CN107952475A - The preparation method of decalin base catalyst - Google Patents
The preparation method of decalin base catalyst Download PDFInfo
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- CN107952475A CN107952475A CN201610895808.XA CN201610895808A CN107952475A CN 107952475 A CN107952475 A CN 107952475A CN 201610895808 A CN201610895808 A CN 201610895808A CN 107952475 A CN107952475 A CN 107952475A
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- 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
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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
- C01B39/023—Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48
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- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- 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
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Abstract
The present invention relates to a kind of preparation method and its usage of decalin base catalyst, 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：Silicon source, silicon source, alkali, water and template are mixed, obtain initial colloid, then 12 composite molecular screens of ZSM 5/ZSM are made in hydrothermal crystallizing；Obtained composite molecular screen is passed through into ion-exchanged, is roasted, silylating reagent obtains decalin base catalyst.Wherein described silicon source is alkaline ammonia stabilized silica sol, source of aluminium is sodium metaaluminate, the inorganic base be sodium hydroxide either potassium hydroxide template be tetraethyl ammonium hydroxide or tetraethylammonium bromide and etamon chloride one or several kinds, colloid mole composition is：SiO2/Al2O3=62~150, R/SiO2=0.15~0.35, H2O：SiO2=13~30, wherein R represents template.Modification 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 reacting middle catalyst exists in the prior art compared with easy in inactivation,
Select the problem of type is not high.A kind of preparation method of new decalin base catalyst 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 of decalin base catalyst
Method, comprises the following steps：
A) silicon source, silicon source, alkali, organic amine template are used as raw material, hydrothermal crystallizing；Obtained ZSM-5/ZSM-12 is compound
Molecular sieve；
C) obtained composite molecular screen is passed through into ion-exchanged, roasted, silylating reagent obtains decalin base catalysis
Agent.
Silicon source wherein used is to include selected from least one of waterglass, Ludox, white carbon, silicon source used being to include
Selected from least one of aluminium alcoholates, sodium metaaluminate, aluminum sulfate, aluminum nitrate, template used dose is to include selected from tetraethyl hydroxide
At least one of ammonium, tetraethylammonium bromide, etamon chloride, the temperature of the hydrothermal crystallizing is 120~200 DEG C, hydro-thermal
When the time of crystallization is 36~144 small；In terms of molal quantity, the silica alumina ratio of the silicon source and silicon source is SiO2：Al2O3=62~
150:1；Template dosage is R：Si=0.15~0.35:1；Water silicon ratio is H2O：SiO2=13~30.
In above-mentioned technical proposal, roasted after crystallization, the calcination temperature is 450~600 DEG C.
In above-mentioned technical proposal, the molecular dynamics diameter of the silylating reagent in organic-silylation modification is more than 0.8nm；
It is preferred that 0.8-10nm, it is further preferable that 0.8-3nm.In one embodiment of the invention, the silylating reagent is triphenyl chlorine silicon
Alkane, a diameter of 2nm of its molecular dynamics.
In above-mentioned technical proposal, the ion of the ion exchange is ammonium ion, including selected from ammonium nitrate or ammonium chloride
At least one.The temperature of the ion exchange is 35~90 DEG C, and at least twice, when each time is 1~24 small, ion is dense
Spend for 0.5~2mol/L.The ion exchange ratio of the ion exchange is 50%~95%.
In above-mentioned technical proposal, the organic-silylation modification procedure includes three steps：Silanization, washing, drying, roasting
Burn.
In above-mentioned technical proposal, organic-silylation be modified in silanization used by cleaning solvent be tetrahydrofuran or N,
Dinethylformamide；Catalyst is organic base used by silanization in organic-silylation modification, more preferably, described
Catalyst is 4-dimethylaminopyridine used by silanization；Used by washing in organic-silylation modification in cleaning solvent
Water content in 10ppm (mass fraction) below.The silanization temperature is room temperature.
In above-mentioned technical proposal, preferred solution is：Addition alkali controls pH more than 13 after silicon source, silicon source mixing, described
Alkaline matter 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-
4.At this moment the sial molal quantity of silicon source and silicon source is preferably in a proportion of 80~100:1.
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 dosages are R：Si=0.2：1.
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.
The method of the present invention is in the catalyst preparation process that decalin base reacts, and this patent is using directly by controlling synthesis
The method of silica alumina ratio in formula, to synthesize ZSM-5/ZSM-12 composite molecular screens.Specifically, the method for the present invention is in decalin base
In the catalyst preparation process of reaction, it is SiO to control the molar ratio of silicon source and silicon source2：Al2O3=62~150:1, control alkali and
The dosage of template, is prepared with a certain proportion of ZSM-5/ZSM-12 composite molecular screens, further ion-exchange treatment,
Roasting has obtained decalin base catalyst, and is further more than the organosilan of 0.8nm by using molecular dynamics diameter
Change reagent and carry out the activity that organic-silylation modification further improves 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%, 2,6-DIPN high selectivity, meanwhile, decalin base catalyst inactivation time length, achieves preferable technology effect
Fruit.
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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 mixed crystal 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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 catalyst.
(6) take step catalyst 10g to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- dimethylamino pyrroles
Pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan neutral to pH
Untill.100 DEG C of baking oven is dried overnight to obtain final finished catalyst.
(7) 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.
(8) 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：A10 mixed crystal original powder 80g are taken, add the NH of 1mol/L4NO3Solution
600ml, is heated in 96~100 DEG C of water-baths, and is stirred continuously and is allowed to exchange uniformly, and when keeping exchange 1 small every time, exchange finishes
Filter and washed with deionized water 1000ml afterwards, 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 P14.
