CN109053360A - A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene - Google Patents
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene Download PDFInfo
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- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
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Abstract
The present invention relates to field of fine chemical, particularly with regard to a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene；A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene disclosed in the method for the present invention, this method carries out preparing styrene in fixed bed reactors using a kind of new catalyst catalysis toluene, a kind of new catalyst uses 2, bis- [(dimethylamino) methyl] phenol of 4- and oxymethylene polymerization prepare phenolic resin, then acidic site of the addition aluminium as catalyst, N- methyl aminopropyltriethoxy dimethoxysilane provide the basic sites for depositing machine amine basic group as catalyst；The catalyst of preparation has acidic site and basic sites simultaneously, show that middle strong basicity position reacts highly advantageous to methylbenzene methanol side chain alkylation, can be improved the utilization rate and styrene purity of methanol.
Description
Technical field
The present invention relates to field of fine chemical, and the side of styrene is prepared particularly with regard to a kind of use benzaldehyde containing neodymium adsorbent
Method.
Background technique
Styrene is mainly used for the production of styrene series resin and butadiene-styrene rubber, and production ion exchange resin and doctor
One of important source material of drug, styrene can also be used in the fields such as pharmacy, dyestuff, pesticide and ore dressing.In World Synthetic Resin
The yield of middle styrene series resin ranks among the best.
CN101052617A discloses a kind of ester for preparing dicarboxyl acylimino levulic acid and trans- -4- oxygen -2-
The method of alkyl pentenoates.This method includes two reaction steps, wherein the first step of described two reaction steps is acetyl
The bromination of alkyl propionates is to obtain the second step of (3 and 5)-acetyl bromide alkyl propionates and the two-step reaction
Pass through (3 and 5)-acetyl bromide alkyl propionates obtained in the first step and dicarboximide anionic reactive, synthesis two
The ester of carboxylic acylimino levulic acid and trans- -4- oxygen -2- alkyl pentenoates.
CN102405205A discloses a kind of method for making furfuryl alcohol be converted into levulinate in one-step reaction, is included in
Product levulinate is added in the reaction mixture of alkylol and furfuryl alcohol in the presence of strong protic acid catalyst, wherein passing through
Be not precipitated in the reactive mixture or cured a small amount of tar residue and realize the levulinate of high yield.
CN104402723A discloses a kind of method that alkyl-glucoside prepares levulinate and formic acid esters, with alkyl
Glucoside is raw material, and in the case where being acidified meso-porous carbon material catalyst action, efficient alcoholysis prepares levulinate and formic acid esters combustion
Material or chemicals.The invention extends the preparation method of levulinate and formic acid esters, and raw material sources are abundant, and reagent is easy to back
It receives, simplifies process flow and production cost, it is environmentally protective.
The low problem of the generally existing use ratio of methanol of method that the above invention or the prior art prepare styrene with toluene, wave
Take a large amount of methanol resources, increases the cost of production styrene.
Summary of the invention
To solve the above-mentioned problems, the present invention provides the sides that a kind of use benzaldehyde containing neodymium adsorbent prepares styrene
Method.
