CN1048990A

CN1048990A - A kind of composite solid-acid catalyst that is used for esterification

Info

Publication number: CN1048990A
Application number: CN 89105336
Authority: CN
Inventors: 陈远东; 申永泰
Original assignee: YANTAI CITY CHEMICAL INDUSTRY INST
Current assignee: YANTAI CITY CHEMICAL INDUSTRY INST
Priority date: 1989-07-25
Filing date: 1989-07-25
Publication date: 1991-02-06

Abstract

A kind of composite solid-acid catalyst that is used for esterification, and preparation method thereof, it is that NaY type molecular sieve with modification is a base catalyst, adds the promotor SnO of 10%-20%, and 20%-40% promotor SnCl ₂Or SnCl ₂2H ₂The reaction product of O and NaOH is made, and uses this catalyzer can reduce temperature of reaction, finishes in esterification 2-3 hour, and transformation efficiency is near 100%.

Description

A kind of composite solid-acid catalyst that is used for esterification

The present invention relates to a kind of NaY type zeolite molecular sieve that is used for the modification of esterification is the catalyzer on basis, adds the composite solid-acid catalyst that promotor is made, and the preparation method of this composite solid-acid catalyst.

Industrial production ester compound is generally used the NaA type of modification, the NaX type, zeolite molecular sieves such as NaY type are catalyzer, the chemistry world first phase in 1987 was published department of chemistry of Nanjing University about " solid acid catalyst synthesizes a dibenzoic diglycol laurate " literary composition, its solid acid catalyst is the NaY type zeolite molecular sieve of modification, be characterized in that active temperature is too high, esterification time is long, generally at 4-8 hour.

For solve above-mentioned ester class produce in the active temperature height, the problem that esterification time is long, we have adopted modified zeolite molecular sieve is base catalyst, SnCl ₂Or SnCl ₂2H ₂The reaction product of O and NaOH is a promotor, and exsiccant SnO is that promotor proportionally has been mixed and made into composite solid-acid catalyst.

The present invention realizes according to the following step: adopting NaY type zeolite molecular sieve is parent, uses NH + ₄, Ca ²⁺, Fe ³⁺, Sn ²⁺, Zn ²⁺After salts solution exchange, oven dry, roasting be as base catalyst, then, and with SnCl ₂Or SnCl ₂2H ₂O and NaOH fed intake in 1: 2 in molar ratio, reacted 15-60 minute down at 30 ℃-100 ℃, and product is dried, in 250 ℃ of-350 ℃ of following roastings as promotor, dry SnO is as promotor, and the NaY type zeolite molecular sieve content according to modification is 40%-70% at last, SnCl ₂Or SnCl ₂2H ₂O and NaOH reaction product are 20%-40%, and SnO is that 10%-20% mixes and just obtained composite solid-acid catalyst.

The composite solid-acid catalyst that the present invention makes can be used for esterification, the esterification of plasticizer production process especially, and it has following advantage:

1, use this catalyzer, esterification time is short, finishes in esterification 2-3 hour, and transformation efficiency is near 100%.

2, use this catalyzer, active temperature is low.

Preparation and effect thereof for this composite solid-acid catalyst is described are exemplified below:

Embodiment 1

In there-necked flask, add 1mol SnCl ₂Looking needs to add appropriate amount of deionized water, be heated to gradation adding 2mol NaOH under 40 ℃ of stirrings, continue reaction 0.5-1 hour down at 95 ℃, the oven dry of reactant impouring furnace pot, after 320 ℃ of following roastings, with dry SnO and Modified NaY type zeolite molecular sieve mixed by weight 7: 3: 1 composite solid-acid catalyst.

Embodiment 2

In there-necked flask, add 1mol SnCl ₂2H ₂O, look and to add an amount of distilled water, be heated to 50 ℃ and stir gradation adding 2mol NaOH, continue reaction 0.5-1 hour down at 90 ℃, the oven dry of reactant impouring furnace pot, in 340 ℃ of following roastings, mix by weight 15: 9: 26 with the NaY type zeolite molecular sieve of exsiccant SnO and modification then and obtain composite solid-acid catalyst.

Embodiment 3

In there-necked flask, add 1mol SnCl ₂Looking needs to add appropriate amount of deionized water, being heated to 40 ℃ stirs and trembles down gradation and add 2mol NaOH, continue reaction 0.5-1 hour down at 95 ℃, the oven dry of reactant impouring furnace pot, after 320 ℃ of following roastings, mixed to obtain composite solid-acid catalyst by weight 4: 1: 5 with the NaY type zeolite molecular sieve of dry SnO and modification.

The effect comparison of advantage of the present invention and existing catalyzer is as follows:

Catalyzer	Sintetics	Esterification time	Temperature of reaction
				Composite solid-acid catalyst	Diethylene glycol dibenzoate	≤ 2.5 hours	160℃－220℃
The SnY molecular sieve catalyst	Diethylene glycol dibenzoate	4-8 hour	170℃－250℃

Claims

1, a kind of composite solid-acid catalyst that is used for esterification is characterized in that adding 10%-20% promotor SnO and 20%-40% promotor SnCl in the catalyzer of the NaY of modification type zeolite molecular sieve for the basis ₂Or SnCl ₂2H ₂The reaction product of O and NaOH is made.

2, a kind of preparation method who is used for the composite solid-acid catalyst of esterification is characterized in that SnCl ₂Or SnCL ₂2H ₂The oven dry of the reaction product of O and NaOH, roasting add together in the NaY type zeolite molecular sieve of modification with exsiccant SnO then and mix.

3, according to the preparation method of the said composite solid-acid catalyst of claim 2, it is characterized in that SnCl ₂Or SnCl ₂2H ₂The molar ratio of O and NaOH reaction is 1: 2, and temperature of reaction is that 30 ℃-100 ℃ reaction times are 15-60 minute, and maturing temperature is 250 ℃-350 ℃.