CN102976903A - Process for synthesizing 2,3,6-trimethylphenol by phenol - Google Patents
Process for synthesizing 2,3,6-trimethylphenol by phenol Download PDFInfo
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Abstract
The invention relates to a process for synthesizing 2,3,6-trimethylphenol by phenol, and belongs to the technical field of medicine chemical industry. The process comprises the following steps of: firstly, carrying out a gas-phase reaction by mixing the phenol with methyl alcohol through a catalyst to obtain 2,6-dimethylphenol; and preparing a 2,3,6-trimethylphenol finished product by carrying out a sulfonation reaction, an esterification reaction, a friedel-crafts acylation reaction and a desulfonation reaction. According to the process for synthesizing the 2,3,6-trimethylphenol by the phenol, the problems that the existing m-cresol raw material is lack so as to seriously restrict the yield of the 2,3,6-trimethylphenol, and the service life of a catalyst is largely reduced and the production cost is increased because a catalytic reaction needs to be carried out at high temperature under high pressure during meta-methylation are solved. According to the process for synthesizing the 2,3,6-trimethylphenol by the phenol, the transformation rate and the selectivity of a reaction are improved; and meanwhile, the preparation cost of products is largely reduced, and the economical benefits and the social benefits are excellent.
Description
Technical field
The present invention relates to a kind of technique by the phenol synthesis 2,3,6-TMP, belong to pharmaceutical chemistry technical field.
Background technology
Three cresols are 2,3,6-TMP, be mainly used in medicine industry, synthesising complex E ring 2,3, the 5-trimethylammonium as the monomer of producing heat resistant poly phenylate engineering plastics and the raw material of polyblend, also is indispensable intermediate in this external some agricultural chemicals, the sterilizing agent production also to the benzene quinhydrones.
At present both at home and abroad the operational path of synthetic three cresols is more, but adapt to industrialized production mainly contain two, the one, take meta-cresol as raw material, methyl alcohol is methylating agent, under catalyst action, uses the gas-solid phase reaction one-step synthesis to produce 2,3,6-TMP.The problem of this technique is that major part relies on import because domestic meta-cresol raw material is in short supply, has therefore seriously restricted the output of China's 2,3,6-TMP.The 2nd, adopting 2,6-xylenol is raw material, and the preparation 2,3,6-TMP directly methylates.Namely the raw material of this technique can methylate by phenol and directly prepare, pass through 2 again, obtain 2 when the position methylates between the 6-xylenol, 3, the 6-pseudocuminol and since between the position need under High Temperature High Pressure catalysis, react when methylating, thereby the life-span of catalyzer is reduced greatly, and selectivity is also poor, and production cost is improved greatly.
Summary of the invention
The object of the invention is to: provide a kind of have higher transformation efficiency and selectivity, the technique of passing through the phenol synthesis 2,3,6-TMP that preparation cost is low.
Technical scheme of the present invention is:
A kind of technique by the phenol synthesis 2,3,6-TMP, it is characterized in that: it may further comprise the steps:
The first step, 2, the preparation of 6-xylenol:
By the fixed bed reactor of Iron oxide catalyst is housed, be that 200～400 ℃, pressure be 0.1～1Mpa, liquid air speed be 0.1～3h in temperature with the mixed solution of phenol and methyl alcohol
-1Condition under, carry out gas phase catalytic reaction, reaction product through separate 2, the 6-xylenol, stand-by.The gas that reactor flows out by air cooling and circulating water after, absorb with methyl alcohol;
The preparation of second step, sulfur trioxide gas:
Adding successively quality in the sulfur trioxide gas producer is 65% oleum, zeolite and Vanadium Pentoxide in FLAKES, is heated between 80～100 ℃ with electric heating cover, and the sulfur trioxide gas of generation is stand-by through nitrogen dilution to 7%.
