阅读说明：本技术 氟石膏渣生长硫酸钙晶须的方法及硫酸钙晶须 (The method and calcium sulfate crystal whiskers of fluorgypsum slag growth calcium sulfate crystal whiskers ) 是由 董国文 赵化奇 李奇勇 念保义 俞泽林 *** 于 2019-08-28 设计创作，主要内容包括：本发明提供一种氟石膏渣生长硫酸钙晶须的方法及硫酸钙晶须,涉及硫酸钙晶须制备领域。以氟石膏渣为原料,对其进行研磨后与水混合得到浆料。在浆料中加入可溶性碳酸盐,搅拌反应后过滤得到第一滤液和第一滤渣。在第一滤渣中加入酸液,搅拌反应后过滤得到第二滤液和第二滤渣。将第一滤液和第二滤液混合得到硫酸钙胶体溶液。在硫酸钙胶体溶液中加入晶型助长剂,水热反应后静置反应,然后干燥得到硫酸钙晶须。该方法能够将废弃的氟石膏渣进行资源再利用,得到高附加值的硫酸钙晶须。制备方法稳定可靠,获得的硫酸钙晶须纯度高,长径比大,市场应用前景广阔。(The present invention provides the method and calcium sulfate crystal whiskers of a kind of fluorgypsum slag growth calcium sulfate crystal whiskers, is related to calcium sulfate crystal whiskers preparation field.Using fluorgypsum slag as raw material, slurry is mixed to get with water after grinding to it.Soluble carbonate salt is added in the slurry, the first filtrate and the first filter residue are obtained by filtration after being stirred to react.Acid solution is added in the first filter residue, the second filtrate and the second filter residue are obtained by filtration after being stirred to react.First filtrate and the second filtrate are mixed to get calcium sulfate colloidal solution.Crystal promoter is added in calcium sulfate colloidal solution, stands reaction after hydro-thermal reaction, is then dried to obtain calcium sulfate crystal whiskers.Discarded fluorgypsum slag can be carried out resource reutilization by this method, obtain the calcium sulfate crystal whiskers of high added value.Preparation method is reliable and stable, and the calcium sulfate crystal whiskers purity is high of acquisition, draw ratio is big, and market application prospect is wide.)

1. a kind of method of fluorgypsum slag growth calcium sulfate crystal whiskers, which comprises the following steps:

S1, after fluorgypsum slag is ground and water is mixed to get slurry；

Soluble carbonate salt is added in the slurry in S2, and the first filtrate and the first filter residue are obtained by filtration after being stirred to react；

S3 is added acid solution in first filter residue, the second filtrate and the second filter residue is obtained by filtration after being stirred to react；

First filtrate and second filtrate are mixed to get calcium sulfate colloidal solution by S4；

Crystal promoter is added in the calcium sulfate colloidal solution, stands reaction after hydro-thermal reaction, is then dried to obtain sulphur by S5 Sour calcium pyroborate, wherein hydrothermal reaction condition is that 2.5~4.5h is reacted under the conditions of 110~155 DEG C.

2. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that in step s 5, The standing reaction time is 2.5~4.5h.

3. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that in step S5, institute The pH value for stating calcium sulfate colloidal solution is 2~4.

4. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that in step S5, institute Stating crystal promoter includes host agent and auxiliary agent, and the host agent is selected from magnesium chloride, citric acid, neopelex and five water sulphur One of sour copper is a variety of.

5. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 4, which is characterized in that the auxiliary agent is selected from One of glycerine, 12 hydrazine aluminum sulfate potassium, dodecyltriethanolamine sulfate are a variety of.

6. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that the crystal form encourages The dosage of agent is 8~12g/L.

7. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that, can in step S2 Soluble carbonate is one of sodium carbonate, potassium carbonate, ammonium carbonate or a variety of.

8. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that in step S3, acid Liquid is selected from concentrated hydrochloric acid or concentrated nitric acid.

