CN1240654C - Method for preparing 2,6-dimethylphenol - Google Patents
Method for preparing 2,6-dimethylphenol Download PDFInfo
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- CN1240654C CN1240654C CN 200410012582 CN200410012582A CN1240654C CN 1240654 C CN1240654 C CN 1240654C CN 200410012582 CN200410012582 CN 200410012582 CN 200410012582 A CN200410012582 A CN 200410012582A CN 1240654 C CN1240654 C CN 1240654C
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Abstract
The present invention relates to a method for preparing 2, 6-dimethylphenol. One of phenol and ortho-methylphenol or a mixture of phenol and ortho-methylphenol and reaction masses of mixed methanol and water pass through a fixed bed reactor filled with ortho-methylated catalysts at the liquid space velocity of 0.5 to 2.0 h<-1>, and 2, 6-dimethylphenol is prepared through gas phase catalysis reaction at 280 to 400 DEG C and under 0 to 1.5Mpa. The ortho-methylated catalysts in the fixed bed reactor filled is composed of ferric oxide, indium oxide, silicon oxide, chromium oxide, calcium oxide, alkali metal oxide and graphite with a mole ratio of 100: 0.5 to 20: 0.1 to 10: 0.1 to 15: 0.01 to 1.5: 0.01 to 2: 0.5 to 15. If the present invention is adopted to synthesize 2, 6-dimethylphenol, the conversion rate of phenol can reach 99%, the ortho-position selectivity can reach 97%, and the catalyst life can reach more than 3000 hours.
Description
Affiliated technical field
The present invention relates to a kind ofly 2, the preparation method of 6-xylenol more particularly, relates to a kind of phenolic compound and methyl alcohol and carry out gas phase catalysis under the ortho-methylation catalyst effect, to prepare 2, the method for 6-xylenol.
Background technology
2, the 6-xylenol is the important monomer and the engineering plastic modification agent of synthetic polyphenylene oxide heat stable resin (PPE), also is the important synthesis material of some medicine intermediates, uses very extensive.
Early stage 2, the 6-xylenol is to separate to obtain from coal tar and petroleum cracking product, yields poorly, and is of poor quality.N.Cullinane in 1945 etc. at first adopt phenol and methyl alcohol to carry out the gas phase catalysis methylation reaction, have synthesized 2, the 6-xylenol.The various countries engineering staff has carried out improvement repeatedly to its preparation method subsequently, has wherein related generally to the improvement of catalyzer, makes 2, and 6-xylenol synthetic selectivity and transformation efficiency improve constantly.
The ortho-methylation catalyst of Application and Development is Al the earliest
2O
3, because its catalytic activity and the selectivity of ortho-methylated replacement are very low, generate a large amount of contrapositions and a position methylated phenol simultaneously, as Japanese Patent JP 7853627, therefore replaced by MgO is catalyst based gradually.
The industrial applications that MgO is catalyst based had once caused the improved upsurge of catalyst development, and for example USP 3446856, USP 4041085, USP 4201880, USP 4554267 etc. all provide MgO catalyst based.Though catalytic activity that MgO is catalyst based and ortho position selectivity are with respect to Al
2O
3Catalyzer is significantly improved, yet the catalyzer that is suitable for suitability for industrialized production also should possess long as far as possible active lifetime is arranged.Although USP 4041085 life-span that MgO is catalyst based extended to 90～100 hours or more from 40～60 hours, with regard to industrial production, the work-ing life of catalyzer is still very short.In addition, have good ortho position selectivity though MgO is catalyst based, but produced a high proportion of contraposition alkylate with edge effect, its adjacent selectivity awaits further to improve.The more important thing is that MgO is catalyst based to be the high temperature modification catalyzer, the temperature of reacting required is very high, reaches 450～550 ℃, thereby has caused energy consumption of reaction big, the shortcoming of poor catalyst stability.