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 10-15 parts of nitrogen, 3-7 parts of toluene vapor and
0.8-1.5 parts of methanol steam is after mixing 2-8h with air speed-1By reaction bed, reacting bed tempertaure is 400-600 DEG C, gas
Body pressure is 0.1-1MPa；After the reaction was completed, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；
It is characterized in that the fixed bed reactors are carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:
According to mass fraction, by carboxylic acid, 20-60 parts of methacrylic acid, 1-5 parts of dimethallyl between 5-20 parts of benzaldehyde
Base silane and 40-80 parts of chloroform are added in reaction kettle, and stirring 20-30min is uniformly mixed, and are then added 0.5-1.5 parts
Methyl triallyl silane, 20-30 parts of hexa-methylene bisacrylamide and 0.2-1.0 parts of photoinitiator α-diethoxybenzene
Ethyl ketone,
The 2,2,6,6- of 5,10,15,20- tetra- (4- pyridyl group) porphyrins of 0.001-0.005 parts by weight, 0.01-0.05 parts by weight
(2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] hexahydroxy piperazine of tetramethyl -3,5- heptane diacid neodymium, 0.01-0.05 parts by weight
Pyridine -2- formic acid, after mixing evenly ultraviolet irradiation 20-30min, grind solid after being fully cured, and use the tumer of 10%-20%
Alcoholic solution impregnates 3 times, each 5-10h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 12-20 parts of 2,4- are added in 30-50 parts of ethyl alcohol,
It is uniformly mixed, 40-60 DEG C of temperature control, 10-15 parts of formalin is added drop-wise in reaction kettle under stirring, speed is added dropwise in control
Degree, is added dropwise in 40-80min, is warming up to 70-90 DEG C, reacts 1-5h, be then added 40-60 parts dimethicone,
10-20 parts of N- methyl aminopropyltriethoxy dimethoxysilane and 0.5-5 parts of metallic aluminium powder, 160-200 DEG C of temperature control, stirring
React 3-6h；Room temperature is cooled to after completing reaction, 8-17 parts of template and 40-80 parts of ethyl alcohol is added, is uniformly mixed
The dry 3-8h at 100-150 DEG C afterwards, then obtained solid is crushed, calcine 5-10h under nitrogen atmosphere, calcination temperature is
It 650-850 DEG C, is ground after cooling, the new catalyst can be obtained.
The formalin concentration is 30%-40%.
The template is poloxamer or Tri-n-Propylamine or tetrabutylammonium chloride.
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene disclosed in the method for the present invention, this method use one
Kind new catalyst catalysis toluene prepares styrene and carries out in fixed bed reactors, and a kind of new catalyst uses 2,
Bis- [(dimethylamino) methyl] phenol of 4- and oxymethylene polymerization prepare phenolic resin, then add acidic site of the aluminium as catalyst,
N- methyl aminopropyltriethoxy dimethoxysilane provides the basic sites for depositing machine amine basic group as catalyst；Preparation is urged
Agent has acidic site and basic sites simultaneously, show that middle strong basicity position reacts highly advantageous to methylbenzene methanol side chain alkylation, can
Improve the utilization rate and styrene purity of methanol.
Specific embodiment
The invention is described further below by specific embodiment:
Embodiment 1
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 13 parts of nitrogen, and 5 parts of toluene vapor and 1.2 parts
Methanol steam be after mixing 5h with air speed-1By reaction bed, reacting bed tempertaure is 500 DEG C, gas pressure 0.6MPa；
After the reaction was completed, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；It is characterized in that described
Fixed bed reactors are carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:, will be between 12 parts of benzaldehyde according to mass fraction
Carboxylic acid, 40 parts of methacrylic acid, 3 parts of dimethallyl base silane and 60 parts of chloroform are added in reaction kettle, stirring
25min is uniformly mixed, and 1 part of methyl triallyl silane, 25 parts of hexa-methylene bisacrylamide and 0.7 part is then added
Photoinitiator α-diethoxy acetophenone, the 5 of 0.002 parts by weight, 10,15,20- tetra- (4- pyridyl group) porphyrins, 0.02 parts by weight
2,2,6,6- tetramethyl -3,5- heptane diacid neodymium, 0.04 parts by weight (2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] six hydroxyls
Phenylpiperidines -2- formic acid, after mixing evenly ultraviolet irradiation 25min, grind solid after being fully cured, and use 15% acetate methanol
Solution impregnates 3 times, each 8h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 16 parts of 2,4- are added in 40 parts of ethyl alcohol, stirring is mixed
It closes uniformly, 50 DEG C of temperature control, 13 parts of formalin is added drop-wise in reaction kettle under stirring, control rate of addition, dripped in 60min
It adds complete, is warming up to 80 DEG C, reacts 3h, 50 parts of dimethicone, 15 parts of N- methyl aminopropyltriethoxy diformazan is then added
Oxysilane and 2.5 parts of metallic aluminium powder, are stirred to react 4h by 180 DEG C of temperature control；Room temperature is cooled to after completing reaction, is added 12
The template and 60 parts of ethyl alcohol of part dry 5h at 130 DEG C after being uniformly mixed, then crush obtained solid,
7h is calcined under nitrogen atmosphere, calcination temperature is 750 DEG C, grinds after cooling, the new catalyst can be obtained.
