CN110152717A - A kind of preparation method and purposes of sulfuric acid modified zeolite molecular sieve - Google Patents

A kind of preparation method and purposes of sulfuric acid modified zeolite molecular sieve Download PDF

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Publication number
CN110152717A
CN110152717A CN201910481113.0A CN201910481113A CN110152717A CN 110152717 A CN110152717 A CN 110152717A CN 201910481113 A CN201910481113 A CN 201910481113A CN 110152717 A CN110152717 A CN 110152717A
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molecular sieve
sulfuric acid
zeolite molecular
acid modified
modified zeolite
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徐玉之
马啸
张金钟
殷治国
王寒寒
齐学振
谢二军
桂乐胜
郑海东
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SHANDONG XINHECHENG PHARMACEUTICAL CO Ltd
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SHANDONG XINHECHENG PHARMACEUTICAL CO Ltd
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    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J29/90—Regeneration or reactivation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The present invention provides a kind of preparation method of sulfuric acid modified zeolite molecular sieve, the modification including preparing H- type zeolite molecular sieve, H- type zeolite molecular sieve；The modification of the H- type zeolite molecular sieve, including dipping sulfuric acid, roasting.The present invention also provides a kind of application of sulfuric acid modified zeolite molecular sieve in synthesis AHMT.The yield of AHMT 93% or so is improved from document and realizes the regeneration of catalyst to 98% or more and apply by the present invention.Modified molecular screen is used to be catalyzed Fu Ke-acylation reaction for catalyst; it eradicates and hydrolyzes a large amount of hydrogen chloride gas of bring by catalyst of alchlor; and eradicate acid solution containing aluminium; the dosage for reducing modified molecular screen is catalyst amount; modified molecular screen is used to generate a large amount of heat when solving quenching alchlor for catalyst simultaneously; prevent reaction product from hydridization occurs; solve the problems, such as that there is also severe corrosion equipments using Bronsted acid as catalyst; and the fatal disadvantages such as quantity of three wastes is big, it is environmentally protective.

Description

A kind of preparation method and purposes of sulfuric acid modified zeolite molecular sieve
Technical field
The invention belongs to chemical technology fields, and in particular to a kind of preparation method and use of sulfuric acid modified zeolite molecular sieve On the way.
Background technique
Tonalid is a kind of daily type fragrance, is ceased with dense powder fragrance, and elegant fragrance, lasting are lasting, gives people one Kind is very comfortable to be felt, the product diffusion power is strong, reconciliation type is good, and acid and alkali-resistance is not easy to change, is chiefly used in the top grades such as perfumed soap face powder Cosmetics.
Tonalid is 7- acetyl group -1,1, and 3,4,4,6- hexamethyl tetrahydronaphthalenes (abbreviation AHMT) pass through intermediate The acetylation reagents such as 1,1,3,4,4,6- hexamethyl tetrahydronaphthalene (abbreviation HMT) and acetic acid or acetic anhydride, are urged lewis acidic It reacts and is made through friedel-craft under change, there is the research of broad research and long period in synthesis field.
In friedel-crafts acylation, traditional catalyst uses lewis acid (alchlor, ferric trichloride, tetrachloro more Change titanium, boron trifluoride etc.) and Bronsted acid (sulfuric acid, hydrofluoric acid, hydrochloric acid etc.), these catalyst are in the main performance of the such reaction of catalysis Poor in selectivity, side reaction is more, and yield is low, and heel rate is high, also results in a large amount of waste water generation and environmental pollution is tight It is again etc. in class environmental issue.
Pivsa-Ar is pointed out in J.Chem.Soc, Perkin Trans I, 1994:1703-1707 using transition metal Chloride is that catalyst carries out acylation reaction, and discovery is higher to certain specific acylation reaction yields, such as to 2- methoxy The conscientious research discovery of the acylation reaction of base naphthalene and acyl chlorides is poor come catalytic selectivity using alchlor, and titanium tetrachloride, chlorination Cuprous equal selectivity, acylation reaction yield are very high.But verifying is carried out to the acylation reaction of tonalid and finds basic nothing Method is reacted, illustrate transition metal chloride be catalyst can only catalysed partial acylation reaction, be not appropriate for all acyls Glycosylation reaction has certain limitation, therefore transition metal chloride cannot make the catalyst of tonalid acylation reaction.
Cornelis points out the bromination that carrier is done with clay in Tetrahedron Lett, 1993,34:3848-3852 Zinc catalyst, Khalikar B.M. point out to do carrier with silica gel in Tetrahedron Lett, 1997,38:1641-1642 Ferric chloride catalyst can greatly improve the lewis acidic service life, but do not point out how it recycles in text, and nothing The related datas such as yield, selectivity.
