CN107954435A - The preparation method and its usage of composite molecular screen - Google Patents
The preparation method and its usage of composite molecular screen Download PDFInfo
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- CN107954435A CN107954435A CN201610898995.7A CN201610898995A CN107954435A CN 107954435 A CN107954435 A CN 107954435A CN 201610898995 A CN201610898995 A CN 201610898995A CN 107954435 A CN107954435 A CN 107954435A
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The present invention relates to a kind of preparation method and its usage of composite molecular screen, it is poor mainly to solve to exist in the prior art decalin base catalyst choice, while the problem of easy in inactivation.The present invention is by using comprising the following steps：A) silicon source, silicon source, alkali, water and template are mixed, obtains initial colloid, then composite molecular screen is made in hydrothermal crystallizing；B) by adjusting the addition and silica alumina ratio of inorganic base and template in initial colloid, 12 composite molecular screens of ZSM 5/ZSM of different proportion are obtained；C) obtained zeolite precursor material is passed through into ion-exchanged, it is then fired, obtain decalin base catalyst；D) decalin base catalyst will be obtained to be applied among decalin base reaction.Template is tetraethyl ammonium hydroxide or the one or several kinds of tetraethylammonium bromide and etamon chloride, and colloid mole composition is：SiO2/Al2O3=62~150, R/SiO2=0.15~0.35, H2O：SiO2=13~30.Composite molecular screen in the present invention is used to show excellent catalytic performance among decalin base reaction.
Description
Technical field
The present invention relates to a kind of preparation method and its usage of decalin base catalyst.
Background technology
2,6- dialkyl group naphthalenes can synthesize 2,6- naphthalenes diacid (2,6-DNA) through peroxidating, and 2,6- naphthalene diacid are that production is new
The raw material of high-performance polyester material-polyethylene naphthalate (PEN) of type, with polybutylene terephthalate (PBT) (PET)
Compare, the performance of PEN is far better.PEN has superior heat resistance, mechanical performance, chemical stability, gas barrier property and resistance to purple
Outside line and radiance；PEN has good transparency as PET, and PEN is the advantage of PET its temperature in use will
35~55 DEG C are higher by, tensile strength is higher by 50%, and barrier property is higher by 5 times；Other markets of PEN are in preparative layer pressing plate, copolymerization
In terms of thing and blend, application prospect is boundless.Since the nineties, external major plastics-production manufacturer and application company are numerous and confused
The world-famous chemical companies such as the synthesis and application of PEN, Amoco, Shell, ICI, Mitsubishi, Sumitomo are invested in all to carry out
Development, exploitation and the application of PEN, the whole world have started the exploitation climax of PEN.
In 2,6- dialkyl group naphthalenes, it is most important that 2,6- dimethylnaphthalenes (2,6-DMN) and 2,6-DIPN (2,6-
DIPN).2,6- dimethylnaphthalenes (2,6-DMN) molecule is small, and it is poor to select type, simultaneously because methylation activity is low, reaction temperature is high, makes
Into the presence of a variety of isomers.2,6-DIPN molecules are big, and isopropyl space steric effect is big, and the ortho position and meta two for making naphthalene substitute
Thing is difficult to generate, so as to reduce the number of isomers, the selectivity of 2,6-DIPN is improved, easy to separating-purifying；Same 2,6-
DMN is compared, and 2,6-DIPN are easier oxidation formation 2,6-DNA, yield higher, therefore the utilization rate higher of atom.
The production capacity 2009 for the petronaphthalene that tar naphthalene and ethylene bottom oil are extracted with aromatic hydrocarbons in C9 in China, coal tar
Year, the yield of refined naphthalene was 100,000 t/a, and developing the downstream high value added product of naphthalene becomes particularly significant up to 200,000 t/a.Naphthalene
Alkylation can obtain many products, wherein with the medical the most extensive of isopropyl naphthalene series of products, and in isopropyl naphthalene series
In product, but it is maximum with the practical value of diisopropyl naphthalene (DIPN) especially 2,6-DIPN (2,6-DIPN).
