CN104826634B - The catalyst and its method for preparing many fluoro benzyl alcohols are reduced for polyfluoro benzoates - Google Patents
The catalyst and its method for preparing many fluoro benzyl alcohols are reduced for polyfluoro benzoates Download PDFInfo
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- CN104826634B CN104826634B CN201510202880.5A CN201510202880A CN104826634B CN 104826634 B CN104826634 B CN 104826634B CN 201510202880 A CN201510202880 A CN 201510202880A CN 104826634 B CN104826634 B CN 104826634B
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Abstract
The invention discloses the catalyst that many fluoro benzyl alcohols are prepared for the reduction of polyfluoro benzoates, the catalyst includes 10~40 parts of 10~50 parts of cupric oxide, 10~30 parts of zinc oxide, 1~5 part of cerium oxide and aluminum oxide in parts by weight, mixing adds graphite in catalyst, and the catalyst is passed through hydrogen treat 20~26 hours at 170 220 DEG C.Catalyst of the present invention is used for the reduction of polyfluoro benzoates and prepares many fluoro benzyl alcohols, good reaction selectivity, high income, it is easy to industrialized production.The present invention is also provided to be used to be passed through hydrogen, 2.0~2.5Mpa of Hydrogen Vapor Pressure, 1~2L/min of hydrogen flowing quantity at the method that the reduction of polyfluoro benzoates prepares many fluoro benzyl alcohols, the loading catalyst in fixed bed reactors, 200~210 DEG C of temperature using the catalyst；The alcoholic solution of polyfluoro benzoates is added with high-pressure metering pump, can be with continuous production, yield is big, and byproduct is only alcohol, it is easy to recycled, the three wastes produced without other techniques, no environmental protection pressure, and the yield of many fluoro benzyl alcohols is more than 90%.
Description
Technical field
The present invention's is related to technical field of fine, and more particularly to one kind prepares polyfluoro benzyl for polyfluoro benzoates
The catalyst and its method of alcohol.
Background technology
Many fluoro benzyl alcohols are the efficient, intermediates of low toxicity pesticide-fenfluthrin.
Existing synthetic route mainly has：
1st, United States Patent (USP)：US6020517, a kind of process that benzylalcohol is prepared by phenyl-pentafluoride nitrile
The reaction mechanism is complicated, and reaction selectivity is bad, and purification difficult, yield is low.
2nd, glad chemical industry in Zhejiang, a kind of preparation method of 2,3,4,5,6- phenyl-pentafluoride methanol, CN101412660A：The reaction
Complicated mechanism, reaction selectivity is bad, and purification difficult, yield is low.
3rd, East China Normal University, the method for synthesizing many fluorophenyl methanols with many fluobenzoic acids of sodium borohydride reduction,
CN101012148A：This method is simple, but has defluorinate by-product, it is not easy to purify.
4th, a kind of Yangnong Chemical Co., Ltd., Jiangsu, new technology for preparing transfluthrin, CN1631869A is open
2,3,5,6- tetrafluorobenzyl alcohols are prepared with reducing agent and aids reduction in a solvent by 2,3,5,6- tetrafluorobenzoic aid esters, with
Sodium borohydride produces a large amount of waste solid inorganic salts as reducing agent, sodium borohydride high cost.
The content of the invention
Limitation based on prior art, the present invention is provided to the catalysis that the reduction of polyfluoro benzoates prepares many fluoro benzyl alcohols
Agent, the catalyst includes 10~50 parts of cupric oxide, 10~30 parts of zinc oxide, 1~5 part of cerium oxide and oxidation in parts by weight
10~40 parts of aluminium.
In catalyst of the present invention, cupric oxide is used as main active component；Zinc oxide, cerium oxide are used as co-catalyst；Aluminum oxide
It is used as carrier.
The effect of cerium oxide is：First scattered cupric oxide and zinc oxide；Secondth, in hydrogen reducing processing and for polyfluoro
Benzoates are prepared in the reaction of many fluoro benzyl alcohols, during high temperature, can play a part of preventing copper, zinc metal crystal nuclei sintering.
Preferably, the catalyst is handled through hydrogen reducing, and the hydrogen reducing processing is to be passed through hydrogen at 170-220 DEG C
Gas disposal 20~26 hours.
