CN105296688B - A kind of preparation method of leather fat - Google Patents

Abstract

The present invention relates to a kind of preparation method of New Leather Fatliquors.The simple process that purpose is to provide is feasible, and three wastes discharge amount is low, environmentally protective, and product quality is stablized, and fatliquoring function is excellent.Technical solution is：A kind of preparation method of New Leather Fatliquors, carries out according to the following steps：The animal and plant fat continuously inputted is heated to certain temperature, then inputs gas phase SO₃Carry out SO₃Membrane-type sulfonation reacts, and controls SO₃Binding capacity；Chlorine is passed through into the vegetable and animals oils after sulfonation, chlorination vegetable and animals oils sulphonic acid ester is produced by chlorination reaction, and control chlorinity；3rd, chlorination vegetable and animals oils sulphonic acid ester alkali neutralization, decoloration, obtain leather fat product.

Description

A kind of preparation method of leather fat

Technical field

The present invention relates to leather chemical industry technical field, more particularly to a kind of New Leather Fatliquors and preparation method thereof.

Background technology

It is long-standing in China that leather fat is prepared using vegetable and animals oils modification.It is generally acknowledged that vegetable and animals oils fatting agent can Assign leather with it is good moisten, filling, the performance such as plentiful, soft and shelf-stable, therefore it is researched and developed and is constantly subjected to people Attention.Especially after the 1980s, the research to vegetable and animals oils method of modifying makes great progress, and improves The class and quality of vegetable and animals oils fatting agents, expands the application in leather chemical industry field.

Up to the present, mainly there are sulphation (sulfonation), chlorination etc. to the common method of modifying of vegetable and animals oils.Wherein sulfuric acid Stability of emulsion can be improved by changing (sulfonation) modified animal and plant fat, improve grease fatliquoring function, but sulphation (sulfonation) When in use, the fractional saturation fatty glyceride in product easily condenses to be formed the fatting agent of modified preparation in leather surface The material of similar bloom, seriously affects leather quality；Animal and plant fat after chlorination modified can improve fast light, shelf-stable performance, Reduce oil mark appearance, but it is chlorination modified after product automatic emulsifying performance it is poor, can not be used directly as leather fat.

Document《The research of CES lard fatting agents》(leather technology, 05 phase in 1985) is reported, Huang Jinxin et al. is by pig Oil carries out chlorination, alcoholysis, sulphation is modified again, obtains a kind of new CES lard fatting agents.This modified method has sulfuric acid concurrently The advantages of changing and is chlorination modified, obtained fatting agent fatliquoring function is excellent, and soft, plentiful, the glossy property of leather is good after stuffing, and Leather surface does not have crystallization and oil mark produces.But the technique, which needs salt to remove, removes a large amount of unreacted sulphur in sulphation process Acid, produces largely larger containing acid and brine waste discharge, environmental pollution；And the technique needs to carry out using part low-carbon alcohols To improve the binding capacity of sulfuric acid, technical process is relative complex for ester exchange.

The content of the invention

The present invention provides a kind of preparation method of New Leather Fatliquors, the simple process is feasible, and three wastes discharge amount is low, It is environmentally protective, and product quality is stablized, and fatliquoring function is excellent.

The technical solution adopted in the present invention is：A kind of preparation method of leather fat, carries out according to the following steps：

1) animal and plant fat continuously inputted is heated to certain temperature, then inputs gas phase SO₃Carry out SO₃Membrane-type sulfonation Reaction, and control SO₃Binding capacity；

2) chlorine is passed through into the vegetable and animals oils after sulfonation, chlorination vegetable and animals oils sulphonic acid ester is produced by chlorination reaction, and Control chlorinity；

3rd, chlorination vegetable and animals oils sulphonic acid ester alkali neutralization, decoloration, obtain leather fat product.

The reaction temperature of sulfonating reaction is 65~75 DEG C in the step 1), SO₃Concentration of the gas in dry air for 4~ 7%, SO₃Binding capacity control is 3~7% (by adjusting animal and plant fat and gas phase SO₃Charge proportion be controlled).

