CN101786947B - Method for preparing benzaldehyde by oxidizing toluene - Google Patents
Method for preparing benzaldehyde by oxidizing toluene Download PDFInfo
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- CN101786947B CN101786947B CN 201010127212 CN201010127212A CN101786947B CN 101786947 B CN101786947 B CN 101786947B CN 201010127212 CN201010127212 CN 201010127212 CN 201010127212 A CN201010127212 A CN 201010127212A CN 101786947 B CN101786947 B CN 101786947B
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- toluene
- phenyl aldehyde
- ion
- benzaldehyde
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 title claims abstract description 351
- 238000000034 method Methods 0.000 title claims abstract description 57
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 4
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 4
- -1 phenyl aldehyde Chemical class 0.000 claims description 77
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 33
- 230000009466 transformation Effects 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- QMZIDZZDMPWRHM-UHFFFAOYSA-L manganese(2+);dibenzoate Chemical compound [Mn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 QMZIDZZDMPWRHM-UHFFFAOYSA-L 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 229910001430 chromium ion Inorganic materials 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VFGRVPOWXBYJFQ-UHFFFAOYSA-N benzoic acid;vanadium Chemical compound [V].OC(=O)C1=CC=CC=C1 VFGRVPOWXBYJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229960002903 benzyl benzoate Drugs 0.000 abstract 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 17
- 229960004217 benzyl alcohol Drugs 0.000 description 17
- 235000019445 benzyl alcohol Nutrition 0.000 description 17
- 239000007789 gas Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000004821 distillation Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 238000005194 fractionation Methods 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- XRYKMKMQJBOVES-UHFFFAOYSA-N C(C1=CC=CC=C1)OC=O.C1=CC=CC=C1 Chemical compound C(C1=CC=CC=C1)OC=O.C1=CC=CC=C1 XRYKMKMQJBOVES-UHFFFAOYSA-N 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000010808 liquid waste Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000012773 agricultural material Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing benzaldehyde by oxidizing toluene. Currently, no method for producing the benzaldehyde has simple reactions as well as high toluene percent conversion and benzaldehyde selectivity. The raw materials comprise 1-59% of toluene, 0.005-5% of master catalyst, oxygen source and 40-98% of benzyl benzoate, wherein the mol ratio of oxygen molecules in the oxygen source to toluene is (0.3-3):1, and the master catalyst is one or more than two of cobalt ions, manganese ions, vanadium ions and nickel ions. The method comprises the following steps: mixing the toluene, master catalyst and benzyl benzoate in a reactor; at the temperature of 140-300 DEG C and under the absolute pressure of 0.05-1.0 Mpa, introducing the oxygen source into the mixed liquor to react for more than 2 hours; and refining the mixed liquor to obtain the benzaldehyde. The toluene percent conversion is higher than 30%, and the benzaldehyde selectivity is higher than 70%. The invention has the advantages of simple reaction, energy conservation, environmental protection, easy separation of products and solvent, and high toluene percent conversion and benzaldehyde selectivity.
Description
Technical field
The present invention relates to a kind of method for preparing phenyl aldehyde, especially relate to a kind of method of preparing benzaldehyde by oxidizing toluene.
Background technology
Phenyl aldehyde is a kind of important fine chemical product, is widely used in the industrial circles such as medicine, dyestuff, spices, agricultural chemicals and material.The production method of present disclosed preparation phenyl aldehyde mainly contains following three kinds: chlorination toluene hydrolysis method, phenylformic acid (ester) reduction method and toluene direct oxidation method, wherein the toluene direct oxidation method comprises vapor phase process and liquid phase method.
Inevitably contain chlorine in the phenyl aldehyde of producing by traditional chlorination toluene hydrolysis method, and the phenyl aldehyde that is used in the industries such as medicine and spices can not contain chlorine, the range of application of the phenyl aldehyde that therefore produces by the chlorination toluene hydrolysis method has been subject to certain restriction, the U.S. that such as the patent No. is US4229379 and US2816144 produces phenyl aldehyde by the chlorination toluene hydrolysis method, this method more disadvantageously can produce a large amount of waste water in process of production, and the processing of these waste water is very difficult, thereby caused larger threat to environment.