The formalin concentration is 35%.
The template is poloxamer.
This experiment use ratio of methanol is 54.85%, and styrene purity is 99.92%.
Embodiment 2
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 13 parts of nitrogen, and 4 parts of toluene vapor and 0.8 part
Methanol steam be after mixing 2h with air speed-1By reaction bed, reacting bed tempertaure is 400 DEG C, gas pressure 0.1MPa；
After the reaction was completed, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；It is characterized in that described
Fixed bed reactors are carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme: according to mass fraction, by carboxylic between 5 parts of benzaldehyde
Acid, 20 parts of methacrylic acid, 1 part of dimethallyl base silane and 40 parts of chloroform are added in reaction kettle, stir 20min
It is uniformly mixed, 0.5 part of methyl triallyl silane, 20 parts of hexa-methylene bisacrylamide and 0.2 part of light is then added
Initiator α-diethoxy acetophenone, the 5 of 0.001 parts by weight, 10,15,20- tetra- (4- pyridyl group) porphyrins, 0.01 parts by weight
(2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] hexahydroxy of 2,2,6,6- tetramethyl -3,5- heptane diacid neodymium, 0.01 parts by weight
Piperidines -2- formic acid, after mixing evenly ultraviolet irradiation 20min, grind solid after being fully cured, molten using 10% acetate methanol
Liquid impregnates 3 times, each 5h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 12 parts of 2,4- are added in 30 parts of ethyl alcohol, stirring is mixed
It closes uniformly, 40 DEG C of temperature control, 10 parts of formalin is added drop-wise in reaction kettle under stirring, control rate of addition, dripped in 40min
It adds complete, is warming up to 70 DEG C, reacts 1h, 40 parts of dimethicone, 10 parts of N- methyl aminopropyltriethoxy diformazan is then added
Oxysilane and 0.5 part of metallic aluminium powder, are stirred to react 3h by 160 DEG C of temperature control；Room temperature is cooled to after completing reaction, is added 8 parts
Template and 40 parts of ethyl alcohol, after being uniformly mixed at 100 DEG C dry 3h, then obtained solid is crushed, in nitrogen
Atmosphere encloses lower calcining 5h, and calcination temperature is 650 DEG C, grinds after cooling, the new catalyst can be obtained.
The formalin concentration is 30%.
The template is tetrabutylammonium chloride.
This experiment use ratio of methanol is 52.73%, and styrene purity is 99.91%.
Embodiment 3
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 15 parts of nitrogen, and 7 parts of toluene vapor and 1.5 parts
Methanol steam be after mixing 8h with air speed-1By reaction bed, reacting bed tempertaure is 600 DEG C, gas pressure 1MPa；Instead
After the completion of answering, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；It is characterized in that described consolidates
Fixed bed reactor is carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:, will be between 20 parts of benzaldehyde according to mass fraction
Carboxylic acid, 60 parts of methacrylic acid, 5 parts of dimethallyl base silane and 80 parts of chloroform are added in reaction kettle, stirring
30min is uniformly mixed, then 1.5 parts of methyl triallyl silane of addition, 30 parts of hexa-methylene bisacrylamide and 1.0 parts
Photoinitiator α-diethoxy acetophenone, the 5 of 0.005 parts by weight, 10,15,20- tetra- (4- pyridyl group) porphyrins, 0.05 weight
Part 2,2,6,6- tetramethyl -3,5- heptane diacid neodymium, 0.05 parts by weight (2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] six
Hydroxy piperidine -2- formic acid, after mixing evenly ultraviolet irradiation 30min, grind solid after being fully cured, and use 20% tumer
Alcoholic solution impregnates 3 times, each 10h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 20 parts of 2,4- are added in 50 parts of ethyl alcohol, stirring is mixed
It closes uniformly, 60 DEG C of temperature control, 15 parts of formalin is added drop-wise in reaction kettle under stirring, control rate of addition, dripped in 80min
It adds complete, is warming up to 90 DEG C, reacts 5h, 60 parts of dimethicone, 20 parts of N- methyl aminopropyltriethoxy diformazan is then added
Oxysilane and 5 parts of metallic aluminium powder, are stirred to react 6h by 200 DEG C of temperature control；Room temperature is cooled to after completing reaction, is added 17 parts
Template and 80 parts of ethyl alcohol, after being uniformly mixed at 150 DEG C dry 8h, then obtained solid is crushed, in nitrogen
Atmosphere encloses lower calcining 10h, and calcination temperature is 850 DEG C, grinds after cooling, the new catalyst can be obtained.