Because MgO is catalyst based also to exist certain defective at aspects such as energy consumption of reaction and catalytic activitys, is progressively replaced by emerging Fe-series catalyst again.Fe-series catalyst is reducing temperature of reaction, is improving aspects such as ortho-methylated selectivity and phenol conversion very big improvement has been arranged, and for example patents such as USP 3716589, USP 3953529, USP 4024195, USP 4227024, EP 19476 all disclose Fe-series catalyst separately.But because the preparation cost of Fe-series catalyst is higher, preparation and reaction conditions require harsh, and the work-ing life of catalyzer is shorter, and its industrial applications is still not ideal enough.This catalyzer that wherein provides with USP4429171 especially is the most representative, this catalyzer is elementary composition by Fe, In, Cr, Si, five kinds of K, in preparation 2, after using this catalyzer in the gas phase catalytic reaction of 6-xylenol, temperature of reaction is reduced to 300～400 ℃, and suitable reaction mixture liquid air speed is 0.1～5h
-1, the phenol conversion of reaction reaches as high as 100%, 2, and the selectivity of 6-xylenol is up to 99.6%.Yet, find that in application this Preparation of catalysts circulation ratio is relatively poor, is difficult to obtain the catalyst prod with stability, simultaneously, when the liquid air speed of reaction mixture increased, the catalytic performance of catalyzer and work-ing life all can reduce fast.
The catalyzer that German patent DE 1948607 provides, it uses ortho-methyl phenol to transform 2, the selectivity of 6-xylenol only is 84%, and in German patent DE 2428056, drops to 92% time as the reaction preference of initial action material by 96.5% with phenol and also has only 150 hours.
Life-span just because of existing ortho-methylation catalyst is shorter, make 2, need continually more catalyst changeout in 6-xylenol synthetic, reduced quantity-produced production efficiency, simultaneously, because ortho-methylation catalyst also exists some above-mentioned problems, also makes 2, phenol conversion and ortho position selectivity during the 6-xylenol is synthetic also have the space of further optimizing.
Summary of the invention
The purpose of this invention is to provide a kind ofly 2, the preparation method of 6-xylenol, this preparation method use a kind of new catalyzer, have prolonged 2, in the continuous synthetic reaction times of 6-xylenol, have improved the transformation efficiency and the ortho position selectivity of reaction.
Of the present invention 2,6-xylenol preparation method be with in phenol, the ortho-methyl phenol one or both mixture and the reaction mass that mixes of first alcohol and water by the fixed-bed reactor of ortho-methylation catalyst are housed, under suitable condition, carry out gas phase catalytic reaction, reaction product is through repeatedly obtaining 2 of needs, 6-dimethyl benzene phenolic product after the continuous rectification.
Ortho-methylation catalyst of the present invention is made up of following compositions:
(a) ferriferous oxide,
(b) indium oxide,
(c) silicon-dioxide,
(d) chromated oxide,
(e) calcium oxide,
(f) at least a alkalimetal oxide and
(g) graphite;
Mole number ratio of components between above-mentioned each composition is a: b: c: d: e: f: g=100: 0.5～20: 0.1～10: 0.1～15: 0.01～1.5: 0.01～2: 0.5～15.
Between each composition further the mole number ratio of components be a: b: c: d: e: f: g=100: 7.5～10: 0.5～2: 0.5～2: 0.2～0.6: 0.01～0.5: 0.5～5.
Alkalimetal oxide wherein can be Li
2O, Na
2O, K
2O, Rb
2O, Cs
2Among the O one or more, best selection is K
2O.
Ferriferous oxide in the catalyzer of the present invention, indium oxide, chromated oxide can exist with the form of multiple valence state, can be Fe as ferriferous oxide
2O, Fe
2O
3, Fe
3O
4Etc. form, indium oxide can be In
2O
3, InO
2Etc. form, chromated oxide can be CrO, Cr
2O
3, CrO
2, CrO
3Etc. form, but when the mole number that calculates each composition is formed, all are form D e with its sesquioxide
2O
3, In
2O
3, Cr
2O
3Calculate.
