CN1100615C - Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol - Google Patents
Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol Download PDFInfo
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- CN1100615C CN1100615C CN98126352A CN98126352A CN1100615C CN 1100615 C CN1100615 C CN 1100615C CN 98126352 A CN98126352 A CN 98126352A CN 98126352 A CN98126352 A CN 98126352A CN 1100615 C CN1100615 C CN 1100615C
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- zeolite
- tertiary butyl
- catalyst
- carrier
- methyl phenol
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Abstract
The present invention relates to a modified zeolite catalyst with a carrier or without a carrier. The zeolite is Y zeolite, or beta zeolite or mordenite of which the sodium content is less than 500 ppm. The zeolite is exchanged with nitrate ions for modification. The present invention also relates to a method for preparing 2-tert-4-methylphenol by the reaction of methylphenol and an alkylating agent on the basis of the existence of the zeolite.
Description
The present invention relates to a kind of zeolite catalyst, more particularly, the present invention relates to a kind of with carrier or not with the modified zeolite catalyst of carrier and use the method for this Preparation of Catalyst 2-tertiary butyl-4-methylphenol.
Zeolite or modified zeolite are well-known as catalyzer.
The 2-tertiary butyl-4-methylphenol is synthetized oxidation preventive agent BHT, 2246 and the important intermediate of 2246-S.Lot of documents has been introduced the synthetic method of the 2-tertiary butyl-4-methylphenol.These methods mainly use mineral acid and ion exchange resin to make catalyzer.Adopt mineral acid to make catalyst process complexity, seriously polluted.And adopting the ion-exchange resin catalyst cost higher, fouled catalyst can not be regenerated sometimes.
Therefore, an object of the present invention is to provide a kind of zeolite catalyst, it can overcome, and the prior art inorganic acid catalyst is seriously polluted, the expensive problem of ion exchange resin.
Another object of the present invention provides a kind of method of using zeolite catalyst to prepare the 2-tertiary butyl-4-methylphenol, and it can overcome prior art complex process, problem such as seriously polluted.
According to one aspect of the present invention, providing a kind of is used to prepare the band carrier of the 2-tertiary butyl-4-methylphenol or is not with the support modification zeolite catalyst, its mesolite is that framework si-al ratio is 15～200 Y zeolite, β zeolite or mordenite, described zeolite contain 10mg/g at the most one or more be selected from following metal: Fe, Co, Ni, Mn, La, Zn and Mg, described modified zeolite prepares by following method: with nitrate solution and silica alumina ratio is sodium content＜500ppm Hydrogen Y zeolite of 15-200, β zeolite or mordenite mix, and carry out ion-exchange under 85-95 ℃ of condition.
According to another aspect of the present invention, the method for a kind of Synthetic 2-tertiary butyl-4-methylphenol is provided, comprise that p-methyl phenol and a kind of alkylating agent react at above-mentioned band carrier or in the presence of not with the modified zeolite catalyst of carrier.
Being used for zeolite of the present invention is Y zeolite, β zeolite or mordenite, and they are can be by the disclosed currently known methods of document synthetic or directly buy from the market, and the silica alumina ratio of these zeolites is greater than 15, preferred 15-200, more preferably 15-150.Commercially available zeolite is a na-pretreated zeolite, available ordinary method, as exchange with ammonium salt solution, ammonium type zeolite after the roasting exchange is converted into h-type zeolite.
Carrier as zeolite of the present invention is silicon-dioxide well known in the art, aluminum oxide, silica-alumina or its precursor.These carriers can directly be bought from the market or be synthetic with currently known methods.
The present invention can not prepare as follows with the modified zeolite of carrier: handle sodium content＜500ppm, silica alumina ratio at a certain temperature greater than 15 Hydrogen Y zeolite, β zeolite or mordenite certain hour with certain density nitrate solution, filtration, dry and roasting, compression molding promptly gets modified zeolite catalyst.
In a preferred embodiment, treatment temp is 85-95 ℃, and be 2～6 hours swap time, and drying temperature is 110-120 ℃, and be 2-4 hour time of drying, and maturing temperature is 550～600 ℃, and roasting time is 2-6 hour.
The preparation of band carrier zeolite catalyst: get the modified zeolite sample, add a certain amount of pseudo-boehmite and a small amount of rare nitric acid, stir evenly the back in 110-120 ℃ of dry 2-4 hour, in 550-600 ℃ of roasting 2-6 hour, compression molding must be with the carrier zeolite catalyst.
Be used for the salt that nitrate of the present invention can be following metal: Fe, Co, Ni, Mn, La, Zn and Mg.