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 original powder that upper step is obtained, numbering are denoted as D2, ZSM-5 are detected as through XRD powder diffractions.
Original powder sodium form is converted into the process of Hydrogen：The A15 original powder 80g that step obtains are taken, add the NH of 1mol/L4NO3Solution
600ml, is heated in 96~100 DEG C of water-baths, and is stirred continuously and is allowed to exchange uniformly, and when keeping exchange 1 small every time, exchange finishes
Filter and washed with deionized water 1000ml afterwards, 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 DB-2.
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 3】
(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 original powder that upper step is obtained, numbering are denoted as D3, ZSM-12 are detected as through XRD powder diffractions.
Original powder sodium form is converted into the process of Hydrogen：The A16 original powder 80g that step obtains are taken, add the NH of 1mol/L4NO3Solution
600ml, is heated in 96~100 DEG C of water-baths, and is stirred continuously and is allowed to exchange uniformly, and when keeping exchange 1 small every time, exchange finishes
Filter and washed with deionized water 1000ml afterwards, 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 DB-3.
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 4】
(1) take【Comparative example 2】And【Comparative example 3】D2 and each 40g of D3, mechanical agitation mixing, be denoted as D4.
(2) mixed crystal original powder sodium form is converted into the process of Hydrogen：Take the D4 that step obtains to mix original powder 80g, 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.
【Embodiment 11】
Take catalyst P10 described in 10g embodiments 10 to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- bis-
Methylamino pyridine, then 2g tri-phenyl chlorides are charged with, stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan
Untill pH neutrality.100 DEG C of baking oven is dried overnight to obtain final finished catalyst DB-11.
【Comparative example 5】
Take catalyst P10 described in 10g embodiments 10 to be placed among 300ml anhydrous tetrahydro furans, and add 0.5g 4- bis-
Methylamino pyridine, then 2g trim,ethylchlorosilanes are charged with, (trim,ethylchlorosilane kinetic diameter is 0.4nm, less than right
The 0.8nm limited in it is required that) stir 30 minutes.Then filter, washed with anhydrous tetrahydro furan untill pH neutrality.Baking oven 100
DEG C it is dried overnight to obtain final finished catalyst DB-5.
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-2 | 6h | 43% |
| DB-3 | 34h | 28% |
| DB-4 | 8h | 33% |
| P11 | 36h | 49% |
| DB-5 | 28h | 41% |
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
ZSM-5 and mechanical mixture ZSM-5/ZSM-12 has longer deactivation time, meanwhile, the ZSM-5/ of control silica alumina ratio synthesis
ZSM-12 mixed crystal materials have higher 2,6- diisopropyl naphthalenes selectivity than ZSM-12 and mechanical mixture ZSM-5/ZSM-12；
Organic-silylation modification can significantly improve 2,6- diisopropyl naphthalenes selectivity and extend deactivation time.For synthesis, control
The ZSM-5/ZSM-12 mixed crystal materials of silica alumina ratio synthesis and appropriate silylating reagent is carried out to it there is preferable naphthalane base
Change catalytic performance.
Claims (10)
1. a kind of preparation method of decalin base catalyst, comprises the following steps：A) silicon source, silicon source, alkali, water and template are mixed
Close, obtain initial colloid, then ZSM-5/ZSM-12 composite molecular screens are made in hydrothermal crystallizing；
B) obtained composite molecular screen is passed through into ion-exchanged, roasted, silylating reagent obtains decalin base catalyst.
Silicon source wherein used be include selected from waterglass, Ludox, white carbon at least one；Silicon source used is to include selected from alcohol
Aluminium, sodium metaaluminate, aluminum sulfate, at least one of aluminum nitrate；Template used dose is to include selected from tetraethyl ammonium hydroxide, tetraethyl
At least one of ammonium 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 decalin base catalyst according to claim 1, it is characterised in that the silicon of the silylating reagent
Alkylators are organic-silylation reagent, and the molecular dynamics diameter of the organic-silylation reagent is more than 0.8nm.
5. the preparation method of decalin base catalyst according to claim 4, it is characterised in that the organic-silylation reagent
The a diameter of 0.8nm-10nm of molecular dynamics.
6. the preparation method of decalin base catalyst according to claim 1, it is characterised in that the ion of the ion exchange
It is specially ammonium nitrate or ammonium chloride and the mixture of the two for ammonium ion；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%.
7. the preparation method of decalin base catalyst according to claim 1, it is characterised in that organic-silylation modification procedure
Including three steps：Silanization, washing, drying, roasting；Cleaning solvent is used by silanization in organic-silylation modification
Tetrahydrofuran or N,N-dimethylformamide；Catalyst is organic base used by silanization in organic-silylation modification；Have
Organic silane be modified in washing used by cleaning solvent water content below 10ppm mass fractions.
A kind of 8. decalin base catalyst being prepared according to any one of claim 1-7 the method.
9. a kind of decalin base catalyst being prepared according to any one of claim 1-7 the method is reacted in decalin base
In application.
10. application according to claim 9, it is characterised in that the reaction condition of the decalin base is to take catalyst to fill
Reaction tube is filled out, naphthalene is mixed with solvent as reaction solution all the way, compares naphthalene for quality：Solvent=1:1~1：8, liquid propene is as another
Reaction solution all the way, propylene air speed are 0.1~1.6h-1；Reacting system pressure is 2.5~5.0Mpa, and reaction temperature is 150~300
℃。
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| CN110694680A (en) * | 2019-11-11 | 2020-01-17 | 湘潭大学 | Catalyst for one-step preparation of 2, 6-dimethylnaphthalene from synthesis gas and 2-methylnaphthalene |
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