At home and abroad, there are many research reports on 2,6-DIPN synthesis, however, in the world, also without maturation
2,6-DIPN production technology, therefore, using naphthalene as raw material, pass through the further investigation to catalyst and reaction process, hair
Opening up 2,6- diisopropyl naphthalenes and its two technic acid of naphthalene has novelty.
Mobil oil companies of the U.S. in 1972 in USP 3702886 announce invented ZSM-5 molecular sieve after, due to
It has higher silica alumina ratio, unique pore passage structure and excellent heat and hydrothermal stability, the shape slective cracking in hydro carbons, alkane
Obtain and its be widely applied in the petrochemical process such as base, isomerization, disproportionation, catalytic dewaxing, etherificate.Its disclosed conjunction
Tetra-alkyl ammonium hydroxide (alkyl number 2~5) is used as template into method, prepared by silicon source, silicon source, water, alkali and template
Reaction mixture obtains ZSM-5 products after crystallization under hydrothermal conditions.But there are lacking in structure and aperture in itself by ZSM-5
Fall into, for example, ZSM-5 be by oval ten-ring straight hole road (0.54nm × 0.56nm) and sinusoidal duct (0.51nm ×
0.54nm) form, this structure size prevents heavy constituent from entering this molecular sieve, and product is not easy to diffuse out in some reactions
Go, reaction is easy to that coking, carbon deposition phenomenon occurs.
The Rosinski and Rubin of Mobil oil companies of the U.S. in 1973 have synthesized ZSM-12 molecular sieves first, its structure
Type is MTW types, has the non-crossing duct of one-dimensional linear that twelve-ring is formed, aperture is 0.57 × 0.61nm, belongs to high silicon class
Zeolite.This pore size between mesoporous and large pore molecular sieve can effectively be realized and most of organic molecules are selected
Shape catalyzed conversion, and the characteristics of hydrocarbon reaction is not easy coking and long service life is shown among catalytic reaction, before
Scape is very wide.
In view of the microcosmic mixing of ZSM-5 and ZSM-12 interaction that may be present, using the advantages of each of which and gram
Take its shortcoming, it is understood that there may be conducive to some characteristics of catalytic reaction, therefore the synthesis of ZSM-5/ZSM-12 mixed crystal materials is in stone
There is critically important theory significance and practical significance in oiling work.
CN104591216A discloses a kind of synthetic method of ZSM-5/ZSM-12 composite molecular screens, using first to ZSM-12 points
Son sieve is ultrasonically treated, then prepared by crystallization after water, alkali, template, silicon source, silicon source mixing pre- crystallization colloid, then will be pre-
The method that crystallization colloid mixes crystallization with the ZSM-12 molecular sieves after processing, obtains ZSM-5/ZSM-12 composite molecular screens.The party
Method needs the prior step such as pre- crystallization, supersound process, complex steps, and is synthesized for substep, regrows, forms composite molecular screen
Stability it is poor, be also not involved with the improvement of the catalytic performance of molecular sieve.
The content of the invention
The technical problems to be solved by the invention are that decalin base catalysts exist in the prior art compared with easy in inactivation, are selected
The problem of type is not high.A kind of preparation method of composite molecular screen is provided, preferably resolves the problem.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of preparation method of composite molecular screen,
Comprise the following steps：
Silicon source, silicon source, alkali, water and template are mixed, obtain initial colloid, then ZSM-5/ZSM- is made in hydrothermal crystallizing
12 composite molecular screens；The molar ratio of ZSM-5 and ZSM-12 is 1 in the composite molecular screen:1~1:4.
