CN1199653A - Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation - Google Patents
Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation Download PDFInfo
- Publication number
- CN1199653A CN1199653A CN 97108074 CN97108074A CN1199653A CN 1199653 A CN1199653 A CN 1199653A CN 97108074 CN97108074 CN 97108074 CN 97108074 A CN97108074 A CN 97108074A CN 1199653 A CN1199653 A CN 1199653A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sio
- solution
- orthoresol
- xylenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims description 11
- 230000015572 biosynthetic process Effects 0.000 title 1
- 238000003786 synthesis reaction Methods 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003426 co-catalyst Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 7
- 229910052906 cristobalite Inorganic materials 0.000 abstract 7
- 239000000377 silicon dioxide Substances 0.000 abstract 7
- 235000012239 silicon dioxide Nutrition 0.000 abstract 7
- 229910052682 stishovite Inorganic materials 0.000 abstract 7
- 229910052905 tridymite Inorganic materials 0.000 abstract 7
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 abstract 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 229930195357 gramphenol Natural products 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZHBYCCVSWKWSMR-UHFFFAOYSA-N 2-hydroperoxybenzoic acid Chemical group OOC1=CC=CC=C1C(O)=O ZHBYCCVSWKWSMR-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The catalyst uses V2O5-Fe2O3 as main catalyst, K2O, CuO, PbO or Ce2O3 as cocatalyst, and SiO2 as carrier to form serial catalyst systems including: V1Fe1Cu0.05K0.05/SiO2; V1Fe1K0.02/SiO2; V1Fe1Pb0.05K0.02/SiO2; V1Fe1Cu0.05Pb0.05K0.02/SiO2; V1Fe1Ce0.05K0.02/SiO2; and V1Fe1CuO0.05K0.02/SiO2. The catalyst has high stability, high activity, long life, high selectivity to o-cresol and 2,6-dimethyl phenol, and no p-cresol impurity produced.
Description
The present invention relates to a series of Catalysts and its preparation methods that phenol gas phase continuous catalysis prepares orthoresol and 2.6-xylenol that are used for, be meant at V especially
2O
5-Fe
2O
3Be major catalyst, add K
2O or CuO, PbO, Ce
2O
3Be co-catalyst, with SiO
2Catalyst series of making for carrier and preparation method thereof.
Orthoresol is the intermediate of synthetic pesticide, medicine, resin, spices, antioxidant etc., mainly prepares pesticide herbicide 2 first 4 chlorine, semiconductor Embedding Material epoxy cresol novolac resin (ECN), salicylide, adjacent hydroxyl salicylic acid etc.2.6-xylenol is the monomer of engineering plastics polyphenylene oxide (PPO) and modification product thereof.
Early stage orthoresol and 2.6-xylenol are to separate to obtain from coal tar and petroleum cracking product, yield poorly, of poor quality.1945, (J Chem Soc 821 such as N Cullinane, 1945) adopt phenol and methanol vapor phase catalytic methylation to carry out pionerring research, 60 succeed in developing magnesia catalyst and industrialization to the seventies General Electric Apparatus Co.(U.S.A.) subsequently, thereby cause the catalyst development focus, the series catalyst of exploitation has Fe
2O
3System, MnO
2System, MgO system, V
2O
5System, Cr
2O
3System etc.MnO wherein
2System and MgO series catalysts are high temperature modification, 400～500 ℃ of reaction temperatures, and poor catalyst activity, the life-span is short; Fe
2O
3And Cr
2O
3Warm type catalyst in being, and company of Japanese Asahi Chemical Industry obtains V by screening
2O
5-Fe
2O
3Series catalysts has active height, and reaction temperature is low, characteristics such as load height.Wherein day disclosure special permission clear 59-196834 of communique (1984) introduces and adopts V
2O
5-Fe
2O
3Be major catalyst, add Cr
2O
3, K
2O is at 350 ℃, phenol: methyl alcohol: water=1: 5: 3, and phenol conversion＞90%, but the orthoresol selectivity has only 20～30%, suitably improves temperature and can keep active, life-span running 600 hours.From document analysis, find, the orthoresol selectivity was low when phenol gas phase methylation reaction existed conversion ratio high, and phenol conversion was low when the orthoresol selectivity was high, therefore, need seek a kind of catalyst, make orthoresol yield (=phenol conversion * orthoresol selectivity) for the highest.
