CN1351904A - Zeolite catalyst and process for preparing 4-tert butyl catechol - Google Patents

Zeolite catalyst and process for preparing 4-tert butyl catechol Download PDF

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Publication number
CN1351904A
CN1351904A CN 00128532 CN00128532A CN1351904A CN 1351904 A CN1351904 A CN 1351904A CN 00128532 CN00128532 CN 00128532 CN 00128532 A CN00128532 A CN 00128532A CN 1351904 A CN1351904 A CN 1351904A
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Prior art keywords
zeolite
pyrocatechol
catalyst
zeolite catalyst
butyl catechol
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CN 00128532
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CN1117625C (en
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孙发群
张天巧
陈晓冬
张信芳
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Beijing Research Institute of Beijing Yanshan Petrochemical Corp
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Abstract

The present invention is a kind of zeolite catlayst with or without carrier. The zeolite in the catalyst is beta zeolite, Y-zeolite, mordenite and ZSM-5 zeolite, mentioned zeolites with Na content less than 500 ppm. The zeolite may be a H-type one or one modified through metal ion exchange or oxide soaking. The present invention also relates to the process of preparing 4-bert-butyl catechol through reaction between catechol and one kind of alkylating agent in the presence of the said zeolite catalyst.

Description

Zeolite catalyst and prepare the method for 4-tert-butyl catechol
The present invention relates to a kind of zeolite catalyst and prepare the method for 4-tert-butyl catechol, specifically, the present invention relates to a kind of with carrier or not with the zeolite catalyst of carrier and use the method for this Preparation of Catalyst 4-tert-butyl catechol.
Zeolite is well-known as catalyzer.
The 4-tert-butyl catechol is to be used for monomeric important stoppers such as vinylbenzene, divinyl and isoprene, also is the oxidation inhibitor of other polymkeric substance such as polyethylene, polypropylene, polystyrene and polyhutadiene, finish etc., and the photostabilizer of organic compound etc.
A lot of documents have been introduced the synthetic method of 4-tert-butyl catechol.These methods mainly use mineral acid, ion exchange resin and atlapulgites such as sulfuric acid, phosphoric acid to make catalyzer.Adopt mineral acid to make the catalyst process complexity, etching apparatus, seriously polluted.Adopt the ion-exchange resin catalyst cost higher, fouled catalyst can not be regenerated sometimes.And it is not high to adopt activated bauxite catalyst to exist catalytic activity, shortcomings such as target product selectivity difference.
Therefore, an object of the present invention is to provide a kind of zeolite catalyst, it has the advantages that 4-tert-butyl catechol selectivity is very high, catalytic activity is higher, and it can overcome, and the prior art inorganic acid catalyst is seriously polluted, ion exchange resin costs an arm and a leg and the problem of activated bauxite catalyst target product selectivity difference.
Another object of the present invention provides a kind of method of using zeolite catalyst to prepare the 4-tert-butyl catechol, and it can overcome prior art complex process, problem such as seriously polluted.
According to one aspect of the present invention, a kind of zeolite catalyst that is used to prepare the 4-tert-butyl catechol is provided, its mesolite is that framework si-al ratio is 10～200 β zeolite, Y zeolite, mordenite and ZSM-5 zeolite.
