CN109529902A - A kind of method that the palladium nickel Pd/carbon catalyst of high stable catalyzes and synthesizes vitamin E intermediate - Google Patents
A kind of method that the palladium nickel Pd/carbon catalyst of high stable catalyzes and synthesizes vitamin E intermediate Download PDFInfo
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Abstract
The invention discloses the methods that a kind of palladium nickel Pd/carbon catalyst of high stable catalyzes and synthesizes vitamin E intermediate, this method is using palladium nickel charcoal as catalyst, it is catalyzed trimethylbenzoquinone hydrogenation synthesis trimethylhydroquinone, wherein the catalyst is using powdered activated carbon as carrier, it is dry after carrier Urea treatment, hot setting is carried out again, pretreated active carbon is first then loaded into promoter metal nickel, and high-temperature activation is carried out to the active carbon of nickel-loaded；Again to supported active metals palladium on nickel charcoal, catalyst precarsor is obtained；It most restores to obtain catalyst through reducing agent afterwards.Compared with the conventional method, not only the activity and selectivity of catalyst is high, while catalyst performance stabilised for the method for the present invention, has and applies performance and well convenient for recycling and reusing.
Description
Technical field
The invention belongs to the synthesis technical fields of vitamin E, and in particular to a kind of palladium nickel Pd/carbon catalyst catalysis of high stable
The method of intermediate of synthetic vitamin E.
Background technique
Vitamin E is one of vitamin that is needed by human but cannot voluntarily synthesizing, adjust human body reproductive function and
It plays an important role on anti-oxidation function, thus becomes one of the three big pillar products of vitamin industry.
It is industrially to prepare the important link of vitamin E that trimethylbenzoquinone, which is reduced to trimethylhydroquinone,.In conventional method,
The process that trimethylbenzoquinone is reduced to trimethylhydroquinone is realized by the way that excessive reducing agent is added.This preparation method is due to excess
The addition of reducing agent, so that the separating-purifying process of product is complicated, and remaining reducing agent can cause environmental pollution, in recent years
Come, catalytic reduction method is widely used.The catalyst that catalytic reduction method uses can be divided into: non-precious metal catalyst and noble metal
Catalyst.Wherein non-precious metal catalyst is such as: magnesium chloride load SiO 2 catalyst, to phenylbenzimidazole sulfonic acid, Raney Ni, carbon materials
It is anti-to expect that the non-precious metal catalysts such as Co catalysts, ferrous acid Mg catalyst, the compound iron halogenation complex compound of load are used as the catalysis
That answers has been reported that.Noble metal catalyst is since catalytic activity is higher, it is low to require reaction condition (temperature, pressure), using more
Come more extensive.Noble metal catalyst reported in the literature has: palladium carbon and platinum carbon catalyst as fixed bed reaction handle and change
Property waste active carbon loaded palladium catalyst, palladium aluminium oxide catalyst etc.；The load of alkali metal containing alumino-silicate was had been reported that in patent
The palladium catalyst etc. of palladium catalyst and metal organic frame load.But bad time of the generally existing catalyst of these noble metal catalysts
The problems such as receipts, bad catalytic activity and relatively poor, catalyst the recycled performance of selectivity.
Summary of the invention
The problem to be solved by the present invention is that the shortcomings that being directed to the above-mentioned prior art, provide that a kind of catalytic activity is high, choosing
Selecting property is good, catalyst circulation apply performance it is good and be convenient for recycling and reusing the method for catalyzing and synthesizing vitamin E intermediate.
Solving technical solution used by above-mentioned technical problem is: trimethylbenzoquinone being dissolved completely in isopropanol, is added
Enter palladium nickel Pd/carbon catalyst, stirring at normal temperature reacts 80~150min in the case where pressure is the hydrogen atmosphere of 0.5~1.5MPa, after having reacted
Reaction solution being filtered, filtrate is purified to obtain vitamin E intermediate --- trimethylhydroquinone, filter cake repeat after being rinsed with isopropanol
It uses.