The purpose of this invention is to provide a series of orthoresol and synthetic catalyst of 2.6-xylenol of being used for, particularly with V
2O
5-Fe
2O
3As major catalyst, add an amount of K
2O or CuO, PbO, Ce
2O
3Be co-catalyst, with SiO
2Be carrier V
1Fe
1Cu
0.05K
0.05/ SiO
2V
1Fe
1Pb
0.05K
0.05/ SiO
2V
1Fe
1Cu
0.05Pb
0.05K
0.02/ SiO
2V
1Fe
1Cu
0.05K
0.1/ SiO; V
1Fe
1Ce
0.05K
0.02/ SiO
2, its gram molecule proportioning is V: Fe: Cu: K: Pb: Ce=1: 1: 0～0.05: 0.02～0.1: 0～0.05: 0～0.05.Specifically the preparation method is, takes by weighing ammonium metavanadate and oxalic acid and mixes in distilled water, and heating is stirred to dissolving, gets solution I; Again with Fe (NO
3)
39H
2O and Cu (NO
3)
2Or Pb (NO
3)
2, Ce (No
3)
3, be dissolved in the distilled water, get solution II, I and II are mixed back product solution III, in solution III, add Ludox again, make SiO
2Content accounts for weight percent of catalyst 30%, drips 37% ammoniacal liquor then while stirring, makes solution PH=7～9; Heating evaporation 120 ℃ of following dried overnight, then 450 ℃ of following roastings 1～2 hour, gets big bulk catalyst again, bulk catalyst is broken into the random small-particle of 10～20 purposes, then with the catalyst small-particle incipient impregnation K after the fragmentation again
2CO
3Solution, dried overnight again under 120 ℃ at last 700 ℃ of following roastings 2 hours, thereby makes catalyst V
2O
5-Fe
2O
3-CuO-K
2O/SiO
2Or V
2O
5-Fe
2O
3-K
2O/SiO
2V
2O
5-Fe
2O
3-CuO-PbO-K
2O/SiO
2V
2O
5-Fe
2O
3-PbO-K
2O/SiO
2V
2O
5-Fe
2O
3-Ce
2O
5-K
2O/SiO
2
Good stability of the present invention, active high, the life-span is long, has improved the selectivity of orthoresol and 2.6-xylenol, and do not have paracresol impurity and generate, at employing V
2O
5-Fe
2O
3-CuO-K
2O/SiO
2Under 350 ℃ of the catalyst, normal pressure, temperature, load 0.1 gram phenol/gram catalyst hour is used for orthoresol and 2.6-xylenol and synthesizes, phenol conversion is more than 75%, the orthoresol selectivity is more than 71%, and 2.6-xylenol selectivity is more than 28%, and catalyst life turns round more than 850 hours.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Take by weighing 55.88 gram ammonium metavanadate (NH
4VO
3) and 10 gram oxalic acid be mixed in the 558 gram distilled water, burn and in the heating stirring and dissolving, get solution (I); Take by weighing 194.8 gram Fe (NO again
3)
39H
2O and 5.7 gram Cu (NO
3)
23H
2O is dissolved in the 195 gram distilled water, gets solution (II), and two solution mix, and get solution (III); In solution (III), add 330 gram Ludox (30%), stir down and drip 37% ammoniacal liquor to PH=7～9, heating evaporation, 120 ℃ of following dried overnight, at 450 ℃ of roasting 1-2 hours, get bulk catalyst, then big block catalyst breakage is become the random small-particle of 10-20 purpose, equal-volume soaks K clearly
2CO
3Solution, 120 ℃ dry 12 hours down, 700 ℃ of following roastings 2 hours in muffle furnace then, the gained metal oxide catalyst is V
1Fe
1Cu
0.05K
0.02/ SiO
2(30%).
