CN103803570B

CN103803570B - Utilize the method that solvent thermal reaction changes attapulgite color

Info

Publication number: CN103803570B
Application number: CN201410071113.0A
Authority: CN
Inventors: 王爱勤; 张志芳; 王文波
Original assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Current assignee: Lanzhou Institute of Chemical Physics LICP of CAS
Priority date: 2014-02-28
Filing date: 2014-02-28
Publication date: 2016-06-22
Anticipated expiration: 2034-02-28
Also published as: CN103803570A

Abstract

The invention provides a kind of method utilizing solvent thermal reaction to change attapulgite color, be by acid treatment after brick-red attapulgite clay by solid-liquid mass ratio 1:25～1:200 dispersed with stirring in dimethylsulfoxide solvent, 4～48h is reacted in 120～200 DEG C when, centrifugation, dry, namely obtain rice white attapulgite。The present invention by the interaction of S=O group in dimethyl sulfoxide with attapulgite, by with ferric effect in attapulgite skeleton, it is achieved the transformation of attapulgite color and luster。The simultaneously changing of transformation of the ferrum valence state structure charge of attapulgite, thus improve attapulgite clay absorbability, the application for the brick-red attapulgite clay of China's rich reserves opens new way。It addition, present invention process is simple, it is easy to controlling, equipment requirements is not high, and cost is low, is conducive to industrialized production。

Description

Utilize the method that solvent thermal reaction changes attapulgite color

Technical field

The present invention relates to a kind of method utilizing solvent thermal reaction to change attapulgite color, particularly relate to and a kind of utilize dimethylsulfoxide solvent thermal response to make the method that brick-red attapulgite is changed into rice white attapulgite, belong to nano silicate material deep processing and preparing technical field。

Background technology

Attapulgite clay is a kind of layer silicate mineral containing Shuifu County's magnalium, owing to having the advantages such as the excellent crystal form looks of uniqueness, micropore canals, bigger specific surface area and good absorption property, obtain application at numerous areas such as fine chemistry industry, composite, function carrier, petrochemical industry and environmental protection in recent years。China have found the concavo-convex handful stone clay deposit of large-scale high-quality as far back as Anhui two province of Soviet Union, later successively in Gansu, Sichuan, Guizhou, Henan, Shanxi, Inner Mongol, Hubei, the ground such as Hebei and Yunnan be found that a collection of mineral deposit (point) successively, mineral resource prospects is considerable。Wherein, the concavo-convex handful stone clay ore reserves that Gansu is verified in recent years has 400,000,000 tons more than。But, attapulgite is in mineralizing process, due to Mg²⁺Shortage cause Mg in octahedral layer²⁺There is major part vacancy the position occupied or is Al³⁺、Fe³⁺Or Fe²⁺Occupied by, and a large amount of Fe³⁺Occupy that to make attapulgite present brick-red。In the concavo-convex handful stone clay of Anhui two province of Soviet Union, the content of concavo-convex handful stone is of a relatively high, and color is white or rice white simultaneously, because researching and developing comparatively system, has formed industrial colony at present。And the concavo-convex handful stone clay ore deposit in other area does not have sizable application, except the content of concavo-convex handful stone relatively not high except, mainly the color and luster in concavo-convex handful stone clay ore deposit is relatively deep, and absorbability is more weak, is unfavorable for the exploitation of product。

In order to improve the color and luster of concavo-convex handful stone clay, first natural concavo-convex handful stone clay is carried out dispersion process by CN101423673 in aqueous phase, prepares nano concavo-convex and holds in both hands stone dispersion liquid, then with TiCl₄Aggregation of Nanometer Titanium Dioxide body is prepared for raw material, again Aggregation of Nanometer Titanium Dioxide body and nano concavo-convex are held in both hands stone and carry out compound, utilize the dissolving with hydrochloric acid that in course of reaction, titanium tetrachloride hydrolysis produces to go out the ferrum element in concavo-convex handful stone, finally use Disodium oxalate. to carry out complexation deironing。CN102660158A also utilizes aluminium hydroxide and aluminium silicate synergic whitening modification dolomite/concavo-convex handful stone。These methods no doubt can play the effect that concavo-convex handful stone brightens, but itself does not brighten from concavo-convex handful stone structure。Thus explore new method of whitening, the utilization of the brick-red concavo-convex handful stone clay of China's rich reserves is had important practical significance。

Summary of the invention

It is an object of the invention to provide a kind of method utilizing solvent thermal reaction to change attapulgite clay color, new approach is opened up in the utilization for brick-red concavo-convex handful stone clay。

The present invention utilizes the method that solvent thermal reaction changes attapulgite color, be by acid treatment after brick-red attapulgite clay by the mass/volume of 1:25～1:200 than dispersed with stirring in dimethylsulfoxide solvent, 4～48h is reacted in 120～200 DEG C when, centrifugation, dry, namely obtain rice white attapulgite。

The present invention utilizes the S=O group in dimethyl sulfoxide, realizes the interaction of S=O group and attapulgite when environment under high pressure, by with ferric effect in attapulgite skeleton, it is achieved the transformation of attapulgite color and luster。The simultaneously changing of transformation of the ferrum valence state structure charge of attapulgite, thus improve attapulgite clay absorbability。Measuring, the present invention change color after rice white attapulgite clay the adsorption capacity of methylene blue is improve more than 2 times。