The 3rd step, sulfonation reaction:
The sulphonating agent that sulfonation reaction is selected is the sulfur trioxide gas of aforesaid method preparation, with prepare 2, the 6-xylenol joins in the autoclave bubbling reactor, simultaneously intensification also passes into through nitrogen dilution to 7% sulfur trioxide gas under 75 ℃ of temperature condition, then with ultra thermostat the autoclave bubbling reactor is carried out the constant temperature water bath insulation, the control temperature of reaction stirs in 80～100 ℃ scope simultaneously, and stirring velocity is controlled at 80～120r/min.Along with the carrying out of reaction, the viscosity of reactant increases gradually, and color and luster is gradually flavescence also.Getting liquid carries out high performance liquid chromatography and detect to analyze 2,6-xylenol: when 4-hydroxyl-3,5-acid dimethyl＜1:99, with the nitrogen of drying sulphur trioxide unnecessary in the reaction solution is taken away, between nitrogen protection borehole cooling to 20～30 ℃, reaction solution is stand-by.
The 4th step, esterification:
The reaction solution that sulfonation reaction is finished is transferred in the four-hole round-bottomed flask, and adding successively massfraction in the reaction solution is 99% industrial methanol and 98% sulfuric acid, control stirring velocity heat temperature raising between 60～80r/min under the nitrogen protection; Be warmed up to reflux state; reflux to begin to extract reaction solution with high performance liquid chromatography after 3 hours and detect; 4-hydroxyl-3 to be detected; 5-acid dimethyl: 4-hydroxyl-3; begin air distillation during 5-acid dimethyl methyl esters＜2:98 and reclaim methyl alcohol; the water that generates to take away partial esterification reaction distills under the complete rear nitrogen protection the concentrated solution cooling, cools to after the room temperature stand-by under the nitrogen protection.
The 5th step, pair gram alkylated reaction:
In the concentrated solution of above-mentioned esterification, add 1; the 2-dichlorobenzene; heat up under the nitrogen protection; begin insulation reaction when being warmed up between 90～110 ℃; reacting took a sample after 3～5 hours detects by high performance liquid chromatography, detects 4-hydroxyl-3,5-acid dimethyl methyl esters: 4-hydroxyl-2; begin the aftertreatment cooling during 3,5-tri-methyl p-toluenesulfonate＜2:98.
The 6th goes on foot, takes off the alkylsulfonyl reaction:
With 4-hydroxyl-2,3, the cooling of 5-tri-methyl p-toluenesulfonate reaction solution, in reaction solution, add entry and begin the oil bath intensification when cooling to 80 ℃, be warmed up to 170 ℃ and kept this thermotonus 2～5 hours, reaction cools to 80 ℃ after finishing, and then add water for cooling layering in static 30 minutes to the room temperature, add 5% sodium bicarbonate aqueous solution washing in the organic phase, so that acid is removed, again the organic phase concentrating under reduced pressure is reclaimed 1, the 2-dichlorobenzene carries out rectifying with concentrated solution after solvent recuperation is complete, gets 2,3,6-pseudocuminol finished product.
Described Iron oxide catalyst consists of with ferric oxide as leading and containing cocatalyst, and cocatalyst comprises manganese oxide, silicon oxide, chromic oxide, calcium oxide, potassium oxide, graphite; The mol ratio of each composition is with chemical formulation: Fe in the Iron oxide catalyst
2O
3: MnO
2: SiO
2: Cr
2O
3: CaO:K
2O:C=1:(0.005～0.2): (0.001～0.1): (0.001～0.15): (0.0001～0.015): (0.0001～0.02): (0.005～0.15).
Its preparation method is:
Taking by weighing successively mol ratio is 1:(0.005～0.2): (0.001～0.1): (0.001～0.15): the Fe (NO of (0.0001～0.015)
3)
39H
2O, Mn(NO
3)
24H
2O, Cr(NO
3)
39H
2O, Na
2SiO
39H
2O, CaCl
22H
2O is added to the water and makes solution, and adding 28% ammonia precipitation process agent to the pH value of solution in the solution is 7.5～8, and leaving standstill wears out makes its co-precipitation; After the throw out washing that obtains, 70-200 ℃ of oven dry, be ground into 50～100 purpose particles, put into 1%K
2CO
3Flood 10～40h in the aqueous solution; Particulate matter behind the dipping is dried under 70-200 ℃ of temperature again, again in 400-600 ℃ of roasting 2-8h, oxide compound has become the same particle of coal dust, add mol ratio and be the graphite of (0.005～0.15) as lubricant and setting agent, finally obtain the columned Iron oxide catalyst of 3 * 3mm behind the compressing tablet.
