CN101138729A - Catalyzer for liquid-phase catalytic oxidation producing of chlorobenzaldehyde by using p-chlorotoluene - Google Patents
Catalyzer for liquid-phase catalytic oxidation producing of chlorobenzaldehyde by using p-chlorotoluene Download PDFInfo
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- CN101138729A CN101138729A CNA2007101803021A CN200710180302A CN101138729A CN 101138729 A CN101138729 A CN 101138729A CN A2007101803021 A CNA2007101803021 A CN A2007101803021A CN 200710180302 A CN200710180302 A CN 200710180302A CN 101138729 A CN101138729 A CN 101138729A
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Abstract
The present invention relates to a catalyst for preparation of p-chlorobenzaldehyde through liquid phase catalytic oxidation. The catalyst is a compound catalyst, which is formed by loading an element provided with catalytic activity on a carrier of aluminum oxide. Active componentS of the catalyst of the present invention are cobalt and manganese, which are loaded on the carrier of the aluminum oxide. The molar ratio of cobalt and manganese is 0.1-5. In addition, the active components of the present invention can also comprise nickel, copper, iron, cerium, lanthanum, magnesium or zirconium and bromine, besides cobalt and manganese. The catalyst of the present invention is applied the reaction course for preparation of p-chlorobenzaldehyde, and is characterized by the simple technique, the high p-chlorobenzaldehyde reaction yield ratio, the low reaction temperature, the simple catalyst separation, and so on.
Description
Technical field
The present invention relates to a kind of support type composite catalyst and its production and use, be a kind of support type composite catalyst that is carried on the carrier alundum exactly, particularly a kind ofly be used for the catalyst that the parachlorotoluene liquid phase catalytic oxidation prepares 4-chloro-benzaldehyde.
Background technology
4-chloro-benzaldehyde is a kind of very important chemical intermediate, and very important using value is all being arranged aspect medicine, agricultural chemicals, the dyestuff.Along with the exploitation of using, the increase of market demand makes the research of 4-chloro-benzaldehyde become a heat subject.Aspect medical, be used to make sedative fenarol, phenalgin butyric acid, veterinary drug robenidine hydrochloride etc.; Aspect agricultural chemicals, uniconazole P, paclobutrazol, chlorocinnamaldehyde and the herbicide that the is used for synthetic coordinate plant growth diffusing important intermediate of fighting the enemy, new pyrrole class insecticidal/acaricidal agent chlorfenapyr, triazole bactericidal agent new varieties triticonazole synthetic; Aspect dyestuff, be used for the intermediate of the gorgeous orchid-6B of synthetic acidic etc.4-chloro-benzaldehyde also can be used as the intermediate of textile auxiliary and photosensitive material.The production capacity of the 4-chloro-benzaldehyde of China is lower at present, main dependence on import.
The liquid phase catalytic oxidation of parachlorotoluene is the main method of preparation 4-chloro-benzaldehyde and parachlorobenzoic-acid, and the traditional method of these products is chlorinolysis or prepares as oxidant with heavy metallic salt.Traditional method exists the chlorination degree of depth and is difficult to problems such as control, serious environmental pollution and technology very complicated.
Along with the attention of people's environmental pollution, researcher turns to viewpoint the Green Chemistry aspect gradually.With hydrogen peroxide, oxygen, air is that oxidant realizes that the oxidation of parachlorotoluene obtains 4-chloro-benzaldehyde, develops new catalyst.
(Applied Catalysis A:General 143,1996 111-124) with the hydrogen peroxide is oxidant to A.P.Singh etc., and acetonitrile is a solvent, and the V-Si molecular sieve is a catalyst, has realized the oxidation of parachlorotoluene under condition of high voltage, has obtained 4-chloro-benzaldehyde.The conversion ratio of this method parachlorotoluene has only 13.4%, and the selectivity of 4-chloro-benzaldehyde is 64.0%, and the yield of 4-chloro-benzaldehyde only is 8.6%, and its reaction time reaches 12 hours; Also produce other accessory substance simultaneously.The shortcoming of this method is that conversion ratio is low, severe reaction conditions and reaction time are long.
