阅读说明：本技术 一种高分散4a沸石及其制备方法、应用 (High-dispersion 4A zeolite, and preparation method and application thereof ) 是由 傅小涛 赵善雷 张智 滕龙 田锋 郭翠红 于 2020-07-01 设计创作，主要内容包括：本发明公开了一种高分散4A沸石及其制备方法、应用,所述高分散4A沸石包括如下原料：4A沸石和分散剂；所述分散剂为如下至少一种：无机磷酸盐、有机物；所述4A沸石和分散剂的质量比为250～500:1。采用本发明的方法可制得高分散4A沸石,这种方法可以利用原有产线,既可生产4A沸石,也可生产高分散性4A沸石,投资低,效率高,方法简单,易于工业化。(The invention discloses a high-dispersion 4A zeolite, a preparation method and an application thereof, wherein the high-dispersion 4A zeolite comprises the following raw materials: 4A zeolite and a dispersant; the dispersant is at least one of the following: inorganic phosphate, organic matter; the mass ratio of the 4A zeolite to the dispersing agent is 250-500: 1. The method can be used for preparing the high-dispersion 4A zeolite, can be used for producing the 4A zeolite and the high-dispersion 4A zeolite by utilizing the original production line, and has the advantages of low investment, high efficiency, simple method and easy industrialization.)

1. A high-dispersion 4A zeolite is characterized by comprising the following raw materials:

4A zeolite and a dispersant;

the dispersant is at least one of the following: inorganic phosphate, organic matter;

the mass ratio of the 4A zeolite to the dispersing agent is 250-500: 1.

2. The high-dispersion 4A zeolite of claim 1, wherein the mass ratio of the 4A zeolite to the dispersant is 300-400: 1.

3. A highly dispersible 4A zeolite as claimed in claim 1 wherein said inorganic phosphate is at least one of: sodium hexametaphosphate, sodium pyrophosphate.

4. A highly dispersible 4A zeolite as claimed in claim 1 wherein said organic material is at least one of: polyethylene glycol, polyacrylamide.

5. The highly dispersed 4A zeolite according to claim 1, wherein when the dispersant is an inorganic phosphate and an organic substance, the mass ratio of the inorganic phosphate to the organic substance is 1-3.5: 1.

6. The high-dispersion 4A zeolite according to claim 5, wherein the mass ratio of the inorganic phosphate to the organic matter is 1.5-2.34: 1.

7. a highly dispersible 4A zeolite as claimed in claim 1 wherein D of said 4A zeolite₅₀3.0 to 4.0 μm, D of the 4A zeolite₉₉5.2 to 6.0 μm.

8. A process for preparing a highly dispersed 4A zeolite as claimed in any one of claims 1 to 7, which comprises,

mixing and dispersing the 4A zeolite and a dispersing agent according to the mass ratio, and coating the surface of the 4A zeolite with the dispersing agent to obtain high-dispersion 4A zeolite;

the dispersant is at least one of the following: inorganic phosphate and organic matter.

9. The method for preparing high-dispersion 4A zeolite according to claim 8, wherein the rotation speed is 500-600 r/min, the mechanical dispersion temperature is 30-150 ℃, and the mechanical dispersion time is 10-60 s.

10. Use of a highly dispersed 4A zeolite according to any one of claims 1 to 7 as a PVC heat stabilizer.

Technical Field

The invention belongs to the technical field of preparation of 4A zeolite, and particularly relates to high-dispersion 4A zeolite, and a preparation method and application thereof.

Background

The 4A zeolite is a white powder which is nontoxic, odorless, tasteless and good in fluidity and is known as sodium aluminosilicate. The 4A zeolite has the characteristics of cation exchange performance, large specific surface area, good adsorption performance and the like, and the 4A zeolite is applied to catalytic materials, wastewater treatment and other aspects. In recent years, it has been reported that 4A zeolite is filled with PP and PE as barrier materials to improve the flame retardant property. The 4A zeolite has the property of absorbing HCl, and the thermal stability effect of the calcium and zinc composite stabilizer can be improved by using the 4A zeolite as a PVC thermal stabilizer.

Most of the existing 4A zeolite products are synthesized by a wet method, the 4A zeolite produced by the method is easy to agglomerate and has poor dispersibility, the existence of the agglomerated particles influences the acid absorption capacity of the 4A zeolite, the stability effect of the PVC heat stabilizer is greatly fluctuated, and the surface smoothness of the PVC products is reduced.

The patent application with application publication number CN102502693A discloses a method for synthesizing large-grain and high-dispersion 4A zeolite, which adopts sodium chlorate solution, sodium silicate solution, ionic membrane liquid alkali and water as raw materials and obtains the 4A zeolite with good grain large dispersion through processes of gelatinizing, two-stage crystallization, washing and drying, particularly two-stage crystallization. Patent application publication No. CN101920974A discloses a method for improving dispersibility of zeolite and reducing average particle size of zeolite, under the action of ultrasonic wave and alkali, binding amorphous components to zeolite particles is separated, and alkali liquor can dissolve part of silicon on the surface of zeolite to form fine grooves on the surface of zeolite. The dissolved silicon is washed clean by water to clean the surface of the zeolite, so that when the zeolite particles are contacted with each other, a layer of air film exists among the zeolite particles, thereby effectively preventing electrostatic force and capillary action and preventing the re-agglomeration of dispersed particles.