Catalyzer of the present invention is to carry out steps such as co-precipitation, oven dry, dipping, oven dry, roasting, compression molding by the initial preparation raw material to each moiety in the catalyzer to prepare.Its concrete preparation method forms proportioning according to above-mentioned catalyzer, respectively the initial preparation material dissolution of component a, b, c, d, e is made solution in water, adding precipitation agent to the pH value of solution is 7.5～8.0 in solution, leaving standstill aging its co-precipitation that makes; After the throw out washing that obtains, under 70～200 ℃ of temperature, dry, be ground into 8～10 purpose particles, the aqueous solution of putting into the initial preparation raw material of component f floods 10～40h; Particulate matter behind the dipping is dried under 70～200 ℃ of temperature once more, in 300～600 ℃ of roast 2～8h, add component g and mix, compressing tablet is made catalyzer.
Catalyzer of the present invention can be shaped to the different shape of multiple dimensions, as strip, column, sheet, spherical etc., yet in industrial practice, find, be pressed into the cylinder shape catalyst of Φ 2 * 2mm～Φ 5 * 5mm, particularly during size Φ 3 * 3mm cylindrical, 2, has better catalytic effect in the building-up process of 6-xylenol.
Wherein, ferriferous oxide, indium oxide, the initial preparation raw material of chromated oxide, calcium oxide, alkalimetal oxide can be its carbonate, nitrate, vitriol, muriate or oxyhydroxide, the initial preparation raw material of indium oxide can also be the simple substance indium.Further, the initial preparation raw material of ferriferous oxide, chromated oxide its nitrate preferably; Indium oxide, the initial preparation raw material of calcium oxide is its muriate preferably; The initial preparation raw material of alkalimetal oxide is its carbonate preferably.
The initial preparation raw material of silicon-dioxide can be silicon sol, water glass or silica gel, and optimal selection is a water glass.
Wherein, the precipitation agent that uses in the co-precipitation step can be urea, ammoniacal liquor, sodium hydroxide, potassium hydroxide and other basic cpd, and best selection is an ammoniacal liquor.
In impregnation steps, the present invention is the aqueous solution use that the initial preparation preparation of raw material of alkalimetal oxide is become concentration 0.1～1.5%, and more the selection of You Huaing is to be mixed with 0.2～0.8% aqueous solution.
The processing condition that further limit in oven dry and the calcination steps are at 120～180 ℃ of oven dry 3～8h, at 400～500 ℃ of roasting 3～5h.
With the suitable reaction conditions of the catalyzer of above-mentioned use be: the temperature of reaction of fixed-bed reactor should be controlled at 280～400 ℃, and particularly 320～390 ℃, pressure-controlling is preferably between 0～1Mpa at 0～1.5Mpa; Reaction mass is with one or both the mixture in phenol, the ortho-methyl phenol: methyl alcohol: the mole ratio of water=1: 2～6: 0～10 is by fixed-bed reactor, wherein especially with ratio the best of 1: 3～5: 0.5～2; The mixed gas of reaction mass is with 0.5～2.0h
-1, but best 0.8～1.2h
-1The liquid air speed pass through fixed-bed reactor.
Wherein, in reaction mass, increase certain water vapour, can play dilution method and answer mixture strength, its reaction at catalyst surface is tended to be steady, reduce on the catalyst surface formation of carbon, thereby improve catalyzer stability, prolong the catalyzer effect in work-ing life.
The internal diameter that is positioned at the reaction tube of fixed-bed reactor is Φ 18～57mm, the preferred especially Φ 32mm of the present invention.
For guaranteeing that reaction mass directly enters fixed-bed reactor with the temperature that requires, the present invention has set gradually preheater, vaporizer and superheater in the front of fixed-bed reactor, and reaction mass reacts by entering in the fixed-bed reactor with the temperature that requires after preheater, vaporizer, the superheater heating respectively earlier again.Wherein the temperature of preheater is controlled at 60～150 ℃, and the temperature of vaporizer is controlled at 150～300 ℃, and the temperature of superheater is controlled at 300～400 ℃, and the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.
Further, the present invention is controlled at 100～120 ℃ with the temperature of preheater, and the temperature of vaporizer is controlled at 200～300 ℃, and the temperature of superheater is controlled at 300～360 ℃.
A coking material strainer has also been installed in the present invention additional between superheater and fixed-bed reactor, be used for filtering reaction mixing of materials gas, to avoid mixed gas to enter the too high catalyst deactivation that causes of reactor afterreaction temperature, the coking of the lost of life and reactor apparatus.