Be used for zeolite catalyst of the present invention and both can have adopted one or more of H β zeolite, HY zeolite, h-mordenite and HZSM-5 zeolite, also can be prepared into the better pyrocatechol alkylation catalyst of performance by modification, described method of modifying is ion-exchange or pickling process.Described modified zeolite contain 10mg/g at the most one or more be selected from following metal: Mg, Ca, Co, Mn and Zn, one or more that perhaps contain 3%～10% (accounting for the zeolite quality) are selected from following oxide compound: P 2O 5, B 2O 3, NiO, Fe 2O 3, CoO and La 2O 3Described modified zeolite can obtain by above-mentioned zeolite being carried out metal ion exchanged or oxide compound dipping.Wherein metal ion-modified zeolite catalyst prepares by following method: the Hydrogen β zeolite, Y zeolite, mordenite and the ZSM-5 zeolite that with nitrate solution and silica alumina ratio are Na content＜500ppm of 10～200 mix, and carry out ion-exchange under 80～100 ℃ of conditions.The oxide modifying zeolite catalyst prepares by following method: the Hydrogen β zeolite, Y zeolite, mordenite and the ZSM-5 zeolite that with silica alumina ratio are Na content＜500ppm of 10～200 are through H 3PO 4, H 3BO 3, Ni (NO 3) 2, Fe (NO 3) 3, Co (NO 3) 2And La (NO 3) 3Aqueous solution impregnation-calcination make, oxide carried amount is 3%～10% (mass percent) of zeolite consumption.
According to another aspect of the present invention, a kind of method of the 4-of preparation tert-butyl catechol is provided, comprise that pyrocatechol and a kind of alkylating agent react in the presence of above-mentioned zeolite catalyst.
Being used for zeolite of the present invention is β zeolite, Y zeolite, mordenite and ZSM-5 zeolite, and they are can be by the document disclosed method synthetic or directly buy from the market, and the silica alumina ratio of these zeolites is greater than 10, preferred 10～200, more preferably 10～150.Commercially available zeolite is a na-pretreated zeolite, available ordinary method, as exchange with ammonium salt aqueous solution, roasting, the ammonium type zeolite after the exchange is converted into h-type zeolite.
Carrier as zeolite of the present invention is aluminum oxide well known in the art, silicon-dioxide, silica-alumina or its precursor.These carriers all can directly be bought from the market or be synthetic with currently known methods.
The present invention can not prepare as follows with the zeolite catalyst of carrier: Hydrogen β zeolite, Y zeolite, mordenite and the ZSM-5 zeolite certain hour of handling sodium content＜500ppm with certain density nitrate solution at a certain temperature, filter, dry also roasting, compression molding promptly gets metal ion-modified zeolite catalyst.
In a preferred embodiment, treatment temp is 80～100 ℃, and be 2～6 hours swap time, and drying temperature is 110～130 ℃, and be 2～4 hours time of drying, and maturing temperature is 500～600 ℃, and roasting time is 2～6 hours.
The preparation of band carrier zeolite catalyst: get the modified zeolite sample, add a certain amount of aluminum oxide and rare nitric acid, mix stirring evenly the back in 100～120 ℃ of dryings 2～6 hours, in 500～600 ℃ of roastings 2～6 hours, compression molding promptly got and is with the carrier zeolite catalyst.
Be used for the salt that nitrate of the present invention can be following metal: Mg, Ca, Co, Mn, Zn.
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 present invention prepares the method for 4-tert-butyl catechol, is in the presence of zeolite catalyst of the present invention, pyrocatechol and a kind of alkylation reactions under the condition for validity that generates the 4-tert-butyl catechol.
