CN100425342C

CN100425342C - Zeolite catalyst and its use for hydrolysis reaction of dihydropyran derivatives

Info

Publication number: CN100425342C
Application number: CNB2005100252910A
Authority: CN
Inventors: 李雪梅; 刘歆文; 张春雷; 邵敬铭
Original assignee: Shanghai Huayi Acrylic Acid Co Ltd
Current assignee: Shanghai Hua Yi new material Co., Ltd
Priority date: 2005-04-21
Filing date: 2005-04-21
Publication date: 2008-10-15
Anticipated expiration: 2025-04-21
Also published as: CN1709573A

Abstract

The present invention relates to a novel zeolite catalyst and an application thereof. The present invention comprises the preparation of the zeolite catalyst and the reaction technique that zeolite catalyzes the hydrolysis of 2-alkoxy-3, 4-dihydropyran to prepare glutaraldehyde or catalyzes the hydrolysis of 2, 3-dihydropyran to prepare 5-hydroxypivalaldehyde. the present invention is characterized in that the zeolite catalyst has the advantages of quick reaction rate, high activity and selectivity, high stability, low corrosiveness, simple separation from a product system and repeated use; the production cost of the glutaraldehyde or the 5-hydroxypivalaldehyde is low.

Description

The application of a kind of zeolite catalyst in the dihydropyran derivatives hydrolysis

Technical field

The present invention relates to the dihydropyran derivatives shown in a kind of new zeolite catalyst and the catalysis general formula (I) thereof (R is alkoxyl or hydrogen) hydrolysis and prepare the reaction process of glutaraldehyde or 5-hydrogenation of hydroxypentylaldehyd.

Background technology

Glutaraldehyde and 5-hydrogenation of hydroxypentylaldehyd, are widely used in various fields because of its excellent performance.Glutaraldehyde is important chemical intermediate and fine chemical product, is widely used in medicine, health, petrochemical industry, light industry and scientific research field.The 5-hydrogenation of hydroxypentylaldehyd, is important organic synthesis raw material, can be used for preparing pentanediol etc.

Glutaraldehyde is mainly prepared by the hydrolysis of alkoxyl dihydropyran.USP 2546018 has described and has not used catalyst and generate the method that glutaraldehyde and alkyl replace glutaraldehyde by the hydrolysis of dihydropyrane compound direct heat, but this method reaction temperature height, process is numerous and diverse, and yield is low, the cost height.JP7226488 has reported the method that adopts inorganic liquid acid to prepare glutaraldehyde as catalysis alkoxyl dihydropyran hydrolysis such as phosphoric acid, sulfuric acid, but the inorganic liquid acid catalyst exists a lot of shortcomings: severe corrosive, equipment anticorrosion is required high, seriously polluted, catalyst separation and product purification process are miscellaneous, product yield is low, and is of poor quality.USP 4244867, EP 0066224 and USP 4448977 have reported a kind of strong acid cation exchange resin catalyst that is used to prepare the glutaraldehyde precursor, but ion exchange resin costs an arm and a leg, and can not regenerate, and cause the production cost height.CN 1137034 has reported the method for alkoxyl dihydropyran hydrolysis preparing glutaric dialdehyde on the beta-zeolite catalyst, but this catalyst reaction speed is slow, stability can not be satisfactory.CN 1371348 has invented a kind of reactor, and has described the reaction process that this reactor is applied to prepare continuously glutaraldehyde, but the situation of relevant catalyst aspect is not introduced.

The 5-hydrogenation of hydroxypentylaldehyd, mainly is that catalyst makes 2 with the concentrated hydrochloric acid, 3-dihydropyran hydrolysis and making.This method building-up process is miscellaneous, and because the severe corrosive of hydrochloric acid to the seriously corroded of equipment, needs to neutralize with aqueous slkali, produces a large amount of waste water, contaminated environment.