In the sulfonating reaction, animal and plant fat charging rate is 4~8kg/h, animal and plant fat and SO₃Feed weight Than for 10~15:1.

In the chlorination reaction, reaction temperature is 60~70 DEG C, and 10~30%, (i.e. the chlorine of product contains for chlorinity control Amount, is controlled by product density after measuring chlorination).

The neutralization alkali is at least one of liquid caustic soda, monoethanolamine, diethanol amine, triethanolamine.

The decolorising agent is at least one of hydrogen peroxide, sodium hypochlorite.

The animal and plant fat is lard, one or more mixing in butter, sheep oil, rapeseed oil.

Compared with prior art, the present invention there are following outstanding advantages：

1st, it has been investigated that, animal and plant fat is first used into gas SO₃After sulfonation, then chlorination is carried out, the SO of product can be made₃Knot Resultant (i.e. SO₃Reacting dose) significantly rise, contrast existing process (by animal and plant fat chlorination, the product of sulphation again), it is tied Resultant can improve 2~3%；For the chlorinity of the invention that can guarantee that product up to 10~30%, this index is (dynamic with existing product at the same time Vegetable fat is through chlorination, alcoholysis, the CES fatting agents that sulfate process produces again) it is basically identical.

2nd, compared to animal and plant fat chlorination, again alcoholysis, sulphation modified technique, this invention simplifies technical process, the three wastes Discharge capacity reduce more than 90%, production efficiency improve more than 50%, and final products show good quality stability and Fatliquoring function.

Embodiment

The preparation method of the present invention is described further with reference to embodiment, while is tested by drum stuffing, will The fatliquoring function of embodiment product and several leather fats of same type currently on the market are contrasted, the name of product of selection And manufacturer is as follows：(a) fullness imparting lard oil (sulphation lard butyl ester)；(b) CES fatting agents (sulphation chlorination lard butyl ester)； (c) DM fatting agents (sulphation neat's foot oil).The present invention is not limited to the embodiment.

Embodiment 1

The lard after heating is pumped into film sulfonator with the flow velocity of 4kg/h with metering pump, while it is 4% to be passed through concentration Sulfur trioxide gas, and recirculated water is accessed in sulphonator chuck, set water temperature is 65 DEG C.After value stabilization to be neutralized, one is picked up Quantitative sulphonic acid ester, controlled at 60 DEG C, is passed through chlorine, and adjusts chlorine flowrate, and product density is before chlorination after controlling chlorination 1.1 again.After the completion of chlorination reaction, it is 9.3 that about 600g chlorination lard sulphonic acid esters are neutralized to pH with 32% liquid caustic soda, adds dioxygen Water decolorization, and add water adjustment solid content, obtain leather fat product.

The present embodiment product SO₃Percentage bound is 4.9%, chlorinity 13.5%, and to 1mol/L hydrochloric acid, 10%NaCl And 1:9 lotions show good stability, reach 24 it is small when it is not stratified.This product and other several same type leather greasings The contrast of agent product fatliquoring function is as follows：

Note："+" quantity is more, shows that effect is better

Embodiment 2

The butter after heating are pumped into film sulfonator with the flow velocity of 5kg/h with metering pump, while it is 6% to be passed through concentration Sulfur trioxide gas, and recirculated water is accessed in sulphonator chuck, set water temperature is 70 DEG C.After value stabilization to be neutralized, one is picked up Quantitative sulphonic acid ester, controlled at 70 DEG C, is passed through chlorine, and adjusts chlorine flowrate, and product density is before chlorination after controlling chlorination 1.1 again.After the completion of chlorination reaction, it is 8.7 that about 800g chlorination butter sulphonic acid esters are neutralized to pH with diethanol amine, adds dioxygen Water decolorization, and add water adjustment solid content, obtain leather fat product.