Chinese patent CN1724500, Wang Jiaqiang etc. are oxidant with the hydrogen peroxide, and acetate is solvent, and the employing mesoporous material is a heterogeneous catalysis, realize the oxidation of parachlorotoluene under the condition of atmospheric low-temperature, have obtained 4-chloro-benzaldehyde.The conversion ratio of parachlorotoluene is 50%, and the selectivity of 4-chloro-benzaldehyde is 99%.The advantage of this method is that conversion ratio and selectivity are all very high; Shortcoming is that the Preparation of Catalyst difficulty is big, and oxidant is a hydrogen peroxide, and the reaction time is long, generally needs 10 hours, makes cost very high.
Family peace (the Catalysis Communications 8 of army (An-Jun Hu), 2007,1279-1283) waiting with oxygen is oxidant, is solvent with acetate-aqueous mixtures, with cobalt salt, manganese salt is catalyst, and normal pressure, cryogenic conditions reaction 10h have down obtained 4-chloro-benzaldehyde.The conversion ratio of parachlorotoluene is 33.7%, and the selectivity of 4-chloro-benzaldehyde is 66.6%, and the yield of 4-chloro-benzaldehyde is 22.4%.The advantage of this method is that cost is low, technology is simple; Shortcoming is that reaction time length, catalyst can not reuse, conversion ratio is lower.
Summary of the invention
The purpose of this invention is to provide the loaded catalyst that a kind of liquid phase oxidation reaction that is used for parachlorotoluene prepares chlorobenzaldehyde.That this catalyst has is active high, selectivity is good, good stability, can reuse, characteristics such as preparation technology is simple, cost is low.
Second purpose of the present invention provides above-mentioned Preparation of catalysts method.
The 3rd purpose of the present invention is to prepare chlorobenzaldehyde with catalyst of the present invention at the liquid phase oxidation reaction of parachlorotoluene.
Activity of such catalysts component of the present invention is cobalt and manganese, and cobalt and manganese is carried on the carrier alundum, and wherein the mol ratio of cobalt and manganese is 0.1～5.
In the activity of such catalysts component of the present invention, except that cobalt and manganese element, also nickel or copper or iron or cerium or lanthanum or magnesium or zr element can be arranged, nickel wherein, copper, iron, cerium, lanthanum, magnesium or the zirconium amount in catalyst equals 1～5% of cobalt and manganese total amount mol ratio.
In the activity of such catalysts component of the present invention, except that cobalt and manganese element, at least the composition that wantonly two kinds of elements in nickel or copper or iron or cerium or lanthanum or magnesium or the zr element also can be arranged, can be the composition of wantonly three kinds of elements perhaps, the amount of the composition of wantonly at least two elements in the nickel that adds in catalyst, copper, iron, cerium, lanthanum, magnesium or the zr element equals 1～5% of cobalt and manganese total amount mol ratio.
The load capacity of the oxide of catalyst activity component of the present invention on carrier alundum is not less than 15% of gross mass.
Also bromine can be arranged in the catalytic component of the present invention, the content of bromine is 1～100% of cobalt and manganese integral molar quantity.
Preparation of catalysts method of the present invention is that the water soluble salt of catalytic component is soluble in water fully in a quantity as required, again alumina carrier is fallen in the solution that is dissolved with each component, again at the moisture content evaporate to dryness that is not higher than under 70 ℃ the temperature solution, after abundant dry the processing again 350 ℃～700 ℃ following roastings 1～5 hour.
Among the preparation method of the present invention, used water-soluble metal salt is the acetate or the nitrate of metal, and used bromine salt is the sylvite or the sodium salt of bromine.
The used alundum (Al of the present invention is preferably γ-Al
2O
3
Catalyst of the present invention can be used for preparing 4-chloro-benzaldehyde.
Element cobalt and manganese in the catalyst of the present invention have synergy, and these two kinds of active constituent loading can be obtained the catalyst that a kind of liquid phase catalytic oxidation with high activity and high selectivity prepares 4-chloro-benzaldehyde to alundum (Al.If find also that through test its catalytic effect will have further improvement when adding comprises one or more composition in the elements such as Ni, Cu, Fe, Ce, Mg, La, Zr again in the active component.
According to method for preparing catalyst provided by the invention, be with two kinds of active constituent loading to alumina catalyst support, dry then, roasting obtains catalyst.This preparation method's advantage is that active component is uniformly dispersed at carrier surface, synergy takes place between two kinds of metal components make catalyst have high activity and high selectivity.
