CN101417234A - Preparation method of catalyst for shape-selective alkylation of naphthalene to produce 2,6-di(tert butyl)naphthalene - Google Patents
Preparation method of catalyst for shape-selective alkylation of naphthalene to produce 2,6-di(tert butyl)naphthalene Download PDFInfo
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- CN101417234A CN101417234A CNA2007101762727A CN200710176272A CN101417234A CN 101417234 A CN101417234 A CN 101417234A CN A2007101762727 A CNA2007101762727 A CN A2007101762727A CN 200710176272 A CN200710176272 A CN 200710176272A CN 101417234 A CN101417234 A CN 101417234A
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Abstract
The invention provides a preparation method used for preparing a catalyst 2, 6-di (tert butyl) naphthalene by shape-selective naphthalene tert-butylation, comprising the steps as follows: a) Y zeolite molecular sieve, with the mass ratio of liquid and solid at 2:1-30:1, is arranged in a buffer system formed by ammonium ion; under the temperature of 25-100DEG C, organic acid used as modifier is added so as to carry out complex dealumination to the zeolite molecular sieve; during the dealumination process, the pH of the buffer system is kept at 3.0-6.0 and the processing time is 0.5-10 hours; and b) the outcome generated in step a) is filtrated and washed to be in a neutral state by deioned water, and baked so as to obtain the shape-selective catalyst. The preparation method uses the organic acid to carry out complex dealumination in the buffer system, carries out chemical modification to the Y-typed zeolite molecular sieve, thus improving the acidic properties and pore distribution of the Y-typed zeolite molecular sieve. The catalyst prepared by the modification method is suitable for the shape-selective naphthalene tert-butyl reaction. The preparation method has low production cost and the catalyst modifier is cheap and easy to be obtained.
Description
Technical field
The present invention relates to a kind of in buffer system Y zeolite molecular sieve complexing dealuminzation under the organic acid effect prepare the method for high-performance shape-selective catalyst, this catalyst can be used for naphthalene tert-butylation selectivity and generates 2,6-di-t-butyl naphthalin (DTBN) reaction.
Background technology
2,6-dialkyl group naphthalene (DAN) is important Organic Chemicals, its oxidation product 2, and what 6-naphthalene dicarboxylic acids and ethylene glycol polymerization obtained gathers 2, and 6-(ethylene naphthalate) (PEN) is a kind of novel high-performance polyester material.The structural high symmetry of PEN makes it have the characteristic of straight chain polymer, PET compares with phenyl polymer, more superior at aspects such as gas barrier property, hear resistance, mechanical performance, radiation resistance, chemical stability and dimensional stabilitys, can be used for making beer bottle, fresh-keeping packaging material, industrial fiber, magnetic recording band and Aero-Space and atomic energy material etc.
2, the synthetic route of 6-DAN is divided into 2 according to the difference of alkyl substituent, 6-dimethylnaphthalene (DMN), 2, and 6-diisopropyl naphthalene (DIPN) and 2,6-DTBN's is synthetic.Wherein, 2,6-DMN mainly extracts or makes by the multistep chemical method is synthetic from raw materials such as coal tar and oil refining byproduct heavy arene.Since 2,6-DMN content in these raw materials low (about 0.1-1%), the raw material components complexity, separating step is numerous and diverse, only is suitable for small-scale production.US5396007, US5073670 and CN1192726A, CN1298374A were raw material with ortho-xylene and butadiene, paraxylene and 1-butylene, toluene and amylene respectively once, successively by totally six steps operation Synthetic 2 such as alkylation dehydrocyclization aromatisation, 6-DMN, process route is longer.Thereby, the decalin base Synthetic 2, the research direction of 6-DAN directly easyly is subjected to common concern gradually with it.But the product of menaphthylization and naphthalene isopropylation is formed complicated, comprises that naphthalene, replaces naphthalene, two replacement naphthalenes, three replace naphthalenes and a small amount of four and replace high-boiling components such as naphthalene, purpose product 2, and the 6-DAN selectivity is low.In addition, complicated product distributes, and also to have brought two of huge difficulty, particularly naphthalene to replace between the isomers boiling point very approaching to separating, and easily forms eutectic near the fusing point, is difficult to be separated from each other by routine distillation or method for crystallising.Thereby the naphthalene tertiary butyl reaction distributes simple with its product, and segregative characteristics receive publicity gradually between the DTBN isomers.