The mass fraction of palladium is 3%~10% in above-mentioned palladium nickel Pd/carbon catalyst, the mass fraction of nickel is 0.2%~
4.5%, the preferably mass fraction of palladium is 5%, and the mass fraction of nickel is 1%~3%；The catalyst is prepared into according to following step
It arrives:
1, powdered activated carbon is added in the aqueous solution of urea that concentration is 3~10mol/L and impregnates 4~8h, centrifugation removal is more
Remaining aqueous solution of urea is deposited at 60~100 DEG C and dries to constant weight, 400~700 DEG C of 3~6h of solidification in nitrogen atmosphere,
Obtain pretreated active carbon.
2, the soluble-salt of nickel is dissolved in deionized water, is uniformly mixing to obtain nickel precursor solution, be then added pre-
The active carbon of processing impregnates 2~6h under agitation, and adding alkali compounds and adjusting the pH of dipping system is 7~11, after
It is filtered after 1~5h of continuous stirring, 60~100 DEG C of dryings are to constant weight after filter cake is washed with deionized to neutrality, then in hydrogen
300~800 DEG C of 2~6h of activation, the active carbon of the nickel-loaded after being activated in atmosphere.
3, the soluble-salt of palladium is dissolved in the water, is uniformly mixing to obtain palladium precursor solution；By the nickel-loaded after activation
Active carbon be added alkali compounds aqueous solution in be beaten, 40~70 DEG C are heated under stirring, then uses jet pump
Palladium precursor solution, cooling, filtering after 2~6h of insulated and stirred is added, reducing agent reduction is added in filter cake after being beaten with deionized water,
Filtering, filter cake is washed with deionized to no chloride ion, dry, obtains palladium nickel Pd/carbon catalyst.
In the preparation step 1 of above-mentioned catalyst, the mass ratio of preferably powdered active carbon and aqueous solution of urea is 1:8~15,
Wherein the granularity of powdered activated carbon is 200~400 mesh.
In the preparation step 2 of above-mentioned catalyst, the soluble-salt of the nickel is nickel nitrate or nickel acetate.
In the preparation step 3 of above-mentioned catalyst, the soluble-salt of the palladium is chlorine palladium acid, water-soluble palladium chloride, chlorine Asia palladium
Any one or more in sour sodium.
In the preparation step 2 and 3 of above-mentioned catalyst, the alkali compounds be sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium bicarbonate, potassium carbonate, any one or more in saleratus, the wherein aqueous solution of alkali compounds described in step 3
Mass fraction is 1%~20%.
In the preparation step 3 of above-mentioned catalyst, the reducing agent is hydrogen, hydrazine hydrate, formic acid, any one in sodium formate
Kind, the temperature of reducing agent reduction is 60~80 DEG C, and the recovery time is 2~4h.
In above-mentioned synthetic method, preferably the addition quality of palladium nickel Pd/carbon catalyst and the volume ratio of trimethylbenzoquinone are 1g:10
~30mL.
Compared with the prior art, the present invention has the following advantages:
1, the present invention first impregnates active carbon in aqueous solution of urea, makes Absorption for Urea on the activated carbon, then makes to adsorb
Urea in active carbon is decomposed into ammonia, and carries out the absorption in situ of ammonia, so that amino molecule be made to be uniformly dispersed in activity
In charcoal.Then in nitrogen atmosphere, ammonolysis craft is nitrogen in high temperature cure process, may be implemented to mix the uniform nitrogen of active carbon
It is miscellaneous.
2, the present invention on pretreated active carbon by loading soluble nickel salt, and in hydrogen atmosphere, carries out to it
Soluble nickel salt is reduced into metallic nickel, and is carried on metallic nickel firmly on active carbon by high-temperature activation, improves catalyst
Activity and selectivity, and improve the antitoxinization performance of catalyst, so that it is applied performance and be improved.
3, the present invention adsorbs precious metal palladium and promoter metal nickel respectively, is restored respectively, avoids while adsorbing
Competitive Adsorption present in journey, while avoiding same reducing condition and cannot be suitable for asking for two kinds of heterogeneity metals simultaneously
Topic.
4, the preparation method of catalyst of the present invention is simple, and metallic particles is small on catalyst, can be highly dispersed on carrier.
Trimethylbenzoquinone hydrogenation synthesis vitamin E intermediate is catalyzed using palladium nickel Pd/carbon catalyst of the present invention, catalyst not only activity it is high and
Stability is high, and reproducible, after a number of uses, metallic particles is not easy to reunite, and it is good to apply performance.
