CN105294377A - Method for nathphalene alkylation - Google Patents
Method for nathphalene alkylation Download PDFInfo
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- CN105294377A CN105294377A CN201410314285.6A CN201410314285A CN105294377A CN 105294377 A CN105294377 A CN 105294377A CN 201410314285 A CN201410314285 A CN 201410314285A CN 105294377 A CN105294377 A CN 105294377A
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Abstract
The invention relates to a method for nathphalene alkylation, and mainly aims to solve the problems of relatively poor catalyst selectivity and high inactivation in the prior art. The method comprises the following steps: a), adopting a silicon source, an aluminum source and an organic amine template as raw materials, carrying out hydrothermal crystallization and deionized water washing in sequence to obtain a zeolite precursor material; b), conducting ion exchange on the obtained zeolite precursor material for modification, calcining the modified material to obtain a nathphalene alkylation catalyst; c) applying the nathphalene alkylation catalyst to a nathphalene alkylation reaction, wherein ions adopted for ion exchange are at least one of alkaline-earth metal ions and lanthanum metal ions. The method has the advantages that the problem of relatively poor catalyst selectivity in the prior art is solved relatively well, and the suitability to industrial production of nathphalene alkylation is very high.
Description
Technical field
The present invention relates to a kind of method of decalin base.
Background technology
2,6-dialkyl group naphthalene can synthesize 2 through peroxidation, 6-naphthalene diacid (2,6-DNA), and 2,6-naphthalene diacid is the raw material producing novel high-performance polyester material-PEN (PEN), and compared with polybutylene terephthalate (PET), the performance of PEN is far better.PEN has superior resistance toheat, mechanical property, chemical stability, gas barrier property and UV resistant and radiance; PEN has good transparency as PET, and the advantage of PEN to PET is that its use temperature will exceed 35 ~ 55 DEG C, and tensile strength exceeds 50%, and barrier property exceeds 5 times; Other market of PEN is that application prospect is boundless in preparative layer pressing plate, multipolymer and blend.Since the nineties, external Ge great plastics-production manufacturer and application company invest in synthesis and the application of PEN one after another, Amoco, Shell, ICI, Mitsubishi, the world-famous chemical company such as Sumitomo has all carried out the development of PEN, exploitation and application, and the whole world has started the exploitation climax of PEN.
In 2,6-dialkyl group naphthalene, the most important thing is 2,6-dimethylnaphthalene (2,6-DMN) and 2,6-DIPN (2,6-DIPN).2,6-dimethylnaphthalene (2,6-DMN) molecule is little, selects type poor, and simultaneously because methylation activity is low, temperature of reaction is high, causes the existence of multiple isomer.2,6-DIPN molecule is large, and sec.-propyl space steric effect is large, the ortho position of naphthalene and a position di-substituted being difficult to is generated, thus decreases the number of isomer, improve the selectivity of 2,6-DIPN, be convenient to separating-purifying; Compare with 2,6-DMN, 2,6-DIPN is more easily oxidized formation 2,6-DNA, and yield is higher, and therefore the utilization ratio of atom is higher.
In China, in the coal-tar middle oil naphthalene of coal tar and ethylene bottom oil and C9, the throughput of the petronaphthalene that aromatic hydrocarbons extracts can reach 200,000 t/a in 2009, and the output of refined naphthalene is 100,000 t/a, and the downstream high value added product of exploitation naphthalene becomes very important.Decalin base can obtain a lot of product, medical the most extensive wherein with isopropyl naphthalene series product, and in isopropyl naphthalene series product, again with diisopropylnaphthalene (DIPN) especially 2, the practical value of 6-diisopropylnaphthalene (2,6-DIPN) is maximum.
At home and abroad, there is a lot of research reports about 2,6-DIPN synthesis, but, in the world, also there is no ripe 2,6-DIPN production technology, therefore, take naphthalene as raw material, by the further investigation to catalyzer and reaction process, development 2,6-DIPN and naphthalene two technic acid thereof have novelty.