Reaction needs to be caused by bromine during parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde, and general way is when reaction bromide to be added in the reaction system.Among the present invention bromine is directly added in the catalyst, not only directly initiation reaction, but also make the operating process of entire reaction more simple.
Catalyst provided by the invention can be used for the liquid phase oxidation reaction of parachlorotoluene under the atmospheric low-temperature condition in the presence of molecular oxygen.Being raw material with the parachlorotoluene promptly, is oxidant with oxygen, carries out heterogeneous liquid-phase catalytic oxidation, the preparation 4-chloro-benzaldehyde, and its reaction temperature is lower, and only in 80～120 ℃ of scopes, the ingredient proportion of catalyst and substrate is 1: 5～1: 20 (mass ratio).Show by correlation test, catalyst of the present invention is applied to prepare has characteristics such as technology is simple, 4-chloro-benzaldehyde reaction yield height, reaction temperature is low, catalyst separation is simple in the 4-chloro-benzaldehyde course of reaction.And during with Preparation of Catalyst 4-chloro-benzaldehyde of the present invention, its reaction required time is significantly smaller than prior art.
Description of drawings
Accompanying drawing 1 is the influence of Co/ in the catalyst (Co+Mn) mol ratio to reaction system.
The specific embodiment
Below by specific embodiment in detail the present invention is described in detail:
The present invention has carried out containing the different contrast tests of measuring the catalyst of cobalts, manganese, test reaction conditions: 10ml parachlorotoluene+20ml acetate+2.0g catalyst; Reaction temperature: 110 ℃, reaction time: 6h, oxygen flow: 30ml/min; Used method for preparing catalyst is: with the Co (OAc) of amount of calculation
24H
2O, Mn (OAc)
24H
2O and KBr are dissolved in the 50ml deionized water, add thermal agitation it is dissolved fully; The Al that market is buied again
2O
3Carrier is poured in the above-mentioned solution, at 65 ℃ with its evaporate to dryness; Then in 120 ℃ of dry 3h, 500 ℃ of roastings are 3 hours in the Ma Fufu stove.
The result of test is referring to accompanying drawing 1, as can be seen from the figure: the first, and along with the amount increase of Co, conversion ratio is to increase afterwards earlier to reduce, and reaches maximum 43.7% at 0.8 place, and conversion ratio is not 6.9% when having Co, and conversion ratio is 32.3% when being Co entirely; The second, along with the amount increase of Co, selectivity is to be to reduce trend always, but downward trend is little; The 3rd, the yield of 4-chloro-benzaldehyde also is to reduce along with the amount of Co increases to increase afterwards earlier, reaches maximum 28.1% at 0.8 place.This shows that the synergy of Co and Mn makes activity of such catalysts and selectivity all increase.Test is also found: with γ-Al
2O
2Its effect of carrier is better than the alumina carrier of other crystal formation; Use its effect of metal nitrate and metal acetate basic identical; Use the sodium salt of bromine basic identical with the sylvite effect of using bromine.
Most preferred embodiment of the present invention below is provided.
Embodiment 1: the preparation of catalyst A and active evaluation
With 2.391g (0.0096mol) Co (OAc)
24H
2O, 0.588g (0.0024mol) Mn (OAc)
24H
2O and 0.714g (0.0060mol) KBr is dissolved in the 50ml deionized water, adds thermal agitation it is dissolved fully; With 10.0g γ-Al
2O
3Carrier is poured in the above-mentioned solution, at 65 ℃ with its evaporate to dryness; Then in 120 ℃ of dry 3h, 500 ℃ of roasting 3h in groom's stove.Obtain catalyst.
