CN1634656A - Catalyst for synthesizing 2,6-dimethylphenol and its preparation process - Google Patents
Catalyst for synthesizing 2,6-dimethylphenol and its preparation process Download PDFInfo
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- CN1634656A CN1634656A CN 200410012583 CN200410012583A CN1634656A CN 1634656 A CN1634656 A CN 1634656A CN 200410012583 CN200410012583 CN 200410012583 CN 200410012583 A CN200410012583 A CN 200410012583A CN 1634656 A CN1634656 A CN 1634656A
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Abstract
This invention relates to a catalyzer to process 2,6-dimethylphenol, which comprises ferric oxide, indium oxide, silicon dioxide, chrome oxide, calcium oxide, alkali metals oxide and graphite as their Moore proportion as 100:0.5-20:0.1-10:0.1-15:0.01-1.5:0.01-2:0.5-15. The catalyzer is made by the following steps: depositing, drying, dipping, drying, burning, pressing and shaping.
Description
Affiliated technical field
The present invention relates to a kind of Synthetic 2 that is used for, the catalyzer of 6-xylenol more particularly, relates to a kind of phenolic compound and methyl alcohol and carries out the gas phase catalytic reaction Synthetic 2, the ortho-methylation catalyst of 6-xylenol the invention still further relates to this Preparation of catalysts method.
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, makes 2, and 6-xylenol synthetic selectivity and transformation efficiency improve constantly.And 2, the raising of 6-xylenol synthesis of selective and transformation efficiency mainly has benefited from updating of its ortho-methylation catalyst.
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 methylate 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.
Summary of the invention
The purpose of this invention is to provide and a kind ofly have high transformation efficiency and selectivity, and long service life, the Synthetic 2 that preparation cost is low, the ortho-methylation catalyst of 6-xylenol.
The present invention also aims to provide the preparation method of this ortho-methylation catalyst.
The Synthetic 2 that is used for provided by the invention, the catalyzer of 6-xylenol 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.
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.
Described at least a alkalimetal oxide can be Li
2O, Na
2O, K
2O, Rb
2O, Cs
2Among the O one or more.Optimal selection wherein 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.
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.
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, catalyzer is pressed into the cylindrical of Φ 2 * 2mm～Φ 5 * 5mm, can improve the unit volume bulk specific gravity of catalyzer, prevent the reaction mass bias current, increase the residence time of reaction mass, good catalytic activity.Particularly preferred dimension Φ 3 * 3mm's is cylindrical, has better catalytic effect.
Catalyzer of the present invention prepares through steps such as co-precipitation, oven dry, dipping, oven dry, roasting, compression moldings, its concrete preparation method forms proportioning according to catalyzer, 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 80～100 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.
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.
Catalyzer provided by the present invention is an optionally alkylation catalyst of a kind of ortho position, be not only applicable to by phenol compound and methyl alcohol reaction Synthetic 2, the 6-xylenol, also be applicable to 2,4, the preparation of 6-Three methyl Benzene phenolic compound, simultaneously, also be suitable for reacting the ortho position alkylphenol compounds that synthesizes other, be with a wide range of applications by phenol compound and alkyl alcohol.
Under the reaction pressure condition of 280～400 ℃ of temperature and 0～1.5Mpa, use phenol, first alcohol and water as reaction raw materials, with 0.5～2.0h
-1The liquid air speed by the fixed-bed reactor Synthetic 2 of catalyst prod of the present invention is housed, the 6-xylenol, the phenol conversion of its reaction has reached more than 99%, the ortho position selectivity has reached more than 97%, simultaneously, can reach more than 3000 hours the work-ing life of catalyzer, illustrates that catalyzer of the present invention not only has good selectivity and transformation efficiency, and significant raising has been arranged work-ing life.
Use the synthetic ortho position of catalyzer provided by the invention alkylphenol compounds, temperature of reaction has obtained further reduction, thereby has reduced required energy consumption and production cost in the reaction.Simultaneously, the raising of catalyst life has also prolonged continuous production time of ortho position alkylphenol compounds, has improved production efficiency.