Above-mentioned catalyst is filled in the quartz glass tube of φ 14mm, loadings is 50 grams, 350 ℃ of reaction temperatures, and raw material phenol: methyl alcohol: water=1: 3.5: 1, catalyst loading 0.16 gram phenol/gram catalyst hour, carrier gas N
2Flow velocity is 100ml/min, and phenol conversion is 75.35%, and the orthoresol selectivity is 71.28%, and 2.6-xylenol selectivity is 28.60%, and orthoresol one way molar yield is 53.71%, impurity such as no paracresol.
Embodiment 2-3 and comparative example 1
Method for preparing catalyst is with embodiment 1, and co-catalyst CuO changes into PbO, Ce
2O
3, adopt their nitrate reaction and get.Phenol methylation reaction process and condition are with embodiment 1, and gained the results are shown in Table 1.
Table 1
Embodiment 4
The Preparation of Catalyst condition consists of V with embodiment 1
1Fe
1K
0.02/ SiO
2(30%), course of reaction and process conditions are with embodiment 1, phenol conversion 56.89%, and orthoresol one way molar yield is 47.030%, and the orthoresol selectivity is 82.67%, and 2.6-xylenol selectivity is 15.62%, and the paracresol selectivity is 1.71%.
Embodiment 5
The Preparation of Catalyst condition consists of V with embodiment 1
1Fe
1Cu
0.05Pb
0.05K
0.02/ SiO
2(30%), course of reaction and process conditions are with embodiment 1, and the gained phenol conversion is 27.79%, and the orthoresol once through yield is 24.16%.
Embodiment 6
The Preparation of Catalyst condition consists of V with embodiment 1
1Fe
1Cu
0.05K
0.1/ SiO
2(30%), reaction condition is with embodiment 1, and phenol conversion is 30.95%.
Embodiment 7
Catalyst is formed and is installed with embodiment 1 raw material proportioning PhOH: MeOH: H
2O=1: 4: 3, N
2Be 120ml/min, catalyst loading is 0.1 gram phenol/gram catalyst hour, and gained the results are shown in Table 2, and the catalyst continuous operation time is 850 hours (not comprising regeneration).Average phenol conversion 65.63%, the orthoresol selectivity is 78.52%, 2.6-xylenol selectivity is 21.15%; Orthoresol one way molar yield is 51.53%.
Table 2
| Reaction time (h) | Reaction temperature (℃) | Phenol conversion (%) | Orthoresol yield (%) | Orthoresol selectivity (%) |
| ????60 | ????320 | ????70.44 | ????53.06 | ????75.32 |
| ????120 | ????325 | ????83.56 | ????55.30 | ????66.18 |
| ????200 | ????330 | ????73.23 | ????45.37 | ????61.95 |
| ????300 | ????335 | ????62.51 | ????50.65 | ????81.03 |
| ????400 | ????340 | ????71.15 | ????55.48 | ????77.98 |
| ????500 | ????350 | ????73.85 | ????56.00 | ????75.80 |
| ????600 | ????350 | ????60.72 | ????50.20 | ????82.68 |
| ????700 | ????350 | ????67.62 | ????53.07 | ????79.81 |
| ????800 | ????350 | ????66.19 | ????52.97 | ????80.03 |
Claims (3)
1, is used for orthoresol and 2.6-xylenol synthetic catalyst and preparation method, it is characterized in that: V
2O
5-Fe
2O
3As the main body catalyst, add an amount of K
2O or CuO, PbO, Ce
2O
3Be co-catalyst, with SiO
2Be carrier, make catalyst series V
1Fe
1Cu
0.05K
0.05/ SiO
2V
1Fe
1K
0.02/ SiO
2V
1Fe
1Pb
0.05K
0.02/ SiO
2V
1Fe
1Cu
0.05Pb
0.05K
0.02/ SiO
2V
1Fe
1Ce
0.05K
0.02/ SiO
2Its gram molecule proportioning is V: Fe: Cu: K: Pb: Ce=1: 1: 0～0.05: 0.02～0.1: 0～0.05: 0～0.05.