The Y zeolite molecular sieve has suitable pore structure, and the shape tert-butyl group of selecting that more and more is used for naphthalene reacts.But Y zeolite molecular sieve silica alumina ratio is low, acid amount height and acid strength is lower, and secondary pore is not too flourishing, is unfavorable for the generation of catalytic alkylation reaction.Therefore the Y zeolite molecular sieve needs to carry out the dealuminzation modification before using, and skeleton is redesigned, and has suitable acid strength and acid amount and suitable pore size distribution, increase by 2, the selectivity of 6-DAN after making modification.The design feature of binding molecule sieve, modification mainly contains following two aspects.The first is carried out at the outer metal cation that exists of framework of molecular sieve, prepares the cationic molecular sieve catalyst of all kinds of differences by ion-exchange; Co is disclosed among the CN1363541
2+, Mn
2+, Ce
2+, Mg
2+The enhancing of appearance stability, knot charcoal are alleviated phenomenon on the modified catalyst of part exchange, disclose selectivity preparation 2 on the Fe replacement sial ZSM-5 molecular sieve catalyst among the CN1489492, the process of 6-DMN.Another kind of is the method for modifying of developing at the crystal aluminosilicate skeleton structure of molecular sieve, as high temperature hydro-thermal method, organic complex reaction method, high temperature gas-phase reaction method and ammonium fluosilicate liquid phase reactor method; Disclose among the CN1807243 to replace by the solid phase isomorphous and obtain Zr and replace sial ZSM-5 molecular sieve catalyst, operated easylier, can be used for the catalytic alkylation reaction of methyl naphthalene with metal fluoride.But the molecular sieve lattice defect is more after the modification of high temperature hydro-thermal method, and amorphous aluminium surface enrichment is unfavorable for improving selectivity; The environmental pollution of High Temperature Gas phase isomorphous substitution technique is heavier; The secondary pore of molecular sieve is few after the modification of ammonium fluosilicate liquid phase reactor method, is unfavorable for improving reactivity, and coking is serious.
Summary of the invention
The object of the present invention is to provide a kind of naphthalene to select shape tert-butylation system 2,6-di-t-butyl naphthalin (DTBN) Preparation of catalysts method, in the hope of a kind of shape-selection and modification method of zeolite molecular sieve is provided for the naphthalene tertiary butyl reaction, by in cushioning liquid, using organic acid complexing dealuminzation, the y-type zeolite molecular sieve is carried out the chemical modification design, thereby improve the acid matter and the pore size distribution of Y zeolite molecular sieve.
For achieving the above object, the naphthalene that is used for provided by the invention is selected shape tert-butylation system 2,6-di-t-butyl naphthalin (DTBN) Preparation of catalysts method, and its step is as follows:
A) buffer system that places ammonium ion solution to form with liquid-solid mass ratio 2:1-30:1 the Y zeolite molecular sieve, add organic acid in 25-100 ℃ and zeolite molecular sieve is carried out the complexing dealuminzation as modifier, keep buffer system pH=3.0-6.0 in the dealumination process, the processing time is 0.5-10 hour;
B) product of step a being filtered, spends deionised water is and obtains target product-naphthalene after neutral, the roasting and select shape tert-butylation catalyst.
Described preparation method, wherein, the Y zeolite molecular sieve is that the NaY zeolite molecular sieve carries out the NH that ion-exchange obtains earlier among the step a
4NaY and NH
4The Y zeolite molecular sieve, wherein the Na ion-exchange degree is greater than 60%; Also can be NH
4NaY and NH
4NaHY and HY zeolite molecular sieve that the further roasting of Y zeolite molecular sieve forms;
Described preparation method, wherein, ammonium ion solution is to be selected from the wherein a kind of or any several mixed solution of ammonium oxalate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate.