Silicon source wherein used be include selected from waterglass, Ludox, white carbon at least one；Silicon source used is to include choosing
From for including selected from aluminium alcoholates, sodium metaaluminate, aluminum sulfate, aluminum nitrate at least one；Template used dose is to include selected from tetraethyl
Ammonium hydroxide, tetraethylammonium bromide, at least one of etamon chloride；
The temperature of the hydrothermal crystallizing is 120~200 DEG C, when the time of hydrothermal crystallizing is 36~144 small；With molal quantity
Meter, the silica alumina ratio of the silicon source and silicon source is SiO2：Al2O3=62~150:1；Template R dosages are R：Si=0.15~
0.35:1；Water silicon ratio is H2O：SiO2=13~30.
In above-mentioned technical proposal, roasted after hydrothermal crystallizing, the calcination temperature is 450~600 DEG C.
In above-mentioned technical proposal, preferred solution is：Addition alkali controls pH more than 13 after silicon source, silicon source mixing, described
Alkali is sodium hydroxide；More preferably, it is 13-15 to control pH.
In above-mentioned technical proposal, the silicon source is alkaline ammonia stabilized silica sol.
In above-mentioned technical proposal, in the ZSM-5/ZSM-12 composite molecular screens, the ratio of ZSM-5 and ZSM-12 are 1:1
~1:4.At this moment the sial mole ratio of silicon source and silicon source is 62~150:1；It is preferred that 1:2~1:3.Silicon with silicon source and silicon source
Aluminium molal quantity proportion is 80~100:1 ZSM-5/ZSM-12 composite molecular screens are preferable for decalin base reaction effect.
In above-mentioned technical proposal, the sial mole ratio SiO of the silicon source and silicon source2：Al2O3For 100：When 1, obtain
Be that opposite crystallization percentage is 1：1 ZSM-5/ZSM-12 composite molecular screens.
In above-mentioned technical proposal, template R dosage preferred scopes are 0.2~0.3:1.
In above-mentioned technical proposal, the temperature of the hydrothermal crystallizing is 160~200 DEG C, and preferred temperature is 180 DEG C；Institute
State the hydrothermal crystallizing time for 48~72 it is small when, the preferred hydrothermal crystallizing time for 60 it is small when；The washing is deionized water；Institute
Calcination temperature is stated as 550 DEG C.
In above-mentioned technical proposal, by ZSM-5/ZSM-12 composite molecular screens, further ion-exchange treatment, roasting are described
The ion of ion exchange is ammonium nitrate or ammonium chloride and the mixture of the two；The temperature of the ion exchange is 35~90
DEG C, at least twice, when each time is 1~24 small, ion concentration is 0.5~2mol/L；The ion of the ion exchange is handed over
Rate is changed as 50%~95%.
The present invention also provides a kind of ZSM-5/ZSM-12 composite molecular sieve catalysts synthesized according to the above method.
The present invention also provides a kind of ZSM-5/ZSM-12 composite molecular sieve catalysts synthesized according to the above method in naphthalane
Application in glycosylation reaction.
This patent is using the method directly by controlling silica alumina ratio in synthesizing formula, to synthesize compound point of ZSM-5/ZSM-12
Son sieve.Specifically, the method for the present invention controls mole of silicon source and silicon source in the catalyst preparation process that decalin base reacts
Than for SiO2：Al2O3=62~150:1, the dosage of alkali and template is controlled, ZSM-5 and ZSM-12 ratios 1 are prepared:1~
1:4 ZSM-5/ZSM-12 composite molecular screens, further ion-exchange treatment, roasting have obtained decalin base catalyst.
The decalin base catalyst prepared using the present invention carries out decalin base reaction, takes 3.0g Catalyst packings to react
Pipe, naphthalene are mixed with hexamethylene as reaction solution, mixed proportion are naphthalene all the way：Hexamethylene=1：5 (molar ratios), naphthalene, flow of cyclohexane
Speed is 1.5g/min, and liquid propene (pressure 4.0MPa) is used as another way reaction solution, flow velocity 0.1g/min；Reacting system pressure
For 4.0Mpa, reaction temperature is 220 DEG C；Reaction result analysis test：2,6-DIPN selectivity 41%, naphthalene conversion ratio
31%, achieve preferable technique effect.
