
3)
26H
2o), 19.7g zirconyl nitrate (ZrO (NO
3)
22H
2o) be dissolved in 3.0kg water and be made into mixed aqueous solution, in the aqueous solution, then add 200g methyl alcohol obtain mixed solution 1.By the sodium carbonate liquor and the precipitant solution 1 that are made into 10wt% soluble in water for sodium carbonate.Respectively two kinds of solution are heated to 60 DEG C, are then instilled in reactor by two kinds of solution simultaneously, control precipitation process temperature in the kettle 60 DEG C, system pH is 6.8, titration time is 1h, aging 1h at 60 DEG C, obtains slurries 1 afterwards.
By 9.6g aluminum nitrate (Al (NO
3)
39H
2o), 16.5g magnesium nitrate (Mg (NO
3)
26H
2o) be dissolved in 90g water and be made into mixing salt solution, then add 4g methyl alcohol, 0.15g Tx-100 and 0.08g lauryl sodium sulfate and mix in this salting liquid and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 2:5, respectively two kinds of solution are heated to 70 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 70 DEG C, system pH are 8.5, titration time is 1h, aging 1h at 80 DEG C, obtains slurries 2 afterwards.
Slurries 1 and slurries 2 mixed, then filter, wash and by filter cake at 110 DEG C of dry 12h, in 350 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst A.
Catalyst reduction: catalyst A is loaded in fixed bed hydrogenation reactor, loaded catalyst 50ml.Catalyst reduces before using under nitrogen and hydrogen mixed gas, keeps mist volume space velocity 300h in reduction process
-1, first temperature of reactor is risen to the mechanical water of 160 DEG C of constant temperature 2h Removal of catalyst absorption, then passes into containing volume fraction 5v%H
2hydrogen and the gaseous mixture of nitrogen carry out prereduction 1h, progressively improve the ratio of hydrogen in hydrogen and nitrogen mixture afterwards to 10v%, 20v%, 50v%, 100%, control this process catalyst bed hot(test)-spot temperature and be no more than 220 DEG C, be finally warming up to 220 DEG C under pure hydrogen atmosphere, reduce 3h.
The catalyst of preparation is used for butyraldehyde gas phase hydrogenation and prepares butanols, evaluating catalyst condition: load 50ml 5*5mm catalyst in the reaction tube of internal diameter 32mm, reaction temperature 120 DEG C, reaction pressure 0.5MPa, hydrogen aldehyde mol ratio 10-30:1.
Embodiment 2
By 274.8g copper nitrate, 570.2g zinc nitrate, 6.6g manganese nitrate Mn (NO
3)
2, 5.6g zirconyl nitrate is dissolved in 2.9kg water and is made into mixed-salt aqueous solution, in the aqueous solution, then adds 200g ethanol obtain mixed solution 1.By the sodium carbonate liquor and the precipitant solution 1 that are made into 10wt% soluble in water for sodium carbonate.Respectively two kinds of solution are heated to 60 DEG C, two kinds of solution are instilled in reactor by the method for employing co-precipitation simultaneously, and control precipitation process temperature in the kettle 60 DEG C, system pH are 7.0, titration time is 1h, and then aging 1h at 70 DEG C, obtains slurries 1.
19.1g aluminum nitrate, 33.1g magnesium nitrate are dissolved in 180g water and are made into mixing salt solution, then adds 14.4g ethanol, 1.56g OP-10 and 0.36g neopelex and mix in this salting liquid and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 1:2, respectively two kinds of solution are heated to 80 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 80 DEG C, system pH are 9.2, titration time is 1h, then aging 1h at 80 DEG C, obtains slurries 2.
Slurries 1 and slurries 2 mixed, then filters, wash and by filter cake at 110 DEG C of dry 12h, and in 320 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst B.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Embodiment 3
314.1g copper nitrate, 522.7g zinc nitrate, 5.7g manganese nitrate are dissolved in 2.8kg water and are made into mixed-salt aqueous solution, in the aqueous solution, then adds 200g propyl alcohol obtain mixed solution 1.By the sodium carbonate liquor being made into 10wt% soluble in water for sodium carbonate, respectively two kinds of solution are heated to 70 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 70 DEG C, body pH are 7.2, titration time is 1h, then aging 1h at 70 DEG C, obtains slurries 1.