Effusive after the reaction from fixed-bed reactor is 2,6-xylenol crude product, the present invention removes other impurity that exists in the product after it is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower, finishing column more successively, has obtained high-quality purified product at last.
The present invention also will reclaim through the front-end volatiles of dealcoholize column, dehydration tower, dephenolize tower and finishing column rectifying output and circulation is used as reaction raw materials, fully the front-end volatiles with output have carried out reasonable use, avoided the waste of material, both reduce the production comprehensive cost, also reduced the environmental emission pollution.
The present invention has significant technique effect with respect to prior art.
At first, catalyzer provided by the invention has had significant raising work-ing life, reach more than 3000 hours, and application catalyzer Synthetic 2 of the present invention, the 6-xylenol, the transformation efficiency of phenol can reach more than 99%, and the ortho position selectivity can reach more than 97%, has good selectivity and transformation efficiency.
Secondly, of the present invention 2,6-xylenol preparation method easy control of process conditions, constant product quality, simultaneously, the raising of catalyst life has also prolonged 2, the continuous production time of 6-xylenol, has improved production efficiency.
The 3rd, the new Fe-series catalyst that the invention provides and use has further reduced temperature of reaction, thereby has reduced required energy consumption in the reaction, has also reduced production cost.
The 4th, the present invention adopts continuous rectificating technique to synthetic 2, and the 6-xylenol is made with extra care, and has not only shortened life cycle of the product, and the purity of product has also had further raising.
Above each point has all reduced by 2, and the production preparation cost of 6-xylenol has the remarkable economical effect.
Embodiment
Embodiment 1
1, Preparation of catalysts
Take by weighing 50KgFe (NO
3)
39H
2O, 3KgInCl
34H
2O, 500gCr (NO
3)
39H
2O, 300gNa
2SiO
39H
2O and 60gCaCl
22H
2O is dissolved in the water of 1000L, and the ammoniacal liquor of dropping 10% is neutralized to pH value of solution=7.0 earlier, continues to be neutralized to pH=7.5～8.0 with 10% ammoniacal liquor again, stirs 1 hour, and solution left standstill was worn out 12 hours.The sedimentation and filtration of separating out and after washing with water, dried 6 hours down in 180 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.5%K of 20L
2CO
3In the solution, in dipping under the room temperature after 16 hours, filtering separation, with the gained particulate matter in 150 ℃ of oven dry 6 hours, 480 ℃ of following roastings 5 hours in stoving oven again.At last, in calcining matter, add 100g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 3 * 3mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: K
2O: C=100: 8.2: 0.85: 1.0: 0.44: 0.15: 3.4.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: ortho-cresol: methyl alcohol: water=1: 1: 7: 1 mole number proportioning, after the reaction mixing raw material is controlled at 100 ℃ preheater, 250 ℃ vaporizer, 330 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 1.0h
-1The liquid air speed be passed in the reactor bed of 350 ℃ of controlled temperature, under normal pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.5% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
Get a certain amount ofly from the reactor eluting gas, after the cooling of air cooling and recirculated water, absorb with methyl alcohol, adopt the composition content of gc analysis reaction product, its result is as shown in the table:
| Reaction times (h) | Phenol conversion (%) | Ortho-methyl phenol content (%) | 2,6-xylenol content (%) | 2 content (%) |
| 10 | 99.98 | 0.73 | 97.77 | 0.85 |
| 50 | 99.95 | 0.41 | 98.33 | 0.65 |
| 500 | 99.95 | 0.36 | 98.28 | 0.71 |
| 1000 | 99.95 | 0.45 | 98.18 | 0.72 |
| 1500 | 99.94 | 0.51 | 98.15 | 0.72 |
| 2000 | 99.93 | 0.60 | 98.03 | 0.73 |
| 2500 | 99.90 | 0.71 | 97.82 | 0.73 |
| 3000 | 99.87 | 1.09 | 97.49 | 0.79 |
Embodiment 2
1, Preparation of catalysts
Take by weighing 55KgFe (NO
3)
39H
2O, 3.5KgInCl
34H
2O, 500gCrCl
36H
2O, 730gNa
2SiO