Brief description of the drawings
Fig. 1 is the XRD diagram of the embodiment of the present invention 10.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
(1) 50g waterglass (SiO is taken2Content is 27.20wt%, modulus 3.2), 0.67g aluminum sulfate, the hydrogen of 96wt%
The tetraethyl ammonium hydroxide aqueous solution 50g of sodium oxide molybdena 1.0g, deionized water 50g, 30wt%, gel is mixed into, with 10% hydrogen-oxygen
Change sodium water solution and adjust PH to 13, when standing 6 is small.When then crystallization 72 is small at 170 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A1, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:1.
(4) the powder 10.3g that step obtains is taken, with the NH of 1mol/L4NO3Solution 200ml is exchanged three times at room temperature, and every time 8
Hour.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) alkylated reaction that naphthalene and propylene are carried out on 15ml fixed bed devices is evaluated.Take 3.0g Catalyst packings anti-
Ying Guan, naphthalene are mixed with hexamethylene as reaction solution, mixed proportion are naphthalene all the way：Hexamethylene=1：5 (molar ratios), naphthalene, hexamethylene
Flow velocity is 1.5g/min, and liquid propene (pressure 4.0MPa) is used as another way reaction solution, flow velocity 0.1g/min.Reaction system pressure
Power is 4.0Mpa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 41%.When the catalyst inactivation time 24 is small.
【Embodiment 2】
(1) by 600 gram of 40% Ludox, 10.1 grams of sodium aluminates (alumina content 42%), 41.6 grams of 30wt% tetraethyls
Ammonium hydroxide (TEAOH), 168.0 grams of tetraethylammonium bromides (TEABr), 16.0 grams of sodium hydroxides and 925.1 grams of water mixing, room temperature
Under stir evenly, stand 6 it is small when.When then crystallization 48 is small at 200 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A2, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:1.
(4) the powder 200g that step obtains is taken, with the NH of 1mol/L4NO3Exchanged three times at 80 DEG C of solution 2000ml, every time
8 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) alkylated reaction that naphthalene and propylene are carried out on 300ml reaction kettle devices is evaluated.5.0g catalyst is taken to be put into instead
Answer among kettle, naphthalene is mixed with isopropanol is used as reaction solution, and mixed proportion is naphthalene：Isopropanol=1：1 (molar ratio), naphthalene, isopropanol
Additive amount is 100g, and reaction temperature is 250 DEG C, when the reaction time is 4 small.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 43%.When the catalyst inactivation time 24 is small.
【Embodiment 3】
(1) the tetraethyl ammonium hydroxide 160g of tert-butyl alcohol aluminium (wt97%) 3.5g, 30wt%, sodium hydroxide 8g is taken to mix,
Then 160g TEOS (wt98%) and 140g deionized waters are added wherein, is stirred evenly at room temperature, when standing 4 is small.Then exist
When crystallization 48 is small at 200 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A3, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:4.
(4) the powder 35g that step obtains is taken, with the NH of 2mol/L4Exchanged three times at 80 DEG C of Cl solution 500ml, every time 8
Hour.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) isomerization reaction of diisopropyl naphthalene, loaded catalyst 5g are carried out on 100ml reaction kettle devices.It is former
The composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among material, and 2,7-DIPN account for 36.9%, and triisopropyl naphthalene accounts for 6.6%.
Reaction temperature is 220 DEG C, when the reaction time is 3 small.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 41%.When the catalyst inactivation time 24 is small.
【Embodiment 4】
(1) Ludox (wt40%) 600g, sodium metaaluminate (alumina content 42%) 8.8g, sodium hydroxide 8g are taken, go from
The tetraethyl ammonium hydroxide 120g of sub- water 800g, 30wt%, mixing, is stirred at room temperature uniformly, when standing 4 is small.Then 200
When crystallization 48 is small at DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 6 times, when then vacuum drying 18 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A4, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:3.