2, according to claim 1, be used for the synthetic Preparation of catalysts method of orthoresol and 2.6-xylenol, it is characterized in that: take by weighing ammonium metavanadate and oxalic acid and mix in distilled water, heating is stirred to dissolving, gets solution I; Again with Fe (NO
3)
39H
2O and Cu (NO
3)
23H
2O or Pb (NO
3)
3, Ce (NO
3)
3, be dissolved in the distilled water, get solution II; With getting solution III after I and the II mixing, in solution III, add Ludox again, make SiO
2Content accounts for weight percent of catalyst 30%, drips 37% ammoniacal liquor then while stirring, makes solution PH=7～9; Heating evaporation 120 ℃ of following dried overnight, then 450 ℃ of following roastings 1～2 hour, gets big bulk catalyst again, bulk catalyst is ground into the random small-particle of 10～20 purposes, then with the small-particle catalyst incipient impregnation K after the fragmentation again
2CO
3Solution, 120 ℃ of following dried overnight, last, 700 ℃ of following roastings 2 hours, thereby make catalyst.
3, according to claim 1 and the 2 described preparation methods that are used for orthoresol and 2.6-xylenol synthetic catalyst, it is characterized in that: the weight ratio of ammonium metavanadate and oxalic acid is 5.5: 1, and distilled water weight is 10 times of ammonium metavanadate in the solution I; Fe (NO in the solution II
3)
39H
2The weight ratio of O and distilled water is 1: 1; SiO in the solution III
2Weight be weight percent of catalyst 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97108074 CN1199653A (en) | 1997-05-19 | 1997-05-19 | Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97108074 CN1199653A (en) | 1997-05-19 | 1997-05-19 | Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1199653A true CN1199653A (en) | 1998-11-25 |
Family
ID=5170105
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97108074 Pending CN1199653A (en) | 1997-05-19 | 1997-05-19 | Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1199653A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339347C (en) * | 2000-09-18 | 2007-09-26 | 旭化成株式会社 | Method for preparing 2,6-dimethylphenol |
| CN101514145B (en) * | 2009-04-05 | 2011-08-17 | 湖南长岭石化科技开发有限公司 | Method for preparing o-cresol |
| CN101514144B (en) * | 2009-04-05 | 2012-02-29 | 湖南长岭石化科技开发有限公司 | Method for preparing o-cresol |
| 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 |
| CN103537291A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation and preparation method of catalyst |
| CN105032442A (en) * | 2015-07-23 | 2015-11-11 | 中国蓝星（集团）股份有限公司 | Gas-phase reaction catalyst, preparation method and application |
| CN108409541A (en) * | 2018-02-09 | 2018-08-17 | 厦门大学 | The catalyst and preparation method thereof of 2,3,6- pseudocuminols is synthesized for metacresol |
| CN109939708A (en) * | 2019-04-03 | 2019-06-28 | 衷晟 | A kind of methyl phenolic compounds manufacturing method |
| CN109954499A (en) * | 2019-04-01 | 2019-07-02 | 埃得新材料有限公司 | A kind of phenol ortho-methylation catalyst and the method using catalyst production ortho-methylated phenol |
| CN113578335A (en) * | 2021-08-26 | 2021-11-02 | 西北大学 | Phenol ortho-position targeted methylation catalyst and preparation method and application thereof |
-
1997
- 1997-05-19 CN CN 97108074 patent/CN1199653A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339347C (en) * | 2000-09-18 | 2007-09-26 | 旭化成株式会社 | Method for preparing 2,6-dimethylphenol |
| CN101514145B (en) * | 2009-04-05 | 2011-08-17 | 湖南长岭石化科技开发有限公司 | Method for preparing o-cresol |
| CN101514144B (en) * | 2009-04-05 | 2012-02-29 | 湖南长岭石化科技开发有限公司 | Method for preparing o-cresol |
| CN103537291B (en) * | 2012-07-12 | 2016-09-07 | 中国石油化工股份有限公司 | Catalyst of ethyl benzene dehydrogenation preparation of styrene and preparation method thereof |