The present invention's beneficial effect compared with prior art is:
1, the present invention is take phenol cheap and easy to get as raw material; Can make 2,3,6-TMP by polystep reaction, solve the raw material sources of preparation of industrialization;
2, used novel catalyzer, successive reaction reached more than 99% the transformation efficiency of phenol without decay in 3 months, and secondary methyl rate reaches more than 98.5%;
3, sulfonation reaction is introduced a functional group in the contraposition of phenolic hydroxyl group, thereby has stoped the methylated possibility of contraposition, has improved the selectivity of reaction;
4, unreacted former methyl alcohol recycled, waste heat recovery is used, and has reduced energy consumption and material consumption, and is not only energy-conservation but also reduce discharging;
5, by intramolecular friedel-crafts reaction methylate greatly improved between the position monomethylation selectivity;
6, used fixed-bed reactor, cost of equipment is reduced.Reduce the preparation cost of 2,3,6-TMP, had significant economic benefit.
Embodiment
Embodiment 1:
Take by weighing successively 500gFe (NO
3)
39H
2O, 30gMn (NO
3)
24H
2O, 5gCr (NO
3)
39H
2O, 3gNa
2SiO
39H
2O and 1gCaCl
22H
2O is dissolved in the 10l water and makes the aqueous solution, and adding 28% ammonia precipitation process agent to the pH value of the aqueous solution in the aqueous solution is 7.5, and leaving standstill wears out made its co-precipitation after 12 hours; After the throw out that obtains filtered and wash with water, oven dry in 6 hours was ground into 50 purpose particles under 150 ℃ of conditions, puts into 300ml1%K
2CO
3Room temperature dipping 30h in the aqueous solution; With again oven dry in 5 hours under 150 ℃ of temperature of the particulate matter behind the dipping, in 500 ℃ of roasting 5h, after oxide compound has become the same particle of coal dust, add 1g graphite as lubricant and setting agent, obtain the right cylinder that columned Iron oxide catalyst is pressed into 3 * 3mm behind the final compressing tablet, obtain an Iron oxide catalyst that is comprised of ferric oxide, manganese oxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mol ratio of the each component in the catalyzer is Fe
2O
3: MnO
2: SiO
2: Cr
2O
3: CaO:K
2O:C=1:0.07:0.0082:0.01:0.006:0.0015:0.03.
The catalyzer of preparation is put into a fixed bed reactor with diameter 15mm internal diameter reaction tube, according to the mole ratio of phenol: methyl alcohol=1:5, is that 0.2MPa, temperature are that 250 ℃ and liquid air speed are 0.5h with the mixed solution of phenol and methyl alcohol at pressure
-1Condition under pass into and carry out gas phase catalytic reaction in the fixed bed reactor, reaction product through separate 2, the 6-xylenol, stand-by.The gas that will flow out from reactor by air cooling and circulating water after, absorb with methyl alcohol, adopt the high-efficient liquid phase chromatogram technique analysis reaction product to form content, its result is as shown in the table:
Adding successively the 200ml quality in the sulfur trioxide gas producer is 65% oleum, zeolite 10g and Vanadium Pentoxide in FLAKES 30g, through nitrogen dilution to 7%, stand-by with the sulfur trioxide gas of 80 ℃ of generations of electric heating cover heating.
With 2 of preparation, 6-xylenol 61g(0.5mol) join in the autoclave bubbling reactor, heat up simultaneously and the 42g(0.525mol after passing into dilution under 75 ℃ of temperature condition) sulfur trioxide gas; Then with ultra thermostat the autoclave bubbling reactor is carried out the constant temperature water bath insulation, the control temperature of reaction stirs with speed 80r/min simultaneously at 80 ℃, so that its sulfonation reaction becomes 4-hydroxyl-3, and the 5-acid dimethyl.Along with the carrying out of reaction, the viscosity of reactant increases gradually, and color and luster is gradually flavescence also.Getting liquid carries out high performance liquid chromatography and detect to analyze 2,6-xylenol: when 4-hydroxyl-3,5-acid dimethyl＜1:99, with the nitrogen of drying sulphur trioxide unnecessary in the reaction solution is taken away, the nitrogen protection borehole cooling is to room temperature, and reaction solution is stand-by.
