CN1283357C - Catalyst for preparing aromatic aldehyde and aliphatic aldehyde and its prepn process - Google Patents
Catalyst for preparing aromatic aldehyde and aliphatic aldehyde and its prepn process Download PDFInfo
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Abstract
The present invention relates to a catalyst for preparing aromatic aldehyde or aliphatic aldehyde and a preparation process thereof, particularly to a catalyst composed of modified nano MnO2 and ZnO composite oxides and used for preparing aromatic aldehyde or aliphatic aldehyde and a preparation process thereof. The provided catalyst has large specific surface area, high reactivity, high conversion rate on acid, high selectivity in the aromatic aldehyde, low reaction temperature, long service life and high efficiency, and is used for preparing the aromatic aldehyde or the aliphatic aldehyde. The preparation process comprises the procedures of adding modification elements, dissolving, forming a precipitate with a precipitating agent, decomposing the precipitate to obtain the MnO2 and ZnO composite oxides, extruding the MnO2 and ZnO composite oxides into strips and calcining. After being used for preparing the aromatic aldehyde or the aliphatic aldehyde, the catalyst can be reduced and activated by using a pressurizing or decompressing method to introduce nitrogen. The catalyst has the advantages of high activity, high selectivity in aldehyde and long service life.
Description
Technical field
The present invention relates to a kind of by modified nanometer MnO
2With the catalyst that the ZnO composite oxides are formed, especially a kind of Catalysts and its preparation method that is used to prepare aromatic aldehyde or fatty aldehyde.
Background technology
Aromatic aldehyde or fatty aldehyde are important fine chemical materials, are widely used in food, pharmacy, toothpaste and the cosmetics industry.At present, aromatic aldehyde, for example the production method of benzaldehyde still follows by the toluene elder generation chlorination conventional method of hydrolysis again.The benzaldehyde that this method is produced is restricted its application in medicine, food, beverage industry owing to chloride.Simultaneously, this production method is because the generation of a large amount of pernicious gases and contaminated environment.Therefore, seek a kind of friendly process that is suitable for suitability for industrialized production aromatic aldehyde or fatty aldehyde and become the direction that various countries' chemist is made great efforts.
At present, the method for obtaining no chlorobenzaldehyde both at home and abroad mainly contains: (1) toluene oxidation method, this method can be divided into vapor phase method and liquid phase method.Though relevant both at home and abroad research report is many because yield too low (generally being not more than 10%), except benzaldehyde as the by-product recovery, adopt this method directly to produce the possibility that benzaldehyde does not still have industrial applications at present.(2) the direct catalytic hydrogenating reduction method of benzoic acid.This is a desirable approach of the no chlorobenzaldehyde of preparation beyond doubt, the used raw material of this technology is single, nontoxic, one step of reaction finishes, the product separation is purified easily and the pernicious gas that produces is few, also makes working condition control easily and adopt normal pressure to reach than low reaction temperatures because adopt; If used carboxylic acid is natural prodcuts, gained aldehyde can keep its natural character well behind hydrogenation, and therefore, this technology is particularly suitable for preparing natural aromatic aldehyde or fatty aldehyde by natural aromatic acid or aliphatic acid.
Prepare corresponding aldehyde desirable approach beyond doubt by the direct catalytic hydrogenating reduction of carboxylic acid, this is because adopt the used material of this technology all nontoxic, the pernicious gas that reaction produces is few, and adopts normal pressure and also make working condition control easily than low reaction temperatures; If used carboxylic acid is natural prodcuts, gained aldehyde can keep its natural character well behind hydrogenation, and therefore, this technology is particularly suitable for preparing natural aromatic aldehyde or fatty aldehyde by natural aromatic acid or aliphatic acid.
Early stage United States Patent (USP) U.S 3517066, U.S 3935265 had once reported respectively by the carboxylic acid or derivatives thereof and had prepared corresponding aldehyde through catalytic hydrogenation, adopted noble metal catalysts such as Pd, Pt to make cost too high owing to the former, though and the latter adopts cheap Al
2O
3Make catalyst, but the selectivity of the conversion ratio of acid and aldehyde is all very low, therefore, the both does not have the value of suitability for industrialized production.During the eighties in 20th century, United States Patent (USP) U.S 4328373, U.S 4613700 and Europe patent EP 0150961 have all reported employing ZrO
2That makes catalyst prepares the catalytic process of aromatic aldehyde by the aromatic acid gas-phase catalytic hydrogenation.Use ZrO
2Though make the selectivity that catalyst has improved sour conversion ratio and aldehyde greatly, also exist problems such as reaction temperature is higher, productive rate is low, catalyst price height.To the nineties in 20th century, also successively there are United States Patent (USP) U.S 5059716 (1991), U.S 5306845 (1994), U.S 5585523 (1996) to report employing TiO respectively
2, Cr
2O
3, SnO
2Make catalyst, prepare the method for corresponding aldehyde by carboxylic acid through gas-phase catalytic hydrogenation.But all can't suitability for industrialized production owing to the optionally unified of conversion ratio that can not reach acid and aldehyde.