The formalin concentration is 40%.
The template is Tri-n-Propylamine.
This experiment use ratio of methanol is 56.71%, and styrene purity is 99.95%.
Embodiment 4
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 13 parts of nitrogen, and 4 parts of toluene vapor and 0.8 part
Methanol steam be after mixing 2h with air speed-1By reaction bed, reacting bed tempertaure is 400 DEG C, gas pressure 0.1MPa；
After the reaction was completed, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；It is characterized in that described
Fixed bed reactors are carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:, will be between 12 parts of benzaldehyde according to mass fraction
Carboxylic acid, 40 parts of methacrylic acid, 3 parts of dimethallyl base silane and 60 parts of chloroform are added in reaction kettle, stirring
25min is uniformly mixed, and 1 part of methyl triallyl silane, 25 parts of hexa-methylene bisacrylamide and 0.7 part is then added
Photoinitiator α-diethoxy acetophenone, the 5 of 0.001 parts by weight, 10,15,20- tetra- (4- pyridyl group) porphyrins, 0.05 parts by weight
2,2,6,6- tetramethyl -3,5- heptane diacid neodymium, 0.01 parts by weight (2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] six hydroxyls
Phenylpiperidines -2- formic acid, after mixing evenly ultraviolet irradiation 25min, grind solid after being fully cured, and use 15% acetate methanol
Solution impregnates 3 times, each 8h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 20 parts of 2,4- are added in 50 parts of ethyl alcohol, stirring is mixed
It closes uniformly, 60 DEG C of temperature control, 15 parts of formalin is added drop-wise in reaction kettle under stirring, control rate of addition, dripped in 80min
It adds complete, is warming up to 90 DEG C, reacts 5h, 60 parts of dimethicone, 20 parts of N- methyl aminopropyltriethoxy diformazan is then added
Oxysilane and 5 parts of metallic aluminium powder, are stirred to react 6h by 200 DEG C of temperature control；Room temperature is cooled to after completing reaction, is added 17 parts
Template and 80 parts of ethyl alcohol, after being uniformly mixed at 150 DEG C dry 8h, then obtained solid is crushed, in nitrogen
Atmosphere encloses lower calcining 10h, and calcination temperature is 850 DEG C, grinds after cooling, the new catalyst can be obtained.
The formalin concentration is 38%.
The template is poloxamer.
This experiment use ratio of methanol is 54.86%, and styrene purity is 99.92%.
Embodiment 5
A kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 15 parts of nitrogen, and 7 parts of toluene vapor and 1.5 parts
Methanol steam be after mixing 8h with air speed-1By reaction bed, reacting bed tempertaure is 600 DEG C, gas pressure 1MPa；Instead
After the completion of answering, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；It is characterized in that described consolidates
Fixed bed reactor is carried out using a kind of catalysis reaction of new catalyst.
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:, will be between 20 parts of benzaldehyde according to mass fraction
Carboxylic acid, 60 parts of methacrylic acid, 5 parts of dimethallyl base silane and 80 parts of chloroform are added in reaction kettle, stirring
30min is uniformly mixed, then 1.5 parts of methyl triallyl silane of addition, 30 parts of hexa-methylene bisacrylamide and 1.0 parts
Photoinitiator α-diethoxy acetophenone, the 5 of 0.003 parts by weight, 10,15,20- tetra- (4- pyridyl group) porphyrins, 0.01 weight
Part 2,2,6,6- tetramethyl -3,5- heptane diacid neodymium, 0.05 parts by weight (2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] six
Hydroxy piperidine -2- formic acid, after mixing evenly ultraviolet irradiation 30min, grind solid after being fully cured, and use 20% tumer
Alcoholic solution impregnates 3 times, each 10h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 12 parts of 2,4- are added in 30 parts of ethyl alcohol, stirring is mixed
It closes uniformly, 40 DEG C of temperature control, 10 parts of formalin is added drop-wise in reaction kettle under stirring, control rate of addition, dripped in 40min
It adds complete, is warming up to 70 DEG C, reacts 1h, 40 parts of dimethicone, 10 parts of N- methyl aminopropyltriethoxy diformazan is then added
Oxysilane and 0.5 part of metallic aluminium powder, are stirred to react 3h by 160 DEG C of temperature control；Room temperature is cooled to after completing reaction, is added 8 parts
Template and 40 parts of ethyl alcohol, after being uniformly mixed at 100 DEG C dry 3h, then obtained solid is crushed, in nitrogen
Atmosphere encloses lower calcining 5h, and calcination temperature is 650 DEG C, grinds after cooling, the new catalyst can be obtained.