(4) the powder 212g that step obtains is taken, with the NH of 1mol/L4Cl solution 2000ml is exchanged three times at room temperature, and every time 8
Hour.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) the isomerization reaction evaluation of diisopropyl naphthalene is carried out on 15ml fixed bed devices.Take 3.0g Catalyst packings
Reaction tube, the composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among raw material, and 2,7-DIPN account for 36.9%, triisopropyl naphthalene
Account for 6.6%.Diisopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 39%.When the catalyst inactivation time 24 is small.
【Embodiment 5】
(1) Ludox (wt40%) 747.1g, the tetrem of sodium metaaluminate (alumina content 42%) 12.3g, 30wt% are taken
Base ammonium hydroxide 468.5g, deionized water 583.7g, mixing, is stirred at room temperature uniformly.With 10% sodium hydrate aqueous solution tune
PH to 13 is saved, when standing 6 is small.When then crystallization 72 is small at 170 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A5, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:3.
(4) the powder 232g that step obtains is taken, with the NH of 1.5mol/L4NO3Solution 2000ml is exchanged three times, often at room temperature
It is secondary 12 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) the isomerization reaction evaluation of single isopropyl naphthalene is carried out on 15ml fixed bed devices.Take 3.0g Catalyst packings
Reaction tube, the composition of single isopropyl naphthalene accounts for 97% for 2-DIPN among raw material, and 2,7-DIPN account for 2.4%, and triisopropyl naphthalene accounts for
0.6%.Single isopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0MPa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 43%.When the catalyst inactivation time is 24 small.
【Comparative example 1】
(1) Ludox (wt40%) 747.1g, the tetrem of sodium metaaluminate (alumina content 42%) 41.0g, 30wt% are taken
Base ammonium hydroxide 468.5g, deionized water 583.7g, mixing, is stirred at room temperature uniformly.With 10% sodium hydrate aqueous solution tune
PH to 13 is saved, when standing 6 is small.When then crystallization 72 is small at 170 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The original powder that upper step is obtained, numbering are denoted as D1, ZSM-5 are detected as through XRD powder diffractions.
(4) the powder 232g that step obtains is taken, with the NH of 1.5mol/L4NO3Solution 2000ml is exchanged three times, often at room temperature
It is secondary 12 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) the isomerization reaction evaluation of single isopropyl naphthalene is carried out on 15ml fixed bed devices.Take 3.0g Catalyst packings
Reaction tube, the composition of single isopropyl naphthalene accounts for 97% for 2-DIPN among raw material, and 2,7-DIPN account for 2.4%, and triisopropyl naphthalene accounts for
0.6%.Single isopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0MPa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6-DIPN selectivity 41%, when the catalyst inactivation time 6 is small, is less than
The 36 of embodiment 5 it is small when.
【Embodiment 6】
(1) white carbon 123g, Ludox (wt40%) 120g, ANN aluminium nitrate nonahydrate 19.8g, 30wt% tetraethyl bromination are taken
Ammonium 187.5g, deionized water 485.2g, sodium hydroxide 6.5g mixing, are stirred at room temperature uniformly.It is water-soluble with 10% sodium hydroxide
Liquid adjusts PH to 13, when standing 6 is small.When then crystallization 48 is small at 200 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A6, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:4.
(4) the powder 241g that step obtains is taken, with the NH of 1.5mol/L4Exchanged three times at 60 DEG C of Cl solution 2000ml, often
It is secondary 8 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) the isomerization reaction evaluation of single isopropyl naphthalene is carried out on 15ml fixed bed devices.Take 3.0g Catalyst packings
Reaction tube, the composition of single isopropyl naphthalene accounts for 97% for 2-DIPN among raw material, and 2,7-DIPN account for 2.4%, and triisopropyl naphthalene accounts for
0.6%.Single isopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0MPa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 41.8%.The catalyst inactivation time is small for 24
When.