| CN103537291A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst for preparing styrene through ethylbenzene dehydrogenation and preparation method of catalyst |
| 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 |
| CN105032442A (en) * | 2015-07-23 | 2015-11-11 | 中国蓝星（集团）股份有限公司 | Gas-phase reaction catalyst, preparation method and application |
| CN105032442B (en) * | 2015-07-23 | 2017-10-20 | 中国蓝星（集团）股份有限公司 | A kind of gas phase reaction catalyst, preparation method and application |
| CN108409541A (en) * | 2018-02-09 | 2018-08-17 | 厦门大学 | The catalyst and preparation method thereof of 2,3,6- pseudocuminols is synthesized for metacresol |
| CN108409541B (en) * | 2018-02-09 | 2020-07-17 | 厦门大学 | Catalyst for synthesizing 2,3,6-trimethylphenol from m-cresol and preparation method thereof |
| CN109954499A (en) * | 2019-04-01 | 2019-07-02 | 埃得新材料有限公司 | A kind of phenol ortho-methylation catalyst and the method using catalyst production ortho-methylated phenol |
| CN109954499B (en) * | 2019-04-01 | 2023-09-26 | 顾卓昳 | Phenol ortho-methylation catalyst and method for producing ortho-methylated phenol by using same |
| CN109939708A (en) * | 2019-04-03 | 2019-06-28 | 衷晟 | A kind of methyl phenolic compounds manufacturing method |
| CN113578335A (en) * | 2021-08-26 | 2021-11-02 | 西北大学 | Phenol ortho-position targeted methylation catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4499197A (en) | Co-gel catalyst manufacture | |
| KR100540016B1 (en) | Catalyst and process for the oxidation of ethane and/or ethylene | |
| DK171209B1 (en) | Process for preparing a metal-containing supported catalyst with reduced metal concentration in its outer layer | |
| US4377555A (en) | Removal of metal from solution | |
| CN1199653A (en) | Catalyst for synthesis of O-cresol and 2,6-dimethyl phenol and its preparation | |
| CN107362798B (en) | Preparation method of Pd-M-based metal catalyst for preparing ethylene by hydrogenation of high-purity acetylene and method for preparing ethylene | |
| KR950000881B1 (en) | New Iron-containing Aluminum Silicates | |
| KR900006439B1 (en) | Process for producing methacrylic acid | |
| CN102029186B (en) | Bicomponent naphtha reforming catalyst and preparation method thereof | |
| KR930006683B1 (en) | Process for preparing catalyst for producing methacrylic acid | |
| US4208537A (en) | Process for the selective ortho-alkylation of phenolic compounds | |
| US4487976A (en) | Etherification of phenol | |
| US20040038811A1 (en) | Fe-doped silica catalyst | |
| US6689712B1 (en) | Process for producing hydrofining catalyst | |
| US4361709A (en) | Process for the production of o-alkylated phenols | |
| CN1428322A (en) | Method for preparing 1,3-propylene glycol by 3-hydroxypropionaldehyde hydrogenation | |
| CN103420816B (en) | Polyformaldehyde dimethyl ether preparation method | |
| US4002693A (en) | Process for the production of o-phenylphenol | |
| CN1197940C (en) | Method for producing good quality diesel oil | |
| CN117942995B (en) | Hydrodeoxygenation oxygen-enriched vacancy Pt-MoO of biomass gas solid systemx/ZrO2Catalyst, preparation method and application | |
| EP2810928B1 (en) | A method for synthesizing polyoxymethylene dimethyl ethers | |
| CN105498829A (en) | Methanol aromatized catalyst as well as preparation method and application thereof | |
| RU2104089C1 (en) | Methane and ethylene conversion catalyst, method of preparation thereof, and method of converting methane into ethylene | |
| EP0191884B1 (en) | Process for the single-stage production of higher aliphatic ketones | |
| US4914074A (en) | Catalyst composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |