CN103992208A - Method for synthesizing 2-tertiary butyl-p-cresol through catalysis of modified Y zeolite - Google Patents
Method for synthesizing 2-tertiary butyl-p-cresol through catalysis of modified Y zeolite Download PDFInfo
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- CN103992208A CN103992208A CN201410238469.9A CN201410238469A CN103992208A CN 103992208 A CN103992208 A CN 103992208A CN 201410238469 A CN201410238469 A CN 201410238469A CN 103992208 A CN103992208 A CN 103992208A
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- cresol
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- tertiary butyl
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- 239000010457 zeolite Substances 0.000 title claims abstract description 64
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 62
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title abstract description 4
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000005342 ion exchange Methods 0.000 claims abstract description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 8
- 239000002168 alkylating agent Substances 0.000 claims abstract description 8
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 20
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000035484 reaction time Effects 0.000 abstract description 7
- 238000005804 alkylation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000009423 ventilation Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000005273 aeration Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing 2-tertiary butyl-p-cresol through catalysis of modified Y zeolite. The method comprises the following step: with modified Y zeolite as a catalyst, carrying out alkylation reaction on an alkylating agent and p-cresol under ordinary pressure so as to prepare the 2-tertiary butyl-p-cresol, wherein the modified Y zeolite is prepared through carrying out ion exchange on NaY zeolite through ammonium chloride, manganous nitrate, lanthanum nitrate or cerous nitrate solutions. The method for synthesizing the 2-tertiary butyl-p-cresol has the advantages of availability in reaction at normal pressure, low reaction temperature, short reaction time, high conversion rate of p-cresol, good selectivity of 2-tertiary butyl-p-cresol, simpleness and convenience in operation, environmental protection and so on.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly a kind of Y zeolite with modification catalyzes and synthesizes the method for the 2-tertiary butyl-p-cresol.
Background technology
The 2-tertiary butyl-p-cresol is important chemical intermediate.It is the important source material of producing bisphenols antioxidant, tensio-active agent and UV light absorber etc., is also widely used in the industries such as polyolefine and polyvinyl chloride.
The industrial production 2-tertiary butyl-p-cresol, be with p-cresol under catalyzer exists with alkylation reactions.Conventional catalyzer has the liquid acid such as the vitriol oil, phosphoric acid or organic sulfonic acid and ion exchange resin etc.Conventional alkylating agent has iso-butylene, the trimethyl carbinol, methyl tertiary butyl ether etc.As everyone knows, the use of liquid acid catalyst causes many drawbacks, such as complex process, by product is many, product separation is difficult, easy etching apparatus, serious environment pollution, catalyzer can not be recycled etc.Although ion-exchange-resin process is etching apparatus, environmental friendliness not, ion exchange resin is at high temperature unstable, and catalytic activity and selectivity are also good not, adds cost higher, and fouled catalyst can not be regenerated sometimes, so catalyzer that neither be desirable.
Summary of the invention
Not enough for prior art, the object of this invention is to provide a kind of method that Y zeolite with modification catalyzes and synthesizes the 2-tertiary butyl-p-cresol.
For achieving the above object, the invention provides a kind of method that Y zeolite with modification catalyzes and synthesizes the 2-tertiary butyl-p-cresol, with the Y zeolite of modification, make catalyzer, under condition of normal pressure, alkylating agent and p-cresol carry out alkylated reaction, the preparation 2-tertiary butyl-p-cresol; The Y zeolite of described modification for to NaY for zeolite ammonium chloride, manganous nitrate, lanthanum nitrate or cerous nitrate solution carry out ion-exchange and make.
Preferably, the number of times of described ion-exchange is for repeatedly.
Further, the number of times of described ion-exchange is 4 times.
Preferably, described alkylating agent is iso-butylene, the trimethyl carbinol, ra-butyl acetate or methyl tertiary butyl ether (MTBE), best with iso-butylene.
Preferably, the mol ratio of described p-cresol and alkylating agent is 1:1～3, and the mass ratio of the Y zeolite catalyzer of described p-cresol and described modification is 1:0.01～0.08.
Preferably, the temperature of described alkylated reaction is 60～90 ℃.
Preferably, the time of described alkylated reaction is 1～10h.