Described preparation method, wherein, modifier is a kind of of oxalic acid, tartaric acid, citric acid and sulfosalicylic acid or any several mixture, is preferably oxalic acid.
Production cost of the present invention is lower, and catalyst modifier is cheap and easy to get, and consumption is few, can effectively improve the selectivity of naphthalene tertiary butyl reaction, and conversion ratio higher (the naphthalene conversion ratio is greater than 70mol%), and 2,6-/2, the 7-DTBN ratio reaches 9.0.
The specific embodiment
Technical scheme of the present invention, it is characterized in that: utilize in the oxalic acid dealuminzation modifying process, there are ionization equilibrium and complexation equilibrium, and the oxalic acid aluminium complex ion volume of three-fold coordination is bigger, stoped the complexing of interior brilliant aluminium atom and oxalic ion, show effectively removing of outer surface upper skeleton aluminium atom, thereby form surperficial silicon-rich layer, outer surface acidity position to the Y zeolite molecular sieve is modified, weakened the side reactions such as transalkylation of purpose product on the outer surface acidity position, to reach the purpose that strengthens selectivity of product.Form a large amount of secondary pores in addition in the modifying process, help the diffusive migration of reactant and product molecule.
Modified zeolite of Y-type molecular sieve catalyst of the present invention is used for naphthalene and selects the shape tertiary butyl reaction, utilize the bigger steric effect of tert-butyl group group and the duct shape selectivity of zeolite molecular sieve, can under relatively mild reaction condition, carry out alkylated reaction, and the product composition distributes simpler.And utilizing 2,6-DTBN and 2,7-DTBN fusing point differ big (being respectively 145-146 ℃ and 82-83 ℃), and 2, the characteristics that 6-DTBN solubility in ethanol is little are effectively isolated purpose product 2,6-DTBN by the method for hot ethanol recrystallization.
The present invention is a raw material A with the naphthalene, is raw material B with the tert-butyl alcohol, is raw material C and with the mol ratio of A:B:C=1:1:30-1:4:300 with the atent solvent, under 120-200 ℃ reaction temperature, under the reaction pressure of 0.5-4.0 MPa, carry out form selected methylation and react Synthetic 2,6-DTBN.Above-mentioned atent solvent does not participate in reaction in course of reaction.This atent solvent is cyclohexane preferably.Naphthalene conversion ratio and 2 among the present invention, 6-DTBN selectivity and 2,6-/2,7-DTBN calculates by sampling gas chromatographic analysis result after the mixed liquor cooling centrifugation in the reactor.
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following examples.
Embodiment 1
Take by weighing aluminium isopropoxide 408g, solid sodium hydroxide 800g is dissolved in it in 3.6Kg water, stirs to add the 2.4Kg Ludox down.Formed initial gel reaction thing is transferred in the seal pot, respectively room temperature crystallization 24 hours, and 60 ℃ of crystallization 48 hours.After the product separating, washing drying, be NaY type zeolite molecular sieve through the identification of phases of XRD thing.
Gained NaY zeolite molecular sieve is through the NH4NO of 1N under the 1:10 condition at 75 ℃, solid-to-liquid ratio
3Carry out ion-exchange and make NH more than twice or four times respectively
4NaY (the Na ion-exchange degree is greater than 75%) and NH
4Y;
The NH of gained
4NaY and NH
4The further roasting of Y forms NaHY, and (each constituent mass percentage composition is: Na
2O:4.18%, Al
2O
3: 22.94%, SiO
2: 72.88%) and the HY zeolite molecular sieve.
Embodiment 2
Restrain the NH that the foregoing descriptions 1 obtain with 20
4NaY type zeolite molecular sieve joins in the 40 gram ammonium nitrate solutions, under 30 ℃ of temperature, adds 3.0 gram sulfosalicylic acids, pH=3.0-4.0, handled 0.5 hour, and filtered, washing was dried 8 hours for 150 ℃, 550 ℃ of roastings 4 hours promptly obtain the modified Y zeolite molecular sieve catalyst, are numbered NH
4NaOY.