Catalyzer of the present invention also has low, the favorable reproducibility of preparation cost, operational condition a wider range, and the advantage that catalytic stability is strong, economy and technical feature are very remarkable.
Embodiment
Embodiment 1
Take by weighing 500gFe (NO successively
3)
39H
2O, 30gInCl
34H
2O, 5gCr (NO
3)
39H
2O, 3gNa
2SiO
39H
2O and 0.6gCaCl
22H
2O is dissolved in the water of 10L, 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 200mL
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 1g 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.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter reaction tube, and according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 3 feeds the reaction mixing raw material, at normal pressure, 350 ℃ and 1.0h
-1React Synthetic 2 under the condition of liquid air speed, the 6-xylenol.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 (%) | 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
Take by weighing 600gFe (NO successively
3)
39H
2O, 10gCr (NO
3)
39H
2O, 6gNa
2SiO
39H
2O and 0.6gCaCl
22H
2O is dissolved in the water of 8L, takes by weighing 13g simple substance indium and is dissolved in the 60mL 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, continue again to be neutralized to pH=7.5～8.0, stirred 1 hour, solution left standstill was worn out 8 hours with 10% ammoniacal liquor.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 200mL
2CO
3In the solution, in dipping under the room temperature after 14 hours, filtering separation, with the gained particulate matter in 150 ℃ of oven dry 5 hours, 500 ℃ of following roastings 4 hours in stoving oven again.At last, in calcining matter, add 1.2g 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, 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: 7.6: 1.43: 1.7: 0.37: 0.15: 3.4.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter reaction tube, and according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 1 feeds the reaction mixing raw material, at 0.1MPa, 355 ℃ and 1.2h
-1React Synthetic 2 under the condition of liquid air speed, the 6-xylenol.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 | ????99.98 | ????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 | ????98.93 | ????1.60 | ????97.03 | ????0.73 |
| ????2500 | ????98.60 | ????2.01 | ????96.52 | ????0.73 |
| ????3000 | ????98.17 | ????3.19 | ????95.49 | ????0.79 |
Embodiment 3
Take by weighing 401gFeCl successively
36H
2O, 40gInCl
34H
2O, 3.3gCrCl
36H
2O, 2.4gNa
2SiO
39H
2O and 1.1gCa (NO
3)
24H
2O is dissolved in the water of 8L, and the NaOH solution of dropping 10% is neutralized to pH=7.5～8.0, 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 8 hours down in 120 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.5%K of 240mL
2CO
3In the solution, in dipping under the room temperature after 12 hours, filtering separation, with the gained particulate matter in 120 ℃ of oven dry 8 hours, 480 ℃ of following roastings 6 hours in stoving oven again.At last, in calcining matter, add 0.8g 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, 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: 9.2: 0.57: 0.8: 0.31: 0.18: 2.3.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter reaction tube, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 1, feed the reaction mixing raw material, under the condition of normal pressure, 350 ℃ and 1.0h-1 liquid air speed, react Synthetic 2, the 6-xylenol.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 | ????99.90 | ????0.6 | ????98.30 | ????0.85 |
| ????50 | ????99.90 | ????0.7 | ????98.00 | ????0.65 |
| ????150 | ????99.00 | ????1.66 | ????97.25 | ????0.75 |
| ????200 | ????98.85 | ????1.66 | ????97.33 | ????0.65 |
Embodiment 4
Take by weighing 550gFe (NO successively
3)
39H
2O, 35gInCl
34H
2O, 5gCrCl
36H
2O, 7.3gNa
2SiO
39H
2O and 0.75gCaCl
22H
2O is dissolved in the water of 10L 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 300mL
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 0.5g 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.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter reaction tube, according to phenol: methyl alcohol: the mole number proportioning of water=1: 5: 5, feed the reaction mixing raw material, under the condition of 0.05Mpa, 360 ℃ and 0.9h-1 liquid air speed, react Synthetic 2, the 6-xylenol.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 5
Take by weighing 424gFeCl successively
36H
2O, 2.5gCrCl
36H
2O, 5.5gNa
2SiO
39H
2O and 1gCaCl
22H
2O is dissolved in the water of 8L, takes by weighing 15g simple substance indium and is dissolved in the 80mL 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, continue again to be neutralized to pH=7.5～8.0, stirred 1 hour, solution left standstill was worn out 12 hours with 10% ammoniacal liquor.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 200mL
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 0.3g 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.