【Embodiment 7】
(1) fetch water glass (SiO2Content is 27.20wt%, modulus 3.2) 80g, white carbon 101g, Ludox
(wt40%) 120g, ANN aluminium nitrate nonahydrate 21.6g, 30wt% tetraethylammonium bromide 210.5g, deionized water 510.3g, mixing,
It is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.The then crystallization 72 at 200 DEG C
Hour.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A7, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:4.
(4) the powder 162g that step obtains is taken, with the NH of 2mol/L4NO3Exchanged three times at 60 DEG C of solution 1500ml, every time
8 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) isomerization reaction of diisopropyl naphthalene, loaded catalyst 5g are carried out on 100ml reaction kettle devices.It is former
The composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among material, and 2,7-DIPN account for 36.9%, and triisopropyl naphthalene accounts for 6.6%.
Reaction temperature is 220 DEG C, when the reaction time is 3 small.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 43.8%.The catalyst inactivation time is small for 24
When.
【Embodiment 8】
(1) Ludox (wt40%) 489g, sodium metaaluminate 8.3g, sodium hydroxide 10g, deionized water 782g, 30wt% are taken
Tetraethylammonium bromide 360g, mixing, is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, it is small to stand 6
When.When then crystallization 48 is small at 190 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A8, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:4.
(4) the powder 202g that step obtains is taken, with the NH of 2mol/L4Exchanged three times at 60 DEG C of Cl solution 1500ml, every time
8 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) isomerization reaction of diisopropyl naphthalene, loaded catalyst 5g are carried out on 100ml reaction kettle devices.It is former
The composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among material, and 2,7-DIPN account for 36.9%, and triisopropyl naphthalene accounts for 6.6%.
Reaction temperature is 220 DEG C, when the reaction time is 3 small.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 41.9%.The catalyst inactivation time is small for 24
When.
【Embodiment 9】
(1) Ludox (wt40%) 462g, sodium metaaluminate 7.6g, sodium hydroxide 9g, deionized water 691g, 30wt% tetra- are taken
Ethyl phosphonium bromide ammonium 339g, mixing, is stirred at room temperature uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, it is small to stand 6
When.When then crystallization 48 is small at 180 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A9, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.The ratio of ZSM-5 and ZSM-12 is 1:4.
(4) the powder 197g that step obtains is taken, with the NH of 1mol/L4Exchanged three times at 80 DEG C of Cl solution 2000ml, every time
8 it is small when.
(5) solid for taking step to exchange, dry, when 550 DEG C of roastings 6 are small, shaping obtains finished catalyst.
(6) the isomerization reaction evaluation of diisopropyl naphthalene is carried out on 15ml fixed bed devices.Take 3.0g Catalyst packings
Reaction tube, the composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among raw material, and 2,7-DIPN account for 36.9%, triisopropyl naphthalene
Account for 6.6%.Diisopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and reaction temperature is 220 DEG C.
(7) reaction result analysis test：2,6- diisopropyl naphthalenes selectivity 41.3%.The catalyst inactivation time is small for 24
When.
【Embodiment 10】
(1) Ludox (wt40%) 512g, sodium metaaluminate 8.5g, sodium hydroxide 9g, deionized water 802g, 30wt% tetra- are taken
Ethyl phosphonium bromide ammonium 190g, 30wt% tetraethyl ammonium hydroxide 78g, 30wt% etamon chloride 65g is mixed, and is stirred at room temperature
Uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.When then crystallization 72 is small at 180 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as A10, and be detected as ZSM-5 through XRD powder diffractions mixes with ZSM-12
Thing.