Traditional crystallization of zeolites catalyzer, adopt raw material based on silicon source, aluminium source, organic amine, crystallization synthetic crystallization zeolite such as Y zeolite, β zeolite, ITQ-30, UZM-8, ITQ-2, ZSM-5, ZSM-12, MCM-22, MCM-56 etc. under certain hydrothermal temperature, then make acid catalyst through steps such as washing, roastings, there is the silicon-aluminum structure of complete crystallization structure, be widely used in the middle of alkylated reaction.US Patent No. 3751506 describes with ZSM-5 the method for the vapor-phase alkylation synthesizing ethyl benzene being catalyzer, ethene and benzene.US Patent No. 3251897 describes the alkylating result of Y zeolite catalyzed olefin liquid phase.EP0433932932A1 describes and adopts mordenite to be the result that catalyzer carries out the alkylated reaction of benzene and alkene, US5672799, US6162416, US5434326, US5198595 report and adopt Beta zeolite to be the result that catalyzer carries out liquid-phase alkylation, and US5362697, US5453554, US6051521, ZL94192390.8 and Zl03158882.4 disclose and have employed the method that MCM-22 and MCM-56 with MWW structure is catalyst olefin liquid phase alkylation synthesis of alkyl benzene.EP0395360A1 describes and adopts liquid aluminum trichloride to be catalyzer, by n-butene and benzene Reactive Synthesis 2-butylbenzene.Document AppliedCatalysisA:General153 (1997) describes with Beta zeolite for catalyzer, with the method for butanols and benzene Reactive Synthesis butylbenzene.
Summary of the invention
Technical problem to be solved by this invention there is decalin base reacting middle catalyst comparatively easy in inactivation in conventional art, selects the problem that type is not high.There is provided a kind of method of new decalin base, it is high that the method has catalyst selectivity, the advantage of good stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for decalin base, comprises the following steps:
A) silicon source, aluminium source, organic amine template is adopted to be raw material, after hydrothermal crystallizing, then through water-washing step, obtained zeolite precursor body material;
B) by obtained zeolite precursor material through ion-exchanged, then through roasting, obtain decalin base catalyzer;
C) will obtain in the middle of decalin base catalyst application to decalin base reaction;
Wherein, the ion-exchanger of described ion-exchange is selected from least one in alkaline-earth metal, lanthanide element; Described silicon source is selected from least one in water glass, silicon sol, white carbon black; Described aluminium source is aluminium alcoholates, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate; Described organic amine is at least one in quadrol, triethylamine, tetraethyl ammonium hydroxide, tetraethylammonium bromide, Tetrabutyl amonium bromide, propylamine, piperidines, hexamethylene imine, diethyl-dimethyl ammonium hydroxide; The temperature of described hydrothermal crystallizing is 120 ~ 200 DEG C, and the time of hydrothermal crystallizing is 12 ~ 240 hours; With molar ratio computing, described silicon source and aluminium source, silica alumina ratio be SiO
2: Al
2o
3=(30 ~ 50): 1; Organic amine amount is organic amine: Si=(0.2 ~ 1.0): 1; The temperature of described ion-exchange is 0 ~ 100 DEG C, and the time is 1 ~ 108 hour, and alkaline-earth metal or lanthanide metal cations concentration are 0.5 ~ 3mol/L.
In technique scheme, preferred version is: described washing is preferably deionization washing; The silica alumina ratio in described silicon source and aluminium source is preferably SiO
2: Al
2o
3=(30 ~ 50): 1; Preferably add alkaline matter control ph after described silicon source, the mixing of aluminium source more than 13, described alkaline matter is preferably at least one in sodium hydroxide, ammoniacal liquor, potassium hydroxide; At least one of ion-exchanger preferably in alkaline-earth metal ions, lanthanide metal ion of described ion-exchange; Be more preferably at least one in alkaline-earth metal metal, the nitrate of lanthanide series metal or halogenide; At least one of described zeolite precursor body material preferably in ZSM-5 molecular sieve, ZSM-12 molecular sieve, SAPO-5 molecular sieve, β zeolite, UZM-8 zeolite, MCM-22 zeolite; The temperature of ion-exchange is preferably 35 ~ 90 DEG C, and number of times is preferably at least twice, and each time is preferably 1 ~ 24 hour, and alkaline-earth metal or lanthanide metal cations concentration are preferably 0.5 ~ 2mol/L; The ion exchange ratio of described ion-exchange is preferably 50% ~ 95%; The temperature of described hydrothermal crystallizing is preferably 150 ~ 200 DEG C, and the time of hydrothermal crystallizing is preferably 12 ~ 48 hours.Described decalin base reaction preferably comprises the transalkylation reaction of the alkylated reaction of the alkylated reaction of naphthalene and propylene, naphthalene and Virahol, the isomerization reaction of diisopropylnaphthalene, the isomerization reaction of single isopropyl naphthalene, many isopropyl naphthalenes and naphthalene.
In technique scheme, preferred scheme is further: before the ion-exchanged carrying out b) step, zeolite precursor body material is preferably without roasting.
In technique scheme, preferred scheme is further: the ion-exchanger of described ion-exchange is preferably at least one in alkali earth metal, be more preferably magnesium ion, at least one more preferably in magnesium nitrate or magnesium chloride, cation concn is 1mol/L more preferably.
In technique scheme, preferred scheme is further: the number of times of described ion-exchange preferably at least one times, is more preferably at least twice, more preferably three times.
Ion exchange ratio described in the present invention refers to cation mole number exchanged in exchangeable cation and the ratio of exchangeable cation total mole number.
In the catalyst preparation process adopting the inventive method to react at decalin base, when template is removed in non-roasting, adopt at least one in alkaline-earth metal, lanthanide element to carry out ion-exchange, especially magnesium ion, obtain decalin base catalyzer.
Adopt the decalin base catalyzer prepared of the present invention to carry out decalin base reaction, especially prepare in the reaction of 2,6-DIPN, with naphthalene and propylene for raw material is temperature of reaction 200 ~ 250 DEG C, reaction pressure 3.6 ~ 5.0MPa, propylene air speed is 1 ~ 2h
-1, naphthalene and propylene molar ratio are 1:(1 ~ 4) condition under, the selectivity of obtained 2,6-DIPN is greater than 40%.
Adopt the decalin base catalyzer prepared of the present invention to carry out decalin base reaction, especially prepare in the reaction of 2,6-DIPN, with naphthalene and Virahol for raw material is temperature of reaction 200 ~ 250 DEG C, reaction pressure 1.0 ~ 5.0MPa, Virahol air speed is 1 ~ 2h
-1, naphthalene and Virahol mol ratio are 1:(1 ~ 4) condition under, the selectivity of obtained 2,6-DIPN is greater than 40%.
The decalin base catalyzer adopting the present invention to prepare carries out decalin base reaction, especially preparing in the reaction of 2,6-DIPN, is that raw material is temperature of reaction 200 ~ 250 DEG C with diisopropylnaphthalene, reaction pressure 1.0 ~ 5.0MPa, diisopropylnaphthalene air speed is 1 ~ 2h
-1, the selectivity of obtained 2,6-DIPN is greater than 40%.
The decalin base catalyzer adopting the present invention to prepare carries out decalin base reaction, especially prepare in the reaction of 2,6-DIPN, with single isopropyl naphthalene for raw material is temperature of reaction 200 ~ 250 DEG C, reaction pressure 1.0 ~ 5.0MPa, single isopropyl naphthalene air speed is 1 ~ 2h
-1, the selectivity of obtained 2,6-DIPN is greater than 40%.
Adopt the decalin base catalyzer prepared of the present invention to carry out decalin base reaction, especially prepare in the reaction of 2,6-DIPN, with many isopropyl naphthalenes and naphthalene for raw material is temperature of reaction 200 ~ 250 DEG C, reaction pressure 1.0 ~ 5.0MPa, naphthalene air speed is 1 ~ 2h
-1, many isopropyl naphthalenes and naphthalene mol ratio are 1:(1 ~ 4) condition under, the selectivity of obtained 2,6-DIPN is greater than 40%.