Further, the time of described alkylated reaction is 2～6h.
Further, the time of described alkylated reaction is 2h.
As a preferred version: a kind of Y zeolite with modification catalyzes and synthesizes the method for the 2-tertiary butyl-p-cresol, makes catalyzer with the Y zeolite of modification, and under condition of normal pressure, iso-butylene and p-cresol carry out alkylated reaction, the preparation 2-tertiary butyl-p-cresol; The Y zeolite of described modification for to NaY for zeolite ammonium chloride, manganous nitrate, lanthanum nitrate or cerous nitrate solution carry out ion-exchange and make.
The number of times of described ion-exchange is 4 times.
The mol ratio of described p-cresol and iso-butylene is 1:3, and the mass ratio of the Y zeolite catalyzer of described p-cresol and described modification is 1:0.03.
The temperature of described alkylated reaction is 70 ℃.
The time of described alkylated reaction is 2h.
Beneficial effect of the present invention: the present invention has reaction for condition of normal pressure, temperature of reaction is low, the reaction times is short, the transformation efficiency of p-cresol is high, the selectivity of the 2-tertiary butyl-p-cresol is good, easy and simple to handle, advantages of environment protection in the synthetic 2-tertiary butyl-p-cresol process.
Embodiment
Following examples are used for illustrating the present invention, but are not used for limiting the scope of the invention.
Embodiment 1 use H-USY (the super steady Y of Hydrogen) zeolite catalysis synthesizes the 2-tertiary butyl-p-cresol
1, preparation H-USY zeolite
Preparation H-USY zeolite carries out in three mouthfuls of round-bottomed flasks.The USY zeolite (USY zeolite is " overstable gamma zeolite ", and it is to make through dealuminzation with NaY zeolite) of getting 50g after roasting 3h, is placed in the NH of 1mol/L in the retort furnace of 500 ℃
4in the Cl aqueous solution, NH
4the Cl aqueous solution and USY zeolite proportioning are 10mL/g, are warming up to 95 ℃ under agitation condition, keep 2h.After filtering, use distilled water wash 5 times.Repeat again 3 ammonium exchanges.After last ammonium exchange, the zeolite filter cake after cleaning is placed in to baking oven in 100 ℃ of dry 5h, then puts into retort furnace in 500 ℃ of roasting 4h, make H-USY zeolite.
2, the preparation 2-tertiary butyl-p-cresol
The preparation of the 2-tertiary butyl-p-cresol is carried out in a there-necked flask.By 15.0g p-cresol and the prepared H-USY zeolite catalyst of 0.45g step 1, add one with magnetic stirring apparatus, prolong, (balloon to be fixed on to prolong top, play sealing and safety effect), in the 100mL round-bottomed flask of thermometer and iso-butylene access tube, under stirring, be warmed up to 80 ℃, pass into lentamente high-purity isobutene gas, adjusting passes into speed, guarantees without gas overflowing reaction flask.After aeration time 8 hours, stop ventilation, at this temperature, be incubated certain hour.P-cresol: the mass ratio of H-USY zeolite is 1:0.03.
3, the analysis of the 2-tertiary butyl-p-cresol product
The 2-tertiary butyl-p-cresol product obtaining from step 2, sample, isolate clear liquid, with GC, carry out quantitative analysis.
The result of H-USY zeolite prepared by different ions exchange times is as shown in table 1.
Table 1 different ions exchange times is prepared the impact of H-USY zeolite on product
As can be seen from Table 1, through the standby H-USY zeolite of 4 secondary ion exchange systems, for the 2-tertiary butyl-p-cresol synthetic, there is higher selectivity.
Embodiment 2 use HY zeolite catalysises synthesize the 2-tertiary butyl-p-cresol
1, preparation HY zeolite
Preparation HY zeolite carries out in a there-necked flask.Get 100g NaY zeolite powder, in the retort furnace of 500 ℃, after roasting 3h, be placed in the NH of 1mol/L
4in the Cl aqueous solution, NH
4the Cl aqueous solution and NaY zeolite proportioning are 10mL/g, are warming up to 95 ℃ under agitation condition, keep 2h.After filtering, use distilled water wash 5 times.Repeat again 3 ammonium exchanges.After last ammonium exchange, the zeolite filter cake after cleaning is placed in to baking oven in 110 ℃ of dry 5h, then puts into retort furnace in 540 ℃ of roasting 3h, make HY zeolite catalyst.