Method of the present invention can be continuously or intermittent 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 80～250 ℃, and pyrocatechol/alkylating agent (mol ratio) is 1～5, available or can be without solvent, solvent/pyrocatechol be 1～10 (mol ratio), and reaction pressure is 1～15atm, be preferably 1～10atm, liquid hourly space velocity 1～5h -1(WHSV) carry out under.
For intermittent mode, available tank reactor well known in the art, mechanical stirring or magnetic agitation.
In a preferred embodiment, the inventive method is at 80～250 ℃, catalyst levels accounts for 0.1～10% of raw material pyrocatechol quality, pyrocatechol/alkylating agent (mol ratio) is 0.2～5, available or can be without solvent, solvent/pyrocatechol be 1～10 (mol ratio), and reaction pressure is 1～15atm, be preferably 1～10atm, the reaction times is to carry out under 0.5～5 hour.
Being used for alkylating agent of the present invention is iso-butylene, the trimethyl carbinol or methyl tertiary butyl ether.
Be used for solvent of the present invention and can use toluene, dimethylbenzene, pentamethylene, hexanaphthene or the trimethyl carbinol.
These alkylating agents, solvent and pyrocatechol can directly be bought from the market.
The method of calculation of yield that are used for the selectivity of transformation efficiency, 4-tert-butyl catechol of the present invention's pyrocatechol and 4-tert-butyl catechol are as follows:
X Pyrocatechol=(n Middle pyrocatechol feeds intake-n The residue pyrocatechol)/n Middle pyrocatechol feeds intake* 100%
S The 4-tert-butyl catechol=n The 4-tert-butyl catechol/ (n Middle pyrocatechol feeds intake-n The residue pyrocatechol) * 100%
Y The 4-tert-butyl catechol=n The 4-tert-butyl catechol/ n Middle pyrocatechol feeds intake* 100%
Nomenclature:
X PyrocatecholThe transformation efficiency of-pyrocatechol
S The 4-tert-butyl catecholThe selectivity of-4-tert-butyl catechol
Y The 4-tert-butyl catecholThe yield of-4-tert-butyl catechol
n Middle pyrocatechol feeds intake-the amount of substance of pyrocatechol in feeding intake
n The 4-tert-butyl catecholThe amount of substance of 4-tert-butyl catechol in the-product
n The residue pyrocatecholThe amount of substance of-reaction back residue pyrocatechol
Further specify the present invention with unrestricted embodiment below.
Embodiment 1
Preparation 400mL0.1mol/L Mg (NO 3) 2The aqueous solution, with 40gNa content is the former powder of H β of 400ppm, be incorporated with in the there-necked flask of taking back flow condenser of agitator, exchange 4 hours down in 100 ℃, drying is 2 hours under 120 ℃, 500 ℃ of following roastings 4 hours, obtaining Mg content was the modified zeolite powder A of 0.90mg/ (g zeolite) then.Compression molding is broken into 40～60 orders.
Embodiment 2
Preparation 400mL0.1mol/L Mg (NO 3) 2The aqueous solution, with 40gNa content is the former powder of H β of 400ppm, be incorporated with in the there-necked flask of taking back flow condenser of agitator, exchange 4 hours down in 100 ℃, drying is 2 hours under 120 ℃, 550 ℃ of following roastings 4 hours,, each then with the new 400mL0.1mol/L Mg (NO for preparing again with the gained zeolite powder 3) 2The aqueous solution repeats above-mentioned steps 3 times, gets zeolite powder B, and compression molding is broken into 40～60 order particles again, and obtaining Mg content is the catalyst B of 1.65mg/ (g zeolite).
Embodiment 3-4
Co (the NO of preparation 0.3mol/L 3) 2The aqueous solution is 3% by the CoO charge capacity, and incipient impregnation is at H β and H β-Al 2O 3On the zeolite, place excessively, 110 ℃ of dryings 2 hours, then 550 ℃ of roastings 4 hours, obtain zeolite powder C and D, compression molding is broken into 40～60 orders, obtains the H β and the H β-Al of CoO modification 2O 3Catalyzer C and D.