The method for improving the dispersibility of the zeolite has high cost and is difficult to produce in a large scale, and a new means for improving the dispersibility of the 4A zeolite is urgently needed at present, so that the dispersibility of the zeolite can be improved, and the industrial production can be easily realized.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides high-dispersion 4A zeolite, a preparation method and application thereof, and aims to solve the problems that the 4A zeolite in the prior art has poor dispersibility and poor acid absorption capability due to easy agglomeration, so that the stability effect of a PVC heat stabilizer fluctuates greatly, and the surface smoothness of a PVC product is reduced.

The invention realizes the purpose through the following technical scheme:

in one aspect, an embodiment of the present invention provides a high-dispersion 4A zeolite, including the following raw materials:

4A zeolite and a dispersant;

the dispersant is at least one of the following: inorganic phosphate, organic matter;

the mass ratio of the 4A zeolite to the dispersing agent is 250-500: 1.

Further, the mass ratio of the 4A zeolite to the dispersing agent is 300-400: 1.

further, the inorganic phosphate is at least one of: sodium hexametaphosphate, sodium pyrophosphate;

further, the organic matter is at least one of: polyethylene glycol, polyacrylamide.

Further, when the dispersing agent is a mixture of inorganic phosphate and organic matter, the mass ratio of the inorganic phosphate to the organic matter is 1-3.5: 1.

Further, the mass ratio of the inorganic phosphate to the organic matter is 1.5-2.34: 1.

further, D of the 4A zeolite₅₀3.0 to 4.0 μm, D₉₉5.2 to 6.0 μm.

In a second aspect, the present invention provides a process for preparing a highly dispersed 4A zeolite, the process comprising,

mixing and dispersing the 4A zeolite and a dispersing agent according to the mass ratio, and coating the surface of the 4A zeolite with the dispersing agent to obtain high-dispersion 4A zeolite;

the dispersant is at least one of the following: inorganic phosphate, organic matter;

further, in the mechanical dispersion, the rotating speed is 500-600 r/min, the mechanical dispersion temperature is 30-150 ℃, and the mechanical dispersion time is 10-60 s.

In a third aspect, the embodiment of the invention provides that the high-dispersion 4A zeolite is used as a PVC heat stabilizer.

The beneficial effects of the invention at least comprise:

the invention provides a high-dispersion 4A zeolite, a preparation method and an application thereof, wherein the high-dispersion 4A zeolite comprises the following raw materials: 4A zeolite and a dispersant; the dispersant is at least one of the following: inorganic phosphate, organic matter; the mass ratio of the 4A zeolite to the dispersing agent is 250-500: 1. The inside of the structure of the high-dispersion 4A zeolite is the 4A zeolite, and the dispersant coats or forms an electric double layer on the surface of 4A zeolite particles, so that the 4A zeolite particles are not agglomerated any more, and the dispersibility of the 4A zeolite is improved. The high-dispersion 4A zeolite has good acid absorption capacity, good effect as a PVC heat stabilizer and good smoothness of PVC products.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is an electron micrograph of a highly dispersed 4A zeolite using an example of the present invention;

FIG. 2 is an electron micrograph of zeolite 4A;

figure 3 is a thermal stability graph of PVC after application of 4A zeolite and highly dispersed 4A zeolite of the present invention to PVC.

In fig. 3, numerals 20, 33, 46, 59, 72, 85, 98, 111, 124, 137, 150, 163 represent the number of heating minutes.

Detailed Description

The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.

Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.

Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.

In order to solve the technical problems, the technical scheme in the embodiment of the invention has the following general idea:

in a first aspect, embodiments of the present invention provide a highly dispersed 4A zeolite, where the highly dispersed 4A zeolite comprises the following components:

4A zeolite and a dispersant;

the dispersant is at least one of the following: inorganic phosphate, organic matter;

the mass ratio of the 4A zeolite to the dispersing agent is 250-500: 1.

The addition amount of the dispersing agent is not too high, too much dispersing agent wastes, too little dispersing agent cannot disperse the agglomerated particles on the surface of the 4A zeolite, and the effect of improving the dispersibility cannot be achieved.

Further, the mass ratio of the 4A zeolite to the dispersing agent is 300-400: 1.

when the ratio of the 4A zeolite to the dispersant is within this range, the highly dispersed 4A zeolite can have a smaller particle size, and hence a better dispersing effect can be obtained.

Further, the inorganic phosphate is at least one of: sodium hexametaphosphate, sodium pyrophosphate.

Further, the organic matter is at least one of: polyethylene glycol, polyacrylamide.

Further, when the dispersing agent is a mixture of inorganic phosphate and organic matter, the mass ratio of the inorganic phosphate to the organic matter is 1-3.5: 1.