The 2.0g catalyst is placed the 50ml there-necked flask, with pipette measure the 10ml parachlorotoluene respectively, 30ml acetate joins in the there-necked flask, puts into magneton; Start and stir, condensing reflux (concentrated sulfuric acid fluid-tight of condenser pipe upper end) is heated to 110 ℃; Keep steady temperature, aerating oxygen (30ml/min), reaction 6h, reaction is cooled to room temperature after finishing.Filter to isolate catalyst, parachlorobenzoic-acid and filtrate; Filtrate is regulated pH=8～9 with the NaOH of 1mol/L, uses dichloromethane extraction then, obtains organic facies and water, and the white solid parachlorobenzoic-acid is separated out in water HCl acidifying, and filtration, drying and aforesaid parachlorobenzoic-acid merge, and weigh; Organic facies is used gas chromatographic analysis with after the anhydrous magnesium sulfate drying, obtains 4-chloro-benzaldehyde and to the quality of chlorobenzene methanol.Calculate the conversion ratio of parachlorotoluene at last, to the selectivity of chlorobenzene methanol, 4-chloro-benzaldehyde and parachlorobenzoic-acid, the yield of 4-chloro-benzaldehyde.The conversion ratio 45.0% of parachlorotoluene, to the selectivity 6.5% of chlorobenzene methanol, the selectivity 62.8% of 4-chloro-benzaldehyde, the selectivity 30.7% of parachlorobenzoic-acid, the yield 28.2% of 4-chloro-benzaldehyde.
Embodiment 2: the same A of catalyst
Activity rating is 100 ℃ except reaction temperature, and all the other are with embodiment 1.The conversion ratio 36.6% of parachlorotoluene, to the selectivity 4.4% of chlorobenzene methanol, the selectivity 61.8% of 4-chloro-benzaldehyde, the selectivity 33.8% of parachlorobenzoic-acid, the yield 22.7% of 4-chloro-benzaldehyde.
Embodiment 3: the same A of catalyst
Activity rating is 20ml except solvent acetic acid, and all the other are with embodiment 1.The conversion ratio 43.7% of parachlorotoluene, to the selectivity 7.4% of chlorobenzene methanol, the selectivity 64.3% of 4-chloro-benzaldehyde, the selectivity 28.3% of parachlorobenzoic-acid, the yield 28.1% of 4-chloro-benzaldehyde.
Embodiment 4: the preparation of catalyst B and activity rating
With 0.598g (0.0096mol) Co (OAc)
24H
2O, 2.353g (0.0024mol) Mn (OAc)
24H
2O and 0.714g (0.0060mol) KBr is dissolved in the 50ml deionized water, adds thermal agitation it is dissolved fully; With 10.0g γ-Al
2O
3Carrier is poured in the above-mentioned solution, at 65 ℃ with its evaporate to dryness; Then in 120 ℃ of dry 3h, 500 ℃ of roasting 3h in groom's stove.Obtain catalyst.
Activity rating is with embodiment 1.The conversion ratio 23.5% of parachlorotoluene, to the selectivity 7.4% of chlorobenzene methanol, the selectivity 68.1% of 4-chloro-benzaldehyde, the selectivity 24.5% of parachlorobenzoic-acid, the yield 16.0% of 4-chloro-benzaldehyde.
Embodiment 5: the preparation of catalyst C and activity rating
Except in active component, adding the ZrCl of Co+Mn integral molar quantity 1%
4(be 0.00012mol, 0.028g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 37.5% of parachlorotoluene, to the selectivity 6.5% of chlorobenzene methanol, the selectivity 60.7% of 4-chloro-benzaldehyde, the selectivity 32.9% of parachlorobenzoic-acid, the yield 22.8% of 4-chloro-benzaldehyde.
Embodiment 6: the preparation of catalyst D and activity rating
Except in active component, adding the Fe (NO) of Co+Mn integral molar quantity 1%
39H
2O (be 0.00012mol, 0.049g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 46.0% of parachlorotoluene, to the selectivity 6.3% of chlorobenzene methanol, the selectivity 61.8% of 4-chloro-benzaldehyde, the selectivity 31.9% of parachlorobenzoic-acid, the yield 28.5% of 4-chloro-benzaldehyde.
Embodiment 7: the preparation of catalyst F and activity rating
Except in active component, adding the Ce (NO) of Co+Mn integral molar quantity 1%
36H
2O (be 0.00012mol, 0.052g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 43.8% of parachlorotoluene is to the selection 5.6 property % of chlorobenzene methanol, the selectivity 61.7% of 4-chloro-benzaldehyde, the selectivity 32.8% of parachlorobenzoic-acid, the yield 27.0% of 4-chloro-benzaldehyde.