Specific embodiment
Below with reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 1000mL 5mol/L and is soaked
6h is steeped, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 650 DEG C of solidification 4h, obtain pretreated active carbon in nitrogen atmosphere within dry 10 hours.
2,4.24g nickel acetate is dissolved in 200mL deionized water water, is uniformly mixing to obtain nickel precursor solution；It will
The pretreated active carbon of 94.5g is added in nickel precursor solution, impregnates 4h under agitation, adds sodium hydroxide and adjusts leaching
The pH of stain system is 8.5, continues to filter after stirring 2h, filter cake is washed with deionized to neutrality, is placed in baking oven 80 DEG C
Drying to constant weight, then 800 DEG C of activation 3h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3,13.823g sodium chloropalladite is dissolved in deionized water and is diluted to 200mL with deionized water, stirred evenly
Obtain palladium precursor solution；The aqueous sodium carbonate that 500mL mass fraction is 1% is added in the active carbon of nickel-loaded after activation
Middle mashing is heated to 55 DEG C under stirring, and palladium precursor solution then is added with jet pump, cools down after insulated and stirred 2h,
Filtering, after filter cake is beaten with deionized water, obtains slurries, is then passed through hydrogen, 60 DEG C of reduction into slurries under stirring
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion by 4h, filtering, 10 hours dry at 80 DEG C
To constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is 0.5%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred in autoclave after being rinsed with isopropanol, and
20mL trimethylbenzoquinone is added into autoclave and 380mL isopropanol apply for the first time.It repeats this and applies step
It applies altogether 10 times.
Embodiment 2
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 800mL 6mol/L and is soaked
4h is steeped, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 680 DEG C of solidification 4h, obtain pretreated active carbon in nitrogen atmosphere within dry 8 hours.
2,8.48g nickel acetate is dissolved in 200mL deionized water water, is uniformly mixing to obtain nickel precursor solution；By 93g
Pretreated active carbon is added in nickel precursor solution, impregnates 4.5h under agitation, adds sodium carbonate and adjusts impregnating
The pH of system is 8.5, continues to filter after stirring 3h, filter cake is washed with deionized to neutrality, is placed in 80 DEG C of drying in baking oven
To constant weight, then 600 DEG C of activation 2.5h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3, the chlorine palladium aqueous acid of 50mL 0.1g/mL is diluted to 200mL with deionized water, before being uniformly mixing to obtain palladium
Drive liquid solution；The active carbon of nickel-loaded after activation is added in the sodium bicarbonate aqueous solution that 500mL mass fraction is 20% and is beaten
Slurry, is heated to 40 DEG C under stirring, and palladium precursor solution then is added with jet pump, and cooling after insulated and stirred 6h is filtered,
After filter cake is beaten with deionized water, slurries are obtained, 50mL formic acid, 70 DEG C of reduction are then added into slurries under stirring
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion by 2h, filtering, 10 hours dry at 80 DEG C
To constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is 2%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the filtrate yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred to autoclave after being rinsed with isopropanol
In, and add into autoclave 20mL trimethylbenzoquinone and 380mL isopropanol apply for the first time.This is repeated to apply
Step is applied 10 times altogether.
Embodiment 3
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 1200mL 4mol/L and is soaked
7h is steeped, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 600 DEG C of solidification 4h, obtain pretreated active carbon in nitrogen atmosphere within dry 9 hours.
2,12.387g nickel nitrate is dissolved in 200mL deionized water water, is uniformly mixing to obtain nickel precursor solution；It will
The pretreated active carbon of 92.5g is added in nickel precursor solution, impregnates 4h under agitation, adds sodium bicarbonate and adjusts leaching
The pH of stain system is 10, continues to filter after stirring 4h, filter cake is washed with deionized to neutrality, is placed in 80 DEG C of bakings in baking oven
It does to constant weight, then 500 DEG C of activation 3.5h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3,8.33g water solubility palladium chloride is dissolved in deionized water and is diluted to 200mL with deionized water, stirred evenly
Obtain palladium precursor solution；The saleratus water that 500mL mass fraction is 12% is added in the active carbon of nickel-loaded after activation
It is beaten in solution, 60 DEG C is heated under stirring, palladium precursor solution then is added with jet pump, it is cold after insulated and stirred 4h
But, it filters, after filter cake is beaten with deionized water, obtains slurries, be then passed through hydrogen into slurries under stirring, 60 DEG C also
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion by former 4h, filtering, and dry 10 is small at 80 DEG C
Up to constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is 2.5%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred in autoclave after being rinsed with isopropanol, and
20mL trimethylbenzoquinone is added into autoclave and 380mL isopropanol apply for the first time.It repeats this and applies step
It applies altogether 10 times.