Further, the mass ratio of the inorganic phosphate to the organic matter is 1.5-2.34: 1.

when the organic matter and the inorganic phosphate are mixed for use, because the difference of the chemical properties of the organic matter and the inorganic phosphate is large, the organic matter is coated preferentially in the coating process of the 4A zeolite particles, if the proportion of the organic matter is large, the coating effect of the inorganic phosphate is difficult to embody, and the coating has adverse effect on the practical application of later-stage PVC; the proper amount of added organic matter can improve the compatibility of the high-dispersion 4A zeolite with organic matter when in application. The ratio of the organic matter to the inorganic phosphate is affected by the ratio of the highly dispersed 4A zeolite to PVC.

Further, D of the 4A zeolite₅₀3.0 to 4.0 μm, D of the 4A zeolite₉₉5.2 to 6.0 μm.

For 4A zeolite with large particle size, a mechanical dispersion method is generally adopted to further reduce the particle size, and the method is simple, good in effect and low in cost. For 4A zeolite (3.0-4.0 μm) with a very small particle size, it is difficult to further disperse under mechanical dispersion because of electrostatic adsorption and van der Waals forces between particles. After inorganic phosphate and 4A zeolite are mixed, during dispersion, the dispersing agent disperses agglomerated particles on the surface of the 4A zeolite, and the agglomerated particles become small; meanwhile, the dispersing agent can coat the surfaces of the 4A zeolite particles or form an electric double layer, so that the dispersed 4A zeolite particles are not agglomerated any more, and the dispersibility of the 4A zeolite is improved. Fig. 1 is an electron micrograph of a highly dispersed 4A zeolite according to an embodiment of the present invention, and fig. 2 is an electron micrograph of a 4A zeolite, and it can be seen from fig. 1 and 2 that the agglomerate grains on the surface of the highly dispersed 4A zeolite are smaller than the agglomerate grains on the surface of the 4A zeolite. The 4A zeolite can be a 4A zeolite produced by existing production processes, such as: the hydrothermal synthesis method is to prepare zeolite slurry by using an aluminum source and a silicon source, and to obtain the zeolite by washing and drying.

In this application, D₅₀For example, D50 is 3.05 μm, and the median particle size of 4A zeolite is more than 50% of 4A zeolite having a particle size of 3.05 μm or more, and 50% of 4A zeolite having a particle size of 3.05 μm or less. D99 was 5.233 μm, and it was found that the content of 4A zeolite having a particle size of less than 5.233 μm was 99%, and the content of 4A zeolite having a particle size of more than 5.233 μm was 1%.

In a second aspect, embodiments of the present invention provide a method for preparing a highly dispersed 4A zeolite, the method comprising,

mixing and dispersing the 4A zeolite and a dispersing agent according to the mass ratio, and coating the surface of the 4A zeolite with the dispersing agent to obtain high-dispersion 4A zeolite;

the dispersant is at least one of the following: inorganic phosphate and organic matter.

Further, the dispersion may be performed in a dispersion apparatus including, but not limited to, any of: mechanical mill, universal mill and vertical pulverizer. The mechanical dispersion can be carried out in any conventional equipment, under the rotating speed provided by the dispersing equipment, the materials entering the dispersing equipment generate strong turbulence, and the 4A zeolite particles are rubbed and collided under the action of the turbulence and combined with inorganic phosphate and organic matters to complete the dispersing action. The dispersion may also be implemented in any other device or method that can function as a dispersion.

Further, in the dispersing process, the rotating speed is 500-600 r/min, the mechanical dispersing temperature is 30-150 ℃, and the mechanical dispersing time is 10-60 s. The mechanical dispersion time is too short and some of the large particles cannot be completely dispersed. During mechanical dispersion, the 4A zeolite is continuously rubbed and collided, so that friction generates heat, and the heat can increase the dispersion temperature and improve the coating effect.

In a third aspect, the embodiment of the invention provides that the high-dispersion 4A zeolite is used as a PVC heat stabilizer.

The invention provides high-dispersion 4A zeolite, a preparation method and application thereof, and the prepared high-dispersion 4A zeolite has small agglomerated particles, good dispersibility and strong acid absorption capacity, so that the effect of a PVC heat stabilizer is stable, and the surface smoothness of a PVC product is reduced. On the basis of the existing 4A zeolite production line, a dispersing agent and dispersing equipment are added between a finished product warehouse and a packaging opening, and the high-dispersion 4A zeolite is obtained by the mechanical mode on the premise of not changing the crystal appearance of the 4A zeolite; meanwhile, the original production line can be utilized to produce the 4A zeolite and the high-dispersity 4A zeolite, so that the investment is low and the efficiency is high; the method is simple and easy to industrialize, and the problems of low efficiency and high cost of preparing the high-dispersion 4A zeolite by using a low-concentration and low-temperature long-time crystallization process are solved.

The highly dispersed 4A zeolite of the present invention, its preparation and use will be further described with reference to the following specific examples.