Embodiment 3
The HY type zeolite molecular sieve that 20 gram the foregoing descriptions 1 are obtained joins in the 200 gram ammonium oxalate solutions, under 80 ℃ of temperature, add 3.0 gram oxalic acid, pH=5.0-6.0 handled 3 hours, filter, washing, 150 ℃ of oven dry 8 hours, 550 ℃ of roastings 4 hours, promptly obtain the modified Y zeolite molecular sieve catalyst, be numbered OY.
Embodiment 4
The NaHY type zeolite molecular sieve that 20 gram the foregoing descriptions 1 are obtained joins in the 400 gram ammonium dihydrogen phosphates, under 80 ℃ of temperature, add the mixed solution of 4.9 gram tartaric acid and citric acid, pH=4.0-5.0 handled 8 hours, filter, washing, 150 ℃ of oven dry 8 hours, 550 ℃ of roastings 4 hours, promptly obtain the modified Y zeolite molecular sieve catalyst, be numbered TY.
Embodiment 5
Restrain the NH that the foregoing descriptions 1 obtain with 20
4The y-type zeolite molecular sieve joins in 600 gram ammonium oxalate and the tartaric mixed solution, under 80 ℃ of temperature, adds 4.5 gram citric acids, handles 3 hours, filter, washing was dried 8 hours for 150 ℃, 550 ℃ of roastings 4 hours promptly obtain the modified Y zeolite molecular sieve catalyst, are numbered CY.
Comparative Examples 1
The NaY type zeolite molecular sieve that 20 gram the foregoing descriptions 1 are obtained joins in the 200 gram ammonium oxalate solutions, under 80 ℃ of temperature, adds 3.0 gram oxalic acid, handles 3 hours, filter, washing was dried 8 hours for 150 ℃, 550 ℃ of roastings 4 hours promptly obtain the modified Y zeolite molecular sieve catalyst, are numbered NaOY.
Comparative Examples 2
The HY type zeolite molecular sieve that 20 gram the foregoing descriptions 1 are obtained joins in the hydrochloric acid solution of 200 grams, under 80 ℃ of temperature, handles 1 hour, filter, washing was dried 8 hours for 150 ℃, 550 ℃ of roastings 4 hours promptly obtain hydrochloric acid modified Y zeolite molecular sieve catalyst, are numbered HY-H.
Embodiment 6
With the naphthalene is raw material A, with the tert-butyl alcohol is raw material B, is raw material C with the cyclohexane, and with the mol ratio of A:B:C=2.25:3:200, add the modified zeolite of Y-type molecular sieve catalyst that the foregoing description 2-5 and above-mentioned Comparative Examples 1-2 obtain respectively, the mass ratio that catalyst and naphthalene feed intake is 1.8:1.Reaction temperature is 160 ℃, and reaction pressure is 2.0 MPas, and the reaction time is that reaction result is as shown in table 1 under 2 hours the condition.
Several modified Y zeolite molecular sieve catalyst of table 1 reaction evaluating result
Claims (6)
1, a kind of naphthalene that is used for is selected shape tert-butylation system 2,6-di-t-butyl naphthalin Preparation of catalysts method, and its step is as follows:
A) buffer system that places ammonium ion solution to form with liquid-solid mass ratio 2:1-30:1 the Y zeolite molecular sieve, add organic acid in 25-100 ℃ and zeolite molecular sieve is carried out the complexing dealuminzation as modifier, keep buffer system pH=3.0-6.0 in the dealumination process, the processing time is 0.5-10 hour;
B) product with step a filters, spends and obtains target product after deionised water is neutrality, roasting.
2, according to the described preparation method of claim 1, wherein, the Y zeolite molecular sieve is the NH that the NaY zeolite obtains through ion-exchange among the step a
4NaY and NH
4The Y zeolite molecular sieve, wherein the Na ion-exchange degree is greater than 60%.
3, according to the described preparation method of claim 2, wherein, the Y zeolite molecular sieve is NH among the step a
4NaY and NH
4NaHY and HY zeolite molecular sieve that the Y zeolite molecular sieve obtains through roasting.