Accompanying drawing explanation
Fig. 1 is the NH of catalyzer prepared by embodiment 5 and comparative example 1
3-TPD test curve, the catalyzer of embodiment 5 preparation is as seen from the figure at cold zone (150 ~ 200 DEG C) NH
3desorption rate obviously than comparative example 1 prepare catalyzer at cold zone (150 ~ 200 DEG C) NH
3desorption rate will be lacked, and corresponding high-temperature zone (250 ~ 300 DEG C) NH
3both desorption rates are basically identical.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
(1) 50g water glass (SiO is got
2content is 27.20wt%, and modulus is 3.2), 0.85g Tai-Ace S 150, the sodium hydroxide 1.0g of 96wt%, the ethylamine solution 50g of deionized water 50g, 70wt%, ZSM-5 crystal seed 0.5g, is mixed into gel, leaves standstill 6 hours, then crystallization 14 hours at 170 DEG C.Filtration obtains white solid, and this solid deionized water repetitive scrubbing is tested into neutrality to pH test paper.Drying obtains the powder 10.3g of non-roasting.Be ZSM-5 zeolite through X-ray powder diffraction analysis.
(2) the powder 10.3g that step obtains is got, with the Mg (NO of 1mol/L
3)
2exchange three times under solution 200ml room temperature, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the alkylated reaction evaluation of naphthalene and propylene.Get 3.0g catalyst loading reaction tubes, naphthalene mixes as a road reaction solution with hexanaphthene, blending ratio is naphthalene: hexanaphthene=1:5 (mol ratio), naphthalene, hexanaphthene flow velocity are 1.5g/min, liquid propene (pressure 4.0MPa) is as another road reaction solution, and flow velocity is 0.1g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 41%.
[embodiment 2]
(1) by 600 gram of 40% silicon sol, 38.9 grams of sodium aluminates (alumina content 42%), 70.6 gram of 25% tetraethyl ammonium hydroxide (TEAOH), 5.0 grams of diethylamine (DEA), 168.0 grams of tetraethylammonium bromides (TEABr), 16.0 grams of sodium hydroxide, the ammonium hydroxide of 136.0 gram 25% and 925.1 grams of water mixing, stir under normal temperature.Then, proceed in stainless steel autoclave, crystallization temperature 140 DEG C, react 96 hours.After reaction terminates, filter, use deionized water wash crystallized product, drying.It is the β zeolite with BEA structure through X-ray powder diffraction analysis.
(2) the powder 200g that step obtains is got, with the Mg (NO of 1mol/L
3)
2exchange three times at solution 2000ml80 DEG C, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 300ml reactor device, carry out the alkylated reaction evaluation of naphthalene and propylene.Getting 5.0g catalyzer puts in the middle of reactor, and naphthalene mixes as reaction solution with Virahol, and blending ratio is naphthalene: Virahol=1:1 (mol ratio), and naphthalene, Virahol addition are 100g, and temperature of reaction is 250 DEG C, and the reaction times is 4 hours.
(5) reaction result analytical test: 2,6-DIPN selectivity 43%.
[embodiment 3]
(1) trimethyl carbinol aluminium (wt97%) 5g is got, diethyl-dimethyl ammonium hydroxide (wt20%) 160g, sodium hydroxide 8g mixes, and then add 160gTEOS (wt98%) and 140g deionized water wherein, stirred at ambient temperature is even.Then proceed in the middle of 1L stainless steel crystallizing kettle, at 150 DEG C, stir crystallization 96 hours.After crystallization terminates, filter, use deionized water wash crystallized product, drying.It is the UZM-8 zeolite with laminate structure through X-ray powder diffraction analysis.
(2) get the powder 35g that step obtains, exchange three times with at magnesium chloride solution 500ml80 DEG C of 2mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 100ml reactor device, carry out the isomerization reaction of diisopropylnaphthalene, loaded catalyst is 5g.In the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Temperature of reaction is 220 DEG C, and the reaction times is 3 hours.
(5) reaction result analytical test: 2,6-DIPN selectivity 41%.