Summary of the invention
It is big that the present invention aims to provide a kind of specific area, reactivity, to the conversion ratio of acid with to the selectivity height of aromatic aldehyde, reaction temperature is low, and the life-span is longer, and what have that suitability for industrialized production is worth is used to effective catalyst for preparing aromatic aldehyde or fatty aldehyde and preparation method thereof.
Another object of the present invention is to above-mentioned effective catalyst is used to prepare aromatic aldehyde or fatty aldehyde, and provide its preparation method.
For this reason, the present invention is according to Mars, Van, the Krevelen mechanism of hydrogenation of carboxylic acids, selected cheap, the metal with moderate strength---the MnO of oxygen bond enthalpy
2Make compound catalyst with ZnO.And whether contain α hydrogen according to reactant acid and select different metals to modify, select suitable precipitating reagent and temperature simultaneously, prepared composite oxide catalysts with nanoscale.
The present invention is said to be used to prepare the effective catalyst of aromatic aldehyde or fatty aldehyde by the nanometer MnO that modifies through element
2Form with the ZnO composite oxides, at MnO
2, in the ZnO composite oxides, MnO
2: the mol ratio of ZnO is 1: (0.1～9), preferably MnO
2: the mol ratio of ZnO is 1: (0.25～4).The modification element that adds can be a kind of among Cr, In, Cu, the Fe, and the molar ratio range of its addition and composite oxides is (0.001～0.2): 1, and optimal selection is (0.01～0.05): 1.
Add to modify element and can be simple substance or its soluble salt,, join in the composite oxides before then should being chosen in moulding if add with simple substance form; If adopt soluble salt, then should add in the entry dissolving and form sediment with manganese salt and zinc salt with precipitating reagent.
The preparation method that the present invention is said to be used to prepare the effective catalyst of aromatic aldehyde or fatty aldehyde the steps include:
1) gets corresponding M nSO by proportioning
4And ZnSO
4, said proportioning is by MnO
2: the mol ratio of ZnO is 1: (0.1～9), preferably MnO
2: the mol ratio of ZnO is 1: (0.25～4);
2) add to modify element, addition is by modifying element: the mol ratio of composite oxides is (0.001～0.2): 1, and optimal selection is (0.01～0.05): 1, said modification element can be a kind of among Cr, In, Cu, the Fe;
3) add in the entry and dissolve, and form sediment with precipitating reagent, used precipitating reagent can adopt a kind of in ammoniacal liquor, urea, carbonate, the oxalates, and the mol ratio of precipitating reagent and composite oxides is 1: (1～2) is preferably 1: (1.1～1.3);
4) sediment is decomposed, get MnO
2With the ZnO composite oxides, decomposition temperature should be controlled at 150～600 ℃, is preferably 200～450 ℃;
5) with the composite oxides extruded moulding, and calcining, getting required catalyst, calcining heat should be controlled at 300～800 ℃, is preferably 400～600 ℃, and calcination time is 1～10h, is preferably 2～6h.
High-temperature calcination formed after catalyst adopted coprecipitation preparation, the decomposition of control temperature, banded extruder moulding.This catalyst has high reactivity and to the selectivity of aldehyde under suitable hydrogen gas hourly space velocity, carboxylic acid liquid hourly space velocity (LHSV) and suitable hydracid intrinsic standoff ratio condition.
The effective catalyst that the present invention is said to be used to prepare aromatic aldehyde or fatty aldehyde can be used for preparing aromatic aldehyde or fatty aldehyde, and the step of its preparation method is:
1) catalyst that is adopted is by the nanometer MnO that modifies through element
2Form with the ZnO composite oxides, at MnO
2, in the ZnO composite oxides, MnO
2: the mol ratio of ZnO is 1: (0.1～9), preferably MnO
2: the mol ratio of ZnO is 1: (0.25～4), the modification element that adds can be a kind of among Cr, In, Cu, the Fe, the mol ratio of its addition and composite oxides is (0.001～0.2): 1, optimal selection is (0.01～0.05): 1, catalyst is added in the reaction tube, packed height is 15～20 times of reaction tube diameter, and the specific area of said composite oxides should be controlled at 10～150m
2G
-1, be preferably 40～80m
2G
-1
2) feed nitrogen with pressurization or decompression method, make oxygen content reduce to below 0.5% by volume;
3) select suitable activation temperature and soak time to feed the hydrogen reducing activation, activation temperature is 150～450 ℃, and the best is 200～400 ℃, and soak time is 12～96h, and the best is 24～72h;
4) select hydrogen gas hourly space velocity, carboxylic acid liquid hourly space velocity (LHSV) and hydracid intrinsic standoff ratio to feed reactant and react, reaction temperature is 300～450 ℃, and the best is 340～420 ℃, and the initial pressure of hydrogen should be controlled at 10
5～10
6Pa, optimum pressure are 1.2 * 10
5～3.0 * 10
5Pa, hydrogen gas hourly space velocity are 400～1400h
-1, the best is 600～1000h
-1, the liquid hourly space velocity (LHSV) of carboxylic acid is 0.005～0.2h
-1, the best is 0.01～0.100h
-1, the hydracid intrinsic standoff ratio is (150～10): 1, and the best is (100～40): 1;
5) collect condensed product, analyze its composition.