Mixed crystal original powder sodium form is converted into the process of Hydrogen：The A10 mixed crystal original powder 80g that Example 10 obtains, add 1mol/
The NH of L4NO3Solution 600ml, is heated in 96~100 DEG C of water-baths, and is stirred continuously and is allowed to exchange uniform, holding exchange 1 every time
Hour, filter after exchange and washed with deionized water 1000ml, then filter, step is washed with deionized and repeats five times.
Then it is dried in vacuo.
Shaping of catalyst process：Take the powder 70g that step obtains and 30g activity γ-Al2O3Mixed-forming, extrusion, vacuum
It is dry, then roast, finished product is denoted as P10.
The isomerization reaction evaluation of diisopropyl naphthalene is carried out on 15ml fixed bed devices.3.0g Catalyst packings are taken to react
Manage, the composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among raw material, and 2,7-DIPN account for 36.9%, and triisopropyl naphthalene accounts for
6.6%.Diisopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and reaction temperature is 220 DEG C.
【Comparative example 2】
(1) Ludox (wt40%) 512g, sodium metaaluminate 20g, sodium hydroxide 20g, deionized water 802g, 30wt% tetra- are taken
Ethyl phosphonium bromide ammonium 190g, 30wt% tetraethyl ammonium hydroxide 78g, 30wt% etamon chloride 65g is mixed, and is stirred at room temperature
Uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.When then crystallization 72 is small at 180 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as D2, ZSM-5 are detected as through XRD powder diffractions.
(1) Ludox (wt40%) 512g, sodium metaaluminate 5g, sodium hydroxide 20g, deionized water 802g, 30wt% tetra- are taken
Ethyl phosphonium bromide ammonium 190g, 30wt% tetraethyl ammonium hydroxide 78g, 30wt% etamon chloride 65g is mixed, and is stirred at room temperature
Uniformly.PH to 13 is adjusted with 10% sodium hydrate aqueous solution, when standing 6 is small.When then crystallization 72 is small at 180 DEG C.
(2) the milky slurries that step obtains are taken to be washed with deionized water 5 times, when then vacuum drying 12 is small.
(3) when taking the solid that step obtains roasting 6 be small at 550 DEG C in Muffle furnace.
The mixed crystal original powder that upper step is obtained, numbering are denoted as D3, ZSM-12 are detected as through XRD powder diffractions.
(1) each 40g of D2 and D3 are taken, mechanical agitation mixing, is denoted as D4.
(2) mixed crystal original powder sodium form is converted into the process of Hydrogen：The D4 mixed crystal original powder 80g that step obtains are taken, add 1mol/L
NH4NO3Solution 600ml, is heated in 96~100 DEG C of water-baths, and is stirred continuously and is allowed to exchange uniformly, keeps exchange 1 small every time
When, filter after exchange and washed with deionized water 1000ml, then filter, step is washed with deionized and repeats five times.And
After be dried in vacuo.
Shaping of catalyst process：Take the powder 70g that step obtains and 30g activity γ-Al2O3Mixed-forming, extrusion, vacuum
It is dry, then roast, finished product is denoted as DB-4.
The isomerization reaction evaluation of diisopropyl naphthalene is carried out on 15ml fixed bed devices.3.0g Catalyst packings are taken to react
Manage, the composition of diisopropyl naphthalene accounts for 22.3% for 2,6-DIPN among raw material, and 2,7-DIPN account for 36.9%, and triisopropyl naphthalene accounts for
6.6%.Diisopropyl naphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and reaction temperature is 220 DEG C.
The deactivation time of the isomerization reaction of diisopropyl naphthalene and the selection of 2,6- diisopropyl naphthalenes under one different catalysts of table
Property
| Catalyst | Deactivation time | 2,6- diisopropyl naphthalenes selectivity |
| P10 | 24h | 41% |
| DB-4 | 8h | 33% |
As shown in Table 1, there is longer deactivation time by the ZSM-5/ZSM-12 mixed crystal materials for controlling silica alumina ratio to synthesize
Higher 2,6- diisopropyl naphthalenes selectivity.Specifically, the ZSM-5/ZSM-12 mixed crystal materials ratio of silica alumina ratio synthesis is controlled
Mechanical mixture ZSM-5/ZSM-12 has longer deactivation time；Meanwhile control the ZSM-5/ZSM-12 mixed crystal of silica alumina ratio synthesis
Material has higher 2,6- diisopropyl naphthalenes selectivity than mechanical mixture ZSM-5/ZSM-12.