As further preferred technical scheme, the hydrogen reducing processing is to be passed through the hydrogen diluted through nitrogen, described
The total flow of nitrogen is 1200~3600L, and the total flow of hydrogen is 300~500L.
Preferred scheme, the hydrogen reducing processing was included with the next stage：
During less than 170 DEG C：Nitrogen is only passed through, flow is 1000~2500ml/min；
170 DEG C~210 DEG C：Nitrogen flow is passed through for 1000~2500ml/min, hydrogen flowing quantity is passed through for 30~50ml/
min；The stage needs the hydrogen reducing diluted with nitrogen；Substantial amounts of heat can be produced in cupric oxide, the reduction process of zinc oxide
With a small amount of water, already scattered copper, zinc metal crystal nuclei is sintered together.Nitrogen can control reduction rate to be unlikely to
It is excessively fierce, and take away the heat that reduction is produced, it is ensured that catalyst is carried out under constant reduction temperature.
210 DEG C~220 DEG C：Be gradually increased hydrogen flowing quantity, gradually decrease nitrogen flow, be passed through nitrogen flow for 0~
1000ml/min, is passed through hydrogen flowing quantity for 100~500ml/min.Improve density of hydrogen, carry out drastic reduction, main reduction compared with
The part of hardly possible reduction, now catalyst is most of has reduced, and heat release is no longer violent.
The catalyst that the present invention is provided is used for the reduction of polyfluoro benzoates and prepares many fluoro benzyl alcohols, and the life-span is 1900~2200
Hour.
The present invention also provides the preparation method that the catalyst for preparing many fluoro benzyl alcohols is reduced for polyfluoro benzoates, and it is special
Levy and be, (ratio presses the parts by weight of its oxide in the catalyst by the solubility salt nitrate or chlorate of copper, zinc and aluminium
Than for 10~50 parts of cupric oxide, 10~30 parts of zinc oxide, 1~5 part of cerium oxide, 10~40 parts of aluminum oxide) mixed with water, 60~
At 70 DEG C, pH7~8, reaction are adjusted；Taking precipitate, dries, is calcined.
As preferred technical scheme, the drying is dried 5~8 hours at 100~110 DEG C；The roasting is 500
It is calcined 4~6 hours at~600 DEG C.
As preferred technical scheme, mixing in the catalyst adds graphite.
The solubility in the organic solvents such as alcohols is low relative to alkane ester type compound for benzoate compounds, viscosity
Greatly.The difficulty of alcohol is reduced into also above alkane ester type compound, common production equipment can meet 200~250 DEG C of production technology
Condition, if improving reaction temperature to improve catalyst activity, can increase manufacturing facilities difficulty, and improving catalyst activity can only add
Big hydrogen flowing quantity.The larger material of viscosity is easy to damage catalyst plus higher hydrogen flowing quantity, and damaged catalyst is not only
Block reactor and inactivate quickly.Screened by many experiments, it has been found that graphite can effectively increase as adhesive
The intensity of catalyst, may be relevant with the chemical property of main component-carbon of graphite, and the element is also extremely stable at high temperature.
Preferably, the weight part ratio of the catalyst and graphite is 100:5~100:10.
The present invention also provides the polyfluoro benzoates method that reduction prepares many fluoro benzyl alcohols, using above-described any
Catalyst, the catalyst hydrogenation reduction polyfluoro benzoate compounds ability is 1~4 mass space velocity.
Mass space velocity of the present invention is that in the unit interval, the catalyst reduction of unit mass handles the quality of raw material.
Reaction mechanism is as follows：
In formula, m=1,2；N=3,4,5
As preferred technical scheme, the loading catalyst in fixed bed reactors is passed through hydrogen at 200~210 DEG C of temperature
Gas, 2.0~2.5Mpa of Hydrogen Vapor Pressure, 1~2L/min of hydrogen flowing quantity；It is molten with the alcohol that high-pressure metering pump adds polyfluoro benzoates
Liquid, flow is 110~120g/h, and the weight ratio of polyfluoro benzoates and alcoholic solution is 1~4；Reaction solution distills out alcoholic solvent
Product is produced, hydrogen is reclaimed and is reused with membrane pump pressurization recovery.
The method that the polyfluoro benzoates reduction that the present invention is provided prepares many fluoro benzyl alcohols, the yield of many fluoro benzyl alcohols is more than
90%.