Embodiment 5-8
Get respectively by embodiment 1, the modified zeolite A of 2 and 3 preparations, B, C and H β zeolite (silica alumina ratio 26.1) 50g add 50g pseudo-boehmite, 1mL nitric acid and 15mL water, after stirring evenly, in 120 ℃ of dryings 2 hours, 550 ℃ of roastings 4 hours, compression molding, be broken into 40～60 order particles, must contain catalyzer E, F, G and the H of zeolite 50% (weight) respectively.
Embodiment 9-14
Use LiNO 3And Ca (NO 3) 2Replace the Mg (NO among the embodiment 2 3) 2, other condition is with embodiment 2, and the gained catalyzer is respectively: Li content is the catalyst I of 1.55mg/ (g zeolite), and Mg content is the catalyzer J of 1.33mg/ (g zeolite).
Use La (NO respectively 3) 3, Ni (NO 3) 2, H 3BO 3And H 3PO 4Replace the Co (NO among the embodiment 3 3) 2, other condition is with embodiment 3, and the gained catalyzer is respectively: La 2O 3Modification H beta-zeolite catalyst K, NiO modification H beta-zeolite catalyst L, B modification H beta-zeolite catalyst M and P modification H beta-zeolite catalyst N.
Embodiment 15-23
The various catalyzer that the foregoing description 1-8 is prepared and H β-Al 2O 3(silica alumina ratio 81.0) estimated in fixed-bed micro-reactor, and granules of catalyst is 40～60 orders, and pyrocatechol/alkylating agent=1 (mol ratio), solvent/pyrocatechol=6 (mol ratio), 140 ℃ of temperature of reaction, normal pressure, liquid hourly space velocity is 5h -1(WHSV).
Embodiment 24-33
Various catalyzer that the foregoing description 9-14 is prepared and H β (silica alumina ratio 27.1), HY (silica alumina ratio 20), mordenite (silica alumina ratio 38.5) and HZSM-5 (silica alumina ratio 50.6) zeolite catalyst are estimated in stainless steel cauldron, catalyst levels accounts for 5% (mass percent) of pyrocatechol consumption, pyrocatechol and alkylating agent feed ratio are 1: 1 (mol ratio), temperature of reaction is 140 ℃, normal pressure, the reaction times is 3 hours.
Comparative Examples 1-5
Use catalyzer H 3PO 4, solid phosphoric acid (H 3PO 4Dipping diatomite makes), ion exchange resin KU-2, zirconium sulfate and solid super-strong acid Fe 2O 3/ SO 4 2-Carry out evaluation test, condition is with embodiment 24, and evaluation result sees the following form.
Embodiment Catalyzer ?X Pyrocatechol/％ ?S The 4-tert-butyl catechol/％ ??Y The 4-tert-butyl catechol/％
???15 ????A ????38.12 ?????98.94 ?????37.72
???16 ????B ????47.34 ?????99.10 ?????46.91
???17 ????C ????69.85 ?????99.21 ?????69.30
???18 ????D ????70.20 ?????99.30 ?????69.71
???19 ????E ????40.73 ?????99.10 ?????40.36
???20 ????F ????51.65 ?????99.25 ?????51.26
???21 ????G ????71.36 ?????99.35 ?????70.90
???22 ????H ????68.18 ?????99.15 ?????67.60
???23 ????Hβ-Al 2O 3 ????66.00 ?????97.50 ?????64.35
???24 ????I ????41.23 ?????98.15 ?????40.47
???25 ????J ????43.69 ?????97.80 ?????42.73
???26 ????K ????60.34 ?????97.65 ?????58.92
???27 ????L ????61.57 ?????98.10 ?????60.40
???28 ????M ????72.88 ?????99.25 ?????72.33
???29 ????N ????69.17 ?????99.11 ?????68.55
???30 ????Hβ ????60.00 ?????99.00 ?????59.40
???31 ????HY ????57.53 ?????82.32 ?????47.36
???32 Mordenite ????62.75 ?????79.21 ?????49.70
???33 ????HZSM-5 ????72.21 ?????89.20 ?????64.41
Comparative Examples
???1 ????H 3PO 4 ????68.72 ?????43.33 ?????29.78
???2 Solid phosphoric acid ????53.62 ?????46.78 ?????25.08
???3 ????KU-2 ????79.15 ?????77.30 ?????61.18
???4 ????ZrSO 4 ????80.13 ?????63.55 ?????50.92
???5 ????Fe 2O 3/SO 4 2- ????12.85 ?????43.63 ?????5.61