9. the method for fluorgypsum slag growth calcium sulfate crystal whiskers according to claim 1, which is characterized in that by the fluorgypsum Slag is before step S1, by following pretreatment: fluorgypsum slag being calcined 30~40min under the conditions of 140~160 DEG C, is calcined Product 2-3mol/L dissolving with hydrochloric acid filters, and is precipitated, obtains pretreated fluorgypsum slag.

10. a kind of calcium sulfate crystal whiskers, which is characterized in that method described in any one is made according to claim 1~9.

Technical field

The present invention relates to calcium sulfate crystal whiskers preparation fields, and in particular to fluorgypsum slag growth calcium sulfate crystal whiskers method and Calcium sulfate crystal whiskers.

Background technique

Calcium sulfate crystal whiskers are in needle-shaped or fibrous crystal under the microscope, are also known as crystal whisker of gypsum, are using gypsum as former material Material is grown, with uniform cross section, shape is complete, internal structure is perfect by artificially controlling with single crystal form.Calcium sulfate Whisker have excellent mechanical property and physical property, such as high tensile strength, elasticity modulus, abrasion performance, high temperature resistant, every Hot, excellent chemical stability and compatibility etc..Therefore, the cost performance of calcium sulfate crystal whiskers is high, and easy to process, papermaking, The industrial circles such as coating, plastics, rubber have widely applied prospect.

Fluorgypsum is the by-product during sulfuric acid solution fluorite production hydrofluoric acid, belongs to II type anhydrous gypsum, is in strong acid Property, the annual discharge amount of the fluorgypsum in China is more than 3,000,000 tons.Most domestic fluorgypsum is all no to be utilized again, and It is directly as waste, not only land occupation resource, but also easy pollution environment.Only small part fluorgypsum be used to prepare Cement, mortar and construction material, added value are low.High added value calcium sulfate crystal whiskers are prepared using cheap calcium resource fluorgypsum, Obtain the new way of solid waste fluorgypsum recycling.

Summary of the invention

The purpose of the present invention is to provide a kind of method of fluorgypsum slag growth calcium sulfate crystal whiskers, the method parameters are held It is easy to control, it is suitable for industrialization large-scale production.

Another object of the present invention is to provide a kind of calcium sulfate crystal whiskers, are obtained with discarded fluorgypsum slag, and product is made Dispersibility and compatibility are good, and quality is high.

The present invention solves its technical problem and adopts the following technical solutions to realize.

A kind of method of fluorgypsum slag growth calcium sulfate crystal whiskers, comprising the following steps:

S1, after fluorgypsum slag is ground and water is mixed to get slurry；

Soluble carbonate salt is added in the slurry in S2, and the first filtrate and the first filter residue are obtained by filtration after being stirred to react；

S3 is added acid solution in first filter residue, the second filtrate and the second filter residue is obtained by filtration after being stirred to react；

First filtrate and second filtrate are mixed to get calcium sulfate colloidal solution by S4；

S5, is added crystal promoter in the calcium sulfate colloidal solution, and reaction is stood after hydro-thermal reaction, then dry To calcium sulfate crystal whiskers, wherein hydrothermal reaction condition is to react 2.5~4.5h under the conditions of 110~155 DEG C.

Further, in a preferred embodiment of the present invention, in step S5, the standing reaction time is 2.5~4.5h.

Further, in a preferred embodiment of the present invention, in step S5, the pH value of the calcium sulfate colloidal solution is 2~ 4。

Further, in a preferred embodiment of the present invention, in step S5, the crystal promoter includes host agent and auxiliary agent, The host agent is selected from one of magnesium chloride, citric acid, neopelex and cupric sulfate pentahydrate or a variety of.

Further, in a preferred embodiment of the present invention, the auxiliary agent is selected from glycerine, 12 hydrazine aluminum sulfate potassium, ten One of dialkyl group sulfuric acid triethanolamine is a variety of.

Further, in a preferred embodiment of the present invention, the dosage of the crystal promoter is 8~12g/L.