The formalin concentration is 33%.
The template is Tri-n-Propylamine.
This experiment use ratio of methanol is 54.17%, and styrene purity is 99.91%.
Comparative example 1
The adsorbent of benzaldehyde containing neodymium, the other the same as in Example 1 is not added.
This experiment use ratio of methanol is 41.71%, and styrene purity is 94.88%.
Comparative example 2
N- methyl aminopropyltriethoxy dimethoxysilane, the other the same as in Example 1 is not added.
This experiment use ratio of methanol is 26.15%, and styrene purity is 99.01%.
Comparative example 3
5,10,15,20- tetra- (4- pyridyl group) porphyrins, the other the same as in Example 1 is not added.
This experiment use ratio of methanol is 27.54%, and styrene purity is 98.81%.
Comparative example 4
2,2,6,6- tetramethyl -3,5- heptane diacid neodymiums, the other the same as in Example 1 is not added.
This experiment use ratio of methanol is 24.51%, and styrene purity is 98.38%.
Comparative example 5
(2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] hexahydroxy piperidines -2- formic acid, the other the same as in Example 1 is not added.
This experiment use ratio of methanol is 36.81%, and styrene purity is 98.14%.
Claims (5)
1. a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene, its technical solution is as follows:
This method is always carried out in fixed bed reactors, according to molar ratio, by 10-15 parts of nitrogen, 3-7 parts of toluene vapor and
0.8-1.5 parts of methanol steam is after mixing 2-8h with air speed-1By reaction bed, reacting bed tempertaure is 400-600 DEG C, gas
Body pressure is 0.1-1MPa；After the reaction was completed, the benzaldehyde contained in styrene is removed using a kind of adsorbent of benzaldehyde containing neodymium；
It is characterized in that the fixed bed reactors are carried out using a kind of catalysis reaction of new catalyst.
2. a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene according to claim 1, it is characterised in that:
The adsorbent of benzaldehyde containing neodymium is prepared according to following scheme:
According to mass fraction, by carboxylic acid, 20-60 parts of methacrylic acid, 1-5 parts of dimethallyl between 5-20 parts of benzaldehyde
Base silane and 40-80 parts of chloroform are added in reaction kettle, and stirring 20-30min is uniformly mixed, and are then added 0.5-1.5 parts
Methyl triallyl silane, 20-30 parts of hexa-methylene bisacrylamide and 0.2-1.0 parts of photoinitiator α-diethoxybenzene
Ethyl ketone,
The 2,2,6,6- of 5,10,15,20- tetra- (4- pyridyl group) porphyrins of 0.001-0.005 parts by weight, 0.01-0.05 parts by weight
(2R) -1- [(9H- fluorenes -9- methoxyl group) carbonyl] hexahydroxy piperazine of tetramethyl -3,5- heptane diacid neodymium, 0.01-0.05 parts by weight
Pyridine -2- formic acid, after mixing evenly ultraviolet irradiation 20-30min, grind solid after being fully cured, and use the tumer of 10%-20%
Alcoholic solution impregnates 3 times, each 5-10h, and then methanol washs, dry, and the adsorbent of benzaldehyde containing neodymium can be obtained.