[embodiment 4]
(1) get silicon sol (wt40%) 600g, sodium metaaluminate 32.4g, sodium hydroxide 8g, deionized water 800g, hexamethylene imine 120g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 150 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 212g that step obtains, exchange three times with under the magnesium nitrate solution 2000ml room temperature of 1mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 39%.
[embodiment 5]
(1) get silicon sol (wt40%) 747.1g, sodium metaaluminate 17.3g, tetraethyl ammonium hydroxide 468.5g, deionized water 383.7g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 160 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 232g that step obtains, at 25 DEG C, exchange three times with the magnesium nitrate solution 2000ml of 1.5mol/L, each 12 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of single isopropyl naphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, the 2-DIPN that consists of of single isopropyl naphthalene accounts for 97%, 2,7-DIPN and accounts 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 temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 43%.
[comparative example 1]
(1) get silicon sol (wt40%) 747.1g, sodium metaaluminate 17.3g, tetraethyl ammonium hydroxide 468.5g, deionized water 383.7g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 160 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 232g that step obtains, roasting (condition), is cooled to 25 DEG C by the powder after roasting, exchanges three times, each 12 hours with the magnesium nitrate solution 2000ml of 1.5mol/L at 25 DEG C.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of single isopropyl naphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, the 2-DIPN that consists of of single isopropyl naphthalene accounts for 97%, 2,7-DIPN and accounts 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 temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 28.9% is much smaller than 43% of embodiment 5.
[embodiment 6]
(1) get white carbon black 203g, sodium metaaluminate 15.7g, tetraethylammonium bromide 203.1g, sodium hydroxide 8g, deionized water 211.7g, mixing, at room temperature stirs.Then proceed in the middle of 1.5L stainless steel crystallizing kettle, crystallization 48 hours at 160 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Be beta zeolite through X-ray powder diffraction analysis.
(2) get the powder 241g that step obtains, exchange three times with at magnesium nitrate solution 2000ml60 DEG C of 1.5mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of single isopropyl naphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, the 2-DIPN that consists of of single isopropyl naphthalene accounts for 97%, 2,7-DIPN and accounts 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 temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 41.8%.
[embodiment 7]
(1) get white carbon black 123g, silicon sol 120g, aluminum nitrate 39.1g, tetraethylammonium bromide 187.5g, deionized water 185.2g, sodium hydroxide 6.5g mixes, and at room temperature stirs.Then proceed in the middle of 1.5L stainless steel crystallizing kettle, crystallization 36 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Be beta zeolite through X-ray powder diffraction analysis.
(2) get the powder 162g that step obtains, exchange three times with at magnesium nitrate solution 1500ml60 DEG C of 2mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 100ml reactor device, carry out the isomerization reaction of diisopropylnaphthalene, loaded catalyst is 5g.In the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Temperature of reaction is 220 DEG C, and the reaction times is 3 hours.
(5) reaction result analytical test: 2,6-DIPN selectivity 43.8%.
[embodiment 8]
(1) fetch water glass 80g, and white carbon black 101g, silicon sol 120g, aluminum nitrate 53.8g, tetraethylammonium bromide 210.5g, sodium hydroxide 8.3g, deionized water 210.3g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Be beta zeolite through X-ray powder diffraction analysis.
(2) get the powder 202g that step obtains, exchange three times with at magnesium nitrate solution 1500ml60 DEG C of 2mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 100ml reactor device, carry out the isomerization reaction of diisopropylnaphthalene, loaded catalyst is 5g.In the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Temperature of reaction is 220 DEG C, and the reaction times is 3 hours.
(5) reaction result analytical test: 2,6-DIPN selectivity 41.9%.
[embodiment 9]
(1) get silicon sol (wt40%) 489g, sodium metaaluminate 34.2g, sodium hydroxide 10g, deionized water 782g, piperidinyl-1 20g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 150 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 197g that step obtains, exchange three times with at magnesium nitrate solution 2000ml80 DEG C of 1mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 41.3%.
[embodiment 10]
(1) get silicon sol (wt40%) 489g, sodium metaaluminate 34.2g, sodium hydroxide 10g, deionized water 782g, piperidinyl-1 20g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 150 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 197g that step obtains, exchange three times with at calcium chloride solution 2000ml60 DEG C of 1mol/L, each 20 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 37.3%.