Embodiment 8: the preparation of catalyst I and activity rating
Except in active component, adding the La (NO) of Co+Mn integral molar quantity 5%
36H
2O (be 0.00060mol, 0.222g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 43.1% of parachlorotoluene, to the selectivity 3.7% of chlorobenzene methanol, the selectivity 59.0% of 4-chloro-benzaldehyde, the selectivity 37.3% of parachlorobenzoic-acid, the yield 25.4% of 4-chloro-benzaldehyde.
Embodiment 9: the preparation of catalyst G and activity rating
Except in active component, adding the Fe (NO) of Co+Mn integral molar quantity 5%
39H
2O (be 0.00060mol, 0.243g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 41.9% of parachlorotoluene, to the selectivity 5.3% of chlorobenzene methanol, the selectivity 62.4% of 4-chloro-benzaldehyde, the selectivity 32.3% of parachlorobenzoic-acid, the yield 26.1% of 4-chloro-benzaldehyde.
Embodiment 10: the preparation of catalyst H and activity rating
Except in active component, adding the Ce (NO) of Co+Mn integral molar quantity 5%
36H
2O (be 0.00060mol, 0.260g) outside, all the other are with embodiment 1.
Activity rating is with embodiment 1.The conversion ratio 42.7% of parachlorotoluene, to the selectivity 5.0% of chlorobenzene methanol, the selectivity 61.4% of 4-chloro-benzaldehyde, the selectivity 33.6% of parachlorobenzoic-acid, the yield 26.2% of 4-chloro-benzaldehyde.
Claims (9)
1. the catalyst of parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde is characterized in that the activity of such catalysts component is cobalt and manganese, and cobalt and manganese is carried on the carrier alundum, and wherein the mol ratio of cobalt and manganese is 0.1～5.
2. the catalyst of parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde according to claim 1, it is characterized in that also having nickel or copper or iron or cerium or lanthanum or magnesium or zr element in the activity of such catalysts component, nickel, copper, iron, cerium, lanthanum, magnesium or the zirconium amount in catalyst equals 1～5% of cobalt and manganese total amount mole.
3. the catalyst of parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde according to claim 1, it is characterized in that also having in the activity of such catalysts component composition of the wantonly at least two kinds of elements in nickel, copper, iron, cerium, lanthanum, magnesium or the zr element, the amount of the composition of the wantonly at least two kinds of elements in the nickel that adds in catalyst, copper, iron, cerium, lanthanum, magnesium or the zr element equals 1～5% of cobalt and manganese total amount mole.
4. according to the catalyst of claim 1 or 2 or 3 described parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehydes, it is characterized in that the catalyst activity component is not less than 15% of gross mass in the load capacity of its oxide on carrier.
5. the catalyst of parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde according to claim 4 is characterized in that also having bromine in the catalytic component, and the content of bromine is 1～100% of cobalt and manganese integral molar quantity.
6. the Preparation of catalysts method of described any parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde of claim 5, it is characterized in that the water soluble salt of catalytic component soluble in water fully in a quantity as required, again alumina carrier is fallen in the solution that is dissolved with each active component, again at the moisture content evaporate to dryness that is lower than under 70 ℃ the temperature solution, through fully downloading sintering 1～5 hour at 350 ℃～700 ℃ again after dry the processing.
7. preparation method according to claim 6 is characterized in that water-soluble metal salt used in the process is the acetate or the nitrate of metal, and used bromine salt is the sylvite or the sodium salt of bromine.
8. preparation method according to claim 7 is characterized in that used alundum (Al is γ-Al
2O
3
9. the catalyst of described any parachlorotoluene liquid phase catalytic oxidation system 4-chloro-benzaldehyde of claim 1 to 5 is used to prepare 4-chloro-benzaldehyde.
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| CN109020801A (en) * | 2018-09-04 | 2018-12-18 | 江苏超跃化学有限公司 | The recovery method of by-product parachlorobenzoic-acid in a kind of p-chlorobenzaldehyde production process |
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| CN112079702A (en) * | 2020-08-31 | 2020-12-15 | 中盐常州化工股份有限公司 | Preparation method of chlorobenzaldehyde |
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| CN114768845A (en) * | 2022-03-22 | 2022-07-22 | 浙江大学 | Preparation method and application of nitrogen-doped carbon quantum dot/bimetal supported catalyst |
| CN114768845B (en) * | 2022-03-22 | 2023-10-13 | 浙江大学 | Preparation method and application of nitrogen-doped carbon quantum dot/bimetal supported catalyst |
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