The reduction of polyfluoro benzoates is used for using above-described any catalyst and prepares many fluoro benzyl alcohols, selecting response
Good, the high income of property, it is easy to industrialized production.
The method that many fluobenzoic acid esters reduction prepare many fluoro benzyl alcohols is provided using the present invention, and fixed bed reactors can be with
Continuous production, yield is big, and byproduct is only alcohol, it is easy to recycled, the three wastes produced without other techniques, acyclic pressurize
Power.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
The preparation of the catalyst of embodiment 1
Catalyst is obtained after cupric oxide 10g, zinc oxide 10g and aluminum oxide 83g are mixed, 5g graphite is added stand-by.
The preparation of the catalyst of embodiment 2
Catalyst is obtained after cupric oxide 50g, zinc oxide 30g, cerium oxide 5g and aluminum oxide 420g are mixed, it is stand-by.
The preparation of the catalyst of embodiment 3
1st, react
235g copper nitrates, 155g zinc nitrates, 10g cerous nitrates, 65g aluminium hydroxides are added in 2000g pure water, are heated to
60~70 DEG C, stirring is lower to add 28% ammoniacal liquor, and regulation pH precipitates it for 7~8, obtained sediment be Kocide SD,
Zinc hydroxide, aluminium hydroxide, the mixture of cerium hydroxide.
2nd, dry
Filtration washing filter cake, 100~110 DEG C of dryings 5~8 hours remove the moisture brought in precipitation, filter process；
3rd, it is calcined
500~600 DEG C are calcined 4~6 hours in Muffle furnace, and the metal of hydroxide state is prepared into oxidation state, oxygen is obtained
Change copper, zinc oxide, cerium oxide and aluminum oxide, Temperature fall to room temperature；
4th, compressing tablet
5g graphite is added per 100g powder solids as adhesive, catalyst is obtained with tabletting machine after being well mixed, directly
Footpath 5mm, thickness 5mm.
The processing of the catalyst hydrogen reducing of embodiment 4
1st, the temperature programmed reduction stage
Catalyst prepared by 60g above-described embodiments 3 is added in diameter 25mm, long 300mm reaction tube.
(1) while nitrogen is passed through, using pipe furnace heating response pipe；
(2) when reaction tube is heated to 170 DEG C, starts to be passed through hydrogen and reduced, the flow for being passed through nitrogen is 1000ml/
Min, is passed through 30~50ml/min of flow of hydrogen, and initial temperature is 170~180 DEG C, the stage main reducing catalyst surface
Part, 5~15 hours recovery times；
(3) further reducing catalyst surface portion, 5~20 hours recovery times and then at 190~200 DEG C；
(4) under reducing catalyst surface 1~2mm parts at 200~210 DEG C, 5~10 hours recovery times；
(5) reactor is finally warming up to 210~220 DEG C, reducing catalyst core, 5~10 hours time.
2nd, program improves hydrogen ratio reduction phase, maintains the temperature at 210~220 DEG C
First it is gradually increased hydrogen and is passed through flow, keeps nitrogen flow constant, hydrogen flowing quantity is brought up into 100~200ml/
Min, is reduced 1~3 hour；
Hydrogen is gradually increased again and is passed through flow, keeps nitrogen flow constant, hydrogen flowing quantity is brought up into 300~400ml/
Min, is reduced 1~3 hour；
Nitrogen inlet is finally reduced, density of hydrogen is brought up into 50%, i.e. hydrogen and is passed through flow to 500ml/min, also
It is former 1~3 hour；
Hydrogen be passed through flow it is constant in the case of, gradually decrease nitrogen and be passed through flow, nitrogen is passed through speed within 2 hours or so
50ml/min is dropped to, stops being passed through nitrogen after being kept for 10 minutes, continues to be passed through hydrogen, catalyst reduction is finished.
Embodiment 5
60g catalyst prepared by Example 1, as described in Example 4 reducing catalyst.
Embodiment 6
60g catalyst prepared by Example 2, according to the method reducing catalyst of embodiment 4.