Using trifluoromethayl sulfonic acid class salt as catalyst, catalytic activity is high and recyclable, reproducible effect causes extensively Research.Using its billows system, metal salt makees catalyst and is reacted in article, and the example of specific implementation is methoxybenzene and acetic acid It is 99%, Desmurs in Tetrahedron lett that the acylation reaction catalysis of acid anhydride, which achieves higher yields, 1997,38:8871- It is pointed out in 8874 for acylation reactions such as less active aromatic hydrocarbons such as toluene, benzene, chlorobenzene using Bi(OT)3Catalyst are waited to be catalyzed It is reacted.The stronger the high requirements on the equipment of trifluoro-methanyl sulfonate corrosivity, while the recycling to subsequent trifluoro-methanyl sulfonate And it applies and does not also provide correct scheme, therefore there are problems in the popularizations such as mass production amplification.
The status of production AHMT is main at present or prepares AHMT as raw material using HMT and chloroacetic chloride, is with methylene chloride Solvent is catalyzed reaction as catalyst using alchlor or Bronsted acid at room temperature, and yield is mostly 93% or so, with alchlor Or Bronsted acid is that catalyst carries out friedel-crafts acylation, existing many disadvantages show themselves in that
1. alchlor is met water and decomposed rapidly, the hydrogen chloride gas of 3 times of tri-chlorination aluminum amount is released, and form the acid for being rich in aluminium Property solution, is industrially difficult to handle.
2. alchlor is corrosive, the dangerous property of operation processing.
3. dosage is larger, equimolar complex compound can be formed with product in acylation reaction, actual amount well beyond React dosage.
4. its hydrolysis is highly exothermic reaction, a large amount of heat is generated, causes temperature of reaction system to rise, so as to cause reaction Under conditions of temperature changes side reaction occurs for product, causes the pollution of organic matter.
It is catalyst there is also severe corrosion equipment using Bronsted acid, the fatal disadvantages such as quantity of three wastes is big.
When above-mentioned alchlor and Bronsted acid are as the catalyst for preparing AHMT, catalyst is converted into discarded or spent acid Water, it is difficult to regeneration or recovery.
Prior art preparation AHMT, yield are up to 93% or so, are difficult have higher breakthrough.
Summary of the invention
To solve the shortcomings of the prior art, the present invention provide the preparation method of sulfuric acid modified zeolite molecular sieve a kind of with Purposes realizes following goal of the invention:
(1) yield of AHMT is improved from 93% or so to 98% or more；
(2) realize catalyst regeneration with apply；
(3) catalyst amount is reduced；
(4) it eradicates and hydrolyzes a large amount of hydrogen chloride gas of bring by catalyst of alchlor, and eradicate acid solution containing aluminium；
(5) it solves to generate a large amount of heat when quenching alchlor, prevents reaction product from hydridization occurs；
(6) it solves the problems, such as using Bronsted acid as severe corrosion equipment existing for catalyst and the fatal disadvantages such as quantity of three wastes is big.
In order to solve the above technical problems, the present invention takes following technical scheme:
A kind of preparation method of sulfuric acid modified zeolite molecular sieve, comprising the following steps:
(1) H- type zeolite molecular sieve is prepared
1. roasting for the first time
Taking quantitative NaZ-5(silica alumina ratio is that 30) molecular screen primary powder is put into Muffle furnace, and 5-10h is roasted under the conditions of nitrogen protection, is roasted Burning temperature is 400-600 DEG C.The preferred 5-8h of calcining time, preferred 400-500 DEG C of maturing temperature.
2. ion exchange
The NaZ-5 original powder that roasting finishes is cooled to room temperature, the NaZ-5 original powder for taking quantitative roasting to finish is put into 0.8- Ion exchange, preferably 1mol/L aqueous ammonium nitrate solution, the dosage of ammonium nitrate solution are carried out in 1.2mol/L aqueous ammonium nitrate solution For 8-20ml/gNaZ-5 original powder, preferably 8-10ml/gNaZ-5 original powder；1-5h is stirred at a temperature of 70-92 DEG C, stirring finishes, mistake Filter, filter cake is washed 3-5 times with quantitative deionized water, and it is to dry 10h system in 120 DEG C of high-temperature cabinets that filter cake taking-up, which is put into temperature, Obtain NH4- type molecular sieve.
The temperature is preferably 70-80 DEG C.