Aromatic acid or aromatic esters refer to a kind of in benzoic acid, methyl benzoate, the dimethyl terephthalate (DMT).Benzoic acid, methyl benzoate, dimethyl terephthalate (DMT) can be highly finished product or thick product.Aromatic aldehyde refers to benzaldehyde, terephthalaldehyde, a kind of in the carboxyl benzaldehyde.That straight chain fatty acid refers to is sad, a kind of in the capric acid, Ye Gui a, famous physician of the Qing Dynasty acid.The straight chain fatty aldehyde refers to a kind of in octanal, capraldehyde, the Ye Gui a, famous physician of the Qing Dynasty aldehyde.
Hydrogen can or contain small amount of nitrogen and the mist of water vapour with pure hydrogen.
Mars, Van, Krevelen mechanism point out that the mechanism that the carboxylic acid catalytic hydrogenation generates corresponding aldehyde is (1) H
2Molecular dissociation is adsorbed on catalyst surface, is combined into H with the oxygen atom of catalyst
2Thereby O forms the partial oxygen space at catalyst surface; (2) hydroxyl oxygen of carboxylic acid is caught by the oxygen space at catalyst surface and is reduced to aldehyde.And the speed of surface reaction by the slow step in two steps rapid determine the metal of catalyst---the oxygen bond enthalpy is excessive or too small all to reacting unfavorable.If metal---the oxygen bond enthalpy is too big, then is unfavorable for the formation in first step oxygen space, otherwise is unfavorable for that then the second step oxygen space catches the hydroxyl oxygen in the carboxylic acid.Therefore, the present invention has selected for use and has had medium metal---the MnO of oxygen bond enthalpy
2, ZnO is as major catalyst.
The present invention makes the oxide that makes have nanoscale by selecting suitable precipitating reagent and deposition condition, because the specific area of catalyst is big, and its catalytic activity height, reaction temperature reduces greatly, thereby is improved the service life of catalyst.
The purpose that adds the modification element is to increase the heat endurance and the activity stability of catalyst.Select suitable modification element and addition, shortened the induction period of catalyst, the active constant phase prolongs.
In sum, main feature of the present invention is: selected to have medium metal---the composite oxides of oxygen bond enthalpy as catalyst to improve selectivity to aldehyde; Select suitable precipitating reagent and deposition condition to have the oxide of nanoscale, and the control by decomposition temperature and calcining heat, guaranteed that catalyst has high activity, high to the selectivity of aldehyde and long life-span with preparation.
Among the present invention, the main accessory substance that is prepared benzaldehyde by benzoic acid hydrogenation is benzene, toluene and phenmethylol, and wherein benzene is the product of benzoic acid high temperature decarboxylation base, can recently prevent its generation by control temperature, the suitable hydracid dividing potential drop of adjusting; Toluene and phenmethylol then are the products of excessive hydrogenation, for avoiding its generation, should regulate suitable hydrogen gas hourly space velocity and suitable product condensation temperature simultaneously according to activity of such catalysts situation control suitable reaction temperature.In addition, add the modification element of some heat endurance that can increase catalyst and activity stability, shortened the induction period of catalyst, the active constant phase prolongs, and this also is favourable to the generation that reduces above accessory substance.
The specific embodiment
The present invention is further illustrated below by several specific embodiments:
Embodiment 1: press MnO
2: the ratio that ZnO (mol ratio, down together) was respectively 1: 9,1: 7,1: 6,1: 4,1: 2,1: 1,2: 1,4: 1,6: 1,7: 1,9: 1 takes by weighing corresponding M nSO
4(A.R) and ZnSO
4(A.R), in modifying element: the ratio that composite oxides were respectively 0.02: 1,0.01: 1,0.05: 1,0.001: 1,0.03: 1,0.2: 1,0.1: 1,0.04: 1,0.003: 1,0.005: 1,0.15: 1 takes by weighing corresponding C r
2(SO
4)
3, three kinds of salt are put into the container back add deionized water till salt all dissolves.
In precipitating reagent: the ratio that composite oxides were respectively 2: 1,1.2: 1,1.3: 1,1.9: 1,1.1: 1,1.8: 1,1.7: 1,1.6: 1,1.2: 1,1.5: 1,1.4: 1 is measured certain density ammoniacal liquor, place suitable drop bottle, slowly splash in the salting liquid again, meanwhile, stirring salting liquid slowly separates out precipitation.After treating that precipitation fully, leave standstill solution, spend suction filtration after the deionised water 3 times behind the mother liquor that inclines.Filter cake is dehydrated at 110 ℃, and obtain ultra-fine MnO 300,200,240,500,600,450,150,280,220,350,180 ℃ of following decomposition respectively
2With the ZnO composite oxides.With this composite oxides extruded moulding and respectively at calcining respectively in 500,450,700,600,400,300,350,500,420,480,520 ℃ the Muffle furnace 4,3,5,2,6,4,10,8,9,7,1 hours, the gained catalyst is expressed as A, B, C, D, E, F, G, H, I, J, K successively in above ratio order at last.