Summary of the invention

The purpose of this invention is to provide a kind of new zeolite catalyst, and prepare application in the reaction of glutaraldehyde or 5-hydrogenation of hydroxypentylaldehyd, in the dihydropyran derivatives shown in the general formula (I) (R is alkoxyl or hydrogen) hydrolysis.Wherein, zeolite catalyst is that the aperture is greater than 5

The Hydrogen silicate zeolite, the Si/Al atomic ratio is 10～200, preferred 10～100; H-type zeolite comprises ZSM-5, ZSM-10, ZSM-11, ZSM-22, ZSM-23, ZSM-48, MOR, MCM-22, MCM-49 or MCM-56, preferred ZSM-22, MCM-22, MCM-49 or MCM-56; This h-type zeolite is that zeolite powder under 50～98 ℃ that hydro-thermal is synthetic is converted into the ammonium type with ammonium chloride or ammonium nitrate solution to its exchange that refluxes, exchange degree is greater than 70%, be preferably greater than 90%, then after 120 ℃ of dryings, roasting 2～5h preparation in air under 500～550 ℃ again.

In dihydropyran derivatives general formula (I), R represents C ₁～C ₂₀Alkoxyl or hydrogen, preferred C ₁～C ₄Alkoxyl or hydrogen, preferred especially methoxy or ethoxy or hydrogen.Dihydropyran derivatives hydrolysis shown in the general formula (I) can be adopted still formula intermittent reaction, also can adopt fixed bed or slurry attitude bed successive reaction.When adopting still formula intermittent reaction mode, catalyst amount is 0.1～20wt%, preferred 2-10wt%; Reaction temperature is 20～200 ℃, preferred 60～100 ℃; The mol ratio of dihydropyran derivatives and water is 1: 1～1: 100, preferred 1: 2～1: 30, and more preferably 1: 7～1: 20; Reaction time is 0.5～10h, preferred 2～6h; Reaction pressure is 0.05～1.0MPa, preferred 0.1～0.5MPa, more preferably normal pressure.When adopting the successive reaction mode, catalyst amount is 0.1～20wt%, is preferably 2～10wt%, and reaction temperature is 20～200 ℃, preferred 40～160 ℃, and more preferably 60～110 ℃; The liquid hourly space velocity (LHSV) of dihydropyran derivatives is 0.1～30h ^-1, preferred 1～10h ^-1The mol ratio of dihydropyran derivatives and water is 1: 1～1: 100, preferred 1: 4～1: 30, and more preferably 1: 7～1: 20; Reaction pressure is 0.05～1.0MPa, preferred 0.1～0.5MPa, more preferably normal pressure.

The present invention has following characteristics:

(1) reaction condition gentleness can realization response under normal pressure and lower temperature.

(2) reaction rate is fast, active and selectivity height, good stability.

(3) toxicity and corrosivity are low, and environmental pollution is little.

(4) catalyst separates simply with the product system, can realize intermittently or successive reaction, and renewable use, production cost is low.

The specific embodiment

To be specified with embodiment below, but content of the present invention be not confined to for the category of embodiment.

Embodiment 1-3

The Hydrogen silicate zeolite MCM-22 zeolite powder that hydro-thermal is synthesized is under 85 ℃, and with 2mol/L ammonium nitrate solution exchange 6h, suction filtration and washing repeat 3 times.The filter cake that obtains obtains h-type zeolite MCM-22 at 120 ℃ of dryings, 550 ℃ of roasting 3h.

Add 1.4kg 2-methoxyl group-3 successively in the 5L reactor that has agitator, thermometer, the h-type zeolite MCM-22 of 4-dihydropyran, 1.8kg deionized water and 56g Different Silicon aluminum ratio reacts 3h, result such as table 1 down at 70 ℃.

Table 1

Embodiment 4-5

Catalyst is the h-type zeolite MCM-22 of Si/Al=25, and reaction condition changes the reaction result such as the table 2 of raw material type with embodiment 2.

Table 2

Embodiment 6-8

Adding the h-type zeolite MCM-22 of Si/Al=25 in fixed bed continuous-flow reaction unit, is 90 ℃, raw material 2-methoxyl group-3 in reaction temperature, and 4-dihydropyran liquid hourly space velocity (LHSV) is 1.5h ^-1Down, change 2-methoxyl group-3, the mol ratio of 4-dihydropyran and water, result such as the table 3 of reaction 10h.