3. second roasts
Quantitative NH4- type molecular sieve is placed on 540-560 DEG C of roasting 5.5-6.5h in Muffle furnace and obtains H- type zeolite molecular sieve.
550 DEG C of roasting 6h obtain H- type zeolite molecular sieve preferably in Muffle furnace.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve of above-mentioned preparation is impregnated in 0.9-1.1mol/L sulfuric acid solution under conditions of 80-90 DEG C, Preferably 1 mol/L sulfuric acid solution.The sulfuric acid solution dosage of dipping is 8-20 ml/g H- type zeolite molecular sieve, and dip time is 3.8-4.2h, preferably 4h, dipping finish, filtration washing, are washed with deionized 3-5 times to neutrality.Sulfuric acid solution dosage is excellent Select 8-12ml/g H- type zeolite molecular sieve.
2. roasting
11-13h is roasted at 115-125 DEG C, by gained catalyst in 540-560 DEG C of roasting 3.5-4.5h, is made sulfuric acid modified Zeolite catalyst；12h preferably is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite is made Catalyst.
(3) activation and regeneration
1. load weighted sulfuric acid modified zeolite catalyst is put into porcelain crucible, 0.8- is calcined at 535-545 DEG C of Muffle furnace It takes out and is cooled to room temperature immediately after 1.2h, be put into reactor and reacted.Activation can be realized.
The activation calcines 1h at preferably 540 DEG C.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, after reaction inactivation at 580-620 DEG C of Muffle furnace It takes out to be cooled to room temperature immediately after lower calcining 4.5-5.5h and be reacted in being immediately placed in reactor.Regeneration can be realized.
The regeneration calcines 5h at preferably 600 DEG C；
Application of the above-mentioned sulfuric acid modified zeolite molecular sieve in synthesis AHMT: it using HMT and acetic acid or acetic anhydride as raw material, is reacting In the presence of solvent, it is catalyzed friedel-crafts acylation under normal temperature and pressure conditions by catalyst of modified zeolite.When HMT is detected through GC Content can stop reacting below 0.5%, stand filtering, and oil is mutually collected, solvent is recovered under reduced pressure, is then evaporated under reduced pressure AHMT can be obtained.
The charge ratio are as follows:
1. HMT and acetic anhydride or quality of acetic acid proportion are 1:6-15, preferably 1:6-8
2. HMT and sulfuric acid modified zeolite catalyst mass ratio are 1:0.1-0.7, preferably 1:0.14-0.5
3. HMT and solvent quality ratio are 1:5-20, preferably 1:5-8
4. reaction temperature is 10-40 DEG C, preferably 20-30 DEG C
3. solvent can be for methylene chloride, chloroform, tetrachloromethane, chloroethanes, 1,2- dichloroethanes, 1,1- dichloro in the step Ethane, 1,1,1- trichloroethanes, 1,1,2- trichloroethanes, chlorobutane, it is one of in Sec-Butyl Chloride be solvent.
The method of the present invention is with intermediate 1,1,3,4,4,6- hexamethyl tetrahydronaphthalene (abbreviation HMT) and acetic acid or acetic anhydride Raw material is catalyzed friedel-crafts acylation as catalyst using sulfuric acid modified zeolite molecular sieve, significantly under normal temperature and pressure conditions The dosage for reducing catalyst, can be realized catalyst recycling and returns set and eradicate aluminium wastewater under the premise of guaranteeing 98% yield Discharge, be conducive to environmental protection, reduce alchlor hydrolysis generate a large amount of heat, conducive to the selectivity of reaction.
The NaZ-5 bought from market is na-pretreated zeolite, it is first become ammonium type zeolite with ammonium nitrate ion exchange, then high Warm calcining and decomposing ammonium ion makes it be changed into h-type zeolite catalysis reaction, then prepares sulfuric acid modified zeolite catalyst, be used for Friedel-Crafts reaction occurs for fcc raw material.
Compared with prior art, beneficial effects of the present invention:
1. sulfuric acid modified zeolite molecular sieve prepared by the present invention is used to prepare AHMT, the AHMT of preparation, purity 96-99.4% (GC), the yield of AHMT 93% or so is improved from document and realizes the regeneration of catalyst to 98-98.30% and applies, apply 5 After secondary, yield is 98% or more；
2. modified molecular screen is used to be catalyzed Fu Ke-acylation reaction for catalyst, to eradicate using alchlor be catalyst hydrolysis The a large amount of hydrogen chloride gas of bring, and eradicate acid solution containing aluminium；
3. reducing catalyst amount, HMT and sulfuric acid modified zeolite catalyst mass ratio are 1:0.1-0.7；Simultaneously using modified point Son sieve is that catalyst solves to generate a large amount of heat when quenching alchlor, prevents reaction product from hydridization occurs；
4. solve the problems, such as that using Bronsted acid be catalyst there is also the fatal disadvantage such as severe corrosion equipment and quantity of three wastes be big, It is environmentally protective；
5. catalyst is fine particle in the present invention, end of reaction can be filtered out, can directly be applied, and be conducive to environmental protection, facilitated behaviour Make.