Embodiment 2: the ammoniacal liquor that replaces embodiment 1 respectively with ammonium carbonate, oxalic acid, precipitating reagent: composite oxides are 1.2: 1, add deionized water in the ammonium carbonate of above-mentioned amount of calculation or the oxalic acid to solid chemical compound all (can consider to use hot water during dissolving oxalic acid) till the dissolving.All the other are with embodiment 1.Prepared catalyst is expressed as A successively
1, B
1, C
1, D
1, E
1, F
1, G
1, H
1, I
1, J
1, K
1(making precipitating reagent) and A with ammonium carbonate
2, B
2, C
2, D
2, E
2, F
2, G
2, H
2, I
2, J
2, K
2(making precipitating reagent) with oxalic acid.
Embodiment 3: they with the ammonium carbonate precipitating reagent, and FeCl
3For modifying the salt of element, all the other are with embodiment 1, and the catalyst that makes is expressed as A
1', B
1', C
1', D
1', E
1', F
1', G
1', H
1', I
1' J
1', K
1'.
Embodiment 4: select commercially available MnO
2After mixing in the ratio of embodiment 1 with ZnO, straight forming and through calcining (calcination condition is identical with embodiment 1) one-tenth catalyst, this catalyst is designated as A
0, B
0, C
0, D
0, E
0, F
0, G
0, H
0, I
0, J
0, K
0
Embodiment 5: get the above-mentioned A of removing
1', B
1', C
1', D
1', E
1', F
1', G
1', H
1', I
1' J
1', K
1' outer each 0.025kg of catalyst, the control reaction temperature is 300 ℃, the initial pressure of hydrogen is 3.0 * 10
5Pa, hydracid intrinsic standoff ratio are 50: 1, and para Toluic Acid's gas-phase catalytic hydrogenation has obtained following experimental result:
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| A 0 | 0.1 | 700 | 85 | 70 | 0.050 |
| B 0 | 0.1 | 700 | 80 | 72 | 0.049 |
| C 0 | 0.1 | 700 | 78 | 72 | 0.048 |
| D 0 | 0.1 | 700 | 75 | 73 | 0.047 |
| E 0 | 0.1 | 700 | 75 | 74 | 0.048 |
| F 0 | 0.1 | 700 | 75 | 75 | 0.048 |
| G 0 | 0.1 | 700 | 73 | 76 | 0.048 |
| H 0 | 0.1 | 700 | 70 | 76 | 0.046 |
| I 0 | 0.1 | 700 | 65 | 77 | 0.044 |
| J 0 | 0.1 | 700 | 60 | 78 | 0.040 |
| K 0 | 0.1 | 700 | 56 | 80 | 0.039 |
| A | 0.1 | 700 | 88 | 90 | 0.069 |
| B | 0.1 | 700 | 90 | 92 | 0.072 |
| C | 0.1 | 700 | 92 | 93 | 0.074 |
| D | 0.1 | 700 | 94 | 93 | 0.076 |
| E | 0.1 | 700 | 95 | 94 | 0.078 |
| F | 0.1 | 700 | 95 | 96 | 0.080 |
| G | 0.1 | 700 | 94 | 96 | 0.079 |
| H | 0.1 | 700 | 92 | 95 | 0.075 |
| I | 0.1 | 700 | 90 | 95 | 0.074 |
| J | 0.1 | 700 | 88 | 94 | 0.072 |
| K | 0.1 | 700 | 86 | 92 | 0.070 |
| A 1 | 0.1 | 700 | 90 | 92 | 0.072 |
| B 1 | 0.1 | 700 | 92 | 94 | 0.073 |
| C 1 | 0.1 | 700 | 94 | 95 | 0.077 |
| D 1 | 0.1 | 700 | 94 | 96 | 0.078 |
| E 1 | 0.1 | 700 | 95 | 96 | 0.080 |
| F 1 | 0.1 | 700 | 96 | 97 | 0.082 |
| G 1 | 0.1 | 700 | 96 | 96 | 0.081 |
| H 1 | 0.1 | 700 | 95 | 95 | 0.078 |
| I 1 | 0.1 | 700 | 95 | 94 | 0.077 |
| J 1 | 0.1 | 700 | 94 | 94 | 0.077 |
| K 1 | 0.1 | 700 | 93 | 92 | 0.073 |
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| A 2 | 0.1 | 700 | 92 | 94 | 0.073 |
| B 2 | 0.1 | 700 | 94 | 95 | 0.077 |
| C 2 | 0.1 | 700 | 95 | 96 | 0.080 |
| D 2 | 0.1 | 700 | 96 | 96 | 0.081 |
| E 2 | 0.1 | 700 | 96 | 98 | 0.082 |
| F 2 | 0.1 | 700 | 97 | 98 | 0.083 |
| G 2 | 0.1 | 700 | 96 | 98 | 0.082 |
| H 2 | 0.1 | 700 | 96 | 97 | 0.082 |
| I 2 | 0.1 | 700 | 95 | 97 | 0.080 |
| J 2 | 0.1 | 700 | 95 | 96 | 0.080 |
| K 2 | 0.1 | 700 | 94 | 96 | 0.079 |
Embodiment 6: get the catalyst identical with embodiment 5, the control reaction temperature is 420 ℃, and the hydracid intrinsic standoff ratio is 50: 1, and the gas-phase catalytic hydrogenation of benzaldehyde has been obtained following experimental result:
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| A 0 | 0.1 | 700 | 92 | 45 | 0.040 |