Phenylformic acid (ester) reduction method refers to be generated by catalytic hydrogenating reduction by phenylformic acid or benzoic ether the method for phenyl aldehyde, although the transformation efficiency of this method and selectivity are all very high, as being described in the United States Patent (USP) of US4987265 in the patent No., transformation efficiency can reach 100% in the greatly excessive situation of hydrogen, and the selectivity of phenyl aldehyde also can reach 95%; Be that the selectivity of phenyl aldehyde can reach 95.63% described in the Chinese patent of CN101456798 in the patent No..Be in the Chinese patent of CN1271717 in the patent No., disclose a kind of method by benzoic ether hydrogenation synthesizing benzaldehyde, the per pass conversion of the method reaches 98%, and the selectivity of phenyl aldehyde reaches 87.5%.Be in the Chinese patent of CN1876616 in the patent No., the selectivity of phenyl aldehyde reaches 99% in the disclosed gas phase hydrogenation method, and yield can reach more than 95%.But the temperature of reaction of phenylformic acid (ester) reduction method must be more than 300 ℃, and energy consumption is very large; Industrial, phenylformic acid is substantially all produced by toluene oxidation, if produce benzoic ether then also need further esterification, and being exactly toluene oxidation originally, phenyl aldehyde produced benzoic intermediate product, be after toluene oxidation generates phenyl aldehyde, phenyl aldehyde continues oxidation again and generates phenylformic acid, and phenylformic acid is again by going back the original production phenyl aldehyde, thereby greatly improved production cost, caused very uneconomical of this production method.
Toluene direct oxidation under gas phase or liquid-phase condition generates the method that phenyl aldehyde is comparatively economy and environmental protection.Be in the United States Patent (USP) of US1321959 as far back as the patent No.s in 1919, disclose a kind of method of gas phase oxidation of toluene producing benzaldehyde, the temperature of reaction of the method is 500-700 ℃, but in this patent, do not provide transformation efficiency and related data optionally, it is reported, a large amount of carbon dioxide generating is arranged in above-mentioned reaction process, the problem that has over oxidation is described.After this, though the gas phase direct oxidation method has development, make progress comparatively slow.Be in the Chinese patent of CN1068755 the patent No.s in 1993, disclose and a kind ofly prepare the method for phenyl aldehyde by gas phase oxidation of toluene that the selectivity of the phenyl aldehyde that is prepared from by the method reaches 60%, the once through yield of phenyl aldehyde can reach 16%.Toluene mainly exists temperature of reaction high by the method for vapor phase process direct oxidation, the defective of the easy over oxidation of toluene, and the selectivity of phenyl aldehyde descends comparatively obvious when improving transformation efficiency.