39H
2O and 75gCaCl
22H
2O is dissolved in the water of 1000L, and is heated to 90 ℃, adds urea and is neutralized to pH=7.5～8.0, stirs 1 hour, and solution left standstill was worn out 12 hours.The sedimentation and filtration of separating out and after washing with water, dried 5 hours down in 150 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 1%Cs of 30L
2CO
3With 0.5%K
2CO
3Mixing solutions in, in dipping under the room temperature after 18 hours, filtering separation, with the gained particulate matter in 150 ℃ of oven dry 4 hours, 400 ℃ of following roastings 8 hours in stoving oven again.At last, in calcining matter, add 50g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 3 * 3mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, Cs2O, potassium oxide and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: Cs
2O: K
2O: C=100: 8.8: 1.89: 1.4: 0.50: 0.21: 0.12: 1.5.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 5, after the reaction mixing raw material is controlled at 110 ℃ preheater, 240 ℃ vaporizer, 320 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 0.9h
-1The liquid air speed be passed in the reactor bed of 360 ℃ of controlled temperature, under 0.05Mpa pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.3% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb with methyl alcohol, adopt the composition content of gc analysis reaction product, its result is as shown in the table:
| Reaction times (h) | Phenol conversion (%) | The ortho-methyl phenol selectivity | 2,6-xylenol selectivity | The 2 selectivity |
| 10 | 99.08 | 0.97 | 97.22 | 0.85 |
| 50 | 99.00 | 1.02 | 97.23 | 0.65 |
| 500 | 98.95 | 1.56 | 97.38 | 0.75 |
| 1000 | 97.00 | 1.88 | 96.18 | 0.72 |
| 1500 | 96.76 | 2.11 | 96.00 | 0.73 |
| 2000 | 95.44 | 2.60 | 95.53 | 0.73 |
| 2500 | 94.56 | 2.88 | 95.42 | 0.77 |
| 3000 | 94.00 | 3.09 | 94.49 | 0.80 |
Embodiment 3
1, Preparation of catalysts
Take by weighing 42.4KgFeCl
36H
2O, 250gCrCl
36H
2O, 550gNa
2SiO
39H
2O and 100gCaCl
22H
2O, be dissolved in the water of 800L, taking by weighing 1.5Kg simple substance indium is dissolved in the 0.8L hydrochloric acid, after treating all dissolvings, join in the above-mentioned solution, the ammoniacal liquor of dropping 10% is neutralized to pH value of solution=7.0 earlier, continues to be neutralized to pH=7.5～8.0 with 10% ammoniacal liquor again, stirred 1 hour, solution left standstill was worn out 12 hours.The sedimentation and filtration of separating out and after washing with water, dried 6 hours down in 180 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 1.27%Cs of 20L
2CO
3In the solution, in dipping under the room temperature after 18 hours, filtering separation, with the gained particulate matter in 180 ℃ of oven dry 3 hours, 480 ℃ of following roastings 5 hours in stoving oven again.At last, in calcining matter, add 30g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 3 * 3mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, Cs2O and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: Cs
2O: C=100: 8.4: 1.24: 0.6: 0.58: 0.15: 0.8.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 3, after the reaction mixing raw material is controlled at 120 ℃ preheater, 280 ℃ vaporizer, 340 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 1.1h
-1The liquid air speed be passed in the reactor bed of 355 ℃ of controlled temperature, under 0.1Mpa pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.4% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
Embodiment 4
1, Preparation of catalysts
Take by weighing 50KgFe (NO
3)
39H
2O, 3.8KgInCl
34H
2O, 800gCr (NO
3)
39H
2O, 330g silicon sol (silica concentration is 30%) and 120gCaSO
42H
2O is dissolved in the water of 1000L, and the ammoniacal liquor of dropping 10% is neutralized to pH value of solution=7.0 earlier, continues to be neutralized to pH=7.5～8.0 with 10% ammoniacal liquor again, stirs 0.5 hour, and solution left standstill was worn out 10 hours.The sedimentation and filtration of separating out and after washing with water, dried 3 hours down in 200 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.5%K of 22L
2CO
3In the solution, in dipping under the room temperature after 16 hours, filtering separation, with the gained particulate matter in 120 ℃ of oven dry 5 hours, 550 ℃ of following roastings 4 hours in stoving oven again.At last, in calcining matter, add 70g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 3 * 3mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: K