Catalyzer can be regenerated with ordinary method, makes it recover active as available common roasting method, for example, bubbling air under 550 ℃ of conditions, roasting can recover activity of such catalysts and selectivity in 4 hours.
The method of Synthetic 2-tertiary butyl of the present invention-4-methylphenol is in the presence of modified zeolite of the present invention, p-methyl phenol and a kind of alkylation reactions under the condition for validity that generates the 2-tertiary butyl-4-methylphenol.
Method of the present invention can be intermittently or continuous mode carry out.
For continuous mode, available equipment well known in the art such as fixed-bed reactor, or existing installation slightly made improvements, this it will be apparent to those skilled in the art that.
In a preferred embodiment, the inventive method is at 50～300 ℃, and alkylating agent/p-methyl phenol mol ratio is 1-5, normal pressure, liquid hourly space velocity 1-5h
-1(WHSV) carry out under.
Being used for alkylating agent of the present invention is iso-butylene, tertiary butyl alcohol or methyl tertiary butyl ether.
These alkylating agents and p-cresol can directly be bought from the market.
The optionally method of calculation that are used for the yield of transformation efficiency, 2,4 phenol (the 2-tertiary butyl-4-methylphenol) of the present invention's p-cresol (p-methyl phenol) and 2,4 phenol are as follows:
The p-cresol transformation efficiency
The amount of p-cresol (mol) in=1-product/amount (mol) * 100% of p-cresol in feeding intake;
The yield of 2,4 phenol
The amount (mol) * 100% of the p-cresol of the amount of 2,4 phenol (mol) in=product/conversion;
The amount (mol) of 2,4 phenol of the selectivity=generation of 2,4 phenol/(amount (mol) of the amount of 2,4 phenol (mol)+BHT in the product) * 100%;
BHT is a 2,6 di tert butyl 4 methyl phenol.
Further specify the present invention with unrestricted enforcement below.
Embodiment 1
Configuration 400ml 0.1M Co (NO
3)
2The aqueous solution, with 40g Na content is the H β zeolite powder of 400ppm, be incorporated with in the there-necked flask of taking back flow condenser of agitator, exchange 4 hours down in 90 ℃, drying is 2 hours under 220 ℃, 550 ℃ of following roastings 4 hours, obtaining cobalt contents was the zeolite powder A of 0.95mg/ (g zeolite) then.
Embodiment 2
Configuration 400ml 0.1M Co (NO
3)
2The aqueous solution, with 40gNa content is that the H β zeolite powder of 400ppm is incorporated with in the there-necked flask of taking back flow condenser of agitator, in 90 ℃ of exchanges 4 hours down, in 120 ℃ of dryings 2 hours, with the zeolite powder of gained, each again with the new 400ml 0.1M Co (NO that disposes
3)
2The aqueous solution repeats above-mentioned steps 2 times, then 550 ℃ of following roastings 4 hours, gets zeolite powder B, and compression molding is broken into 20-40 order particle again, and obtaining cobalt contents is the catalyst B of 1.44mg/ (g zeolite).
Embodiment 3-5
Get zeolite powder A, B and H β zeolite (silica alumina ratio 81.8) 100g respectively by embodiment 1 and 2 preparations, add 100g pseudo-boehmite (butt, the production of Wenzhou aluminium manufacturer), 1.5ml nitric acid and 30ml water, after stirring evenly, in 120 ℃ of dryings 2 hours, 550 ℃ of roastings 4 hours, compression molding, be broken into 20～40 order particles, must contain catalyzer C, D and the E of zeolite 50 weight % respectively.
Embodiment 6-9
Use Ni (NO respectively
3)
2, Mn (NO
3)
2, La (NO
3)
3And Mg (NO
3)
2Replace the Co (NO among the embodiment 2
3)
2Other condition is with embodiment 2, the catalyzer of gained is respectively: Ni content is that catalyzer F, the Mn content of 1.55mg/ (g zeolite) is the catalyzer G of 1.22mg/ (g zeolite), and La content is that catalyzer H and the Mg content of 1.94mg/ (g zeolite) is the catalyst I of 1.18mg/ (g zeolite).