The patent No. in nineteen sixty-eight is in the United States Patent (USP) of US3387036, the method of a kind of liquid-phase oxidation of toluene producing benzaldehyde and phenylcarbinol is disclosed, this reaction is to carry out under 170-220 ℃ in temperature, the transformation efficiency of phenyl aldehyde only has at most 10% in the method, and the selectivity of phenyl aldehyde is not high yet.Be in the United States Patent (USP) of US6495726 and the patent No. in 2004 to be in the United States Patent (USP) of US6743952 the patent No.s in 2002, all reported in the organic acid medium, under 60-130 ℃ temperature, carry out the method for liquid phase catalytic oxidation toluene take cobalt salt as Primary Catalysts, transformation efficiency at toluene is in the situation of 15-25%, and the selectivity of phenyl aldehyde is 40-50%.Be to gather in the Chinese patent of CN1296937 and at the Chinese patent that the patent No. in 2004 is CN1522996 in the patent No. of calendar year 2001, the method for preparing phenyl aldehyde by liquid phase oxidation is all disclosed, the method adopts a kind of special bromide as promotor, and the selectivity of phenyl aldehyde only has about 20%.Be in the patent of CN1485131 the patent No.s in 2004, the method that a kind of liquid-phase oxidation of toluene prepares phenyl aldehyde and phenylcarbinol is disclosed, in solvent-free situation, the temperature of catalyzed reaction is 180-195 ℃, the pressure of reaction is 0.8-1.2MPa, when the transformation efficiency of toluene was 13%, the overall selectivity of phenyl aldehyde and phenylcarbinol was 86.6%.Be in the Chinese patent of CN1663941 the patent No.s in 2005, disclose a kind of method by the liquid-phase oxidation of toluene producing benzaldehyde, the temperature of this reaction is 90-160 ℃, and when the transformation efficiency of toluene was 10%, the selectivity of phenyl aldehyde reached 62%.Be in the United States Patent (USP) of US7189882 the patent No. in 2007, reported in acetic aid medium that when temperature is 70-180 ℃ and pressure when being 1-80bar, when the transformation efficiency of toluene was not higher than 25%, the selectivity of phenyl aldehyde reached 60-75%.Be in the United States Patent (USP) of US7411099 the patent No.s in 2008, the selectivity of the phenyl aldehyde of report reaches 76%.Be in the Chinese patent of CN101607867 the patent No.s in 2009, adopted the method for multi-stage oxidizing reactor and gas-liquid separator series connection, toluene conversion has reached more than 95%, and the overall selectivity of phenyl aldehyde and phenylcarbinol reaches more than 50%, but the low conversion rate of single-stage reactor, energy consumption is high.Above-mentionedly prepare in the method for phenyl aldehyde by the direct liquid phase oxidation of toluene, all can not satisfy guarantee the toluene high conversion in, guarantee that phenyl aldehyde has highly selective; Although adopt organic acid that situation is taken on a new look to some extent, increased sepn process and introduced other impurity.
Be in the Chinese patent of CN1528726 the patent No.s in 2004, disclose a kind of in acidity or neutral ion liquid and acetic acid mixed solvent, the method for preparing phenyl aldehyde by liquid-phase oxidation aromatic hydrocarbons side chain, at 115-120 ℃ of lower oxidation toluene, when the transformation efficiency of toluene is 42%, the selectivity of phenyl aldehyde is 48%, the selectivity of phenylcarbinol acetic ester is 58%, this method is used a large amount of expensive ionic liquid and acetate solvates, greatly improved production cost, and product separation is comparatively difficult, the market of produced simultaneously phenylcarbinol acetic ester is little, need further to process to reclaim phenylcarbinol and acetic acid, industrial production is uneconomical.
In sum, also there is not at present a kind of reaction simple, energy-conserving and environment-protective, product and solvent are easily separated and reclaim the method for the production phenyl aldehyde that the toluene conversion in the reaction and phenyl aldehyde selectivity are simultaneously higher.
Summary of the invention
The object of the invention is to overcome above shortcomings in the prior art, and provide a kind of reaction simple, energy-conserving and environment-protective, product and solvent are easily separated and reclaim the method for the preparing benzaldehyde by oxidizing toluene that the toluene conversion in the reaction and phenyl aldehyde selectivity are simultaneously higher.
The present invention addresses the above problem the technical scheme that adopts: used raw material comprises that weight percent is the toluene of 1-59% in the method for this preparing benzaldehyde by oxidizing toluene, weight percent is the Primary Catalysts of 0.005-5%, the oxygen source that contains oxygen molecule is as the peruscabin of solvent; The weight percent of described peruscabin is 40-98%, and the oxygen molecule in the described oxygen source and the mol ratio of toluene are (0.3-3): 1, and described Primary Catalysts is one or more in cobalt ion, mn ion, vanadium ion, the nickel ion; Toluene, Primary Catalysts and peruscabin be added to obtain mixed solution in the reactor, then it is 140-300 ℃ in temperature, absolute pressure is under the condition of 0.05-1.0Mpa, passing into the oxygen source that contains oxygen molecule in the above-mentioned mixed solution reacts, reaction times makes phenyl aldehyde at last more than 2 hours to making with extra care through reacted mixed solution; The transformation efficiency of described toluene is more than 30%, and the selectivity of described phenyl aldehyde is more than 70%.
Comprise in the raw material of the present invention that weight percent is the peruscabin of 75-94%.
Raw material of the present invention comprises that also weight percent is the promotor of 0.005-5%, and this promotor is one or more in cupric ion, iron ion, zine ion, the chromium ion.
Raw material of the present invention also comprises the bromide as promotor.
Primary Catalysts of the present invention is one or more in cobaltous benzoate, manganese benzoate, phenylformic acid vanadium, the nickel benzoate.
The temperature of mixed solution of the present invention when reaction is 180-250 ℃, and absolute pressure is 0.08-0.4Mpa.
The oxygen source that contains oxygen molecule of the present invention is air.
The present invention compared with prior art has the following advantages and effect: reaction efficiency is high, and the transformation efficiency of toluene is up to more than 30%, and the selectivity of phenyl aldehyde reaches more than 70%, and the transformation efficiency of toluene and the selectivity of phenyl aldehyde are improved simultaneously greatly; Reaction process is simple, and product and solvent are easily separated, and solvent reclaims easily and utilizes, thereby has reduced production cost and simplified technical process; The waste liquid and the waste residue that produce in the reaction process are few, and clean environment firendly can not produce environment and destroy.
Adopt peruscabin as solvent, peruscabin is that toluene oxidation prepares one of benzoic by product, generated by esterification by toluene oxidation intermediate product phenylcarbinol and phenylformic acid, therefore, the present invention adopts peruscabin can avoid producing new by product as solvent in reaction system, be convenient to product separation and purification, improve the quality of product.
Primary Catalysts metal ion among the present invention is one or more in cobalt ion, mn ion, vanadium ion, the nickel ion, also can select the metal ions such as cupric ion, iron ion, zine ion, chromium ion as promotor.The salt of these several metal ion species can be various organic salts and inorganic salt, for avoiding producing other by products, provides the preferred benzoate of salt of metal ion.Because bromine can produce comparatively serious corrosion to stainless steel equipment, in the situation that conversion unit allows, can also select bromide as promotor.
The present invention can be that intermittent type carries out, and also can be that continous way is carried out, preferred continuous processing on industrial production.If adopt intermittent type to carry out, the present invention can carry out as follows: add solvent benzol benzyl formate, toluene and catalyzer in reactor, pass into air and keep having certain pressure in the reactor, then unlikely boiling when making reaction solution be heated to temperature of reaction is opened heating reaction solution is heated to temperature of reaction, passes into air reaction by certain flow, the water that reaction generates and methylbenzene azeotropic are out, through condensation and oily water separation, toluene turns back in the reactor, and water is as liquid waste disposal.Stopped reaction when reaction reaches processing requirement is closed air.After going out toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid by fractionation by distillation, contain capable of circulation the applying mechanically of mother liquor of peruscabin and catalyzer, unreacted toluene turns back to and continues reaction in the reactor.Toluene per pass conversion when the present invention adopts intermittent type to carry out reaches more than 30%, and the phenyl aldehyde selectivity reaches more than 70%.
If the present invention adopts continous way to carry out, the toluene feed mode can adopt the vapor phase toluene charging, the peruscabin that liquid toluene feed or employing are reclaimed, these three kinds of modes of catalyzer and toluene parallel feeding, the preferred peruscabin that reclaims, the mode of catalyzer and toluene parallel feeding, can be with a certain amount of solvent benzol benzyl formate, toluene and catalyzer join in the reactor, be heated to temperature of reaction, pass into the air of certain flow, add peruscabin with certain flow, the mixed solution of catalyzer and toluene, and constantly emit reaction solution and make the liquid level in the reactor remain on certain height, the reaction solution fractionation by distillation of emitting phenyl aldehyde, phenylcarbinol and phenylformic acid, remaining peruscabin and catalyzer mother liquor mix with raw material toluene after purified and turn back in the reactor.Contain toluene, phenyl aldehyde and water in the gas phase on the reactor, fractionation by distillation after condensation, phenyl aldehyde is as product, and peruscabin, catalyzer mother liquor mix with raw material toluene and turn back to continuation reaction in the reactor, and water is as liquid waste disposal.Toluene per pass conversion when the present invention adopts continous way to carry out reaches more than 30%, and the phenyl aldehyde selectivity reaches more than 75%.
Embodiment
The present invention is described in further detail below by embodiment, and following examples are explanation of the invention and the present invention is not limited to following examples.
Embodiment 1:
The method of preparing benzaldehyde by oxidizing toluene is as follows in the present embodiment, in the 500ml reactor, add solvent benzol benzyl formate 240g, toluene 60g and catalyzer cobaltous benzoate 3.0g, open and stir, passing into air, to make the absolute pressure in the reactor be 0.3MPa, then open heating reaction solution is heated to 180-185 ℃, passing into air flow quantity is 0.4L/min, keeping the absolute pressure of reactor is 0.35MPa, the water that reaction generates and methylbenzene azeotropic are out, through condensation and oily water separation, the toluene Returning reactor, water is as liquid waste disposal.Reacted 6 hours, and closed air cooling.Through chromatogram ration analysis, contain toluene 28.6g, phenyl aldehyde 28.3g, phenylcarbinol 3.2g and phenylformic acid 4.2g in the reaction solution, the transformation efficiency of toluene is 52.3%, the selectivity of phenyl aldehyde is 78.3%.After reaction solution goes out toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid by fractionation by distillation, contain capable of circulation the applying mechanically of mother liquor of peruscabin and catalyzer, continue reaction next time behind the unreacted toluene recovery.
Embodiment 2
With 280g solvent benzol benzyl formate, 20g toluene and 3.0g cobaltous benzoate, 1.0g manganese benzoate joins in the 500ml reactor, open and stir, react under the normal pressure, passing into air flow quantity is 0.2L/min, being heated to temperature of reaction is 225-230 ℃, flow with 30g/h adds peruscabin, the mixed solution of catalyzer and toluene, the content of toluene is 30% in the mixed solution, constantly emitting reaction solution makes the liquid level in the reactor remain on starting altitude, the reaction solution fractionation by distillation of emitting phenyl aldehyde, phenylcarbinol and phenylformic acid add after remaining peruscabin and catalyzer mother liquor are purified that 30% raw material toluene mixes again and turn back in the reactor with the flow velocity of 30g/h; Stop simultaneously adding the mixed solution of fresh peruscabin, catalyzer and toluene.Gas phase on the reaction solution contains toluene, phenyl aldehyde and water, the toluene of gas phase, phenyl aldehyde and water taken out of by gas and after condensation fractionation by distillation, phenyl aldehyde is as product, continues as raw material behind the toluene recovery, water is as liquid waste disposal.Successive reaction 32 hours is carried out chromatogram ration analysis to reaction solution and all products, gets phenyl aldehyde 257g, phenylformic acid 25g, unreacted toluene 45.8g; The per pass conversion of toluene is 37.3%, and the selectivity of phenyl aldehyde is 85%, and the phenylformic acid selectivity is 7.2%.
Embodiment 3
With 500g solvent benzol benzyl formate, 40g toluene and 6.0g cobaltous benzoate, 1.0g manganese benzoate, 0.5g nickel benzoate joins in the 800ml bubbling column reactor, react under the normal pressure, passing into air flow quantity is 0.2L/min, being heated to temperature of reaction is 220-225 ℃, flow velocity with 30g/h adds peruscabin, the mixed solution of catalyzer and toluene, toluene level is 30% in the mixed solution, constantly emitting reaction solution makes the interior liquid level of reactor remain on starting altitude, the reaction solution fractionation by distillation of emitting phenyl aldehyde, phenylcarbinol and phenylformic acid, the raw material toluene of remaining peruscabin and the purified adding 30% of catalyzer mother liquor mix and turn back in the reactor with the flow velocity of 30g/h; Stop simultaneously adding the mixed solution of fresh peruscabin, catalyzer and toluene.Contain toluene, phenyl aldehyde and water in the gas phase on the reaction solution, the gas phase that contains toluene, phenyl aldehyde and water taken out of by gas and after condensation fractionation by distillation, phenyl aldehyde is as product, toluene recovery continues as raw material, water is as liquid waste disposal.Successive reaction 30 hours is carried out chromatogram ration analysis to reaction solution and all products, gets phenyl aldehyde 246g, phenylformic acid 22g, unreacted toluene 65.1g; The toluene per pass conversion is 31.2%, and the phenyl aldehyde selectivity is 87.3%, and the phenylformic acid selectivity is 6.8%.
Embodiment 4
280g solvent benzol benzyl formate, 20g toluene and 3.0g cobaltous benzoate, 1.0g manganese benzoate are joined the 500ml reactor, open and stir, react under the normal pressure, passing into air flow quantity is 0.2L/min, and being heated to temperature of reaction is 225-230 ℃, flow with 9g/h adds toluene, gas phase contains toluene, phenyl aldehyde and water on the reaction solution, takes fractionation by distillation after condensation out of by gas, and phenyl aldehyde is as product, toluene recovery continues as raw material reaction, and water is as liquid waste disposal.Successive reaction 35 hours is carried out chromatogram ration analysis to reaction solution and all products, gets phenyl aldehyde 229g, phenylformic acid 37.8g, unreacted toluene 83g; The toluene per pass conversion is 30.2%, and the phenyl aldehyde selectivity is 78.7%, and the phenylformic acid selectivity is 11.3%.Reaction solution continues to use through Distillation recovery phenyl aldehyde, phenylcarbinol and phenylformic acid and after removing other impurity of part.
Embodiment 5
In the 500ml reactor, add solvent benzol benzyl formate 200g, toluene 100g and catalyzer cobaltous benzoate 3.0g, open and stir, pass into air and make that absolute pressure is 0.5MPa in the reactor, then open heating reaction solution is heated to 180-185 ℃, passing into air flow quantity is 0.4L/min, and keeping the reactor absolute pressure is 0.5MPa, the water that reaction generates and methylbenzene azeotropic are out, through condensation and oily water separation, toluene turns back in the reactor, and water is as liquid waste disposal.Reacted 7 hours, and closed air cooling.Through chromatogram ration analysis, contain toluene 39.5g in the reaction solution, contain phenyl aldehyde 49.4g, phenylcarbinol 3.9g, phenylformic acid 17.9g, the transformation efficiency of toluene are 60.5%, the phenyl aldehyde selectivity is 70.9%.After reaction solution goes out toluene, phenyl aldehyde, phenylcarbinol and phenylformic acid by fractionation by distillation, contain capable of circulation the applying mechanically of mother liquor of peruscabin and catalyzer, unreacted toluene recovery continues lower secondary response.
Table 1 embodiment 6-embodiment 11
Table 2 embodiment 12-embodiment 16
| Parameter type | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 |
| Toluene (% by weight) | 17 | 18 | 19.5 | 19.5 | 20 |
Table 3 embodiment 17-embodiment 21
Table 4 embodiment 22-embodiment 26
The design parameter of embodiment 6-embodiment 26 sees Table 1-table 4, and processing method and embodiment 1 among the embodiment 6-embodiment 26 are similar, so locate no longer to describe in detail.Temperature of reaction among the present invention preferably between 180-250 ℃, preferably more than 5 hours, usually select between 5-10 hour by the required reaction times.
Although the present invention with embodiment openly as above; but it is not to limit protection scope of the present invention; any technician who is familiar with this technology not breaking away from change and the retouching of doing in the spirit and scope of the present invention, all should belong to protection scope of the present invention.