| B 0 | 0.1 | 700 | 94 | 48 | 0.035 |
| C 0 | 0.1 | 700 | 95 | 50 | 0.032 |
| D 0 | 0.1 | 700 | 95 | 50 | 0.025 |
| E 0 | 0.1 | 700 | 96 | 52 | 0.023 |
| F 0 | 0.1 | 700 | 96 | 55 | 0.025 |
| G 0 | 0.1 | 700 | 96 | 60 | 0.025 |
| H 0 | 0.1 | 700 | 97 | 64 | 0.022 |
| I 0 | 0.1 | 700 | 96 | 68 | 0.018 |
| J 0 | 0.1 | 700 | 95 | 70 | 0.014 |
| K 0 | 0.1 | 700 | 94 | 72 | 0.010 |
| A | 0.1 | 700 | 88 | 90 | 0.067 |
| B | 0.1 | 700 | 90 | 92 | 0.068 |
| C | 0.1 | 700 | 92 | 93 | 0.070 |
| D | 0.1 | 700 | 94 | 93 | 0.072 |
| E | 0.1 | 700 | 95 | 94 | 0.072 |
| F | 0.1 | 700 | 95 | 96 | 0.075 |
| G | 0.1 | 700 | 94 | 96 | 0.074 |
| H | 0.1 | 700 | 92 | 95 | 0.072 |
| I | 0.1 | 700 | 90 | 95 | 0.070 |
| J | 0.1 | 700 | 88 | 94 | 0.068 |
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| K | 0.1 | 700 | 86 | 92 | 0.066 |
| A 1 | 0.1 | 700 | 90 | 92 | 0.070 |
| B 1 | 0.1 | 700 | 92 | 94 | 0.073 |
| C 1 | 0.1 | 700 | 94 | 95 | 0.074 |
| D 1 | 0.1 | 700 | 94 | 96 | 0.075 |
| E 1 | 0.1 | 700 | 95 | 96 | 0.077 |
| F 1 | 0.1 | 700 | 96 | 97 | 0.076 |
| G 1 | 0.1 | 700 | 96 | 96 | 0.075 |
| H 1 | 0.1 | 700 | 95 | 95 | 0.074 |
| I 1 | 0.1 | 700 | 95 | 94 | 0.074 |
| J 1 | 0.1 | 700 | 94 | 94 | 0.073 |
| K 1 | 0.1 | 700 | 93 | 92 | 0.072 |
| A 2 | 0.1 | 700 | 92 | 94 | 0.072 |
| B 2 | 0.1 | 700 | 94 | 95 | 0.074 |
| C 2 | 0.1 | 700 | 95 | 96 | 0.076 |
| D 2 | 0.1 | 700 | 96 | 96 | 0.078 |
| E 2 | 0.1 | 700 | 96 | 98 | 0.080 |
| F 2 | 0.1 | 700 | 97 | 98 | 0.082 |
| G 2 | 0.1 | 700 | 96 | 98 | 0.082 |
| H 2 | 0.1 | 700 | 96 | 97 | 0.080 |
| I 2 | 0.1 | 700 | 95 | 97 | 0.080 |
| J 2 | 0.1 | 700 | 95 | 96 | 0.080 |
| K 2 | 0.1 | 700 | 95 | 96 | 0.079 |
Embodiment 7: get F
0, D, E, F, G, H, D
1, E
1, F
1, G
1, H
1, D
2, E
2, F
2, G
2, H
2Each 1.4kg of catalyst, the control reaction temperature is 370～380 ℃, the hydracid intrinsic standoff ratio is 50: 1, and the gas-phase catalytic hydrogenation of benzaldehyde has been obtained following experimental result:
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| F 0 | 0.1 | 700 | 70 | 70 | 0.052 |
| D | 0.1 | 700 | 85 | 88 | 0.065 |
| E | 0.1 | 700 | 90 | 90 | 0.071 |
| F | 0.1 | 700 | 95 | 92 | 0.077 |
| G | 0.1 | 700 | 94 | 90 | 0.074 |
| H | 0.1 | 700 | 94 | 88 | 0.073 |
| D 1 | 0.1 | 700 | 88 | 90 | 0.069 |
| E 1 | 0.1 | 700 | 92 | 92 | 0.074 |
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Benzoic acid conversion ratio (%) | Benzaldehyde selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| F 1 | 0.1 | 700 | 95 | 94 | 0.078 |
| G 1 | 0.1 | 700 | 94 | 90 | 0.074 |
| H 1 | 0.1 | 700 | 94 | 90 | 0.074 |
| D 2 | 0.1 | 700 | 90 | 90 | 0.071 |
| E 2 | 0.1 | 700 | 95 | 93 | 0.078 |
| F 2 | 0.1 | 700 | 98 | 96 | 0.082 |
| G 2 | 0.1 | 700 | 97 | 92 | 0.078 |
| H 2 | 0.1 | 700 | 97 | 92 | 0.078 |
Embodiment 8: get catalyst A
1', B
1', C
1', D
1', E
1', F
1', G
1', H
1', I
1' J
1', K
1' each 0.025kg, the control reaction temperature is 350 ℃, the hydracid intrinsic standoff ratio is 60: 1.Sad gas-phase catalytic hydrogenation has been obtained following experimental result:
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Sad conversion ratio (%) | Octanal selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| A 1′ | 0.08 | 600 | 55 | 60 | 0.023 |
| B 1′ | 0.08 | 600 | 56 | 70 | 0.027 |
| C 1′ | 0.08 | 600 | 56 | 70 | 0.027 |
| D 1′ | 0.08 | 600 | 57 | 72 | 0.028 |
| E 1′ | 0.08 | 600 | 57 | 74 | 0.029 |
| F 1′ | 0.08 | 600 | 58 | 75 | 0.030 |
| G 1′ | 0.08 | 600 | 58 | 74 | 0.030 |
| H 1′ | 0.08 | 600 | 56 | 73 | 0.029 |
| I 1′ | 0.08 | 600 | 56 | 72 | 0.028 |
| J 1′ | 0.08 | 600 | 55 | 72 | 0.027 |
| K 1′ | 0.08 | 600 | 54 | 70 | 0.026 |
Embodiment 9: get catalyst D
1', E
1', F
1', G
1', H
1' each 1.4kg, the control reaction temperature is 340～350 ℃, the hydracid intrinsic standoff ratio is 60: 1.Sad gas-phase catalytic hydrogenation has been obtained following experimental result:
| Catalyst | Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Sad conversion ratio (%) | Octanal selectivity (%) | Space-time yield (aldehyde) (kg/kgh) |
| D 1′ | 0.08 | 600 | 50 | 55 | 0.019 |
| E 1′ | 0.08 | 600 | 52 | 58 | 0.021 |
| F 1′ | 0.08 | 600 | 55 | 60 | 0.023 |
| G 1′ | 0.08 | 600 | 54 | 60 | 0.023 |
| H 1′ | 0.08 | 600 | 54 | 58 | 0.022 |
Embodiment 10: press MnO
2: ZnO (mol ratio, down with) be that 1: 1 ratio takes by weighing corresponding manganese sulfate (A.R) and zinc sulfate (A.R), by modifying element: composite oxides be 0.02: 1 ratio take by weighing corresponding chromium sulfate (A.R) put into slowly add behind the enough big container deionized water up to salt is whole dissolve till.
In precipitating reagent: composite oxides are that 1.2: 1 ratio places suitable drop bottle with the oxalic acid (A.R) of amount of calculation, add deionized water up to it all till the dissolving.Then oxalic acid solution is slowly splashed in the salting liquid, meanwhile, stir salting liquid at a slow speed precipitation is slowly separated out.After treating that precipitation fully, leave standstill solution, spend suction filtration after the deionised water 3 times behind the mother liquor that inclines.Filter cake is dehydrated at 110 ℃, and obtain ultra-fine MnO 300 ℃ of following decomposition
2With the ZnO composite oxides.Calcine with this composite oxides extruded moulding and in 500 ℃ Muffle furnace at last and got catalyst A in 4 hours.
Embodiment 11: with manganese sulfate (A.R), zinc sulfate (A.R) and chromium sulfate (A.R) among industrial manganic sulfate, industrial sulphuric acid zinc and the industrial sulphuric acid chromium replacement embodiment 10, all the other steps make catalyst B with embodiment 10 respectively.
Embodiment 12: replace chromium sulfate (A.R) with ferric nitrate (A.R), all the other steps make catalyst C with embodiment 10.
Embodiment 13: get catalyst A 0.025kg, control hydrogen gas hourly space velocity (GHSV) is 700h
-1, benzoic acid liquid hourly space velocity (LHSV) (LHSV) is 0.1h
-1, methyl benzoate liquid hourly space velocity (LHSV) (LHSV) is 0.15h
-1, investigated the influence that reaction temperature para Toluic Acid's (methyl benzoate) gas-phase catalytic hydrogenation prepares the benzaldehyde experimental result respectively.
| Reaction temperature (℃) | Conversion ratio (%) | Selectivity (%) | Space-time yield (kg/kgh) | ||||
| Benzaldehyde | Phenmethylol | Toluene | Benzene | ||||
| 350 | BZ | 70.5 | 98.0 | 0.8 | 0.3 | 0 | 0.060 |
| MB | 55.0 | 95.0 | 2.0 | 0.8 | 0.1 | 0.057 | |
| 360 | BZ | 85.0 | 97.5 | 1.0 | 0.5 | 0.1 | 0.071 |
| MB | 63.0 | 94.2 | 2.5 | 1.2 | 0.15 | 0.064 | |
| 370 | BZ | 95.0 | 97.0 | 1.0 | 0.8 | 0.15 | 0.08 |
| MB | 75.2 | 90.0 | 2.5 | 3.0 | 0.2 | 0.074 | |
| 380 | BZ | 98.5 | 96.0 | 1.5 | 1.5 | 0.2 | 0.082 |
| MB | 80.0 | 87.5 | 3.0 | 4.0 | 0.3 | 0.076 | |
| 390 | BZ | 99.0 | 94.0 | 2.0 | 2.0 | 0.3 | 0.081 |
| MB | 85.0 | 83.0 | 4.5 | 7.0 | 0.5 | 0.076 | |
| 400 | BZ | 99.5 | 90.2 | 3.0 | 3.0 | 0.4 | 0.077 |
| MB | 88.0 | 79.2 | 6.0 | 8.5 | 1.0 | 0.075 | |
| 420 | BZ | 99.8 | 82 | 4.0 | 6.5 | 1.5 | 0.070 |
| MB | 90.2 | 70.5 | 8.5 | 11.0 | 1.5 | 0.067 | |
Embodiment 14, respectively get catalyst A 0.025kg, under 380 ℃, investigated the influence to reaction result of the liquid hourly space velocity (LHSV) of benzoic acid BZ (methyl benzoate MB) and hydrogen gas hourly space velocity.
| Liquid hourly space velocity (LHSV) (LHSV/h -1) | Gas hourly space velocity (GHSV/h -1) | Conversion ratio (%) | Selectivity (%) | ||||
| Benzaldehyde | Phenmethylol | Toluene | Benzene | ||||
| 0.12 | 1100 | BZ | 82.0 | 92.8 | 2.0 | 1.2 | 3.0 |
| MB | 80.3 | 90.1 | 2.2 | 3.2 | 0.3 | ||
| 0.12 | 900 | BZ | 83.4 | 90.5 | 2.3 | 2.2 | 4.0 |
| MB | 82.4 | 89.0 | 2.5 | 4.0 | 0.6 | ||
| 0.12 | 700 | BZ | 85.0 | 88.3 | 2.5 | 3.0 | 5.0 |
| MB | 84.0 | 88.0 | 2.8 | 5.0 | 0.8 | ||
| 0.12 | 500 | BZ | 86.5 | 82.2 | 2.8 | 6.0 | 7.5 |
| MB | 85.8 | 85.2 | 3.0 | 6.3 | 1.8 | ||
| 0.12 | 400 | BZ | 88.0 | 74.0 | 3.5 | 9.0 | 10.0 |
| MB | 87.2 | 80.5 | 3.2 | 8.0 | 3.0 | ||
| 0.14 | 600 | BZ | 73.2 | 74.0 | 1.5 | 0.8 | 18.2 |
| MB | 80.0 | 85.0 | 2.8 | 8.2 | 1.2 | ||
| 0.13 | 600 | BZ | 78.2 | 78.5 | 1.8 | 1.2 | 14.0 |
| MB | 82.2 | 84.0 | 3.0 | 9.2 | 0.8 | ||
| 0.12 | 600 | BZ | 86.0 | 86.0 | 2.0 | 1.5 | 6.5 |
| MB | 85.0 | 83.2 | 3.2 | 10.5 | 0.6 | ||
| 0.11 | 600 | BZ | 93.0 | 91.5 | 2.2 | 1.8 | 2.0 |
| MB | 88.2 | 82.3 | 3.4 | 11.5 | 0.5 | ||
| 0.10 | 600 | BZ | 98.5 | 94.0 | 2.2 | 2.0 | 0.2 |
| MB | 90.0 | 81.2 | 3.6 | 12.3 | 0.3 | ||
| 0.09 | 600 | BZ | 99.8 | 96.0 | 1.0 | 2.2 | 0.1 |
| MB | 92.2 | 80.0 | 4.0 | 13.2 | 0.1 | ||
Embodiment 15, get catalyst A 1.40kg, and the control reaction temperature is 380 ± 5 ℃, and acid (ester) liquid hourly space velocity (LHSV) is 0.1h
-1, the hydrogen gas hourly space velocity is 650 ± 50h
-1, para Toluic Acid's's (methyl benzoate) gas-phase catalytic hydrogenation has obtained following experimental result:
| Reactant | Conversion ratio (%) | Selectivity (%) | Space-time yield (aldehyde) (kg/kgh) | |||
| Benzaldehyde | Phenmethylol | Toluene | Benzene | |||
| Benzoic acid | 98.0 | 94.5 | 1.0 | 2.2 | 0.8 | 0.08 |
| Methyl benzoate | 89.0 | 80.2 | 4.0 | 10.2 | 0.5 | 0.054 |
Embodiment 16, get catalyst B 140kg, and the control reaction temperature is (370 ± 5) ℃, and the acid solution hourly space velocity is 0.08h
-1, the hydrogen gas hourly space velocity is 650h
-1, para Toluic Acid's's (industrial goods) gas-phase catalytic hydrogenation has obtained following experimental result:
| Reactant | Conversion ratio (%) | Selectivity (%) | Space-time yield (aldehyde) (kg/kgh) | |||
| Benzaldehyde | Phenmethylol | Toluene | Benzene | |||
| Benzoic acid | 99.0 | 83.2 | 5.0 | 7.5 | 1.0 | 0.057 |
Embodiment 17, get catalyst C1.40kg, and the control reaction temperature is (350 ± 5) ℃, and the acid solution hourly space velocity is 0.08h
-1, the hydrogen gas hourly space velocity is 600h
-1, the gas-phase catalytic hydrogenation of sad (industrial goods) has been obtained following experimental result:
| Reactant | Conversion ratio (%) | Selectivity (%) | Space-time yield (aldehyde) (kg/kgh) | ||
| Octanal | Octanol | 15 ketone | |||
| Sad | 60 | 75.0 | 3.0 | 18.2 | 0.031 |
Embodiment 18, get catalyst A 0.025kg, and the control reaction temperature is 370 ℃, and the ester liquid hourly space velocity (LHSV) is 0.10h
-1, the hydrogen gas hourly space velocity is 800h
-1, the gas-phase catalytic hydrogenation of dimethyl terephthalate (DMT) has been obtained following experimental result:
| Reactant | Conversion ratio (%) | Selectivity (%) | Space-time yield (aldehyde) (kg/kgh) | ||
| Single aldehyde | Dialdehyde | Paraxylene | |||
| Dimethyl terephthalate (DMT) | 70.5 | 60.2 | 16.0 | 9.5 | 0.044 |
Claims (7)
1, is used to prepare the catalyst of aromatic aldehyde or fatty aldehyde, it is characterized in that the nanometer MnO that modifies by through element
2Form with the ZnO composite oxides, at MnO
2, in the ZnO composite oxides, MnO
2: the mol ratio of ZnO is 1: 0.1～9, and the modification element of adding is a kind of among Cr, In, Cu, the Fe, and the mol ratio of its addition and composite oxides is 0.001～0.2: 1; Its preparation method is:
1) gets corresponding M nSO by proportioning
4And ZnSO
4, described proportioning is by MnO
2: the mol ratio of ZnO is 1: 0.1～9;
2) get the soluble salt of a certain amount of modification element by proportioning, described proportioning is by modifying element: described MnO