The reaction solution that sulfonation reaction is finished is transferred in the 500ml four-hole round-bottomed flask; the industrial methanol and the 59g(0.6mol that add successively 100ml massfraction 99% in the reaction solution) 98% sulfuric acid; speed with 60r/min under the nitrogen protection stirs; heat to backflow with oil bath simultaneously; make it carry out esterification; reaction generates 4-hydroxyl-3; 5-acid dimethyl methyl esters; reflux to begin to extract reaction solution with high performance liquid chromatography after 3 hours and detect; 4-hydroxyl-3 to be detected; 5-acid dimethyl: 4-hydroxyl-3; begin air distillation during 5-acid dimethyl methyl esters＜2:98 and reclaim methyl alcohol; the water that generates to take away the partial esterification reaction distills and protects concentrated solution stand-by under the complete rear nitrogen.
The concentrated solution of finishing esterification is transferred in the 1000ml four-hole round-bottomed flask; in the concentrated solution of esterification, add 1,2-dichlorobenzene 300ml, begin insulation when being warming up to 95 ℃ under the nitrogen protection and pay the gram alkylated reaction; reaction generates 4-hydroxyl-2; 3,5-tri-methyl p-toluenesulfonate, reacting took a sample after 5 hours detects by high performance liquid chromatography; detect 4-hydroxyl-3; 5-acid dimethyl methyl esters: begin the aftertreatment cooling when 4-hydroxyl-2,3,5-tri-methyl p-toluenesulfonate＜2:98.
With 4-hydroxyl-2; 3; add 20g water when 5-tri-methyl p-toluenesulfonate reaction solution cools to 80 ℃ and begin oil bath and heat up; be warmed up to 170 ℃ and keep this temperature to take off alkylsulfonyl reaction in 4 hours; reaction cools to 80 ℃ after finishing; and then adding 250ml water for cooling leaves standstill layering in 30 minutes to room temperature; in organic phase, add the stirring of 200ml5% sodium bicarbonate aqueous solution, stir and leave standstill layering in 30 minutes after 30 minutes, so that acid is removed; again the organic phase concentrating under reduced pressure is reclaimed 1; the 2-dichlorobenzene carries out rectifying with concentrated solution after solvent recuperation is complete, gets 51g 2; 3,6-pseudocuminol finished product.63 ℃～64 ℃ of 2,3,6-pseudocuminol fusing points, purity: 99.2%, content: 99%.
Embodiment 2
Take by weighing successively 550gFe (NO
3)
39H
2O, 35gMn (NO
3)
24H
2O, 5gCr (NO
3)
39H
2O, 6gNa
2SiO
39H
2O and 1.5gCaCl
22H
2O is dissolved in the 10l water and makes the aqueous solution, and adding 28% ammonia precipitation process agent to the pH value of the aqueous solution in the aqueous solution is 7.5, and leaving standstill wears out made its co-precipitation after 14 hours; After the throw out that obtains filtered and wash with water, oven dry in 4 hours was ground into 70 purpose particles under 180 ℃ of conditions, puts into 300ml1%K
2CO
3Room temperature dipping 30h in the aqueous solution; With again oven dry in 3 hours under 180 ℃ of temperature of the particulate matter behind the dipping, be 550 ℃ of roasting 3h after the oven dry, after oxide compound has become the same particle of coal dust, add 0.5g graphite as lubricant and setting agent, obtain the right cylinder that columned Iron oxide catalyst is pressed into 3 * 3mm behind the final compressing tablet, obtain an Iron oxide catalyst that is comprised of ferric oxide, manganese oxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mol ratio of the each component in the catalyzer is: Fe
2O
3: MnO
2: SiO
2: Cr
2O
3: CaO:K
2O:C=
1:0.073:0.015:0.0087:0.0089:0.0015:0.015。
The catalyzer of preparation is put into a fixed bed reactor with diameter 15mm internal diameter reaction tube, according to the mole ratio of phenol: methyl alcohol=1:5, is that 0.5MPa, temperature are that 300 ℃ and liquid air speed are 1h with the mixed solution of phenol and methyl alcohol at pressure
-1Condition under pass into and carry out gas phase catalytic reaction in the fixed bed reactor, reaction product through separate 2, the 6-xylenol, stand-by.The gas that will flow out from reactor by air cooling and circulating water after, absorb with methyl alcohol, adopt the high-efficient liquid phase chromatogram technique analysis reaction product to form content, its result is as shown in the table:
Adding successively the 200ml quality in the sulfur trioxide gas producer is 65% oleum, zeolite 10g and Vanadium Pentoxide in FLAKES 30g, through nitrogen dilution to 7%, stand-by with the sulfur trioxide gas of 90 ℃ of generations of electric heating cover heating.