The present embodiment product SO₃Percentage bound is 6.7%, chlorinity 15.4%, and to 1mol/L hydrochloric acid, 10%NaCl And 1:9 lotions show good stability, reach 24 it is small when it is not stratified.This product and other several same type leather greasings The contrast of agent product fatliquoring function is as follows：

Sample ID	The present embodiment product	Fullness imparting lard oil	CES fatting agents	DM fatting agents
					Coloring	++++	+++	+++	++
Oil sense	++++	+++	++++	++
					Flexibility	++++	+++	+++	++

Note："+" quantity is more, shows that effect is better

Embodiment 3

By the lard after heating, sheep oil with mass ratio 1:1 mixing, with metering pump by miscella with the flow pump of 6.5kg/h Enter film sulfonator, while be passed through concentration and be 7% sulfur trioxide gas, and recirculated water is accessed in sulphonator chuck, set Water temperature is 75 DEG C.After value stabilization to be neutralized, a certain amount of sulphonic acid ester is picked up, controlled at 65 DEG C, is passed through chlorine, and adjust chlorine Flow, product density is 1.2 times before chlorination after controlling chlorination., will about 850g chlorination miscella sulphonic acid esters after the completion of chlorination reaction It is 8.9 to be neutralized to pH with 32% liquid caustic soda, adds hydrogen peroxide for decoloration, and adds water adjustment solid content, obtains leather fat product.

The present embodiment product SO₃Percentage bound is 5.4%, chlorinity 19.3%, and to 1mol/L hydrochloric acid, 10%NaCl And 1:9 lotions show good stability, reach 24 it is small when it is not stratified.This product and other several same type leather greasings The contrast of agent product fatliquoring function is as follows：

Sample ID	The present embodiment product	Fullness imparting lard oil	CES fatting agents	DM fatting agents
					Coloring	+++	+++	+++	++
Oil sense	++++	+++	++++	++
					Flexibility	++++	+++	+++	++

Note："+" quantity is more, shows that effect is better

Embodiment 4

Rapeseed oil is pumped into film sulfonator with the flow velocity of 8kg/h with metering pump, while is passed through three oxidations that concentration is 6% Sulphur gas, and recirculated water is accessed in sulphonator chuck, set water temperature is 70 DEG C.After value stabilization to be neutralized, a certain amount of sulphur is picked up Acid esters, controlled at 70 DEG C, is passed through chlorine, and adjusts chlorine flowrate, and product density is 1.3 times before chlorination after controlling chlorination. After the completion of chlorination reaction, about 800g chlorination rapeseed oils sulphonic acid ester is first neutralized to pH as 5.0 with triethanolamine, then with 32% liquid caustic soda It is 8.2 to be neutralized to pH, adds hydrogen peroxide for decoloration, and adds water adjustment solid content, obtains leather fat product.

The present embodiment product SO₃Percentage bound is 3.6%, chlorinity 23.8%, and to 1mol/L hydrochloric acid, 10%NaCl And 1:9 lotions show good stability, reach 24 it is small when it is not stratified.This product and other several same type leather greasings The contrast of agent product fatliquoring function is as follows：

Note："+" quantity is more, shows that effect is better.

Claims (1)

1. a kind of preparation method of leather fat, carries out according to the following steps：

1) animal and plant fat continuously inputted is heated to certain temperature, then inputs gas phase SO₃Carry out SO₃Membrane-type sulfonation reacts, And control SO₃Binding capacity；

2) chlorine is passed through into the vegetable and animals oils after sulfonation, chlorination vegetable and animals oils sulphonic acid ester is produced by chlorination reaction, and control Chlorinity；

3) chlorination vegetable and animals oils sulphonic acid ester alkali neutralization, decoloration, obtain leather fat product；

The reaction temperature of sulfonating reaction is 65~75 DEG C in the step 1), SO₃Concentration of the gas in dry air is 4~7%, SO₃Binding capacity is controlled 3~7%；

In the sulfonating reaction, animal and plant fat charging rate is 4~8kg/h, animal and plant fat and SO₃Feed weight ratio be 10~15:1；

In the chlorination reaction, reaction temperature is 60~70 DEG C, and chlorinity is controlled 10~30%；

The neutralization alkali is at least one of liquid caustic soda, monoethanolamine, diethanol amine, triethanolamine；

The decolorising agent is at least one of hydrogen peroxide, sodium hypochlorite；

The animal and plant fat is lard, one or more mixing in butter, sheep oil, rapeseed oil.