2With the mol ratio of ZnO composite oxides be 0.001～0.2: 1, described modification element is a kind of among Cr, In, Cu, the Fe;
3) with step 1) and 2) material got adds and dissolves in the entry, and forms sediment with precipitating reagent, and used precipitating reagent adopts a kind of in ammoniacal liquor, urea, carbonate, the oxalates, and the mol ratio of precipitating reagent and composite oxides is 1: 1～2;
4) sediment is decomposed 150～600 ℃ temperature;
5) then carry out extrusion modling, and calcining, getting required catalyst, calcining heat is 300～800 ℃, calcination time is 1～10h.
2, the catalyst that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 1 is characterized in that at MnO
2, in the ZnO composite oxides, MnO
2: the mol ratio of ZnO is 1: 0.25～4, and its addition of modification element of adding and the mol ratio of composite oxides are 0.01～0.05: 1.
3, the catalyst that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 1 is characterized in that in step 1), and described proportioning is by MnO
2: the mol ratio of ZnO is 1: 0.25～4; In step 2) in, the addition of modifying element is by modifying element: the mol ratio of composite oxides is 0.01～0.05: 1; In step 3), the mol ratio of precipitating reagent and composite oxides is 1: 1.1～1.3; In step 4), the sediment decomposition temperature is 200～450 ℃; In step 5), calcining heat is 400～600 ℃, and calcination time is 2～6h.
4, the catalyst that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 1 is used to prepare aromatic aldehyde or fatty aldehyde.
5, the catalyst that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 1 is used to prepare the method for aromatic aldehyde or fatty aldehyde, it is characterized in that the steps include:
1) catalyst that is adopted is by the nanometer MnO that modifies through element
2Form with the ZnO composite oxides, at MnO
2, in the ZnO composite oxides, MnO
2: the mol ratio of ZnO is 1: 0.1～9, the modification element that adds is a kind of among Cr, In, Cu, the Fe, the mol ratio of its addition and composite oxides is 0.001～0.2: 1, catalyst is added in the reaction tube, packed height is 15～20 times of reaction tube diameter, and the specific area of described composite oxides is 10～150m
2G
-1
2) feed nitrogen with pressurization or decompression method, make oxygen content reduce to below 0.5% by volume;
3) select suitable activation temperature and soak time to feed the hydrogen reducing activation, activation temperature is 150～450 ℃, and soak time is 12～96h;
4) select hydrogen gas hourly space velocity, carboxylic acid liquid hourly space velocity (LHSV) and hydracid intrinsic standoff ratio to feed reactant and react, reaction temperature is 300～450 ℃, and the initial pressure of hydrogen is 10
5～10
6Pa, hydrogen gas hourly space velocity are 400～1400h
-1, the liquid hourly space velocity (LHSV) of carboxylic acid is 0.005～0.2h
-1, the hydracid intrinsic standoff ratio is 150～10: 1;
5) collect condensed product, analyze its composition.
6, the method that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 5 is characterized in that in step 1) MnO
2: the mol ratio of ZnO is 1: 0.25～4, and modifying the addition of element and the mol ratio of composite oxides is 0.01～0.05: 1, and the specific area of described composite oxides is 40～80m
2G
-1In the activation temperature described in the step 3) is 200～400 ℃, and soak time is 24～72h; In step 4), reaction temperature is 340～420 ℃, and the initial pressure of hydrogen is 1.2 * 10
5～3.0 * 10
5Pa, hydrogen gas hourly space velocity are 600～1000h
-1, the liquid hourly space velocity (LHSV) of carboxylic acid is 0.01～0.100h
-1, the hydracid intrinsic standoff ratio is 100～40: 1.
7, the method that is used to prepare aromatic aldehyde or fatty aldehyde as claimed in claim 5 is characterized in that described aromatic aldehyde refers to benzaldehyde, terephthalaldehyde, a kind of in the carboxyl benzaldehyde.
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