Embodiment 6
Take by weighing 500gFe (NO successively
3)
39H
2O, 38gInCl
34H
2O, 8gCr (NO
3)
39H
2O, 3.3g silicon sol (silica concentration is 30%) and 1.2gCaSO
42H
2O is dissolved in the water of 10L, 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 220mL
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 0.7g 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.
Embodiment 7
Take by weighing 580gFe (NO successively
3)
39H
2O, 6gCr (NO
3)
39H
2O, 4.7gNa
2SiO
39H
2O and 1.37gCa (NO
3)
24H
2O is dissolved in the water of 10L, takes by weighing 18g simple substance indium and is dissolved in the 80mL 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, continue again to be neutralized to pH=7.5～8.0, stirred 2 hours, solution left standstill was worn out 10 hours with 10% ammoniacal liquor.The sedimentation and filtration of separating out and after washing with water, dried 8 hours down in 150 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.38%Na of 240mL
2CO
3In the solution, in dipping under the room temperature after 12 hours, filtering separation, with the gained particulate matter in 150 ℃ of oven dry 6 hours, 600 ℃ of following roastings 3 hours in stoving oven again.At last, in calcining matter, add 0.6g 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: 10.9: 1.15: 1.0: 0.40: 0.15: 1.7.
Embodiment 8
Take by weighing 450gFeCl successively
36H
2O, 42gInCl
34H
2O, 4.6gCr (NO
3)
39H
2O, 6.2gNa
2SiO
39H
2O and 0.8gCaCl
22H
2O is dissolved in the water of 10L, 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 200mL
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 0.4g 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.
Embodiment 9
Take by weighing 425gFeCl successively
36H
2O, 33gInCl
34H
2O, 3.8gCrCl
36H
2O, 3.8gNa
2SiO
39H
2O and 0.65gCaCl
22H
2O is dissolved in the water of 10L, and the ammoniacal liquor of dropping 10% is neutralized to pH value of solution=7.0, 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 180 ℃.Throw out after the oven dry is ground into 8～10 purpose particles, puts into the 0.2%K of 400mL
2CO
3In the solution, in dipping under the room temperature after 20 hours, filtering separation, with the gained particulate matter in 120 ℃ of oven dry 8 hours, 480 ℃ of following roastings 6 hours in stoving oven again.At last, in calcining matter, add 1g 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: 7.1: 0.85: 0.9: 0.37: 0.09: 2.6.
Embodiment 10
Take by weighing 525gFe (NO successively
3)
39H
2O, 25gInCl
34H
2O, 5.5gCr (NO
3)
39H
2O, 4.5gNa
2SiO
39H
2O and 0.7gCaCl
22H
2O is dissolved in the water of 10L 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 300mL
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 0.9g 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.