Further, in a preferred embodiment of the present invention, in step S2, soluble carbonate salt is sodium carbonate, potassium carbonate, carbon One of sour ammonium is a variety of.

Further, in a preferred embodiment of the present invention, in step S3, acid solution is selected from concentrated hydrochloric acid or concentrated nitric acid.

Further, in a preferred embodiment of the present invention, by the fluorgypsum slag before step S1, by following pre- place Reason: calcining 30~40min for fluorgypsum slag under the conditions of 140~160 DEG C, and calcined product 2-3mol/L dissolving with hydrochloric acid filters, It is precipitated, obtains pretreated fluorgypsum slag.

The present invention proposes a kind of calcium sulfate crystal whiskers, which is characterized in that is made according to above-mentioned method.

The calcium sulfate crystal whiskers that the method for the fluorgypsum slag growth calcium sulfate crystal whiskers of the embodiment of the present invention and growth obtain have Beneficial effect is:

It grows to obtain the calcium sulfate crystal whiskers of high added value with discarded fluorgypsum slag, it is at low cost, it is from a wealth of sources, have very big Environmental benefit and economic benefit.The growth that calcium sulfate crystal whiskers are controlled by crystal promoter, hydrothermal reaction condition, obtains major diameter Than suitable calcium sulfate crystal whiskers, and product surface is smooth, dispersibility and compatibility are good in organic media.

Detailed description of the invention

In order to illustrate the technical solution of the embodiments of the present invention more clearly, below will be to needed in the embodiment attached Figure is briefly described, it should be understood that the following drawings illustrates only certain embodiments of the present invention, therefore is not construed as pair The restriction of range for those of ordinary skill in the art without creative efforts, can also be according to this A little attached drawings obtain other relevant attached drawings.

Fig. 1 is the pictorial diagram of calcium sulfate crystal whiskers made from the 1 of the embodiment of the present invention；

Fig. 2 is the electron microscope of calcium sulfate crystal whiskers made from the 1 of the embodiment of the present invention；

Fig. 3 is the electron microscope of calcium sulfate crystal whiskers made from the 2 of the embodiment of the present invention；

Fig. 4 is the electron microscope of calcium sulfate crystal whiskers made from the 3 of the embodiment of the present invention；

Fig. 5 is the electron microscope of calcium sulfate crystal whiskers made from the 4 of the embodiment of the present invention；

Fig. 6 is the electron microscope of calcium sulfate crystal whiskers made from the 5 of the embodiment of the present invention；

Fig. 7 is the electron microscope of calcium sulfate crystal whiskers made from the 6 of the embodiment of the present invention.

Specific embodiment

It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase Product.

The calcium sulfate that the method to the fluorgypsum slag growth calcium sulfate crystal whiskers of the embodiment of the present invention and growth obtain below is brilliant It must be specifically described.

The embodiment of the present invention provides a kind of method of fluorgypsum slag growth calcium sulfate crystal whiskers, comprising the following steps:

S1, after fluorgypsum slag is ground and water is mixed to get slurry；

Soluble carbonate salt is added in the slurry in S2, and the first filtrate and the first filter residue are obtained by filtration after being stirred to react；

S3 is added acid solution in first filter residue, the second filtrate and the second filter residue is obtained by filtration after being stirred to react；

First filtrate and second filtrate are mixed to get calcium sulfate colloidal solution by S4；

S5, is added crystal promoter in the calcium sulfate colloidal solution, and reaction is stood after hydro-thermal reaction, then dry To calcium sulfate crystal whiskers, wherein hydrothermal reaction condition is to react 2.5~4.5h under the conditions of 110~155 DEG C.

Further, in the preferred embodiment, fluorgypsum slag carries out following pre-process before the use:

Fluorgypsum slag is calcined 30~40min by S0 under the conditions of 140~160 DEG C, and calcined product is molten with 2-3mol/L hydrochloric acid Solution filters, and is precipitated, obtains pretreated fluorgypsum slag.Calcining and acid dissolution step first are carried out to fluorgypsum slag, can effectively be gone Except a part of impurity, in addition, it is more preferable by the grindability of pretreated fluorgypsum slag, be conducive to the progress of subsequent step.