Embodiment 10-18
Various catalyzer that the foregoing description is prepared and HY (silica alumina ratio is 20) zeolite catalyst is estimated in microreactor, the reactor caliber is 7mm, catalyst packing height is 150mm, useful volume is 15ml, p-cresol and the employing of alkylating agent raw material are also flowed continuous underfeed mode, 100 ℃ of temperature of reaction, iso-butylene/p-cresol=3 (mol ratio), the air speed 1h of p-cresol
-12,4 phenol of embodiment catalyzer p-cresol 2,4 phenol
Conversion ratio % is selective, yield % 10 C 50.89 98.28 50.01 11 D 55.88 97.80 54.65 12 E 36.15 99.25 35.88 13 F 31.4 98.94 31.09 14 G 37.85 99.10 37.51 15 H 35.22 99.21 34.94 16 I 32.18 99.30 31.95 17 HY 61.54 83.21 51.20 18 D of %*49.35 92.51 45.65 Comparative Examples, 1 Ni-Al
2O
312.75 40.23 5.13 Comparative Examples, 2 Amberlyst-15 24.77 79.86 19.78
*Except that temperature of reaction is 160 ℃, other condition is with embodiment 11,
Comparative Examples 1-2
Use catalyst n i-Al
2O
3(this catalyzer is for using Ni (NO
3)
2Dipping γ-Al
2O
3Make, Ni content is 12mg/gAl
2O
3) and ion exchange resin (Am berlyst-15) carry out evaluation test, condition is with embodiment 10, evaluation result sees the above table.
Claims (4)
1. method for preparing the 2-tertiary butyl-4-methylphenol, comprise that p-methyl phenol and a kind of alkylating agent react with carrier or in the presence of not with the modified zeolite catalyst of carrier a kind of, its mesolite is that framework si-al ratio is 15～200 Y zeolite, the β zeolite, mordenite, described zeolite contain 10mg/g at the most one or more be selected from following metal: Fe, Co, Ni, Mn, La, Zn and Mg, described modified zeolite prepares by following method: with nitrate solution and silica alumina ratio is the Hydrogen Y zeolite of 15-200 sodium content＜500ppm, β zeolite or mordenite mix, and carry out ion-exchange under 85～95 ℃ of conditions.
2. according to the method for claim 1, it is characterized in that described zeolite silica alumina ratio is 50-150.
3. according to the process of claim 1 wherein that reaction is under 50～300 ℃ temperature, alkylating agent/p-methyl phenol=1-5 (mol ratio), normal pressure, liquid hourly space velocity 1-5 hour
-1(WHSV) carry out under.
4. according to each method of claim 1 to 3, wherein alkylating agent is iso-butylene, tertiary butyl alcohol or methyl tertiary butyl ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126352A CN1100615C (en) | 1998-12-28 | 1998-12-28 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98126352A CN1100615C (en) | 1998-12-28 | 1998-12-28 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1258566A CN1258566A (en) | 2000-07-05 |
| CN1100615C true CN1100615C (en) | 2003-02-05 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126352A Expired - Fee Related CN1100615C (en) | 1998-12-28 | 1998-12-28 | Modified zeolite catalyst and its application in preparing 2-tert-butyl-4-methyl phenol |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102249862A (en) * | 2010-05-19 | 2011-11-23 | 复旦大学 | Application of phenol compounds in preparation of anti-complement medicines |
| US8704006B2 (en) * | 2010-12-10 | 2014-04-22 | Chevron Oronite Company Llc | Skewed and middle attached linear chain alkylphenol and method of making the same |
| CN107649170B (en) * | 2017-09-30 | 2020-02-21 | 宝鸡文理学院 | A kind of supported molecular sieve catalyst for synthesizing 4-methyl-2,6-di-tert-butylphenol and its application |
| CN110038628A (en) * | 2019-05-10 | 2019-07-23 | 北京化工大学 | Acetylene carbonylation prepares the catalyst and its application method of methyl acrylate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568655A (en) * | 1984-10-29 | 1986-02-04 | Mobil Oil Corporation | Catalyst composition comprising Zeolite Beta |
| CN1035316A (en) * | 1988-02-25 | 1989-09-06 | 中国石油化工总公司石油化工科学研究院 | The hydrocarbon reforming catalyst that contains the β zeolite |
| CN1142986A (en) * | 1994-12-13 | 1997-02-19 | 大连理工大学 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
-
1998
- 1998-12-28 CN CN98126352A patent/CN1100615C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4568655A (en) * | 1984-10-29 | 1986-02-04 | Mobil Oil Corporation | Catalyst composition comprising Zeolite Beta |
| CN1035316A (en) * | 1988-02-25 | 1989-09-06 | 中国石油化工总公司石油化工科学研究院 | The hydrocarbon reforming catalyst that contains the β zeolite |
| CN1142986A (en) * | 1994-12-13 | 1997-02-19 | 大连理工大学 | Preparation of modified macro-porous zeolite catalyst and synthetic isopropyl aromatic hydrocarbon |
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| CN1258566A (en) | 2000-07-05 |
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