Embodiment 7
Using pentafluoro benzoic acid ethyl ester as raw material and the catalyst of the reduction treatment of embodiment 4, five fluoro benzyl alcohols are prepared
Catalyst reduction terminates, and cools to 200~210 DEG C, keeps hydrogen to be passed through flow 0.5L/min when cooling.Will
Hydrogen Vapor Pressure increases to 2.0~2.5Mpa, and increase hydrogen flowing quantity to 2L/min adds pentafluoro benzoic acid ethyl ester with high-pressure metering pump
Ethanol solution (ethanol weight is 2 times of five fluorine Ethyl formates), be passed through 110~120g/h of speed, reclaim hydrogen membrane pump
Pressurization recovery is reused, and is obtained reaction solution and is distilled out ethanol, ethanol can be reused.
GC is analyzed；Raw material conversion per pass 98%, reaction selectivity 99%.Catalyst life can reach 1900~2200
Between hour.
60g catalyst has been loaded in the experiment in fixed bed reactors, is opened from pentafluoro benzoic acid ethyl ester ethanol solution is passed through
Begin to reaction 1000 hours, pentafluoro benzoic acid ethyl ester 36.67kg is added altogether, five fluoro benzyl alcohol 28.7kg are obtained, yield 95%,.
Embodiment 8
Using pentafluoro benzoic acid methyl esters as raw material and the catalyst of the reduction treatment of embodiment 4, five fluoro benzyl alcohols are prepared
Catalyst reduction terminates, and cools to 200~210 DEG C, keeps hydrogen to be passed through flow 0.5L/min when cooling.Will
Hydrogen Vapor Pressure increases to 2.0-2.5Mpa, and increase hydrogen flowing quantity to 2L/min adds pentafluoro benzoic acid methyl esters with high-pressure metering pump
Methanol solution (methanol weight is 2 times of raw material), be passed through 110~120g/h of speed, reclaim hydrogen and pressurizeed with membrane pump and reclaimed
Reuse, obtain reaction solution distilling off solvent methanol, methanol can be recycled, unreacted raw material is isolated in rectifying, it is former
Material can be with reuse.
GC analyzes conversion per pass 88%, reaction selectivity 99%.Catalyst life can reach 2200-2400 hours
Between.
Fixed bed reactors have loaded 60g catalyst, to reaction since being passed through the ethanol solution of pentafluoro benzoic acid methyl esters
1000 hours, pentafluoro benzoic acid methyl esters 36.67kg is added altogether, and rectifying obtains five fluoro benzyl alcohol 27kg, reclaims raw material pentafluoro benzoic acid
Methyl esters 3.67kg, yield 93%.
Embodiment 9
Using polytetrafluoroethylene ethyl benzoate as raw material and the catalyst of the reduction treatment of embodiment 4, tetrafluorobenzyl alcohol is prepared
Catalyst reduction terminates, and cools to 200~210 DEG C, keeps hydrogen to be passed through speed 0.5L/min when cooling.Will
Hydrogen Vapor Pressure increases to 2.0~2.5Mpa, and increase hydrogen flowing quantity to 2.5L/min adds tetrafluorobenzoic aid second with high-pressure metering pump
The ethanol solution (ethanol weight is 2 times of five fluorine Ethyl formates) of ester, is passed through 190~200g/h of speed, reclaims hydrogen barrier film
Pump pressurization recovery is reused, and is obtained reaction solution and is distilled out ethanol, ethanol can be reused.
GC is analyzed；Raw material conversion per pass 90%, reaction selectivity 99%.Catalyst life can reach 2000~2200
Between hour.
Fixed bed reactors have loaded 60g catalyst, to reaction since being passed through the ethanol solution of polytetrafluoroethylene ethyl benzoate
1000 hours, polytetrafluoroethylene ethyl benzoate 66.67kg is added altogether, tetrafluorobenzyl alcohol 45.7kg is obtained, and reclaims raw material tetrafluorobenzoic aid second
Ester 5.3kg, yield 92%.
Comparative example 1
Using pentafluoro benzoic acid ethyl ester as raw material and the catalyst of the reduction treatment of embodiment 5, five fluoro benzyl alcohols are prepared
Catalyst reduction terminates, and cools to 200~210 DEG C, keeps hydrogen to be passed through flow 0.5L/min when cooling.Will
Hydrogen Vapor Pressure increases to 2.0~2.5Mpa, and increase hydrogen flowing quantity to 2L/min adds pentafluoro benzoic acid ethyl ester with high-pressure metering pump
Ethanol solution (ethanol weight is 2 times of five fluorine Ethyl formates), be passed through 110~120g/h of speed, reclaim hydrogen membrane pump
Pressurization recovery is reused, and is obtained reaction solution and is distilled out ethanol, ethanol can be reused.