With 2 of preparation, 6-xylenol 61g(0.5mol) join in the autoclave bubbling reactor, heat up simultaneously and the 42g(0.525mol after passing into dilution under 75 ℃ of temperature condition) sulfur trioxide gas; Then with ultra thermostat the autoclave bubbling reactor is carried out the constant temperature water bath insulation, the control temperature of reaction stirs with speed 100r/min simultaneously at 90 ℃, so that its sulfonation generates 4-hydroxyl-3,5-acid dimethyl.Along with the carrying out of reaction, the viscosity of reactant increases gradually, and color and luster is gradually flavescence also.Getting liquid carries out high performance liquid chromatography and detect to analyze 2,6-xylenol: when 4-hydroxyl-3,5-acid dimethyl＜1:99, with the nitrogen of drying sulphur trioxide unnecessary in the reaction solution is taken away, the nitrogen protection borehole cooling is to room temperature, and reaction solution is stand-by.
The reaction solution that sulfonation reaction is finished is transferred in the 500ml four-hole round-bottomed flask; the industrial methanol and the 59g(0.6mol that add successively 100ml massfraction 99% in the reaction solution) 98% sulfuric acid; speed with 70r/min under the nitrogen protection stirs; heat to backflow with oil bath simultaneously; make it carry out esterification; reaction generates 4-hydroxyl-3; 5-acid dimethyl methyl esters; reflux to begin to extract reaction solution with high performance liquid chromatography after 3 hours and detect; 4-hydroxyl-3 to be detected; 5-acid dimethyl: 4-hydroxyl-3; begin air distillation during 5-acid dimethyl methyl esters＜2:98 and reclaim methyl alcohol; the water that generates to take away the partial esterification reaction distills and protects concentrated solution stand-by under the complete rear nitrogen.
The concentrated solution of finishing esterification is transferred in the 1000ml four-hole round-bottomed flask; in the concentrated solution of esterification, add 1,2-dichlorobenzene 300ml, begin insulation when being warming up to 100 ℃ under the nitrogen protection and pay the gram alkylated reaction; reaction generates 4-hydroxyl-2; 3,5-tri-methyl p-toluenesulfonate, reacting took a sample after 4 hours detects by high performance liquid chromatography; detect 4-hydroxyl-3; 5-acid dimethyl methyl esters: begin the aftertreatment cooling when 4-hydroxyl-2,3,5-tri-methyl p-toluenesulfonate＜2:98.
With 4-hydroxyl-2; 3; add 20g water when 5-tri-methyl p-toluenesulfonate reaction solution cools to 80 ℃ and begin oil bath and heat up; be warmed up to 170 ℃ and keep this temperature to take off alkylsulfonyl reaction in 3 hours; reaction cools to 80 ℃ after finishing; and then adding 250ml water for cooling leaves standstill layering in 30 minutes to room temperature; in organic phase, add the stirring of 200ml5% sodium bicarbonate aqueous solution, stir and leave standstill layering in 30 minutes after 30 minutes, so that acid is removed; again the organic phase concentrating under reduced pressure is reclaimed 1; the 2-dichlorobenzene carries out rectifying with concentrated solution after solvent recuperation is complete, gets 54.4g 2; 3,6-pseudocuminol finished product.63.2 ℃～64.1 ℃ of 2,3,6-pseudocuminol fusing points, purity: 99.4%, content: 99.2%.