Claims (11)

1. one kind with carrier or not with the zeolite catalyst of carrier, its mesolite is that framework si-al ratio is 10～200 β zeolite, Y zeolite, mordenite and ZSM-5 zeolite.
2. its mesolite of zeolite catalyst according to claim 1 is H β zeolite, HY zeolite, h-mordenite, HZSM-5 zeolite and composition thereof.
3. according to the zeolite catalyst of claim 1, its mesolite contains at the most 10mg/g, and one or more are selected from following metal: Mg, Ca, Co, Mn and Zn, and one or more that perhaps contain 3%～10% (accounting for the zeolite quality) are selected from following oxide compound: P 2O 5, B 2O 3, NiO, Fe 2O 3, CoO and La 2O 3
4. according to the zeolite catalyst of claim 1, the silica alumina ratio of wherein said zeolite is 10～150.
5. according to each zeolite catalyst of claim 1-4, wherein carrier is γ, β, α, η, δ aluminum oxide or aluminium hydroxide or diatomite.
6. the method for a synthetic 4-tert-butyl catechol comprises the reaction in the presence of each zeolite catalyst of claim 1-7 of pyrocatechol and a kind of alkylating agent.
7. according to the method for claim 6, wherein reaction is carried out with continuous or intermittent mode.
8. according to the method for claim 6 or 7, wherein continuous mode is under 80～250 ℃ temperature, pyrocatechol/alkylating agent=1～5 (mol ratio), solvent/pyrocatechol=1～10 (mol ratio), reaction pressure is 1～15atm, is preferably 1～10atm, liquid hourly space velocity 1～5h -1(WHSV) carry out under.
9. according to the method for claim 6 or 7, wherein intermittent mode is under 80～250 ℃ temperature, pyrocatechol/alkylating agent=0.2～5, solvent/pyrocatechol=1～10 (mol ratio), reaction pressure is 1～15atm, be preferably 1～10atm, catalyst levels accounts for that 0.1～10% time of raw material pyrocatechol quality carries out.
10. according to the method for claim 6, wherein alkylating agent is iso-butylene, the trimethyl carbinol or methyl tertiary butyl ether.
11. according to the method for claim 6, wherein solvent is toluene, dimethylbenzene, pentamethylene, hexanaphthene or the trimethyl carbinol.
CN 00128532 2000-11-15 2000-11-15 Zeolite catalyst and process for preparing 4-tert butyl catechol Expired - Lifetime CN1117625C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464574A (en) * 2010-11-18 2012-05-23 中国石油化工股份有限公司 Preparation method of p-alkyl catechol
CN104549138A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Ni-containing molecular sieve adsorbent and preparation method thereof
CN105536858A (en) * 2015-12-15 2016-05-04 陕西延长石油（集团）有限责任公司 Preparation method of catalyst and preparation method of ethanolamine
CN106669828A (en) * 2016-11-28 2017-05-17 宣城市聚源精细化工有限公司 Preparation method of catalyst applied to alkylation reaction of toluene and tertiary butanol
CN107377869A (en) * 2017-08-02 2017-11-24 合肥市田源精铸有限公司 A kind of sand mulling craft for improving clay green-sand combination property
CN112169830A (en) * 2020-10-16 2021-01-05 万华化学集团股份有限公司 Preparation method of basic metal oxide @ ZSM-5 catalyst, catalyst prepared by preparation method and application of catalyst
CN114669321A (en) * 2022-04-21 2022-06-28 杭州电子科技大学 Cobalt-containing zeolite catalyst and preparation method and application thereof

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CN101279743B (en) * 2007-04-04 2011-08-17 中国石油化工股份有限公司 Intergrowth molecular sieve and method for synthesizing same

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102464574A (en) * 2010-11-18 2012-05-23 中国石油化工股份有限公司 Preparation method of p-alkyl catechol
CN102464574B (en) * 2010-11-18 2015-02-25 中国石油化工股份有限公司 Preparation method of p-alkyl catechol
CN104549138A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Ni-containing molecular sieve adsorbent and preparation method thereof
CN105536858A (en) * 2015-12-15 2016-05-04 陕西延长石油（集团）有限责任公司 Preparation method of catalyst and preparation method of ethanolamine
CN105536858B (en) * 2015-12-15 2018-02-06 陕西延长石油（集团）有限责任公司 A kind of preparation method of catalyst and a kind of preparation method of monoethanolamine
CN106669828A (en) * 2016-11-28 2017-05-17 宣城市聚源精细化工有限公司 Preparation method of catalyst applied to alkylation reaction of toluene and tertiary butanol
CN107377869A (en) * 2017-08-02 2017-11-24 合肥市田源精铸有限公司 A kind of sand mulling craft for improving clay green-sand combination property
CN112169830A (en) * 2020-10-16 2021-01-05 万华化学集团股份有限公司 Preparation method of basic metal oxide @ ZSM-5 catalyst, catalyst prepared by preparation method and application of catalyst
CN114669321A (en) * 2022-04-21 2022-06-28 杭州电子科技大学 Cobalt-containing zeolite catalyst and preparation method and application thereof

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