Further, in the preferred embodiment, in step S1, the solid-liquid ratio of fluorgypsum slag and water is 80~120g/L. It is further preferable that the solid-liquid ratio of fluorgypsum slag and water is 100g/L.The concentration for controlling slurry both guarantees going on smoothly for reaction, Avoid reagent dosage excessive again.

Further, in step S2, soluble carbonate salt is selected from one of sodium carbonate, potassium carbonate, ammonium carbonate or a variety of. It is further preferable that soluble carbonate salt is selected from sodium carbonate.It is further preferred that excessive sodium carbonate is added in the slurry, guarantee Precipitating completely, and accelerates reaction rate.

Further, it in step S2, after 50~70min of first slurry agitation time, adds sodium carbonate and stirs 1~1.5h, Guarantee that reaction sufficiently carries out, the first filter residue and the first filtrate containing a large amount of sulfate ions is obtained by filtration.

Further, in step S3, first the first filter residue is mixed with water according to 150~250g/L of solid-liquid ratio, then plus Enter acid solution, acid solution is selected from concentrated hydrochloric acid or concentrated nitric acid.It is further preferred that acid solution is concentrated hydrochloric acid (mass fraction is about 37%).

Further, in step S3, mixing time is 50~70min, obtains the second filtrate containing a large amount of calcium ions.

Further, in step S5, the pH value for adjusting calcium sulfate colloidal solution is 2~4.Under the conditions of the pH, crystal form is helped Long agent can advantageously promote the axial growth of sodium sulphate calcium pyroborate, improve draw ratio.

Further, in step S5, crystal promoter includes host agent and auxiliary agent, and host agent is selected from magnesium chloride, citric acid, 12 One of sodium alkyl benzene sulfonate and cupric sulfate pentahydrate are a variety of.It is further preferred that host agent is the magnesium chloride that mass ratio is 1:1 With the mixture of neopelex.The mixture is selected, can be improved reaction speed, promotes whisker growth.

Further, auxiliary agent is selected from one of glycerine, 12 hydrazine aluminum sulfate potassium, dodecyltriethanolamine sulfate Or it is a variety of.It is further preferable that selection of auxiliary mass ratio is the dodecyltriethanolamine sulfate and 12 hydrazine aluminum sulfates of 1:2 Potassium.Auxiliary agent is added in hydro-thermal reaction system, sulfate ion is capable of providing and promotes whisker growth, and on the crystal face of whisker Good suction-operated occurs, the whisker of high length-diameter ratio is promoted to generate.

Further, in step S5, the dosage of crystal promoter is 8~12g/L.Further, host agent and auxiliary agent Amount ratio is 10:1~3.

Further, in step S5, hydro-thermal reaction step includes: that 0.5~1h is first reacted under the conditions of 110~125 DEG C, is stirred Mixing speed is 500~600r/min, then 3.5~4h of hydro-thermal reaction under the conditions of 140~145 DEG C, mixing speed is 250~ 300r/min.Hydrothermal reaction condition has great influence to the growth of whisker.Growth temperature is too low to be easy to cause whisker to be bonded to Laminated structure, growth temperature is excessively high, then is easy to cause secondary nucleation, forms particle surface.First given birth at a lower temperature It is long, and high-speed stirred is carried out, nucleation rapidly, and avoids adhesion.Then it grows, and is stirred at low speed at a higher temperature, Make nucleus fast-growth, avoids whisker from being cut off, obtain that surface is smooth, and the calcium sulfate crystal whiskers of high length-diameter ratio.

Further, in the preferred embodiment, in step S5, standing the cooling reaction time is 2.5~4.5h.Keep one Fixed standing cooling time, promote the complete growth of whisker.

The present invention also provides a kind of calcium sulfate crystal whiskers, are made according to above-mentioned method.

Feature and performance of the invention are described in further detail with reference to embodiments.