Specific embodiment:
Technical solution of the present invention is further illustrated below by embodiment and comparative example, but protection scope of the present invention is not by reality Apply the limitation of example.
A kind of embodiment 1: preparation method of sulfuric acid modified zeolite molecular sieve
The following steps are included:
(1) H- type zeolite molecular sieve is prepared
1. roasting for the first time
The NaZ-5(silica alumina ratio for taking 4.5g is that 30) molecular screen primary powder is put into Muffle furnace, and 5h is roasted under the conditions of nitrogen protection, is roasted Temperature is 400 DEG C.
2. ion exchange
The NaZ-5 original powder that roasting finishes is cooled to room temperature, 4.4g is obtained and roasts the NaZ-5 original powder finished.4.4g is taken to roast Complete NaZ-5 original powder, which is put into 1mol/L aqueous ammonium nitrate solution, carries out ion exchange, and the dosage of aqueous ammonium nitrate solution is 36ml, 5h is stirred at a temperature of 70 DEG C, stirring finishes, and filter cake is washed with deionized 3-5 times for filtering, and filter cake taking-up is put into temperature and is In 120 DEG C of high-temperature cabinets, dries 10h and NH is made4Type molecular sieve about 4.7g.
3. second roasts
It is 4.5g that the NH4- type molecular sieve of 4.7g, which is placed on 550 DEG C of roasting 6h in Muffle furnace to obtain H- type zeolite molecular sieve,.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve 4.5g of above-mentioned preparation is impregnated in 1mol/L sulfuric acid solution under conditions of 80 DEG C, is impregnated Sulfuric acid solution dosage be 35.2ml, dip time 4h, dipping finishes, filtration washing, be washed with deionized 3-5 time extremely in Property.
2. roasting
12h is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite catalyst 4.3g is made.
(3) activation and regeneration
1. the sulfuric acid modified zeolite catalyst of 4.3g will be claimed to be put into porcelain crucible, taken immediately after calcining 1h at 540 DEG C of Muffle furnace It is cooled to room temperature and is reacted in being immediately placed in reactor out, activation can be realized.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, is forged at 600 DEG C of Muffle furnace after reaction inactivation It burns 5h and takes out to be cooled to room temperature to be put into reactor later and reacted, realize regeneration.
Above-mentioned catalyst is preparing the application in AHMT
It takes HMT21.6g solid to be put into the four-hole boiling flask of 1000ml, weighs methylene chloride 108g and be put into the 1000ml for filling HMT Flask in, stirring 0.5h to HMT is completely dissolved, and dissolution assembles reaction unit after finishing, and is taken out activation at this time and is finished The sulfuric acid modified zeolite of 4.3g is put into four-hole boiling flask, stirring, and acetic acid 129.6g is added and is warming up to 20 DEG C, samples inspection after reaction 7h It surveys, when the G/C content of HMT is less than 0.5%, stopping reaction standing filtering, obtains filter cake about 4.5g, obtain filtrate 258.7g, be recovered under reduced pressure Rectifying can obtain finished product 26.32g(GC content 96.2% after solvent) yield is 98.14%(in terms of HMT) filter cake directly returned Set.
1 filter cake of table applies number and yield table
A kind of preparation method of sulfuric acid modified zeolite molecular sieve of embodiment 2
Include the following steps
(1) H- type zeolite molecular sieve is prepared
1. roasting for the first time
The NaZ-5(silica alumina ratio for taking 33g is that 30) molecular screen primary powder is put into Muffle furnace, and 8h is roasted under the conditions of nitrogen protection, is roasted Temperature is 400 DEG C.
2. ion exchange
Will the NaZ-5 original powder that finishes of roasting be cooled to room temperature 32.9g roasts the NaZ-5 original powder finished, take 32.4g roasting to finish NaZ-5 original powder be put into 1mol/L aqueous ammonium nitrate solution and carry out ion exchange, the dosage of ammonium nitrate is 324ml；In 75 DEG C of temperature Degree is lower to stir 1h, and stirring finishes, and filters, filter cake is washed with deionized 3-5 times, and it is 120 DEG C that filter cake taking-up, which is put into temperature, In high-temperature cabinet, dries 10h and NH is made4Type molecular sieve about 32.6g.