Embodiment 3:
Take by weighing successively 500gFe (NO
3)
39H
2O, 30gMn (NO
3)
24H
2O, 5gCr (NO
3)
39H
2O, 4.5gNa
2SiO
39H
2O and 1.5gCaCl
22H
2O is dissolved in the 10l water and makes the aqueous solution, and adding 28% ammonia precipitation process agent to the pH value of the aqueous solution in the aqueous solution is 7.5, and leaving standstill wears out made its co-precipitation after 12 hours; After the throw out that obtains filtered and wash with water, oven dry in 5 hours was ground into 90 purpose particles under 160 ℃ of conditions, puts into 300ml1%K
2CO
3Room temperature dipping 30h in the aqueous solution; With again oven dry in 4.5 hours under 160 ℃ of temperature of the particulate matter behind the dipping, in 450 ℃ of roasting 7h, after oxide compound has become the same particle of coal dust, add 1.5g graphite as lubricant and setting agent, obtain the right cylinder that columned Iron oxide catalyst is pressed into 3 * 3mm behind the final compressing tablet, obtain an Iron oxide catalyst that is comprised of ferric oxide, manganese oxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mol ratio of the each component in the catalyzer is Fe
2O
3: MnO
2: SiO
2: Cr
2O
3: CaO:K
2O:C=
1:0.07:0.012:0.01:0.009:0.0015:0.045。
The Iron oxide catalyst of preparation is put into a fixed bed reactor with diameter 15mm internal diameter reaction tube, according to the mol ratio of phenol compound: methyl alcohol=1:5, be that 0.8MPa, temperature are that 400 ℃ and liquid air speed are 2h with the mixed solution of phenol and methyl alcohol at pressure
-1Condition under pass into and carry out gas phase catalytic reaction in the fixed bed reactor, reaction product through separate 2, the 6-xylenol, stand-by.The gas that will flow out from reactor by air cooling and circulating water after, absorb with methyl alcohol, adopt the high-efficient liquid phase chromatogram technique analysis reaction product to form content, its result is as shown in the table:
Adding successively the 200ml quality in the sulfur trioxide gas producer is 65% oleum, zeolite 10g and Vanadium Pentoxide in FLAKES 30g, through nitrogen dilution to 7%, stand-by with the sulfur trioxide gas of 100 ℃ of generations of electric heating cover heating.
With 2 of preparation, 6-xylenol 61g(0.5mol) join in the autoclave bubbling reactor, heat up simultaneously and the 42g(0.525mol after passing into dilution under 75 ℃ of temperature condition) sulfur trioxide gas; Then with ultra thermostat the autoclave bubbling reactor is carried out the constant temperature water bath insulation, the control temperature of reaction stirs with speed 120r/min simultaneously at 120 ℃, so that its sulfonation generates 4-hydroxyl-3,5-acid dimethyl.Along with the carrying out of reaction, the viscosity of reactant increases gradually, and color and luster is gradually flavescence also.Getting liquid carries out high performance liquid chromatography and detect to analyze 2,6-xylenol: when 4-hydroxyl-3,5-acid dimethyl＜1:99, with the nitrogen of drying sulphur trioxide unnecessary in the reaction solution is taken away, the nitrogen protection borehole cooling is to room temperature, and reaction solution is stand-by.
The reaction solution that sulfonation reaction is finished is transferred in the 500ml four-hole round-bottomed flask; the industrial methanol and the 59g(0.6mol that add successively 100ml massfraction 99% in the reaction solution) 98% sulfuric acid; speed with 80r/min under the nitrogen protection stirs; heat to reflux with oil bath simultaneously and carry out esterification; reaction generates 4-hydroxyl-3; 5-acid dimethyl methyl esters; reflux to begin to extract reaction solution with high performance liquid chromatography after 3 hours and detect; 4-hydroxyl-3 to be detected; 5-acid dimethyl: 4-hydroxyl-3; begin air distillation during 5-acid dimethyl methyl esters＜2:98 and reclaim methyl alcohol; the water that generates to take away the partial esterification reaction distills and protects concentrated solution stand-by under the complete rear nitrogen.
