CN110550877B - Method for producing alpha high-strength gypsum by semi-permeable membrane method - Google Patents
Method for producing alpha high-strength gypsum by semi-permeable membrane method Download PDFInfo
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- CN110550877B CN110550877B CN201910879080.5A CN201910879080A CN110550877B CN 110550877 B CN110550877 B CN 110550877B CN 201910879080 A CN201910879080 A CN 201910879080A CN 110550877 B CN110550877 B CN 110550877B
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- gypsum
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- strength gypsum
- ammonium salt
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/032—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate
Abstract
The invention discloses a method for producing alpha high-strength gypsum by a semi-permeable membrane method, belonging to the field of building materials. The method mainly comprises the steps of increasing the solubility of gypsum in an industrial side plant by using ammonium salt to dissolve the gypsum, reducing the concentration of the ammonium salt by using a semi-permeable membrane structure to further reduce the solubility of calcium sulfate, crystallizing and separating out calcium sulfate dihydrate, controlling the crystallization of the calcium sulfate dihydrate to develop towards a short column by using a crystal-transforming agent, and finally converting the calcium sulfate dihydrate into alpha high-strength gypsum under the condition of 145-200 ℃. The method has the advantages of industrial solid waste as raw materials, high added value of products, simple process, recyclable ammonium salt solution and water, economy and environmental protection.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for producing alpha high-strength gypsum by a semi-permeable membrane method.
Background
A large amount of industrial by-product gypsum is generated in China every year, including phosphogypsum, desulfurized gypsum, fluorgypsum and the like, and the industrial by-product gypsum is piled in large amount, so that great adverse effects are caused to resource environment. The main means of utilizing industrial by-product gypsum to produce building construction and high-strength gypsum to make them be consumed is disclosed.
At present, the gypsum of an industrial side-product factory is treated by adopting a calcination method to produce beta-semi-hydrated gypsum, namely building gypsum, but the building gypsum has performance defects and low added value. Compared with the prior art, the alpha high-strength gypsum has excellent performance and high added value, so the production of the alpha high-strength gypsum is a better choice for consuming the byproduct gypsum in the industry.
The existing processes for producing the alpha high-strength gypsum mainly comprise an autoclaved method and a hydrothermal method. The steam pressing method is used for producing the alpha high-strength gypsum in a high-pressure saturated steam environment, is a widely adopted alpha high-strength gypsum production process at present, and has the problems of high energy consumption, discontinuous production and the like. The hydrothermal method is used for preparing the alpha high-strength gypsum in a saturated salt solution environment, and has the problems of complex process and difficult solution of pollution of the salt solution to the alpha high-strength gypsum, so the hydrothermal method cannot be widely applied.
Disclosure of Invention
The invention aims to provide a method for producing alpha high-strength gypsum by a semi-permeable membrane method, which utilizes common industrial by-product gypsum to produce the alpha high-strength gypsum, purifies the industrial by-product gypsum and improves the use value of the industrial by-product gypsum.
In order to achieve the purpose, the invention provides the following technical scheme:
the method comprises the following specific steps:
(1) putting the industrial byproduct gypsum raw material and the ammonium salt solution into a dissolving tank, and stirring and dissolving;
(2) putting the solution in the dissolving tank into a crystallizing tank, and adding a crystal transformation agent;
(3) introducing tap water into a semi-permeable membrane pipeline in the crystallization tank, and waiting for crystallization and precipitation of calcium sulfate in the crystallization tank;
(4) taking out the calcium sulfate dihydrate precipitate in the crystallization tank, drying and dehydrating to obtain the alpha high-strength gypsum;
(5) putting the solution in the semipermeable membrane into a dissolving tank after adjusting the concentration of ammonium salt;
(6) the water vapor generated in the dryer is condensed and then is introduced into a semi-permeable membrane pipeline.
Preferably, the raw material can be industrial by-product gypsum such as calcium sulfate, desulfurized gypsum and the like.
Preferably, the ammonium salt is ammonium chloride, triammonium citrate or ammonium bicarbonate, and the concentration of ammonium ions in the ammonium salt is 1.5-2 mol/L.
Preferably, the added crystal transformation agent is aluminum sulfate, aluminum potassium sulfate, or the like.
Preferably, the crystallization time is from 0.5 to 1 hour.
Preferably, the semi-permeable membrane in the semi-permeable membrane tube has a pore diameter of 0.3-0.5 nm.