[embodiment 11]
(1) get silicon sol (wt40%) 489g, sodium metaaluminate 34.2g, sodium hydroxide 10g, deionized water 782g, piperidinyl-1 20g, mixing, at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 72 hours at 150 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 197g that step obtains, exchange three times with at ca nitrate soln 2000ml60 DEG C of 1mol/L, each 8 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 36.7%.
[embodiment 12]
(1) get silicon sol (wt40%) 512g, sodium metaaluminate 32.5g, sodium hydroxide 9g, deionized water 802g, piperidines 40g, hexamethylene imine 87g mixes, and at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 213g that step obtains, exchange three times with at magnesium nitrate solution 2000ml60 DEG C of 1mol/L, each 10 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 43.9%.
[comparative example 2]
(1) get silicon sol (wt40%) 512g, sodium metaaluminate 32.5g, sodium hydroxide 9g, deionized water 802g, piperidines 40g, hexamethylene imine 87g mixes, and at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder roasting that step obtains, obtain powder 177g, exchange three times with at magnesium nitrate solution 2000ml60 DEG C of 1mol/L, each 10 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 28.7% is much smaller than 43.9% of embodiment 13.
[comparative example 3]
(1) get silicon sol (wt40%) 512g, sodium metaaluminate 32.5g, sodium hydroxide 9g, deionized water 802g, piperidines 40g, hexamethylene imine 87g mixes, and at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder roasting that step obtains, obtain powder 177g, exchange three times with at ammonium nitrate solution 2000ml60 DEG C of 1mol/L, each 10 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 31.7% is much smaller than 43.9% of embodiment 13.
[embodiment 13]
(1) get silicon sol (wt40%) 512g, sodium metaaluminate 32.5g, sodium hydroxide 9g, deionized water 802g, piperidines 40g, hexamethylene imine 87g mixes, and at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 213g that step obtains, exchange three times with at cerous nitrate solution 2000ml50 DEG C of 1mol/L, each 10 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 38.9%.
[embodiment 14]
(1) get silicon sol (wt40%) 512g, sodium metaaluminate 32.5g, sodium hydroxide 9g, deionized water 802g, piperidines 40g, hexamethylene imine 87g mixes, and at room temperature stirs.Then proceed in the middle of 2L stainless steel crystallizing kettle, crystallization 48 hours at 180 DEG C.After crystallization terminates, filter, use deionized water wash crystallized product, drying.Through the MCM-22 zeolite that X-ray powder diffraction analysis is MWW structure.
(2) get the powder 213g that step obtains, exchange three times with at solution of cerium chloride by oxidation 2000ml50 DEG C of 1mol/L, each 10 hours.
(3) get step and exchange the solid obtained, dry, 550 DEG C of roastings 6 hours, shapingly obtain finished catalyst.
(4) on 15ml fixed bed device, carry out the isomerization reaction evaluation of diisopropylnaphthalene.Get 3.0g catalyst loading reaction tubes, in the middle of raw material, 2, the 6-DIPN that consists of of diisopropylnaphthalene accounts for 22.3%, 2,7-DIPN and accounts for 36.9%, and triisopropyl naphthalene accounts for 6.6%.Diisopropylnaphthalene flow velocity is 2g/min.Reacting system pressure is 4.0Mpa, and temperature of reaction is 220 DEG C.
(5) reaction result analytical test: 2,6-DIPN selectivity 39.1%.