The concentrated solution of finishing esterification is transferred in the 1000ml four-hole round-bottomed flask; in the concentrated solution of esterification, add 1,2-dichlorobenzene 300ml, begin insulation when being warming up to 105 ℃ under the nitrogen protection and pay the gram alkylated reaction; reaction generates 4-hydroxyl-2; 3,5-tri-methyl p-toluenesulfonate, reacting took a sample after 3 hours detects by high performance liquid chromatography; detect 4-hydroxyl-3; 5-acid dimethyl methyl esters: begin the aftertreatment cooling when 4-hydroxyl-2,3,5-tri-methyl p-toluenesulfonate＜2:98.
With 4-hydroxyl-2; 3; add 20g water when 5-tri-methyl p-toluenesulfonate reaction solution cools to 80 ℃ and begin oil bath and heat up; be warmed up to 170 ℃ and keep this temperature to take off alkylsulfonyl reaction in 5 hours; reaction cools to 80 ℃ after finishing; and then adding 250ml water for cooling leaves standstill layering in 30 minutes to room temperature; in organic phase, add the stirring of 200ml5% sodium bicarbonate aqueous solution, stir and leave standstill layering in 30 minutes after 30 minutes, so that acid is removed; again the organic phase concentrating under reduced pressure is reclaimed 1; the 2-dichlorobenzene carries out rectifying with concentrated solution after solvent recuperation is complete, gets 52.5g 2; 3,6-pseudocuminol finished product.63 ℃～64 ℃ of 2,3,6-pseudocuminol fusing points, purity: 99.1%, content: 99%.
The content that is not described in detail in this specification sheets belongs to the known prior art of this area professional and technical personnel.
Claims (2)
1. technique by the phenol synthesis 2,3,6-TMP, it is characterized in that: it may further comprise the steps:
The first step, 2, the preparation of 6-xylenol:
By the fixed bed reactor of Iron oxide catalyst is housed, be that 200～400 ℃, pressure be 0.1～1Mpa, liquid air speed be 0.1～3h in temperature with the mixed solution of phenol and methyl alcohol
-1Condition under, carry out gas phase catalytic reaction, reaction product through separate 2, the 6-xylenol, stand-by; The gas that reactor flows out by air cooling and circulating water after, absorb with methyl alcohol;
The preparation of second step, sulfur trioxide gas:
Adding successively quality in the sulfur trioxide gas producer is 65% oleum, zeolite and Vanadium Pentoxide in FLAKES, is heated between 80～100 ℃ with electric heating cover, and the sulfur trioxide gas of generation is through nitrogen dilution to 7%;
The 3rd step, sulfonation reaction
The sulphonating agent that sulfonation reaction is selected is the sulfur trioxide gas of aforesaid method preparation, with prepare 2, the 6-xylenol joins in the autoclave bubbling reactor, simultaneously intensification also passes into through nitrogen dilution to 7% sulfur trioxide gas under 75 ℃ of temperature condition, then with ultra thermostat the autoclave bubbling reactor is carried out the constant temperature water bath insulation, the control temperature of reaction stirs in 80～100 ℃ scope simultaneously, and stirring velocity is controlled at 80～120r/min; Along with the carrying out of reaction, the viscosity of reactant increases gradually, and color and luster is gradually flavescence also; Getting liquid carries out high performance liquid chromatography and detect to analyze 2,6-xylenol: when 4-hydroxyl-3,5-acid dimethyl＜1:99, with the nitrogen of drying sulphur trioxide unnecessary in the reaction solution is taken away, between nitrogen protection borehole cooling to 20～30 ℃, reaction solution is stand-by;
The 4th step, esterification:
The reaction solution that sulfonation reaction is finished is transferred in the four-hole round-bottomed flask, and adding successively massfraction in the reaction solution is 99% industrial methanol and 98% sulfuric acid, control stirring velocity heat temperature raising between 60～80r/min under the nitrogen protection; Be warmed up to reflux state, reflux to begin to extract reaction solution with high performance liquid chromatography after 3 hours and detect, 4-hydroxyl-3 to be detected, 5-acid dimethyl: 4-hydroxyl-3, begin air distillation during 5-acid dimethyl methyl esters＜2:98 and reclaim methyl alcohol, the water that generates to take away partial esterification reaction distills under the complete rear nitrogen protection the concentrated solution cooling, cools to after the room temperature stand-by under the nitrogen protection;
The 5th step, pair gram alkylated reaction:
In the concentrated solution of above-mentioned esterification, add 1, the 2-dichlorobenzene, heat up under the nitrogen protection, begin insulation reaction when being warmed up between 90～110 ℃, reacting took a sample after 3～5 hours detects by high performance liquid chromatography, detects 4-hydroxyl-3,5-acid dimethyl methyl esters: 4-hydroxyl-2, begin the aftertreatment cooling during 3,5-tri-methyl p-toluenesulfonate＜2:98;
The 6th goes on foot, takes off the alkylsulfonyl reaction:
With 4-hydroxyl-2,3, the cooling of 5-tri-methyl p-toluenesulfonate reaction solution, in reaction solution, add entry and begin the oil bath intensification when cooling to 80 ℃, be warmed up to 170 ℃ and kept this thermotonus 2～5 hours, reaction cools to 80 ℃ after finishing, and then add water for cooling layering in static 30 minutes to the room temperature, add 5% sodium bicarbonate aqueous solution washing in the organic phase, so that acid is removed, again the organic phase concentrating under reduced pressure is reclaimed 1, the 2-dichlorobenzene carries out rectifying with concentrated solution after solvent recuperation is complete, gets 2,3,6-pseudocuminol finished product.