Embodiment 4
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 900mL 7mol/L and is soaked
5.5h is steeped, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 650 DEG C of solidification 4h, obtain pretreated active carbon in nitrogen atmosphere within 11 hours for lower drying.
2,14.86g nickel nitrate is dissolved in 200mL deionized water water, is uniformly mixing to obtain nickel precursor solution；It will
The pretreated active carbon of 90.5g is added in nickel precursor solution, impregnates 4h under agitation, adds sodium hydroxide and adjusts leaching
The pH of stain system is 10.5, continues to filter after stirring 4h, filter cake is washed with deionized to neutrality, is placed in baking oven 80 DEG C
Drying to constant weight, then 680 DEG C of activation 2.5h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3,8.33g water solubility palladium chloride is dissolved in deionized water and is diluted to 200mL with deionized water, stirred evenly
Obtain palladium precursor solution；It is water-soluble that the potassium carbonate that 800mL mass fraction is 15% is added in the active carbon of nickel-loaded after activation
It is beaten in liquid, 50 DEG C is heated under stirring, palladium precursor solution then is added with jet pump, it is cold after insulated and stirred 3h
But, it filters, after filter cake is beaten with deionized water, obtains slurries, 50g sodium formate is then added into slurries under stirring,
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion, does at 80 DEG C by 80 DEG C of reduction 3h, filtering
To constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is within dry 10 hours
4.5%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred in autoclave after being rinsed with isopropanol, and
20mL trimethylbenzoquinone is added into autoclave and 380mL isopropanol apply for the first time.It repeats this and applies step
It applies altogether 10 times.
Embodiment 5
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 1500mL 3mol/L and is soaked
8h is steeped, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 400 DEG C of solidification 6h, obtain pretreated active carbon in nitrogen atmosphere within dry 12 hours.
2,7.43g nickel nitrate is dissolved in 200mL deionized water water, is uniformly mixing to obtain nickel precursor solution；By 94g
Pretreated active carbon is added in nickel precursor solution, impregnates 6h under agitation, adds potassium hydroxide and adjusts impregnating
The pH of system is 11, continues to filter after stirring 2h, filter cake is washed with deionized to neutrality, is placed in baking oven and is dried to for 80 DEG C
Constant weight, then 400 DEG C of activation 6h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3,13.82g sodium chloropalladite is dissolved in deionized water and is diluted to 200mL with deionized water, stirred evenly
Obtain palladium precursor solution；The aqueous sodium carbonate that 800mL mass fraction is 6% is added in the active carbon of nickel-loaded after activation
Middle mashing is heated to 70 DEG C under stirring, and palladium precursor solution then is added with jet pump, cools down after insulated and stirred 4h,
Filtering, after filter cake is beaten with deionized water, obtains slurries, is then passed through hydrogen, 60 DEG C of reduction into slurries under stirring
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion by 4h, filtering, 10 hours dry at 80 DEG C
To constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is 1%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred in autoclave after being rinsed with isopropanol, and
20mL trimethylbenzoquinone is added into autoclave and 380mL isopropanol apply for the first time.It repeats this and applies step
It applies altogether 10 times.
Embodiment 6
1, the powdered activated carbon that 100g granularity is 200~400 mesh is added in the aqueous solution of urea of 1300mL 10mol/L
5h is impregnated, is centrifuged in centrifuge, aqueous solution of urea extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
To constant weight, 700 DEG C of solidification 3h, obtain pretreated active carbon in nitrogen atmosphere within 11 hours for lower drying.
2,12.72g nickel acetate is dissolved in 200mL deionized water, is uniformly mixing to obtain nickel precursor solution；By 94g
Pretreated active carbon is added in nickel precursor solution, impregnates 6h under agitation, adds sodium hydroxide and adjusts impregnating
The pH of system is 7.5, continues to filter after stirring 2h, filter cake is washed with deionized to neutrality, is placed in 80 DEG C of drying in baking oven
To constant weight, then 300 DEG C of activation 2h, the active carbon of the nickel-loaded after being activated in hydrogen atmosphere.