2O: C=100: 10.4: 0.94: 1.6: 0.56: 0.15: 2.4.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 1, after the reaction mixing raw material is controlled at 130 ℃ preheater, 260 ℃ vaporizer, 340 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 1.2h
-1The liquid air speed be passed in the reactor bed of 345 ℃ of controlled temperature, under 0.07Mpa pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.6% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
Embodiment 5
1, Preparation of catalysts
Take by weighing 45KgFeCl
36H
2O, 4.2KgInCl
34H
2O, 460gCr (NO
3)
39H
2O, 620gNa
2SiO
39H
2O and 80gCaCl
22H
2O is dissolved in the water of 1000L, and the NaOH solution of dropping 10% is neutralized to pH=7.5～8.0, stirs 1 hour, and solution left standstill was worn out 8 hours.The sedimentation and filtration of separating out and after washing with water, dried 4 hours down in 200 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.5%K of 20L
2CO
3In the solution, in dipping under the room temperature after 18 hours, filtering separation, with the gained particulate matter in 180 ℃ of oven dry 4 hours, 350 ℃ of following roastings 8 hours in stoving oven again.At last, in calcining matter, add 40g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 3 * 3mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, potassium oxide and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: K
2O: C=100: 8.6: 1.32: 0.7: 0.43: 0.15: 1.0.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: methyl alcohol: the mole number proportioning of water=1: 4: 1, after the reaction mixing raw material is controlled at 100 ℃ preheater, 220 ℃ vaporizer, 325 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 0.8h
-1The liquid air speed be passed in the reactor bed of 350 ℃ of controlled temperature, under normal pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.5% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
Embodiment 6
1, Preparation of catalysts
Take by weighing 52.5KgFe (NO
3)
39H
2O, 2.5KgInCl
34H
2O, 550gCr (NO
3)
39H
2O, 450gNa
2SiO
39H
2O and 70gCaCl
22H
2O is dissolved in the water of 1000L and is heated to 90 ℃, adds urea again and is neutralized to pH value of solution=7.5, stirs 1 hour, with aging 10 hours of solution left standstill.The sedimentation and filtration of separating out and after washing with water, dried 4 hours down in 180 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.2%Na of 30L
2CO
3In the solution, in dipping under the room temperature after 15 hours, filtering separation, with the gained particulate matter in 150 ℃ of oven dry 6 hours, 500 ℃ of following roastings 6 hours in stoving oven again.At last, in calcining matter, add 90g graphite, carry out compressing tablet after thorough mixing is even, be pressed into the right cylinder of Φ 4 * 4mm, obtain a catalyzer of being made up of ferric oxide, Indium sesquioxide, silicon-dioxide, chromic oxide, calcium oxide, sodium oxide and graphite, the mole number ratio of components of each composition is Fe in this catalyzer
2O
3: In
2O
3: SiO
2: Cr
2O
3: CaO: Na
2O: C=100: 6.6: 1.22: 1.1: 0.49: 0.10: 2.9.
2,2, the preparation of 6-xylenol
The catalyzer for preparing put into one have Φ 32mm internal diameter reaction tube fixed-bed reactor, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 2, after the reaction mixing raw material is controlled at 105 ℃ preheater, 250 ℃ vaporizer, 300 ℃ superheater heating by temperature respectively, filter through the coking material strainer again, with 1.0h
-1The liquid air speed be passed in the reactor bed of 340 ℃ of controlled temperature, under 0.08Mpa pressure, react Synthetic 2, the 6-xylenol, wherein the heat of preheater, vaporizer, superheater and fixed-bed reactor provides by fused salt.Reaction back effusive 2, after 6-xylenol crude product is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower and finishing column successively, remove other impurity that exists in the product, having obtained content at last, to reach 99.4% high quality refining 2,6-dimethyl benzene phenolic product.The front-end volatiles that rectifying produces reclaim the back circulation and are used for the reaction raw materials use.