3. second roasts
It is 32.4g that the NH4- type molecular sieve of 32.6g, which is placed on 550 DEG C of roasting 6h in Muffle furnace to obtain H- type zeolite molecular sieve,.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve 32.4g of above-mentioned preparation is impregnated in 1mol/L sulfuric acid solution under conditions of 90 DEG C.Leaching The sulfuric acid solution dosage of stain is 324ml, dip time 4h, and dipping finishes, and filtration washing is washed with deionized 3-5 times extremely It is neutral.
2. roasting
12h is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite catalyst 32.2g is made.
(3) activation and regeneration
1. the sulfuric acid modified zeolite catalyst of 32.2g will be claimed to be put into porcelain crucible, taken immediately after calcining 1h at 540 DEG C of Muffle furnace It is cooled to room temperature and is reacted in being immediately placed in reactor out, activation can be realized.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, is forged at 600 DEG C of Muffle furnace after reaction inactivation It burns 5h and takes out to be cooled to room temperature immediately later and reacted in being immediately placed in reactor, regeneration can be realized.
Above-mentioned catalyst is preparing the application in AHMT
It takes HMT107.0g solid to be put into the four-hole boiling flask of 2000ml, weighs 856.0 g of chloroform and be put into 2000 ml for filling HMT Flask in, stirring 0.5 h to HMT is completely dissolved, and dissolution assembles reaction unit after finishing, and is taken out activation at this time and is finished The sulfuric acid modified zeolite of 32.2g is put into four-hole boiling flask, stirring, and 856 g of acetic acid is added and is warming up to 25 DEG C, samples after 5 h of reaction Detection, when the G/C content of HMT is less than 0.5 %, stopping reaction standing filtering, obtains about 32.3 g of filter cake, filtrate decompression is recycled molten Rectifying can obtain 129.01 g(GC content 97.2% of finished product after agent) yield is 98.11 %(in terms of HMT) filter cake directly returned Set.
2 filter cake of table applies number and yield table
A kind of preparation method of sulfuric acid modified zeolite molecular sieve of embodiment 3
The following steps are included:
(1) H- type zeolite molecular sieve is prepared
1. roasting for the first time
The NaZ-5(silica alumina ratio for taking 32.4g is that 30) original powder molecular sieve is put into Muffle furnace, and 8h is roasted under the conditions of nitrogen protection, is roasted Burning temperature is 450 DEG C.
2. ion exchange
Will the NaZ-5 original powder that finishes of roasting be cooled to room temperature 32.2g roasts the NaZ-5 original powder finished, take 32.2g roasting to finish NaZ-5 original powder be put into 1mol/L aqueous ammonium nitrate solution and carry out ion exchange, the dosage of ammonium nitrate is 324ml；In 80 DEG C of temperature Degree is lower to stir 5h, and stirring finishes, and filters, filter cake is washed with deionized 3-5 times, and it is 120 DEG C that filter cake taking-up, which is put into temperature, In high-temperature cabinet, dries 10h and NH is made4Type molecular sieve about 32.6g.
3. second roasts
It is 32.4g that the NH4- type molecular sieve of 32.6g, which is placed on 550 DEG C of roasting 6h in Muffle furnace to obtain H- type zeolite molecular sieve,.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve 32.4g of above-mentioned preparation is impregnated in 1mol/L sulfuric acid solution under conditions of 80 DEG C.Leaching The sulfuric acid solution dosage of stain is 389ml, dip time 4h, and dipping finishes, and filtration washing is washed with deionized 3-5 times extremely It is neutral.
2. roasting
12h is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite catalyst 32.3g is made.
(3) activation and regeneration.
1. the sulfuric acid modified zeolite catalyst of 32.3g will be claimed to be put into porcelain crucible, taking-up after 1h is calcined at 540 DEG C of Muffle furnace It is cooled to room temperature, is put into reactor and is reacted, realize activation.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, is forged at 600 DEG C of Muffle furnace after reaction inactivation It burns 5h and takes out to be cooled to room temperature immediately later and reacted in being immediately placed in reactor, regeneration can be realized.