GC monitoring reactions, find reaction 150 hours, conversion ratio is begun to decline, and is run to after 200 hours, conversion ratio declines
Drop to conversion ratio behind 80%, 350 hours after by 90%, 300 hour and drop to 70%, stop reaction.
Take out after catalyst breaks into pieces, find there is obvious copper metal powder in catalyst, inherently the copper of nucleus form/
Zinc solid solution has sintered the copper of graininess into, loses catalytic activity.
The catalyst of metallic cerium is not added, because copper component is easily sintered, causes reaction to turn while catalytic life is short
Rate is low, and reactant, which has to pass through rectifying, can just isolate product and raw material.
Comparative example 2
Using pentafluoro benzoic acid ethyl ester as raw material and the catalyst of the reduction treatment of embodiment 6, five fluoro benzyl alcohols are prepared
Catalyst reduction terminates, and cools to 200~210 DEG C, keeps hydrogen to be passed through flow 0.5L/min when cooling.Will
Hydrogen Vapor Pressure increases to 2.0~2.5Mpa, and increase hydrogen flowing quantity to 2L/min adds pentafluoro benzoic acid ethyl ester with high-pressure metering pump
Ethanol solution (ethanol weight is 2 times of five fluorine Ethyl formates), be passed through 110~120g/h of speed, reclaim hydrogen membrane pump
Pressurization recovery is reused, and is obtained reaction solution and is distilled out ethanol, ethanol can be reused.
GC monitoring reactions, find reaction 300 hours, conversion ratio is begun to decline, and is run to after 400 hours, conversion ratio declines
Drop to 80% after by 90%, 450 hour, now reaction pressure becomes big, is fed using high-pressure metering pump more and more difficult, stops
Reaction.
Catalyst is taken out, discovery is that the catalyst of sheet is damaged originally, becomes the graininess differed in size, top
Catalyst breakage is even more serious.
Claims (2)
1. the method that the reduction of polyfluoro benzoates prepares many fluoro benzyl alcohols, it is characterised in that catalyst hydrogenation reduces many fluorobenzene first
Acid esters compound ability is 1~4 mass space velocity, and the mass space velocity is that in the unit interval, the catalyst of unit mass is also
The quality of raw material is managed in original place,
It is passed through hydrogen at the loading catalyst in fixed bed reactors, 200~210 DEG C of temperature, 2.0~2.5Mpa of Hydrogen Vapor Pressure,
1~2L/min of hydrogen flowing quantity；The alcoholic solution of polyfluoro benzoates is added with high-pressure metering pump, flow is 110~120g/h, many
Fluobenzoic acid esters and the weight of alcoholic solution ratio are 1~4；Many fluoro benzyl alcohols are produced after reaction solution separated alcohol,
The catalyst is made as follows：
(1) react：235g copper nitrates, 155g zinc nitrates, 10g cerous nitrates, 65g aluminium hydroxides are added in 2000g pure water, plus
Heat is to 60~70 DEG C, and stirring is lower to add 28% ammoniacal liquor, and regulation pH precipitates it for 7~8, and obtained sediment is hydroxide
Copper, zinc hydroxide, aluminium hydroxide, the mixture of cerium hydroxide；
(2) dry：Filtration washing filter cake, 100~110 DEG C of dryings 5~8 hours remove the water brought in precipitation, filter process
Point；
(3) it is calcined：500~600 DEG C are calcined 4~6 hours in Muffle furnace, and the metal of hydroxide state is prepared into oxidation state, obtained
To cupric oxide, zinc oxide, cerium oxide and aluminum oxide, Temperature fall to room temperature；
(4) compressing tablet：5g graphite is added per 100g powder solids as adhesive, must be catalyzed with tabletting machine after being well mixed
Agent, diameter 5mm, thickness 5mm.
2. the method that polyfluoro benzoates reduction according to claim 1 prepares many fluoro benzyl alcohols, it is characterised in that described
The yield of many fluoro benzyl alcohols is more than 90%.
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| JP5441526B2 (en) * | 2009-07-01 | 2014-03-12 | 三菱瓦斯化学株式会社 | Method for producing alicyclic alcohol |
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