Claims (10)
1, a kind of preparation 2, the method of 6-xylenol, be with in phenol, the ortho-methyl phenol one or both mixture and the reaction mass that mixes of first alcohol and water by the fixed-bed reactor of ortho-methylation catalyst are housed, at 280～400 ℃ of temperature, pressure 0～1.5Mpa, liquid air speed 0.5～2.0h
-1Condition under carry out gas phase catalytic reaction, Synthetic 2, the 6-xylenol is characterized in that described ortho-methylation catalyst is made up of following compositions:
(a) ferriferous oxide,
(b) indium oxide,
(c) silicon-dioxide,
(d) chromated oxide,
(e) calcium oxide,
(f) at least a alkalimetal oxide and
(g) graphite;
Wherein, the mole number ratio of components between each composition is a: b: c: d: e: f: g=100: 0.5～20: 0.1～10: 0.1～15: 0.01～1.5: 0.01～2: 0.5～15.
2, preparation 2 according to claim 1, the method for 6-xylenol is characterized in that described alkalimetal oxide can be Li
2O, Na
2O, K
2O, Rb
2O, Cs
2Among the O one or more.
3, preparation 2 according to claim 1, the method for 6-xylenol is characterized in that described alkalimetal oxide is K
2O.
4, preparation 2 according to claim 1, the method for 6-xylenol is characterized in that catalyzer is pressed into the cylindrical of φ 2 * 2mm～φ 5 * 5mm.
5, preparation 2 according to claim 1, the method for 6-xylenol, the mole ratio that it is characterized in that described reaction mass are one or both the mixtures in phenol, the ortho-methyl phenol: methyl alcohol: water=1: 2～6: 0.5～10.
6, preparation 2 according to claim 1, the method for 6-xylenol, the mole ratio that it is characterized in that described reaction mass are one or both the mixtures in phenol, the ortho-methyl phenol: methyl alcohol: water=1: 3～5: 0.5～2.
7, preparation 2 according to claim 1, the method for 6-xylenol, the temperature of reaction that it is characterized in that described fixed-bed reactor are 320～390 ℃, pressure is that the liquid air speed of 0～1Mpa, reaction mass is 0.8～1.2h
-1
8, preparation 2 according to claim 1, the method of 6-xylenol, it is characterized in that reaction mass earlier by entering in the fixed-bed reactor after preheater, vaporizer, the superheater heating, wherein the temperature of preheater is controlled at 60～150 ℃, the temperature of vaporizer and is controlled at 150～300 ℃, the temperature of superheater and is controlled at 300～400 ℃ again.
9, preparation 2 according to claim 1, the method of 6-xylenol, it is characterized in that the product crude product that obtains after the reaction is purified through the continuous rectification of dealcoholize column, dehydration tower, dephenolize tower, finishing column more successively in fixed-bed reactor after, obtain purified product.
10, preparation 2 according to claim 9, the method for 6-xylenol is characterized in that the front-end volatiles through dealcoholize column, dehydration tower, dephenolize tower and finishing column rectifying output are reclaimed and circulation is used as reaction raw materials.
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|---|---|---|---|
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| CN102924237A (en) * | 2012-10-08 | 2013-02-13 | 蓝星化工新材料股份有限公司 | Method for preparing o-cresol and 2,6-dimethyl phenol in mode of reducing unit consumption of methanol |
| CN109395711B (en) * | 2018-11-30 | 2020-05-19 | 中国科学院大连化学物理研究所 | Preparation method of boron-scandium catalyst and application of boron-scandium catalyst in synthesis of 2, 6-dimethylphenol |
| CN109970514B (en) * | 2019-03-04 | 2021-10-19 | 宝鸡文理学院 | Method for synthesizing phenol in anisole process by catalytic refining methanol method |
| CN110437039A (en) * | 2019-07-30 | 2019-11-12 | 埃得新材料有限公司 | A kind of energy-efficient 2,6- xylenol production technology |
| CN113264815B (en) * | 2020-02-17 | 2022-11-29 | 北京天辰昊桦科技有限公司 | Production method and production device of ten-thousand-ton-grade polymerized pure 2, 6-dialkyl phenol |
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