Claims (6)
1. the method for a preparing benzaldehyde by oxidizing toluene, used raw material comprises that weight percent is the toluene of 1-59% in the method, weight percent is the Primary Catalysts of 0.005-5%, contains the oxygen source of oxygen molecule, as the peruscabin of solvent; The weight percent of described peruscabin is 40-98%, and the oxygen molecule in the described oxygen source and the mol ratio of toluene are 0.3-3:1, and described Primary Catalysts is one or more of the inorganic salt of cobalt ion, mn ion, vanadium ion, nickel ion or organic salt; Toluene, Primary Catalysts and peruscabin be added to obtain mixed solution in the reactor, then it is 140-300 ℃ in temperature, absolute pressure is under the condition of 0.05-1.0Mpa, passing into the oxygen source that contains oxygen molecule in the above-mentioned mixed solution reacts, reaction times makes phenyl aldehyde at last more than 2 hours to making with extra care through reacted mixed solution; The transformation efficiency of described toluene is more than 30%, and the selectivity of described phenyl aldehyde is more than 70%, and the described oxygen source that contains oxygen molecule is air.
2. the method for preparing benzaldehyde by oxidizing toluene according to claim 1, it is characterized in that: the weight percent of described peruscabin is 75-94%.
3. the method for preparing benzaldehyde by oxidizing toluene according to claim 1 and 2, it is characterized in that: described raw material comprises that also weight percent is the promotor of 0.005-5%, and this promotor is one or more of the inorganic salt of cupric ion, iron ion, zine ion, chromium ion or organic salt.
4. the method for preparing benzaldehyde by oxidizing toluene according to claim 1 and 2, it is characterized in that: described raw material also comprises the bromide as promotor.
5. the method for preparing benzaldehyde by oxidizing toluene according to claim 1 and 2, it is characterized in that: described Primary Catalysts is one or more in cobaltous benzoate, manganese benzoate, phenylformic acid vanadium, the nickel benzoate.
6. the method for preparing benzaldehyde by oxidizing toluene according to claim 1 and 2 is characterized in that: the temperature of described mixed solution when reaction is 180-250 ℃, and absolute pressure is 0.08-0.4Mpa.
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| CN103265416A (en) * | 2013-05-23 | 2013-08-28 | 南京大学 | Method for preparing benzaldehyde from methylbenzene with high selectivity |
| CN104693002A (en) * | 2015-03-11 | 2015-06-10 | 南京工业大学 | Method for preparing benzaldehyde by oxidizing toluene |
| CN108435188A (en) * | 2015-07-31 | 2018-08-24 | 永春新盛环保科技有限公司 | A kind of preparation method of toluene direct oxidation producing benzaldehyde catalyst |
| CN106883116A (en) * | 2015-12-15 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of toluene catalytic oxidation benzoic acid, benzaldehyde, the method for Ergol |
| CN110075882A (en) * | 2019-05-09 | 2019-08-02 | 南京工程学院 | A kind of application of transition metal composite oxide catalytic agent in catalysis toluene oxidation synthesizing benzoic acids benzyl ester |
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| CN1296937A (en) * | 2000-05-08 | 2001-05-30 | 湖南大学 | Process for preparing benzoic acid, henzaldehyde and benzyl alcohol |
| CN1663941A (en) * | 2004-03-01 | 2005-09-07 | 中国科学院大连化学物理研究所 | A method for selectively oxidizing toluene to synthesize benzaldehyde |
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing benzoic acid by liquid-phase oxidation of toluene |
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| CN1296937A (en) * | 2000-05-08 | 2001-05-30 | 湖南大学 | Process for preparing benzoic acid, henzaldehyde and benzyl alcohol |
| CN1663941A (en) * | 2004-03-01 | 2005-09-07 | 中国科学院大连化学物理研究所 | A method for selectively oxidizing toluene to synthesize benzaldehyde |
| CN101613269A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing benzoic acid by liquid-phase oxidation of toluene |
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