3. a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene according to claim 1, it is characterised in that:
The new catalyst is prepared according to following scheme:
According to mass fraction, bis- [(dimethylamino) methyl] phenol of 12-20 parts of 2,4- are added in 30-50 parts of ethyl alcohol,
It is uniformly mixed, 40-60 DEG C of temperature control, 10-15 parts of formalin is added drop-wise in reaction kettle under stirring, speed is added dropwise in control
Degree, is added dropwise in 40-80min, is warming up to 70-90 DEG C, reacts 1-5h, be then added 40-60 parts dimethicone,
10-20 parts of N- methyl aminopropyltriethoxy dimethoxysilane and 0.5-5 parts of metallic aluminium powder, 160-200 DEG C of temperature control, stirring
React 3-6h；Room temperature is cooled to after completing reaction, 8-17 parts of template and 40-80 parts of ethyl alcohol is added, is uniformly mixed
The dry 3-8h at 100-150 DEG C afterwards, then obtained solid is crushed, calcine 5-10h under nitrogen atmosphere, calcination temperature is
It 650-850 DEG C, is ground after cooling, the new catalyst can be obtained.
4. a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene according to claim 4, it is characterised in that:
The formalin concentration is 30%-40%.
5. a kind of method that use benzaldehyde containing neodymium adsorbent prepares styrene according to claim 4, it is characterised in that:
The template is poloxamer or Tri-n-Propylamine or tetrabutylammonium chloride.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960910A (en) * | 2020-07-24 | 2020-11-20 | 浙江环化科技有限公司 | Method for preparing styrene by efficiently alkylating toluene and methanol side chains |
| CN113831032A (en) * | 2021-05-03 | 2021-12-24 | 浙江红狮环保股份有限公司 | Cement clinker generation method using gold tailing slag as raw material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912788A (en) * | 2010-07-31 | 2010-12-15 | 太原理工大学 | Amino-containing resorcin aluminum bifunctional catalyst as well as synthetic method and application thereof |
| CN102380413A (en) * | 2011-08-26 | 2012-03-21 | 上海华谊（集团）公司 | Alkaline molecular sieve catalyst for preparation of styrene, and preparation method thereof |
| US20120296141A1 (en) * | 2011-05-22 | 2012-11-22 | Fina Technology, Inc. | Addition of a base to enhance product yield in alkylation reactions |
| CN104069837A (en) * | 2014-06-27 | 2014-10-01 | 广东石油化工学院 | Adsorbing agent for removing trace benzaldehyde impurities in styrene |
| CN106238008A (en) * | 2016-07-28 | 2016-12-21 | 王金明 | A kind of preparation method of 8 acetoxyl group octanal purification adsorbents |
-
2018
- 2018-09-25 CN CN201811117188.2A patent/CN109053360A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912788A (en) * | 2010-07-31 | 2010-12-15 | 太原理工大学 | Amino-containing resorcin aluminum bifunctional catalyst as well as synthetic method and application thereof |
| US20120296141A1 (en) * | 2011-05-22 | 2012-11-22 | Fina Technology, Inc. | Addition of a base to enhance product yield in alkylation reactions |
| CN102380413A (en) * | 2011-08-26 | 2012-03-21 | 上海华谊（集团）公司 | Alkaline molecular sieve catalyst for preparation of styrene, and preparation method thereof |
| CN104069837A (en) * | 2014-06-27 | 2014-10-01 | 广东石油化工学院 | Adsorbing agent for removing trace benzaldehyde impurities in styrene |
| CN106238008A (en) * | 2016-07-28 | 2016-12-21 | 王金明 | A kind of preparation method of 8 acetoxyl group octanal purification adsorbents |
Non-Patent Citations (1)
| Title |
|---|
| WANG, B ET AL.: "Side-chain Alkylation of Toluene With Methanol over a Novel Solid Acid-base Catalyst", 《ENERGY SOURCES PART A-RECOVERY UTILIZATION AND ENVIRONMENTAL EFFECTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111960910A (en) * | 2020-07-24 | 2020-11-20 | 浙江环化科技有限公司 | Method for preparing styrene by efficiently alkylating toluene and methanol side chains |
| CN113831032A (en) * | 2021-05-03 | 2021-12-24 | 浙江红狮环保股份有限公司 | Cement clinker generation method using gold tailing slag as raw material |
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