Claims (10)
1. a kind of preparation method of composite molecular screen, comprises the following steps：
Silicon source, silicon source, alkali, water and template are mixed, obtain initial colloid, then hydrothermal crystallizing is made ZSM-5/ZSM-12 and answers
Close molecular sieve；The molar ratio of ZSM-5 and ZSM-12 is 1 in the composite molecular screen:1~1:4；
Silicon source wherein used be include selected from waterglass, Ludox, white carbon at least one；
Silicon source used be include selected from aluminium alcoholates, sodium metaaluminate, aluminum sulfate, aluminum nitrate at least one；
Template used dose is to include selected from least one of tetraethyl ammonium hydroxide, tetraethylammonium bromide, etamon chloride；
The temperature of the hydrothermal crystallizing is 120~200 DEG C, when the time of hydrothermal crystallizing is 36~144 small；In terms of molal quantity, institute
The silica alumina ratio for stating silicon source and silicon source is SiO2：Al2O3=62~150:1；Template R dosages are R：Si=0.15~0.35:1；Water
Silicon ratio is H2O：SiO2=13~30.
2. the preparation method of decalin base catalyst according to claim 1, it is characterised in that add after silicon source, silicon source mixing
Alkali is added to control pH more than 13.
3. the preparation method of decalin base catalyst according to claim 2, it is characterised in that the alkali is sodium hydroxide.
4. the preparation method of composite molecular screen according to claim 1, it is characterised in that the silicon source is alkaline ammonia stable type
Ludox.
5. the preparation method of composite molecular screen according to claim 1, it is characterised in that the silica alumina ratio of the silicon source and silicon source
For SiO2：Al2O3=80~100:1.
6. the preparation method of composite molecular screen according to claim 1, it is characterised in that the template R dosages are R：Si
=0.2~0.3:1.
7. the preparation method of decalin base catalyst according to claim 1, it is characterised in that ZSM-5/ZSM-12 is compound
Molecular sieve, further ion-exchange treatment, roasting, the ion of the ion exchange for ammonium nitrate or ammonium chloride and the two
Mixture；The temperature of the ion exchange is 35~90 DEG C, and at least twice, when each time is 1~24 small, ion concentration is
0.5~2mol/L.
A kind of 8. ZSM-5/ZSM-12 composite molecular sieve catalysts synthesized according to any one of claim 1-7 the method.
9. a kind of ZSM-5/ZSM-12 composite molecular sieve catalysts synthesized according to any one of claim 1-7 the method are in naphthalene
Application in alkylated reaction.
10. application according to claim 9, it is characterised in that naphthalane base is carried out using the catalyst described in claim 8
Change reaction, take Catalyst packing reaction tube, naphthalene is mixed with solvent as reaction solution, mass mixing ratio are naphthalene all the way：Solvent=
1:1~1：8, for liquid propene as another way reaction solution, propylene air speed is 0.1~1.6h-1；Reacting system pressure for 2.5~
5.0Mpa, reaction temperature are 150~300 DEG C.
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| CN107954812A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The method of decalin base |
| CN112742464A (en) * | 2021-01-22 | 2021-05-04 | 常州大学 | Preparation method and application method of composite molecular sieve catalyst for synthesizing alkylphenol |
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| CN104591216A (en) * | 2013-11-04 | 2015-05-06 | 中国石油化工股份有限公司 | ZSM-5/ZSM-12 composite molecular sieve and synthetic method thereof |
| CN105268471A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Naphthalene alkylation catalyst preparation method |
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