28.7g aluminum nitrate, 49.6g magnesium nitrate are dissolved in 267g water and are made into mixing salt solution, then in this salting liquid, add 22g propyl alcohol, 1.3g neopelex and 4.5g AEO (AEO-9), and mix and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 3:5, respectively two kinds of solution are heated to 70 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 70 DEG C, system pH are 8.0, titration time is 1h, then aging 1h at 80 DEG C, obtains slurries 2.
Slurries 1 and slurries 2 mixed, then filters, wash and by filter cake at 110 DEG C of dry 12h, and in 320 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst C.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Embodiment 4
392.6g copper nitrate, 427.6g zinc nitrate, 11.4g manganese nitrate, 5.6g zirconyl nitrate are dissolved in 2.9kg water and are made into mixed-salt aqueous solution, in the aqueous solution, then adds 200g methyl alcohol obtain mixed solution 1.By the sodium carbonate liquor being made into 10wt% soluble in water for sodium carbonate.Respectively two kinds of solution are heated to 70 DEG C, two kinds of solution are instilled in reactor by the method for employing co-precipitation simultaneously, and control precipitation process temperature in the kettle 70 DEG C, body pH are 7.5, titration time is 1h, and then aging 1h at 80 DEG C, obtains slurries 1.
19.1g aluminum nitrate, 33.1g magnesium nitrate are dissolved in 180g water and are made into mixing salt solution, then adds 14.4g methyl alcohol, 3.8g Tween 80 and 1.9g neopelex and mix in this salting liquid and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 1:2, respectively two kinds of solution are heated to 80 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 80 DEG C, system pH are 9.0, titration time is 1h, then aging 2h at 80 DEG C, obtains slurries 2.
Slurries 1 and slurries 2 mixed, then filters, wash and by filter cake at 110 DEG C of dry 12h, and in 360 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst D.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Embodiment 5
392.6g copper nitrate, 427.6g zinc nitrate, 17.0g manganese nitrate, 2.8g zirconyl nitrate are dissolved in 2.9kg water and are made into mixed-salt aqueous solution, in the aqueous solution, then adds 200g ethanol obtain mixed solution 1.By the sodium carbonate liquor being made into 10wt% soluble in water for sodium carbonate, respectively two kinds of solution are heated to 70 DEG C.Two kinds of solution are instilled in reactor by the method for employing co-precipitation simultaneously, and control precipitation process temperature in the kettle 70 DEG C, body pH are 7.5, titration time is 1h, and then aging 1h at 80 DEG C, obtains slurries 1.
19.1g aluminum nitrate, 33.1g magnesium nitrate are dissolved in 180g water and are made into mixing salt solution, then adds 14.4g ethanol, 0.38g neopelex and 1.15g OP-10 and mix in this salting liquid and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 3:5, respectively two kinds of solution are heated to 80 DEG C, adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 80 DEG C, system pH are 7.5, titration time is 1h, then aging 2h at 80 DEG C, obtains slurries 2.
Slurries 1 and slurries 2 mixed, then filters, wash and by filter cake at 110 DEG C of dry 12h, and in 360 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst E.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Embodiment 6
274.8g copper nitrate, 522.7g zinc nitrate, 17.0g manganese nitrate, 5.6g zirconyl nitrate are dissolved in 2.8kg water and are made into mixed-salt aqueous solution, in the aqueous solution, then adds 200g propyl alcohol obtain mixed solution 1.By the sodium carbonate liquor being made into 10wt% soluble in water for sodium carbonate, respectively two kinds of solution are heated to 60 DEG C.Two kinds of solution are instilled in reactor by the method for employing co-precipitation simultaneously, and control precipitation process temperature in the kettle 60 DEG C, body pH are 6.8, titration time is 1h, and then aging 1h at 80 DEG C, obtains slurries 1.
47.8g aluminum nitrate, 82.7g magnesium nitrate are dissolved in 450g water and are made into mixing salt solution, then adds 36g propyl alcohol, 1.2g lauryl sodium sulfate and 4.56g Tween 80 and mix in this salting liquid and obtain mixed solution 2.The sodium hydrate aqueous solution of 10wt% aqueous sodium carbonate and 10wt% is mixed to get precipitant solution 2 by 2:5, respectively two kinds of solution is heated to 80 DEG C.Two kinds of solution are instilled in reactor by the method for employing co-precipitation simultaneously, and control precipitation process temperature in the kettle 80 DEG C, system pH are 7.0, titration time is 1h, and then aging 2h at 80 DEG C, obtains slurries 2.