4, according to the described preparation method of claim 1, wherein, ammonium ion solution is to be selected from the wherein a kind of or any several mixed solution of ammonium oxalate, ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium phosphate, ammonium dihydrogen phosphate (ADP) and diammonium hydrogen phosphate.
5, according to the described preparation method of claim 1, wherein, modifier is a kind of of oxalic acid, tartaric acid, citric acid and sulfosalicylic acid or any several mixture.
6, according to the described preparation method of claim 5, wherein, modifier is oxalic acid.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101762727A CN101417234A (en) | 2007-10-24 | 2007-10-24 | Preparation method of catalyst for shape-selective alkylation of naphthalene to produce 2,6-di(tert butyl)naphthalene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101762727A CN101417234A (en) | 2007-10-24 | 2007-10-24 | Preparation method of catalyst for shape-selective alkylation of naphthalene to produce 2,6-di(tert butyl)naphthalene |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513146A (en) * | 2011-11-23 | 2012-06-27 | 开滦能源化工股份有限公司 | Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof |
| CN105601459A (en) * | 2015-12-01 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation |
| CN105983432A (en) * | 2015-02-09 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of silicon group-containing catalytic cracking catalyst |
| CN108704607A (en) * | 2018-05-29 | 2018-10-26 | 沈阳理工大学 | A kind of preparation method of Y type molecular sieve air purifying preparation |
| CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
| CN110862097A (en) * | 2019-11-25 | 2020-03-06 | 北京化工大学 | Preparation method of high-silicon Y-type molecular sieve |
| CN112808298A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
| CN112808297A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
-
2007
- 2007-10-24 CN CNA2007101762727A patent/CN101417234A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102513146A (en) * | 2011-11-23 | 2012-06-27 | 开滦能源化工股份有限公司 | Catalyst for compounding 2, 6-dimethylnaphthalene and preparing method thereof |
| CN105983432A (en) * | 2015-02-09 | 2016-10-05 | 中国石油天然气股份有限公司 | Preparation method of silicon group-containing catalytic cracking catalyst |
| CN105983432B (en) * | 2015-02-09 | 2018-12-25 | 中国石油天然气股份有限公司 | A kind of preparation method of the catalytic cracking catalyst containing silicon substrate |
| CN105601459A (en) * | 2015-12-01 | 2016-05-25 | 中国科学院大连化学物理研究所 | Method for preparing 2-methyl-6-tert-butylnaphthalene from 2-methylnaphthalene through alkylation |
| CN108704607A (en) * | 2018-05-29 | 2018-10-26 | 沈阳理工大学 | A kind of preparation method of Y type molecular sieve air purifying preparation |
| CN108704607B (en) * | 2018-05-29 | 2020-10-16 | 沈阳理工大学 | Preparation method of Y-type molecular sieve air purifying agent |
| CN109433253B (en) * | 2018-11-30 | 2020-11-27 | 中国科学院大连化学物理研究所 | Catalyst for preparing 2, 6-di-tert-butyl naphthalene by naphthalene shape-selective alkylation and preparation method and application thereof |
| CN109433253A (en) * | 2018-11-30 | 2019-03-08 | 中国科学院大连化学物理研究所 | The catalyst and its preparation method and application of 2,6- di-t-butyl naphthalin is prepared for naphthalene form selected methylation |
| CN112808298A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
| CN112808297A (en) * | 2019-11-18 | 2021-05-18 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
| CN112808298B (en) * | 2019-11-18 | 2023-07-11 | 中国石油化工股份有限公司 | Catalyst containing hierarchical pore Y-type molecular sieve and preparation method thereof |
| CN112808297B (en) * | 2019-11-18 | 2023-07-14 | 中国石油化工股份有限公司 | Solid acid alkylation catalyst and preparation method thereof |
| CN110862097A (en) * | 2019-11-25 | 2020-03-06 | 北京化工大学 | Preparation method of high-silicon Y-type molecular sieve |
| CN110862097B (en) * | 2019-11-25 | 2021-08-10 | 北京化工大学 | Preparation method of high-silicon Y-type molecular sieve |
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