Table 3

Embodiment 9-11

Reaction condition changes reaction temperature with embodiment 7, result such as the table 4 of reaction 10h.

Table 4

Embodiment 12-16

Reaction condition changes raw material 2-methoxyl group-3 with embodiment 10, the liquid hourly space velocity (LHSV) of 4-dihydropyran, result such as the table 5 of reaction 10h.

Table 5

Embodiment 17-20

Adopt the different former powder of Hydrogen silicate zeolite, the Preparation of Catalyst condition is with embodiment 1, and reaction condition is with embodiment 7, result such as table 6.

Table 6

Comparative example 1-4

Preparation of Catalyst condition and reaction condition change catalyst type with embodiment 1, result such as table 7 behind the reaction 3h.

Table 7

Comparative example 5

In fixed bed continuous-flow reaction unit, carry out successive reaction.Catalyst is the Hydrogen β zeolite of Si/Al=25, and reaction condition is with embodiment 7.Reaction 2h, pyrans conversion ratio and glutaraldehyde yield are respectively 98.9% and 94.3%.Along with the carrying out of reaction, activity reduces gradually, reaction 160h, and pyrans conversion ratio and glutaraldehyde yield reduce to 58.7% and 45.7% respectively.

Claims

1, the application of a kind of zeolite catalyst in the dihydropyran derivatives hydrolysis shown in general formula (I), it is characterized in that this catalyst be the aperture greater than

The Hydrogen silicate zeolite:

Described Hydrogen silicate zeolite comprises HZSM-10, HZSM-11, HZSM-22, HZSM-23, HZSM-48, HMCM-22, HMCM-49 or HMCM-56, and the Si/Al atomic ratio in the Hydrogen silicate zeolite is 10～200;

In the general formula (I), R represents C ₁～C ₂₀Alkoxyl;

Still formula intermittent reaction is adopted in the dihydropyran derivatives hydrolysis, or adopts fixed bed or slurry attitude bed successive reaction;

Adopt the reaction condition of still formula intermittent reaction to be: catalyst amount is 0.1～20wt%, and reaction temperature is 20～200 ℃, and the mol ratio of dihydropyran derivatives and water is 1: 1～1: 100, and the reaction time is 0.5～10h, and reaction pressure is 0.06～1.0MPa; Adopt the reaction condition of successive reaction to be: catalyst amount is 0.1～20wt%, and reaction temperature is 20～200 ℃, and the liquid hourly space velocity (LHSV) of dihydropyran derivatives is 0.1～30h ^-1, the mol ratio of dihydropyran derivatives and water is 1: 1～1: 100, reaction pressure is 0.05～1.0MPa.

2, application according to claim 1 is characterized in that: adopt the condition of still formula intermittent reaction to be: catalyst amount is 2～10wt%; Reaction temperature is 60～100 ℃; The mol ratio of dihydropyran derivatives and water is 1: 2～1: 30; Reaction time is 2～6h; Reaction pressure is 0.1～0.5MPa; Adopt the reaction condition of successive reaction to be: catalyst amount is 2～10wt%, and reaction temperature is 40～160 ℃, and the liquid hourly space velocity (LHSV) of dihydropyran derivatives is 1～15h ^-1The mol ratio of dihydropyran derivatives and water is 1: 4～1: 30, and reaction pressure is 0.05～1.0MPa.

3, application according to claim 1 is characterized in that: the Hydrogen silicate zeolite is: HZSM-22, HMCM-22, HMCM-49 or HMCM-56.

4, application according to claim 1 is characterized in that: the Si/Al atomic ratio in the Hydrogen silicate zeolite is 10～100.

5, application according to claim 1 is characterized in that: R representation methoxy or ethyoxyl.

6, application according to claim 1 is characterized in that: Hydrogen silicate zeolite catalyst prepares by ion-exchange; Zeolite powder under 50～98 ℃ that hydro-thermal is synthetic is converted into the ammonium type with ammonium chloride or ammonium nitrate solution exchange, and exchange degree is greater than 70%, and then under 500～550 ℃ in air roasting 2～5h.