Slurries 1 and slurries 2 mixed, then filters, wash and by filter cake at 110 DEG C of dry 12h, and in 400 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst F.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Comparative example 1
Adopt conventional copper zinc-aluminium coprecipitation.274.8g copper nitrate, 570.2g zinc nitrate, 95.6g aluminum nitrate are dissolved in 3.0kg water and are made into mixed-salt aqueous solution, by the sodium carbonate liquor being made into 10wt% soluble in water for sodium carbonate, respectively two kinds of solution is heated to 60 DEG C.Adopt the method for co-precipitation, two kinds of solution are instilled in reactor simultaneously, control precipitation process temperature in the kettle 60 DEG C, body pH are 7.0, titration time is 1h, then aging 1h at 60 DEG C, then filter, to wash and by filter cake at 110 DEG C of dry 12h, and in 350 DEG C of roasting 3h, compression molding obtains 5*5mm cylinder (diameter 5mm, height 5mm) catalyst afterwards, obtains catalyst G.
Catalyst reduction and performance evaluation are with reference to embodiment 1.
Comparative example 2
Preparation process with embodiment 3, but does not add ethanol, obtains catalyst H.
Comparative example 3
Preparation process with embodiment 3, but does not add surfactant, obtains catalyst I.
Be embodiment 1-6 and comparative example 1-3 prepare catalyst composition as shown in table 1, in catalyst shot copper footpath and Catalyst Pore Structure Parameters as shown in table 2, the performance evaluation of catalyst is as shown in table 3:
Table 1 catalyst forms
| Catalyst is numbered | Cupric oxide % | Zinc oxide % | Aluminium oxide % | Magnesia % | Manganese oxide % | Zirconia % |
| A | 35 | 60 | 1 | 0.5 | 0 | 3.5 |
| B | 35 | 60 | 2 | 1 | 1 | 1 |
| C | 40 | 55 | 3 | 1.5 | 0.5 | 0 |
| D | 50 | 45 | 2 | 1 | 1 | 1 |
| E | 50 | 45 | 2 | 1 | 1.5 | 0.5 |
| F | 35 | 55 | 5 | 2.5 | 1.5 | 1.0 |
| G | 35 | 60 | 5 | 0 | 0 | 0 |
| H | 40 | 55 | 3 | 1.5 | 0.5 | 0 |
| I | 40 | 55 | 3 | 1.5 | 0.5 | 0 |
Shot copper footpath and Catalyst Pore Structure Parameters in table 2 catalyst
Table 3 butyraldehyde hydrogenation reaction result
As shown in Table 2, catalyst A is little to the Cu particle diameter of F, specific area and pore volume large, catalyst stability is good, run Cu particle diameter in 1000h rear catalyst and do not occur obviously to grow up, and in the catalyst G to I of comparative example operation 1000h rear catalyst, Cu particle occurs obviously to grow up.As shown in Table 3, under identical butyraldehyde Feed space velocities, catalyst A is low to F bed hot(test)-spot temperature, and catalyst activity is high, selective good, and catalyst G to the I beds hot(test)-spot temperature of comparative example is high, and catalyst activity is low, poor selectivity.
Claims (10)
1. a preparation method for aldehyde gas phase hydrogenation catalyst, comprises the following steps:
(1) by a certain proportion of copper-containing compound, zinc compound and be mixed with the aqueous solution containing manganese compound and/or zirconium-containing compound, in the aqueous solution, add alcohol be again mixed with mixed solution 1, by mixed solution 1 and the precipitating reagent aqueous solution 1 and drip is fixed, agingly obtain slurries 1;
(2) a certain proportion of aluminum contained compound, magnesium-containing compound are mixed with the aqueous solution, in the aqueous solution, add alcohol be again mixed with mixed solution 2, and surfactant is added in mixed solution 2, by mixed solution 2 and the precipitating reagent aqueous solution 2 and drip is fixed, agingly obtain slurries 2;
(3) slurry 1 and slurry 2 are mixed, then filter, wash, drying, roasting, compression molding, obtain catalyst.
2. method according to claim 1, is characterized in that, in step (1), control precipitation process pH within the scope of 6.5-8.0, and drip fixed temperature controls at 50-80 DEG C, aging temperature is 50-80 DEG C, and ageing time is 0.5-2h.
3. method according to claim 1, is characterized in that, in step (2), control precipitation process pH within the scope of 6.5-9.5, and drip fixed temperature controls at 60-90 DEG C, aging temperature is 60-90 DEG C, and ageing time is 1-4h.