The catalyzer of embodiment 5～10 was participated in reaction after 50 hours, the composition content of analytical reaction product, its result is as shown in the table:
| Proportioning | Temperature of reaction (℃) | Pressure (Mpa) | Liquid air speed (h -1) | Phenol conversion (%) | Ortho-methyl phenol selectivity (%) | 2,6-xylenol selectivity (%) | 2 selectivity (%) | |
| Embodiment 5 | ??1∶5∶3 | ??350 | ??0.07 | ????0.9 | ??99.80 | ????0.7 | ????98.10 | ????0.55 |
| Embodiment 6 | ??1∶5∶1 | ??335 | ??0.5 | ????1.0 | ??99.90 | ????0.7 | ????98.00 | ????0.65 |
| Embodiment 7 | ??1∶5∶5 | ??365 | Normal pressure | ????1.0 | ??99.77 | ????0.6 | ????98.23 | ????0.55 |
| Embodiment 8 | ??1∶5∶1 | ??360 | ??0.2 | ????0.8 | ??98.90 | ????0.8 | ????97.89 | ????0.83 |
| Embodiment 9 | ??1∶5∶5 | ??355 | ??0.4 | ????1.2 | ??99.90 | ????0.7 | ????98.30 | ????0.68 |
| Embodiment 10 | ??1∶5∶3 | ??340 | ??0.3 | ????0.9 | ??99.10 | ????0.7 | ????98.11 | ????0.76 |
Comparative example 1
Take by weighing 500gFe (NO successively
3)
39H
2O, 30gInCl
34H
2O, 5gCr (NO
3)
39H
2O, 3gNa
2SiO
39H
2O and 0.6gCaCl
22H
2O is dissolved in the water of 10L, 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 200mL
2CO
3In the solution, after flooding 16 hours under the room temperature, filtering separation, the gained particulate matter was dried 6 hours in 150 ℃, 480 ℃ of following roastings 5 hours in stoving oven again, 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 and potassium oxide, 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=100: 8: 1: 1: 0.4: 0.15.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter, according to the reaction conditions Synthetic 2 among the embodiment 1,6-xylenol.After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb, adopt the composition content of gc analysis reaction product with methyl alcohol.
Comparative example 2
Take by weighing 500gFe (NO successively
3)
39H
2O, 30gInCl
34H
2O, 5gCr (NO
3)
39H
2O and 3gNa
2SiO
39H
2O is dissolved in the water of 10L, 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 200mL
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 1g 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, 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: K
2O: C=100: 8: 1: 1: 0.15: 3.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter, according to the reaction conditions Synthetic 2 among the embodiment 1,6-xylenol.After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb, adopt the composition content of gc analysis reaction product with methyl alcohol.
Comparative example 3
Take by weighing 500gFe (NO successively
3)
39H
2O, 5gCr (NO
3)
39H
2O, 3gNa
2SiO
39H
2O and 0.6gCaCl
22H
2O is dissolved in the water of 10L, 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 200mL
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 1g 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, 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: SiO
2: Cr
2O
3: CaO: K
2O: C=100: 1: 1: 0.4: 0.15: 3.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter, according to the reaction conditions Synthetic 2 among the embodiment 1,6-xylenol.After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb, adopt the composition content of gc analysis reaction product with methyl alcohol.
Comparative example 4
Take by weighing 500gFe (NO successively
3)
39H
2O, 30gInCl
34H
2O, 3gNa
2SiO
39H
2O and 0.6gCaCl
22H
2O is dissolved in the water of 10L, 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 200mL
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 1g 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, 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: CaO: K
2O: C=100: 8: 1: 0.4: 0.15: 3.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter, according to the reaction conditions Synthetic 2 among the embodiment 1,6-xylenol.After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb, adopt the composition content of gc analysis reaction product with methyl alcohol.
Comparative example 5
Take by weighing 500gFe (NO successively
3)
39H
2O, 30gInCl
34H
2O, 5gCr (NO
3)
39H
2O, 3gNa
2SiO
39H
2O and 0.7gCaSO
42H
2O is dissolved in the water of 10L, 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 ℃.480 ℃ of following roastings 5 hours in stoving oven again.At last, in calcining matter, add 1g 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 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: C=100: 8: 1: 1: 0.4: 3.
The catalyzer for preparing is put into the fixed-bed reactor with Φ 15mm internal diameter, according to the reaction conditions Synthetic 2 among the embodiment 1,6-xylenol.After will cooling off by air cooling and recirculated water from the gas that reactor flows out, absorb, adopt the composition content of gc analysis reaction product with methyl alcohol.