Preferably, the drying temperature in the dryer is 145-200 ℃, and the drying time is 2-3 h.
Preferably, the drying temperature in the dryer is 145-200 ℃, and the drying time is 2-3 h.
Preferably, the water vapor generated in the dryer is condensed and used in a semi-permeable membrane pipeline of the crystallization tank.
The equipment used by the method is divided into a crystallization tank as a core: the crystallization tank is divided into a tank body and a semi-permeable membrane pipeline, wherein the semi-permeable membrane pipeline is a semi-permeable membrane with the aperture of 0.3-0.5nm and can allow ammonium ions to pass through and retain calcium ions.
The reaction principle of the method is as follows:
(1) under the environment of high-concentration ammonium salt solution, the solubility of calcium sulfate is high, and a large amount of industrial byproduct gypsum raw materials are dissolved to a saturated state;
(2) in a crystallization tank, under the action of concentration gradient, ammonium ions move to the interior of a semi-permeable membrane pipeline, calcium ions cannot pass through the semi-permeable membrane pipeline, the solubility of calcium sulfate is rapidly reduced due to the reduction of the concentration of ammonium salts in the solution, and calcium sulfate dihydrate begins to crystallize and precipitate;
(3) interfering calcium sulfate dihydrate crystallization by using a crystal transformation agent to enable the crystal development to be carried out towards a short column shape;
(4) under the action of high temperature, the calcium sulfate dihydrate is crystallized and converted into alpha high-strength gypsum.
Compared with the prior art, the invention has the advantages that the technical scheme is as follows;
(1) the method utilizes the industrial byproduct gypsum to produce the alpha high-strength gypsum, takes solid waste as raw materials, is cheap and easy to obtain, is beneficial to environmental protection, and improves the added value of the industrial byproduct gypsum;
(2) the ammonium salt solution and the water in the process can be recycled, so that the using amount of the water and the ammonium salt can be saved;
(3) the invention has simple process and low cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic diagram of the structure of a crystallization tank of the present invention.
FIG. 3 is a schematic diagram of a three-dimensional structure of a crystallization tank according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Please refer to fig. 1-3:
example 1 is: 10kg of Yuntian chemical group phosphogypsum is taken, and the high-strength gypsum is prepared by adopting a semi-permeable membrane method, which comprises the following steps:
(1) putting the phosphogypsum gypsum raw material and an ammonium salt solution (a triammonium citrate solution, wherein the concentration of ammonium ions in ammonium salt is 1.5mol/L) into a dissolving tank, and stirring and dissolving;
(2) putting the solution in the dissolving tank into a crystallizing tank, and adding a crystal transformation agent (aluminum sulfate, 10 g);
(3) introducing tap water into a semi-permeable membrane pipeline in the crystallization tank, and waiting for crystallization and precipitation of calcium sulfate in the crystallization tank;
(4) and (3) taking out calcium sulfate dihydrate precipitate in the crystallization tank after 1h, and drying and dehydrating for 3h at 145 ℃ to obtain the alpha high-strength gypsum.
Example 2: 10kg of Yuntian chemical group phosphogypsum is taken, and the high-strength gypsum is prepared by adopting a semi-permeable membrane method, which comprises the following steps:
(1) putting the phosphogypsum raw material and an ammonium salt solution (an ammonium chloride solution, wherein the concentration of ammonium ions in ammonium salt is 2mol/L) into a dissolving tank, and stirring for dissolving;
(2) putting the solution in the dissolving tank into a crystallizing tank, and adding a crystal transformation agent (aluminum sulfate, 10 g);
(3) introducing tap water into a semi-permeable membrane pipeline in the crystallization tank, and waiting for crystallization and precipitation of calcium sulfate in the crystallization tank;
(4) after 1h, the calcium sulfate dihydrate precipitate in the crystallization tank is taken out, and the alpha high-strength gypsum is obtained after drying and dehydration for 2h at 200 ℃.