Above-mentioned catalyst is preparing the application in AHMT
It takes HMT64.8g solid to be put into the four-hole boiling flask of 2000ml, weighs 1,2- dichloroethanes 518.4g and be put into and fill HMT's In the flask of 2000ml, stirring 0.5h to HMT is completely dissolved, and dissolution assembles reaction unit after finishing, and takes out activated at this time The sulfuric acid modified zeolite of complete 32.3g is put into four-hole boiling flask, stirring, and acetic acid 518.4g is added and is warming up to 30 DEG C, after reacting 4h Sample detection, when the G/C content of HMT is less than 0.5%, stopping reaction standing filtering, obtains filter cake about 32.6g, filtrate decompression is recycled Rectifying can obtain finished product 76.46g(GC content 99.2% after solvent) yield is 98.00%(in terms of HMT) filter cake directly returned Set.
3 filter cake of table applies number and yield table
A kind of preparation method of sulfuric acid modified zeolite molecular sieve of embodiment 4
The following steps are included:
(1) preparation of modified catalyst
1. roasting for the first time
The NaZ-5(silica alumina ratio for taking 22g is that 30) molecular screen primary powder is put into Muffle furnace, and 5h is roasted under the conditions of nitrogen protection, is roasted Temperature is 500 DEG C.
2. ion exchange
The NaZ-5 original powder that finishes of roasting is cooled to room temperature to obtain the NaZ-5 original powder g that finishes of 21.8 roastings, 21.8g roasting is taken to finish NaZ-5 original powder be put into 1mol/L aqueous ammonium nitrate solution and carry out ion exchange, the dosage of ammonium nitrate is 175.2ml；At 80 DEG C At a temperature of stir 3h, stirring finishes, filtering, filter cake is washed with deionized 3-5 time, by filter cake taking-up be put into temperature be 120 In DEG C high-temperature cabinet, dries 10h and NH is made4Type molecular sieve about 22g.
3. second roasts
It is 21.9g that the NH4- type molecular sieve of 22g, which is placed on 550 DEG C of roasting 6h in Muffle furnace to obtain H- type zeolite molecular sieve,.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve 21.9g of above-mentioned preparation is impregnated in 1mol/L sulfuric acid solution under conditions of 80 DEG C.Leaching The sulfuric acid solution dosage of stain is 175.2ml, dip time 4h, and dipping finishes, and filtration washing is washed with deionized 3-5 times To neutrality.
2. roasting
12h is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite catalyst 21.5g is made.
(3) activation and regeneration
1. the sulfuric acid modified zeolite catalyst of 21.5g will be claimed to be put into porcelain crucible, taken immediately after calcining 1h at 540 DEG C of Muffle furnace It is cooled to room temperature and is reacted in being immediately placed in reactor out, activation can be realized.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, is forged at 600 DEG C of Muffle furnace after reaction inactivation It burns 5h and takes out to be cooled to room temperature immediately later and reacted in being immediately placed in reactor, regeneration can be realized.
Above-mentioned catalyst is preparing the application in AHMT
It takes HMT43.2g solid to be put into the four-hole boiling flask of 1000ml, weighs 1,1- monochlorethane 216g and be put into and fill HMT's In the flask of 1000ml, stirring 0.5h to HMT is completely dissolved, and dissolution assembles reaction unit after finishing, and takes out activated at this time The sulfuric acid modified zeolite of complete 21.5g is put into four-hole boiling flask, stirring, and acetic anhydride 259.2g is added and is warming up to 20 DEG C, reacts 4.5h Sample detection later, when the G/C content of HMT is less than 0.5%, stopping reaction standing filtering, filter cake about 21.7g is obtained, by filtrate decompression Rectifying can obtain finished product 51.00g(GC content 99.2% after recycling design) yield be 98.05%(in terms of HMT) filter cake directly into Go back set.
4 filter cake of table applies number and yield table
A kind of embodiment 5: preparation method of sulfuric acid modified zeolite molecular sieve
The following steps are included:
(1) H- type zeolite molecular sieve is prepared
1. roasting for the first time
The NaZ-5(silica alumina ratio for taking 22g is that 30) molecular screen primary powder is put into Muffle furnace, and 5h is roasted under the conditions of nitrogen protection, is roasted Temperature is 500 DEG C.
2. ion exchange
Will the NaZ-5 original powder that finishes of roasting be cooled to room temperature 21.9g roasts the NaZ-5 original powder finished, take 21.9g roasting to finish NaZ-5 original powder be put into 1mol/L aqueous ammonium nitrate solution and carry out ion exchange, the dosage of ammonium nitrate is 175.2ml；At 80 DEG C At a temperature of stir 1h, stirring finishes, filtering, filter cake is washed with deionized 3-5 time, by filter cake taking-up be put into temperature be 120 In DEG C high-temperature cabinet, dries 10h and NH is made4Type molecular sieve about 22.1g.