4. method according to claim 1, it is characterized in that, copper-containing compound in step (1), zinc compound and the concentration of metal ions containing the aqueous solution of manganese compound and/or zirconium-containing compound are 0.5-3.0mol/L, wherein copper and zinc mol ratio are 1:2 to 3:2, and copper and manganese and/or zirconium mol ratio are 9:1 to 150:1; In step (2), the concentration of metal ions of the aqueous solution of aluminum contained compound and magnesium-containing compound is 0.5-3.0mol/L, and wherein magnalium mol ratio is 1:1 to 5:1, preferred 2:1 to 4:1, more preferably 2:1 to 3:1.
5. method according to claim 1, is characterized in that, described alcohol is one or more in methyl alcohol, ethanol, propyl alcohol, butanols, and described in step (1) and (2), the consumption of alcohol is respectively the 1-20% of water quality, preferred 1-10%, more preferably 5-10%.
6. the method according to any one of claim 1-5, it is characterized in that, described surfactant is by non-ionic surface active agent: one or more and anion surfactant in OP-10, Tween 80, Tx-100, AEO AEO-9: one or more in neopelex, lauryl sodium sulfate, methyl sodiosul foaliphatate are composite to be formed, non-ionic surface active agent and anion surfactant compound proportion are 1:1 to 5:1 by mass, preferred 1:1 to 4:1, more preferably 2:1 to 4:1.
7. the method according to claim 1 or 6, is characterized in that, the addition of described surfactant is the 0.1-10% of aqueous solvent and alcohol quality summation, preferred 0.5-5%, more preferably 0.5-3%.
8. method according to claim 1, is characterized in that, the precipitating reagent of described step (1) is one or more in sodium carbonate, potash, sodium acid carbonate, saleratus, NaOH, potassium hydroxide, ammonium carbonate, carbonic hydroammonium and ammoniacal liquor; The precipitating reagent of described step (2) is the compound precipitants that sodium carbonate and/or potash form with NaOH and/or potassium hydroxide, in precipitating reagent, sodium carbonate and/or potash and NaOH and/or potassium hydroxide mass ratio are 1:1 to 1:10, preferred 2:5 to 4:5, more preferably 2:5 to 3:5.
9. method according to claim 1, is characterized in that, described copper-containing compound is one or more of copper nitrate, copper chloride and copper acetate; Aluminum contained compound is one or more of aluminum nitrate, aluminium chloride and aluminium acetate; Zinc compound is one or more of zinc nitrate, zinc chloride and zinc acetate; One or more in manganese nitrate, manganese chloride and manganese acetate are selected from containing manganese compound; Magnesium-containing compound is one or more in magnesium nitrate, magnesium chloride and magnesium acetate; Zirconium-containing compound be selected from zirconyl nitrate and zirconium oxychloride one or both; In step (3), described baking temperature is 90-120 DEG C, and drying time is 6-18h, and sintering temperature is 300-400 DEG C, roasting time 2-8h.
10. the catalyst that the method according to any one of claim 1-9 is obtained; it is characterized in that; by overall catalyst weight; catalyst composition comprises: cupric oxide 30-55wt%; aluminium oxide 1-10wt%; zinc oxide 40-65wt%, one or both 0.1-5wt% in manganese oxide and zirconia, magnesia 0.1-5wt%;
Preferably, catalyst of the present invention composition comprises: cupric oxide 31-50wt%, aluminium oxide 1-8wt%, zinc oxide 45-64wt%, one or both 0.2-3wt% in manganese oxide and zirconia, and magnesia 0.2-5wt%, by overall catalyst weight;
More preferably, catalyst of the present invention composition comprises: cupric oxide 35-50wt%, aluminium oxide 1-5wt%, zinc oxide 45-60wt%, and one or both 0.5-3wt% in manganese oxide and zirconia, magnesia 0.5-5wt%, by overall catalyst weight.
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| JP7019813B2 (en) | 2017-12-06 | 2022-02-15 | ワンファ ケミカル グループ カンパニー，リミテッド | Catalyst for producing α-phenylethanol by hydrogenation of acetophenone, its production method and application |
| US11167280B2 (en) | 2017-12-06 | 2021-11-09 | Wanhua Chemical Group Co., Ltd. | Catalyst for preparing α-phenylethanol by hydrogenation of acetophenone, preparation method thereof and application thereof |
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