The performance of the high-strength gypsum prepared in example 1 and example 2 was tested according to the national standard alpha high-strength gypsum (JC/T2038-2010), and the results are shown in Table 1:
table 1 performance index table for architectural phosphogypsum in example 1 and example 2
As can be seen from the table above, each index of the phosphorus building gypsum obtained by the semi-permeable membrane method provided by the invention meets the requirement of the national standard alpha 25 grade.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. A method for producing alpha high-strength gypsum by a semi-permeable membrane method is characterized by comprising the following specific steps:
(1) putting the industrial byproduct gypsum raw material and the ammonium salt solution into a dissolving tank, and stirring and dissolving;
(2) putting the solution in the dissolving tank into a crystallizing tank, and adding a crystal transformation agent;
(3) introducing tap water into a semi-permeable membrane pipeline in the crystallization tank, and waiting for crystallization and precipitation of calcium sulfate in the crystallization tank;
(4) taking out the calcium sulfate dihydrate precipitate in the crystallization tank, drying and dehydrating to obtain the alpha high-strength gypsum;
(5) putting the solution in the semipermeable membrane into a dissolving tank after adjusting the concentration of ammonium salt;
(6) condensing the water vapor generated in the dryer, and introducing the water vapor into a semipermeable membrane pipeline; wherein the ammonium salt is ammonium chloride, triammonium citrate or ammonium bicarbonate, and the concentration of ammonium ions in the ammonium salt is 1.5-2 mol/L; the diameter of the semi-permeable membrane in the semi-permeable membrane tube is 0.3-0.5 nm; the added crystal transformation agent is aluminum sulfate and aluminum potassium sulfate.
2. The method for producing the alpha high-strength gypsum by the semipermeable membrane method according to claim 1, wherein the raw material is calcium sulfate or desulfurized gypsum.
3. The method for producing alpha high-strength gypsum according to claim 1, wherein the crystallization time is 0.5-1 h.
4. The method for producing alpha high-strength gypsum through the semipermeable membrane method according to claim 1, wherein the drying temperature in the dryer is 145-200 ℃ and the drying time is 2-3 h.
5. The method for producing the alpha high-strength gypsum by the semipermeable membrane method according to claim 1, wherein the low-concentration ammonium salt solution generated in the semipermeable membrane pipeline in the crystallization pond can be recycled.
6. The method for producing alpha high-strength gypsum through the semipermeable membrane method according to claim 1, wherein the water vapor generated in the dryer is condensed and used in a semipermeable membrane pipeline of a crystallization pond.
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| JPS5257087A (en) * | 1975-11-06 | 1977-05-11 | Ebara Infilco Co Ltd | Desalting method |
| CN101255024A (en) * | 2008-03-27 | 2008-09-03 | 蚌埠华东石膏有限公司 | Method for producing architectural gypsum by lemon acid gypsum |
| CN101730671A (en) * | 2007-05-01 | 2010-06-09 | Bpb有限公司 | Gypsum based compositions |
| CN104176957A (en) * | 2014-08-10 | 2014-12-03 | 安徽锦洋氟化学有限公司 | Method for modifying fluorine gypsum by using redispersible latex powder |
| CN108178177A (en) * | 2018-03-08 | 2018-06-19 | 蒋央芳 | A kind of preparation method of low agglomeration nano calcium carbonate |
| CN108778469A (en) * | 2016-02-02 | 2018-11-09 | 特雷维系统公司 | The hyperfiltration and its application method of osmotic pressure auxiliary |
| CN109137084A (en) * | 2018-09-10 | 2019-01-04 | 昆明理工大学 | A kind of method of salting out method production Dihydrate gypsum whiskers |
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2019
- 2019-09-18 CN CN201910879080.5A patent/CN110550877B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5257087A (en) * | 1975-11-06 | 1977-05-11 | Ebara Infilco Co Ltd | Desalting method |
| CN101730671A (en) * | 2007-05-01 | 2010-06-09 | Bpb有限公司 | Gypsum based compositions |
| CN101255024A (en) * | 2008-03-27 | 2008-09-03 | 蚌埠华东石膏有限公司 | Method for producing architectural gypsum by lemon acid gypsum |
| CN104176957A (en) * | 2014-08-10 | 2014-12-03 | 安徽锦洋氟化学有限公司 | Method for modifying fluorine gypsum by using redispersible latex powder |
| CN108778469A (en) * | 2016-02-02 | 2018-11-09 | 特雷维系统公司 | The hyperfiltration and its application method of osmotic pressure auxiliary |
| CN108178177A (en) * | 2018-03-08 | 2018-06-19 | 蒋央芳 | A kind of preparation method of low agglomeration nano calcium carbonate |
| CN109137084A (en) * | 2018-09-10 | 2019-01-04 | 昆明理工大学 | A kind of method of salting out method production Dihydrate gypsum whiskers |
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