3,50mL 0.1g/mL chlorine palladium aqueous acid is diluted to 200mL with deionized water, is uniformly mixing to obtain palladium forerunner
Liquid solution；The active carbon of nickel-loaded after activation is added in the sodium bicarbonate aqueous solution that 1000mL mass fraction is 8% and is beaten,
It is heated to 60 DEG C under stirring, palladium precursor solution, cooling, filtering after insulated and stirred 2h, filter then is added with jet pump
After cake is beaten with deionized water, slurries are obtained, 50mL formic acid, 70 DEG C of reduction are then added into slurries under stirring
Obtained filter cake is washed with deionized to silver nitrate solution and examines without chloride ion by 2.5h, filtering, and dry 10 is small at 80 DEG C
Up to constant weight, palladium nickel Pd/carbon catalyst is obtained, the mass percent of palladium is 5% in catalyst, and the mass percent of nickel is 1%.
4,20mL trimethylbenzoquinone and 380mL isopropanol are added in autoclave, stirring to dissolving completely, then plus
Enter 1g palladium nickel Pd/carbon catalyst, after air in nitrogen displacement autoclave, then hydrogen displacement nitrogen, it recycles three times, keeps hydrogen
Atmospheric pressure 1.0MPa, speed of agitator are under 1000 turns/min, and normal-temperature reaction 120min filters reaction solution after having reacted, filtrate
With the yield of gas chromatography mass spectrometry chromatography trimethylhydroquinone, filter cake is all transferred in autoclave after being rinsed with isopropanol, and
20mL trimethylbenzoquinone is added into autoclave and 380mL isopropanol apply for the first time.It repeats this and applies step
It applies altogether 10 times.
Comparative example 1
The step 1 of embodiment 1 is changed to: by 100g granularity be 200~400 mesh powdered activated carbon be added 1000mL go from
6h is impregnated in sub- water, is centrifuged in centrifuge, water extra in carbon removal slurry is removed, then precipitating is placed in baking oven, at 80 DEG C
It dries to constant weight.Step 2 and step 3 are same as Example 1, obtain palladium nickel Pd/carbon catalyst.
Comparative example 2
In the step 1 of embodiment 1, the hot setting after drying to constant weight without nitrogen atmosphere, other steps are precipitated
It is same as Example 1, obtain palladium nickel Pd/carbon catalyst.
Comparative example 3
In embodiment 1, without the process of nickel-loaded in step 2, palladium carbon catalyst is prepared merely.
Comparative example 4
In the step 2 of embodiment 1, filter cake directly carries out step 3 without the reduction of hydrogen atmosphere after drying to constant weight
Supported palladium.
The experimental result of above-described embodiment 1~6 and comparative example 1~4 is shown in Table 1.
The yield of 1 different catalysts of table catalysis trimethylbenzoquinone hydrogenation synthesis trimethylhydroquinone
As it can be seen from table 1 using catalyst prepared by the present invention for being catalyzed trimethylbenzoquinone synthesis trimethylhydroquinone
Reaction in, due to addition and the step-by-step reduction of doping vario-property and promoter metal nickel to active carbon, catalyst in activity and
Stability significantly improves, and after applying 10 times, catalytic activity is basically unchanged.