3. second roasts
It is 22 g that the NH4- type molecular sieve of 22.1g, which is placed on 550 DEG C of roasting 6h in Muffle furnace to obtain H- type zeolite molecular sieve,.
(2) modification of H- type zeolite molecular sieve
1. impregnating sulfuric acid
The H- type zeolite molecular sieve 22g of above-mentioned preparation is impregnated in 1mol/L sulfuric acid solution under conditions of 85 DEG C.Dipping Sulfuric acid solution dosage be 175.2ml, dip time 4h, dipping finishes, and filtration washing is washed with deionized 3-5 times extremely It is neutral.
2. roasting
12h is roasted at 120 DEG C, by gained catalyst in 550 DEG C of roasting 4h, sulfuric acid modified zeolite catalyst 21.7g is made.
(3) activation and regeneration
1. the sulfuric acid modified zeolite catalyst of 21.7g will be claimed to be put into porcelain crucible, taken immediately after calcining 1h at 540 DEG C of Muffle furnace It is cooled to room temperature and is reacted in being immediately placed in reactor out, activation can be realized.
2. load weighted deactivated zeolite catalyst is put into porcelain crucible, is forged at 600 DEG C of Muffle furnace after reaction inactivation It burns 5h and takes out to be cooled to room temperature immediately later and reacted in being immediately placed in reactor, regeneration can be realized.
Above-mentioned catalyst is preparing the application in AHMT:
It takes HMT151.2g solid to be put into the four-hole boiling flask of 2000ml, weighs chlorobutane 756g and be put into the 1000ml's for filling HMT In flask, stirring 0.5h to HMT is completely dissolved, and dissolution assembles reaction unit after finishing, and takes out the 21.7g that activation finishes at this time Sulfuric acid modified zeolite is put into four-hole boiling flask, stirring, and acetic anhydride 907.2g is added and is warming up to 30 DEG C, samples inspection after reaction 3.5h Survey, but HMT in G/C content after 0.5%, stop reaction, stand filtering, filter cake about 30.4g is obtained, by filtrate decompression recycling design Rectifying later can obtain finished product 180.1g(GC content 98.3%) yield be 98.03%(in terms of HMT) filter cake directly carry out back cover i.e. It can.
5 filter cake of table applies number and yield table
Illustrate 1: initial R&D process, using commercially available ZSM-5, NaZ-5, NaZ-3, acidic resins, mesoporous silicon oxide come Catalysis reaction screening catalyst system, and respectively for unmodified NaZ-5, the only NaZ-5 of calcination process, modification but unactivated NaZ-5, modification and the NaZ-5 activated, investigate that roasting, the results are shown in Table 6 for the modified, influence that activates to reaction.
Illustrate 2: feed intake index and the reaction condition for the embodiment 5 that 6 application conditions of table use
Table 6
NaZ-5 roasting refers to (to be roasted) for the first time after roasting finishes, and is not carried out sulfuric acid solution dipping and is modified, directly feeds intake Reaction；
NaZ-5 with it is sulfuric acid modified it is (unactivated) refer to do not activated after modified complete, directly carry out the reaction that feeds intake；
NaZ-5 is activated after referring to modified complete with sulfuric acid modified (activation), directly carries out the reaction that feeds intake；
Illustrate 3: after determination roasts NaZ-5 zeolite molecular sieve, is modified, activates to the influence of reaction, using respectively Sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, Loprazolam, trifluoroacetic acid, the ethanol solution of phosphotungstic acid, silico-tungstic acid ethanol solution to its into Row study on the modification, modified finish are activated later, and concrete application situation such as uses feed intake index and the reaction condition of embodiment 5 Obtain the following table 7:
Table 7
Can be seen that by upper table can obtain preferable catalytic effect using sulfuric acid (1mol/L).
Listed above is only specific embodiment, and those of ordinary skill in the art can be direct from present disclosure All deformations for exporting or associating are within the scope of the invention.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention Protection scope.

Claims (10)

1. a kind of preparation method of sulfuric acid modified zeolite molecular sieve, it is characterised in that: including preparing H- type zeolite molecular sieve, H- type The modification of zeolite molecular sieve；The modification of the H- type zeolite molecular sieve, including dipping sulfuric acid, roasting.
2. a kind of preparation method of sulfuric acid modified zeolite molecular sieve according to claim 1, it is characterised in that: the dipping H- type zeolite molecular sieve under conditions of 80-90 DEG C, is impregnated in 0.9-1.1mol/L sulfuric acid solution, dip time by sulfuric acid For 3.8-4.2h, sulfuric acid solution dosage is 8-20 ml/g H- type zeolite molecular sieve.