Claims (9)
1. a method for decalin base, comprises the following steps:
A) silicon source, aluminium source, organic amine template is adopted to be raw material, after hydrothermal crystallizing, then through water-washing step, obtained zeolite precursor body material;
B) by obtained zeolite precursor material through ion-exchanged, then through roasting, obtain decalin base catalyzer;
C) decalin base catalyst application will be obtained in decalin base reaction;
Wherein, the ion-exchanger of described ion-exchange is selected from least one in alkaline-earth metal, lanthanide element; Described silicon source is selected from least one in water glass, silicon sol, white carbon black; Described aluminium source is aluminium alcoholates, sodium metaaluminate, Tai-Ace S 150, aluminum nitrate; Described organic amine is at least one in quadrol, triethylamine, tetraethyl ammonium hydroxide, tetraethylammonium bromide, Tetrabutyl amonium bromide, propylamine, piperidines, hexamethylene imine, diethyl-dimethyl ammonium hydroxide; The temperature of described hydrothermal crystallizing is 120 ~ 200 DEG C, and the time of hydrothermal crystallizing is 12 ~ 240 hours; With molar ratio computing, the silica alumina ratio in described silicon source and aluminium source is SiO
2: Al
2o
3=(30 ~ 200): 1; With molar ratio computing, organic amine amount is organic amine: Si=(0.2 ~ 1.0): 1; The temperature of described ion-exchange is 0 ~ 100 DEG C, and the time is 1 ~ 108 hour, and alkaline-earth metal or lanthanide metal cations concentration are 0.5 ~ 3mol/L.
2. the method for decalin base according to claim 1, adds alkaline matter control ph more than 13 after it is characterized in that described silicon source, the mixing of aluminium source.
3. the method for decalin base according to claim 2, is characterized in that described alkaline matter is at least one in sodium hydroxide, ammoniacal liquor, potassium hydroxide.
4. the method for decalin base according to claim 1, is characterized in that the ion-exchanger of described ion-exchange is selected from least one in alkaline-earth metal metal, the nitrate of lanthanide series metal or halogenide.
5. the method for decalin base according to claim 1, is characterized in that described zeolite precursor body material is selected from least one in ZSM-5 molecular sieve, ZSM-12 molecular sieve, SAPO-5 molecular sieve, β zeolite, UZM-8 zeolite, MCM-22 zeolite.
6. the method for decalin base according to claim 1, it is characterized in that the temperature of described ion-exchange is 35 ~ 90 DEG C, be at least twice, each time is 1 ~ 24 hour, and alkaline-earth metal or lanthanide metal cations concentration are 0.5 ~ 2mol/L.
7. the method for decalin base according to claim 1, is characterized in that the ion exchange ratio of described ion-exchange is 50% ~ 95%.
8. the method for decalin base according to claim 1, it is characterized in that the temperature of described hydrothermal crystallizing is 150 ~ 200 DEG C, the time of hydrothermal crystallizing is 12 ~ 48 hours.
9. the method for decalin base according to claim 1, is characterized in that described decalin base reaction comprises at least one in the transalkylation reaction of the alkylated reaction of the alkylated reaction of naphthalene and propylene, naphthalene and Virahol, the isomerization reaction of diisopropylnaphthalene, the isomerization reaction of single isopropyl naphthalene, many isopropyl naphthalenes and naphthalene.
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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 |
| CN107954435A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method and its usage of composite molecular screen |
| CN107954436A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method of composite molecular screen |
| CN109876854A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of naphthalene liquid-phase oxidation catalyst, preparation method and application |
| CN112661587A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Process for preparing 2, 6-dialkylnaphthalene |
| CN114478157A (en) * | 2022-01-06 | 2022-05-13 | 常州大学 | Preparation method of long-chain dialkyl naphthalene type lubricating oil base oil |
| CN114558611A (en) * | 2022-03-24 | 2022-05-31 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application thereof in preparation of 2, 6-diisopropyl naphthalene |
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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 |
| CN107954435A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method and its usage of composite molecular screen |
| CN107954436A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The preparation method of composite molecular screen |
| CN109876854A (en) * | 2017-12-06 | 2019-06-14 | 中国科学院大连化学物理研究所 | A kind of naphthalene liquid-phase oxidation catalyst, preparation method and application |
| CN112661587A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Process for preparing 2, 6-dialkylnaphthalene |
| CN114478157A (en) * | 2022-01-06 | 2022-05-13 | 常州大学 | Preparation method of long-chain dialkyl naphthalene type lubricating oil base oil |
| CN114558611A (en) * | 2022-03-24 | 2022-05-31 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application thereof in preparation of 2, 6-diisopropyl naphthalene |
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