Claims (10)
1. the method that a kind of palladium nickel Pd/carbon catalyst of high stable catalyzes and synthesizes vitamin E intermediate, it is characterised in that: by trimethyl
Benzoquinones is dissolved completely in isopropanol, and palladium nickel Pd/carbon catalyst is added, and in the case where pressure is the hydrogen atmosphere of 0.5~1.5MPa, room temperature is stirred
80~150min of reaction is mixed, filters reaction solution after having reacted, filtrate is purified to obtain vitamin E intermediate --- trimethyl hydrogen
Quinone, filter cake are reused after being rinsed with isopropanol；
The mass fraction of palladium is 3%~10% in above-mentioned palladium nickel Pd/carbon catalyst, and the mass fraction of nickel is 0.2%~4.5%,
It is prepared according to following step:
(1) powdered activated carbon is added in the aqueous solution of urea that concentration is 3~10mol/L and impregnates 4~8h, centrifugation removal is extra
Aqueous solution of urea is deposited at 60~100 DEG C and dries to constant weight, and 400~700 DEG C of 3~6h of solidification, obtain in nitrogen atmosphere
Pretreated active carbon；
(2) soluble-salt of nickel is dissolved in deionized water, is uniformly mixing to obtain nickel precursor solution, pretreatment is then added
Active carbon, under agitation impregnate 2~6h, add alkali compounds adjust dipping system pH be 7~11, continue to stir
It is filtered after mixing 1~5h, 60~100 DEG C of dryings are to constant weight after filter cake is washed with deionized to neutrality, then in hydrogen atmosphere
In 300~800 DEG C of 2~6h of activation, the active carbon of the nickel-loaded after being activated；
(3) soluble-salt of palladium is dissolved in the water, is uniformly mixing to obtain palladium precursor solution；By the work of the nickel-loaded after activation
Property charcoal be added alkali compounds aqueous solution in be beaten, 40~70 DEG C are heated under stirring, is then added with jet pump
Reducing agent reduction, mistake is added in palladium precursor solution, cooling after 2~6h of insulated and stirred, filtering, filter cake after being beaten with deionized water
Filter, filter cake is washed with deionized to no chloride ion, dry, obtains palladium nickel Pd/carbon catalyst.
2. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (1), the mass ratio of the powdered activated carbon and aqueous solution of urea is 1:8~15, wherein powdered activated carbon
Granularity is 200~400 mesh.
3. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (2) and (3), the alkali compounds is sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, carbonic acid
Any one or more in potassium, saleratus.
4. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 3 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (3), the mass fraction of the aqueous solution of the alkali compounds is 1%~20%.
5. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (2), the soluble-salt of the nickel is nickel nitrate or nickel acetate.
6. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (3), the soluble-salt of the palladium be chlorine palladium acid, water-soluble palladium chloride, any one in sodium chloropalladite or
It is a variety of.
7. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (3), the reducing agent is hydrogen, hydrazine hydrate, formic acid, any one in sodium formate.
8. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 7 catalyzes and synthesizes vitamin E intermediate, special
Sign is: in step (3), the temperature of the reduction is 60~80 DEG C, and the recovery time is 2~4h.
9. the palladium nickel Pd/carbon catalyst of high stable described in any one catalyzes and synthesizes vitamin E intermediate according to claim 1~8
Method, it is characterised in that: the mass fraction of palladium is 5% in the palladium nickel Pd/carbon catalyst, and the mass fraction of nickel is 1%~3%.
10. the method that the palladium nickel Pd/carbon catalyst of high stable according to claim 1 catalyzes and synthesizes vitamin E intermediate,
Be characterized in that: the addition quality of the palladium nickel Pd/carbon catalyst and the volume ratio of trimethylbenzoquinone are 1g:10~30mL.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110339851A (en) * | 2019-07-15 | 2019-10-18 | 浙江师范大学 | Catalyst for preparing 2,3,5-trimethylhydroquinone by hydrogenation of 2,3,5-trimethylbenzoquinone and preparation method thereof |
| CN114130416A (en) * | 2021-12-16 | 2022-03-04 | 浙江微通催化新材料有限公司 | Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction |
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| CN1339437A (en) * | 2000-08-18 | 2002-03-13 | 罗切维他命股份公司 | Process for preparing (full racemic)-alpha-tocopherol |
| JP2006249036A (en) * | 2005-03-14 | 2006-09-21 | Honshu Chem Ind Co Ltd | Method for producing 2, 3, 5-trimethylhydroquinone |
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| CN1339437A (en) * | 2000-08-18 | 2002-03-13 | 罗切维他命股份公司 | Process for preparing (full racemic)-alpha-tocopherol |
| JP2006249036A (en) * | 2005-03-14 | 2006-09-21 | Honshu Chem Ind Co Ltd | Method for producing 2, 3, 5-trimethylhydroquinone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110339851A (en) * | 2019-07-15 | 2019-10-18 | 浙江师范大学 | Catalyst for preparing 2,3,5-trimethylhydroquinone by hydrogenation of 2,3,5-trimethylbenzoquinone and preparation method thereof |
| CN114130416A (en) * | 2021-12-16 | 2022-03-04 | 浙江微通催化新材料有限公司 | Preparation method of carbon-supported multi-metal catalyst and application of carbon-supported multi-metal catalyst in N-alkylation reaction |
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