3. a kind of preparation method of sulfuric acid modified zeolite molecular sieve according to claim 1, it is characterised in that:
The preparation H- type zeolite molecular sieve, including roasting for the first time, ion exchange, second of roasting；The ion exchange, takes The NaZ-5 original powder finished is roasted for the first time be put into 0.8-1.2mol/L aqueous ammonium nitrate solution carry out ion exchange, ammonium nitrate water The dosage of solution is 8-20ml/gNaZ-5 original powder；1-5h is stirred at a temperature of 70-92 DEG C, stirring finishes, and filter cake is washed in filtering, Filter cake, which is dried, is made NH4- type molecular sieve.
4. a kind of preparation method of sulfuric acid modified zeolite molecular sieve according to claim 3, it is characterised in that: described first NaZ-5 molecular screen primary powder is roasted 5-10h by secondary roasting under nitrogen protection, maturing temperature is 400-600 DEG C.
5. a kind of preparation method of sulfuric acid modified zeolite molecular sieve according to claim 3, it is characterised in that: described second NH4- type molecular sieve is roasted 5.5-6.5h at 540-560 DEG C and obtains H- type zeolite molecular sieve by secondary roasting.
6. a kind of preparation method of sulfuric acid modified zeolite molecular sieve according to claim 1, it is characterised in that: the roasting It burns, roasts 11-13h at 115-125 DEG C, in 540-560 DEG C of roasting 3.5-4.5h, sulfuric acid modified Zeolite molecular sieve catalysis is made Agent.
7. a kind of application of sulfuric acid modified zeolite molecular sieve in synthesis AHMT, it is characterised in that: the sulfuric acid modified zeolite point Son sieve is after overactivation, for synthesizing AHMT；The activation method is that will state sulfuric acid modified zeolite molecular sieve at 535-545 DEG C It takes out and is cooled to room temperature immediately after calcining 0.8-1.2h, carry out catalysis reaction immediately.
8. a kind of application of the sulfuric acid modified zeolite molecular sieve according to claim 1 in synthesis AHMT, it is characterised in that: After the sulfuric acid modified zeolite molecular sieve inactivation, by regeneration, synthesis AHMT can be reused for；The regeneration method is 580- Taking-up immediately is cooled to room temperature after calcining 4.5-5.5h at 620 DEG C, carries out catalysis reaction immediately.
9. a kind of application of the sulfuric acid modified zeolite molecular sieve according to claim 1 in synthesis AHMT, it is characterised in that: Reaction raw materials HMT and acetic anhydride or quality of acetic acid proportion are 1:6-15；
The mass ratio of HMT and sulfuric acid modified zeolite molecular sieve is 1:0.1-0.7；
HMT and solvent quality ratio are 1:5-20.
10. a kind of application of the sulfuric acid modified zeolite molecular sieve according to claim 1 in synthesis AHMT, feature exist In: reaction temperature is 10-40 DEG C；Solvent is methylene chloride, chloroform, tetrachloromethane, chloroethanes, 1,2- dichloroethanes, 1,1- bis- Chloroethanes, 1,1,1- trichloroethanes are 1,1,2- trichloroethanes, chlorobutane, one of in Sec-Butyl Chloride.
CN201910481113.0A 2019-06-04 2019-06-04 A kind of preparation method and purposes of sulfuric acid modified zeolite molecular sieve Withdrawn CN110152717A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735061A (en) * 2021-11-04 2021-12-03 清大国华环境集团股份有限公司 Method for recovering bromine from hazardous waste liquid containing bromine-substituted aromatic hydrocarbon
CN114887656A (en) * 2022-06-06 2022-08-12 大连理工大学 Preparation method of modified nano H beta zeolite catalyst for selective synthesis of 6-acyl-2-methoxynaphthalene

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113735061A (en) * 2021-11-04 2021-12-03 清大国华环境集团股份有限公司 Method for recovering bromine from hazardous waste liquid containing bromine-substituted aromatic hydrocarbon
CN113735061B (en) * 2021-11-04 2022-02-11 清大国华环境集团股份有限公司 Method for recovering bromine from hazardous waste liquid containing bromine-substituted aromatic hydrocarbon
CN114887656A (en) * 2022-06-06 2022-08-12 大连理工大学 Preparation method of modified nano H beta zeolite catalyst for selective synthesis of 6-acyl-2-methoxynaphthalene

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Application publication date: 20190823