2, the preparation 2-tertiary butyl-p-cresol
The preparation of the 2-tertiary butyl-p-cresol is carried out in a there-necked flask.By 15.0g p-cresol and the prepared HY zeolite catalyst of 0.75g step 1, add one with magnetic stirring apparatus, prolong, (balloon to be fixed on to prolong top, play sealing and safety effect), in the 100mL round-bottomed flask of thermometer and iso-butylene access tube, under stirring, be warmed up to 70 ℃, slowly pass into high-purity isobutene gas, adjusting passes into speed, guarantees without gas overflowing reaction flask.Aeration time (is contrast experiment with ventilation 2h, 4h, 6h and 8h respectively) after a few hours, stops ventilation.P-cresol: the mass ratio of HY zeolite is 1:0.05.
3, the analysis of the 2-tertiary butyl-p-cresol product
The 2-tertiary butyl-p-cresol product obtaining from step 2, sample, isolate clear liquid, with GC, carry out quantitative analysis.
The analytical results of the 2-tertiary butyl-p-cresol product prepared by the different alkylated reaction time is as shown in table 2.
The impact of different alkylated reaction time of table 2 on product
Data presentation in table 2, along with the prolongation in reaction times, the transformation efficiency of p-cresol is almost constant, but the yield of the 2-tertiary butyl-p-cresol and selectivity all reduce along with the prolongation in reaction times.Therefore, the alkylated reaction time is advisable with 2h.
Embodiment 3
1, preparation HY zeolite is with embodiment 2 steps 1.
2, the preparation 2-tertiary butyl-p-cresol
The preparation of the 2-tertiary butyl-p-cresol is carried out in a there-necked flask.By the prepared HY zeolite catalyst of the step 1 of 15.0g p-cresol and specified rate, add one with magnetic stirring apparatus, prolong, (balloon to be fixed on to prolong top, play sealing and safety effect), in the 100mL round-bottomed flask of thermometer and iso-butylene access tube, under stirring, be warmed up to 80 ℃, slowly pass into high-purity isobutene gas, adjusting passes into speed, guarantees without gas overflowing reaction flask.After aeration time 4 hours, stop ventilation.P-cresol: the mass ratio of HY zeolite is 1:0.01～0.05.
3, the analysis of the 2-tertiary butyl-p-cresol product
The 2-tertiary butyl-p-cresol product obtaining from step 2, sample, isolate clear liquid, with GC, carry out quantitative analysis.
The analytical results of the 2-tertiary butyl-p-cresol product prepared by different catalysts consumption is as shown in table 3.
The impact of table 3 different catalysts consumption on product
Note: catalyst levels is p-cresol: catalyzer (mass ratio)
As can be seen from Table 3, along with the increase of catalyst levels, the transformation efficiency of p-cresol and the corresponding raising of the 2-tertiary butyl-p-cresol yield, but rangeability is not obvious.Consider, catalyst levels is more suitable with p-cresol: catalyzer=1:0.03 (mass ratio).
Embodiment 4
1, Mn, La, the element modified HY zeolite of Ce for preparation
HY zeolite is used respectively to Mn (NO
3)
2, La (NO
3)
3and Ce (NO
3)
3solution exchanges, and obtains respectively corresponding each modified Y zeolite (part H in HY zeolite containing Mn, La, Ce
+respectively by Mn
2+, La
3+or Ce
3+replace and obtain).The preparation method of HY zeolite is with step 1 in embodiment 2.
Preparation method is as follows:
Mn (the NO that is 1mol/L by concentration by the HY zeolite making
3)
2solution is at 95 ℃
Carry out ion-exchange 4h, solution and zeolite proportioning are 10mL/g, after filtering, use distilled water wash, 110 ℃ of dry 3h, and 500 ℃ of roasting 3h, obtain the sample Mn-HY-1 once exchanging with Mn.By aforesaid operations, repeat to obtain Mn-HY-2 1 time; Repetitive operation obtains Mn-HY-3 2 times; Repetitive operation obtains Mn-HY-4 3 times.Repetitive operation is to improve ion-exchange degree, lower same.