The acid treatment process of brick-red attapulgite clay is: by the brick-red attapulgite clay pulverized by the mass/volume of 1:10～1:50 than, in the acid solution (sulphuric acid or hydrochloric acid) being dispersed in mass concentration 1～10%, stirring 1～4h, crosses 200 mesh sieves and removes impurity；It is washed with water to pH=5～6 after centrifugation, dries, pulverize and get final product。The effect of acid treatment is: one side decomposes the impurity such as the carbonate of attapulgite clay association；The duct of attapulgite clay can be dredged on the other hand further, be conducive to the interaction of attapulgite and dimethyl sulfoxide。

Dimethylsulfoxide solvent used can be recycled, it is possible to decrease production cost。

In sum, the present invention passes through dimethylsulfoxide solvent thermal response, realize brick-red attapulgite to white attapulgite transformation while, be effectively increased the absorbability of attapulgite, the application for the brick-red attapulgite clay of China's rich reserves opens new way。It addition, present invention process is simple, it is easy to controlling, equipment requirements is not high, and cost is low, is conducive to industrialized production。

Detailed description of the invention

Method solvent thermal reaction of the present invention being changed attapulgite clay color below by specific embodiment is described further。

Embodiment 1

Under agitation, brick-red for 20g attapulgite clay is dispersed in the sulfuric acid solution that 200mL mass concentration is 5%, crosses 200 mesh sieves after stirring 2h and remove the impurity such as quartz sand；It is washed with water to pH=6 after centrifugation, at 105 DEG C, then dries 4h, pulverize, cross 200 mesh sieves, obtain acid treatment attapulgite clay。

Acid treatment attapulgite clay is dispersed in 600mL dimethyl sulfoxide, stirs 30min, be uniformly dispersed and be placed in 1L autoclave, it is reaction 12h at 180 DEG C in temperature, centrifugation after Temperature fall, then dries 4h at 105 DEG C, namely obtains rice white attapulgite。

Embodiment 2

Under agitation, brick-red for 15g attapulgite clay is dispersed in the sulfuric acid solution that 200mL mass concentration is 10%, crosses 200 mesh sieves after stirring 2h and remove the impurity such as quartz sand；It is washed with water to pH=5 after centrifugation, at 105 DEG C, then dries 4h, pulverize, cross 200 mesh sieves, obtain acid treatment attapulgite clay。

Acid treatment attapulgite clay is dispersed in 600mL dimethyl sulfoxide, stirs 30min, be uniformly dispersed and be placed in 1L autoclave, it is reaction 24h at 160 DEG C in temperature, after Temperature fall, centrifugation, after drying 4h at 105 DEG C, namely obtain rice white attapulgite。

Embodiment 3

Under agitation, brick-red for 15g attapulgite clay is dispersed in the hydrochloric acid solution that 200mL mass concentration is 10%, cross 200 mesh sieves after stirring 2h and remove the impurity such as quartz sand, pH value=6 it are washed with water to after being performing centrifugal separation on, then pulverize 200 mesh sieves after drying 4h at 105 DEG C, obtain acid treatment attapulgite clay。

Acid treatment attapulgite clay is dispersed in 600mL dimethyl sulfoxide, stirs 30min, be uniformly dispersed and be placed in 1L autoclave, be reaction 6h at 200 DEG C in temperature, after Temperature fall, centrifugation, after drying 4h at 105 DEG C, namely obtain rice white attapulgite。

Embodiment 4

Under agitation, brick-red for 10g attapulgite clay is dispersed in the sulfuric acid solution that 200mL mass concentration is 8%, cross 200 mesh sieves after stirring 2h and remove the impurity such as quartz sand, pH value=6 it are washed with water to after being performing centrifugal separation on, then pulverize 200 mesh sieves after drying 4h at 105 DEG C, obtain acid treatment attapulgite clay。

Acid treatment attapulgite clay is dispersed in 600mL dimethyl sulfoxide, stirs 30min, be uniformly dispersed and be placed in 1L autoclave, be reaction 6h at 150 DEG C in temperature, after Temperature fall, centrifugation, after drying 4h at 105 DEG C, namely obtain rice white attapulgite。

Claims

1. utilize the method that solvent thermal reaction changes attapulgite color, be by acid treatment after brick-red attapulgite clay dispersed with stirring in dimethylsulfoxide solvent, in 120～200 DEG C when react 4～48h, centrifugation, dry, namely obtain rice white attapulgite；

The acid treatment process of described brick-red attapulgite clay is: by the brick-red attapulgite clay pulverized by the mass/volume of 1:10～1:50 than, in the acid solution being scattered in mass concentration 1～10%, stirring 1～4h, crosses 200 mesh sieves and removes impurity；It is washed with water to pH=5～6 after centrifugation, dries, pulverize and get final product；The unit of described mass/volume ratio is g/mL。

2. utilize the method that solvent thermal reaction changes attapulgite color as claimed in claim 1, it is characterised in that: the mass/volume of brick-red attapulgite clay and dimethylsulfoxide solvent ratio is for 1:25～1:200g/mL。

3. utilize the method that solvent thermal reaction changes attapulgite color as claimed in claim 1, it is characterised in that: described acid solution is sulfuric acid solution or hydrochloric acid solution。