2. the technique by the phenol synthesis 2,3,6-TMP according to claim 1 is characterized in that: described Iron oxide catalyst consists of with ferric oxide as leading and containing cocatalyst, and cocatalyst comprises
Manganese oxide, silicon oxide, chromic oxide, calcium oxide, potassium oxide, graphite; The mol ratio of each composition is with chemical formulation: Fe in the Iron oxide catalyst
2O
3: MnO
2: SiO
2: Cr
2O
3: CaO:K
2O:C=1:(0.005～0.2): (0.001～0.1): (0.001～0.15): (0.0001～0.015): (0.0001～0.02): (0.005～0.15);
The preparation method of Iron oxide catalyst is:
Taking by weighing successively mol ratio is 1:(0.005～0.2): (0.001～0.1): (0.001～0.15): the Fe (NO of (0.0001～0.015)
3)
39H
2O, Mn(NO
3)
24H
2O, Cr(NO
3)
39H
2O, Na
2SiO
39H
2O, CaCl
22H
2O is added to the water and makes solution, and adding 28% ammonia precipitation process agent to the pH value of solution in the solution is 7.5～8, and leaving standstill wears out makes its co-precipitation; After the throw out washing that obtains, 70-200 ℃ of oven dry, be ground into 50～100 purpose particles, put into 1%K
2CO
3Flood 10～40h in the aqueous solution; Particulate matter behind the dipping is dried under 70-200 ℃ of temperature again, again in 400-600 ℃ of roasting 2-8h, oxide compound has become the same particle of coal dust, add mol ratio and be the graphite of (0.005～0.15) as lubricant and setting agent, finally obtain the columned Iron oxide catalyst of 3 * 3mm behind the compressing tablet.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894178A (en) * | 2022-11-15 | 2023-04-04 | 中唯炼焦技术国家工程研究中心有限责任公司 | High-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol |
| CN115894178B (en) * | 2022-11-15 | 2024-05-14 | 中唯炼焦技术国家工程研究中心有限责任公司 | Efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720478A (en) * | 1984-08-17 | 1988-01-19 | Huels Aktiengesellschaft | Catalyst for the orthomethylation of phenols |
| CN1566052A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing cresol |
-
2012
- 2012-11-27 CN CN201210489579.3A patent/CN102976903B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4720478A (en) * | 1984-08-17 | 1988-01-19 | Huels Aktiengesellschaft | Catalyst for the orthomethylation of phenols |
| CN1566052A (en) * | 2003-06-27 | 2005-01-19 | 中国科学院兰州化学物理研究所 | Process for preparing cresol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115894178A (en) * | 2022-11-15 | 2023-04-04 | 中唯炼焦技术国家工程研究中心有限责任公司 | High-efficiency catalytic preparation method of high-purity 1,1' -bi-2-naphthol |
| CN115894178B (en) * | 2022-11-15 | 2024-05-14 | 中唯炼焦技术国家工程研究中心有限责任公司 | Efficient catalytic preparation method of high-purity 1,1' -bi-2-naphthol |
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