The HY zeolite making is adopted to La (NO for aforesaid method
3)
3solution carries out ion-exchange, can obtain corresponding various modified Y zeolite La-HY-1, La-HY-2, La-HY-3 and La-HY-4 containing La.
The HY zeolite making is adopted to Ce (NO for aforesaid method
3)
3solution carries out ion-exchange, can obtain corresponding various modified Y zeolite Ce-HY-1, Ce-HY-2, Ce-HY-3 and Ce-HY-4 containing Ce.
2, the preparation 2-tertiary butyl-p-cresol
The preparation of the 2-tertiary butyl-p-cresol is carried out in a there-necked flask.The preparation of 15.0g p-cresol and 0.75g step 1 used respectively to Mn, La, the element modified HY zeolite catalyst of Ce, add one with magnetic stirring apparatus, prolong, (balloon to be fixed on to prolong top, play sealing and safety effect), in the 100mL round-bottomed flask of thermometer and iso-butylene access tube, under stirring, be warmed up to 70 ℃, slowly pass into high-purity isobutene gas, adjusting passes into speed, guarantees without gas overflowing reaction flask.After aeration time 8h, stop ventilation.P-cresol: the mass ratio of Modified HY Zeolite catalyzer is 1:0.05.
3, the analysis of the 2-tertiary butyl-p-cresol product
The 2-tertiary butyl-p-cresol product obtaining from step 2, sample, isolate clear liquid, with GC, carry out quantitative analysis.
With the element modified HY zeolites as catalysts of difference, the analytical results of the prepared 2-tertiary butyl-p-cresol product is as shown in table 4.
Table 4 is the impact on product with different element modified HY zeolites as catalysts
Although, above used general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvements it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (9)
1. with the Y zeolite of modification, catalyze and synthesize a method for the 2-tertiary butyl-p-cresol, it is characterized in that, with the Y zeolite of modification, make catalyzer, under condition of normal pressure, alkylating agent and p-cresol carry out alkylated reaction, the preparation 2-tertiary butyl-p-cresol;
The Y zeolite of described modification for to NaY for zeolite ammonium chloride, manganous nitrate, lanthanum nitrate or cerous nitrate solution carry out ion-exchange and make.
2. method according to claim 1, is characterized in that, the number of times of described ion-exchange is for repeatedly.
3. method according to claim 2, is characterized in that, the number of times of described ion-exchange is 4 times.
4. according to the arbitrary described method of claim 1-3, it is characterized in that, described alkylating agent is iso-butylene, the trimethyl carbinol, ra-butyl acetate or methyl tertiary butyl ether.
5. method according to claim 4, is characterized in that, the mol ratio of described p-cresol and alkylating agent is 1:1～3, and the mass ratio of the Y zeolite catalyzer of described p-cresol and described modification is 1:0.01～0.08.
6. according to the arbitrary described method of claim 1-5, it is characterized in that, the temperature of described alkylated reaction is 60～90 ℃.
7. method according to claim 6, is characterized in that, the time of described alkylated reaction is 1～10h.
8. method according to claim 7, is characterized in that, the time of described alkylated reaction is 2～6h.
9. method according to claim 8, is characterized in that, the time of described alkylated reaction is 2h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410238469.9A CN103992208B (en) | 2014-05-30 | 2014-05-30 | A kind of Y zeolite of modification catalyzes and synthesizes the method for 2-t-butyl-p-cresol |
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| CN107649170A (en) * | 2017-09-30 | 2018-02-02 | 宝鸡文理学院 | A kind of carried molecular sieve catalyst for synthesizing the DI-tert-butylphenol compounds of 4 methyl 2,6 and its application |
| CN112479877A (en) * | 2020-12-21 | 2021-03-12 | 江苏极易新材料有限公司 | Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate |
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| CN107649170B (en) * | 2017-09-30 | 2020-02-21 | 宝鸡文理学院 | Supported molecular sieve catalyst for synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof |
| CN112479877A (en) * | 2020-12-21 | 2021-03-12 | 江苏极易新材料有限公司 | Synthesis process of 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate |
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