The catalyzer that embodiment 1, comparative example 1～comparative example 5 are used compares evaluation in the performance of reaction after 200 hours, obtains result as shown in the table.
| Catalyst performance | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Phenol conversion (%) | 99.93％ | 95.02％ | ??90.93 | ??98.20 | ??98.7 | ??85.95 |
| Ortho-methyl phenol selectivity (%) | 0.60％ | 4.14％ | ??5.68 | ??13.0 | ??4.90 | ??18.45 |
| 2,6-xylenol selectivity (%) | 98.03％ | 90.01％ | ??84.03 | ??86.1 | ??93.80 | ??80.18 |
| 2 selectivity (%) | 0.73％ | 0.80％ | ??0.53 | ??0.53 | ??0.72 | ??1.72 |
Claims (10)
1, be used for Synthetic 2, the catalyzer of 6-xylenol is characterized in that being 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, the Synthetic 2 that is used for according to claim 1, the catalyzer of 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, the Synthetic 2 that is used for according to claim 1, the catalyzer of 6-xylenol is characterized in that described alkalimetal oxide is K
2O.
4, the Synthetic 2 that is used for according to claim 1, the catalyzer of 6-xylenol, the initial preparation raw material that it is characterized in that described a, b, d, e, each composition of f can be its carbonate, nitrate, vitriol, muriate or oxyhydroxide, and the initial preparation raw material of c composition is silicon sol, water glass or silica gel.
5, the Synthetic 2 that is used for according to claim 1, the catalyzer of 6-xylenol, the initial preparation raw material that it is characterized in that described a, d composition is its nitrate, the initial preparation raw material of b, e composition is its muriate, the initial preparation raw material of f composition is its carbonate, and the initial preparation raw material of c composition is a water glass.
6, the Synthetic 2 that is used for according to claim 1, the catalyzer of 6-xylenol is characterized in that catalyzer is pressed into the cylindrical of Φ 2 * 2mm～Φ 5 * 5mm.
7, the described Synthetic 2 that is used for of claim 1,6-xylenol Preparation of catalysts method, it is characterized in that forming proportioning according to catalyzer, 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.
8, the Synthetic 2 that is used for according to claim 7,6-xylenol Preparation of catalysts method is characterized in that described precipitation agent can be urea, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
9, the Synthetic 2 that is used for according to claim 7,6-xylenol Preparation of catalysts method is characterized in that described precipitation agent is an ammoniacal liquor.
10, the Synthetic 2 that is used for according to claim 7,6-xylenol Preparation of catalysts method is characterized in that the concentration of the initial preparation aqueous solution of raw material of described component f is 0.1～1.5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100125836A CN100546716C (en) | 2004-10-08 | 2004-10-08 | Be used for Synthetic 2, the Catalysts and its preparation method of 6-xylenol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100125836A CN100546716C (en) | 2004-10-08 | 2004-10-08 | Be used for Synthetic 2, the Catalysts and its preparation method of 6-xylenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1634656A true CN1634656A (en) | 2005-07-06 |
| CN100546716C CN100546716C (en) | 2009-10-07 |
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ID=34845664
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790637A (en) * | 2018-08-01 | 2020-02-14 | 中国科学院大连化学物理研究所 | Method for producing 2, 6-xylenol by phenol alkylation |
| CN112316944A (en) * | 2020-10-28 | 2021-02-05 | 中国矿业大学 | Phenolic compound high ortho-position selectivity alkylation Ni @ Fe2O3Preparation and use of metal catalysts |
-
2004
- 2004-10-08 CN CNB2004100125836A patent/CN100546716C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790637A (en) * | 2018-08-01 | 2020-02-14 | 中国科学院大连化学物理研究所 | Method for producing 2, 6-xylenol by phenol alkylation |
| CN112316944A (en) * | 2020-10-28 | 2021-02-05 | 中国矿业大学 | Phenolic compound high ortho-position selectivity alkylation Ni @ Fe2O3Preparation and use of metal catalysts |
| CN112316944B (en) * | 2020-10-28 | 2021-12-17 | 中国矿业大学 | Phenolic compound high ortho-position selectivity alkylation Ni @ Fe2O3Preparation and use of metal catalysts |
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