CN105523742A - Phosphogypsum composite material and manufacturing method thereof - Google Patents
Phosphogypsum composite material and manufacturing method thereof Download PDFInfo
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- CN105523742A CN105523742A CN201410504940.4A CN201410504940A CN105523742A CN 105523742 A CN105523742 A CN 105523742A CN 201410504940 A CN201410504940 A CN 201410504940A CN 105523742 A CN105523742 A CN 105523742A
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- phosphogypsum
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- phosphogypsum composite
- modified ardealite
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Abstract
The present invention provides a phosphogypsum composite material and a manufacturing method thereof. The composite material comprises a sheet-like substrate layer, wherein the substrate layer is made from an inorganic component modified phosphogypsum and an organic component polyethylene. The present invention further provides a manufacturing method of the phosphogypsum composite material. According to the present invention, the phosphogypsum utilization rate is improved, and the problems of soil resource occupation and serious pollution of the phosphogypsum can be fundamentally solved.
Description
[technical field]
The present invention relates to chemical field, particularly relate to a phosphogypsum composite material and its manufacture method.
[background technology]
Phosphogypsum (referred to as PG) is the industrial residue of phosphoric acid or Phosphate Fertilizer Industry and the discharge of some synthetic detergent industry.As agriculture production big country, in recent years, the development of China's phosphate fertilizer industry is very fast, and in 2006, had related data to show, China has become the first in the world production of phosphate fertilizer state.Along with the fast development of phosphate fertilizer industry, as the residue phosphogypsum of production of phosphate fertilizer discharge, its accumulating amount and newly-increased quantity are also quite surprising, on the ground such as Guizhou, Yunnan, Sichuan, Hubei that phosphorus ore and phosphorus chemical industry are concentrated, we are seen everywhere and are piled into the phosphogypsum on mountain, as far back as the end of the year 2011, the accumulative phosphogypsum piled up more than 300,000,000 tons of China, will be equivalent to each Chinese and will bear more than 200 kilogram of waste residue.
The accumulation of flood tide phosphogypsum occupies a large amount of land resources and does not say, containing fluorochemical in phosphogypsum, free phosphoric acid, P2O5, the impurity such as phosphoric acid salt, it not only can cause phosphogypsum in the process of storing up, cause the problem of environmental pollution, and phosphogypsum is after chance rain drop erosion, take away part soluble impurity, to underground, pollution is caused to soil, in addition soluble impurity enters after in water or river and also can pollute water quality, rural areas in our country majority are direct Drinking Waters, water source after phosphogypsum pollutes directly enters human body, great threat is caused to the physical and mental health of the people.In addition, wind erosion also creates topsoil, and phosphogypsum brings serious " land, water and air " pollution problem to us, and the harmful heavy metal chemical substances such as the arsenic contained in phosphogypsum, cadmium, mercury will reach centuries to the impact that environment causes.In recent years, the report about phosphogypsum harm residents ' health also gets more and more, and as long-term drinking phosphogypsum polluted source can cause osteoporosis, renal lesions, increases the message such as canceration probability and allows people feel with one's hair standing on end.Government has also issued the relevant policies of stacking application etc. about solid waste time and again for this problem, as the standard defining industrial solid wastes storage and dispose in [general industrial solid waste storage, disposal site Environmental capacity standard].But in the implementation of policy, the stacking of many phosphogypsums does not all meet national standard, the livelihood issues that the pollution of phosphogypsum brings still exists.Have again, the pollution problem that the formulation of standard also fails also can not fundamentally solve phosphogypsum stacked by phosphogypsum, we can not allow its unlimited accumulation go down, we should from the source of eliminating phosphogypsum accumulating amount, reduce it and pile up quantity, fundamentally solve the problem that its land occupation resource and " land, water and air " are polluted, therefore, we are while standard deposited by control industrial solid wastes, and the utilization that more center of gravity should be transferred to phosphogypsum comes up.
Existing phosphogypsum is mainly used in following several respects:
A, for Cement industry (cement setting retarder, producing sulfuric acid and jointly cement);
B, produce gypsum building material product (brushing gypsum, plastering gupsum, gypsum mortar, gesso, Thistle board, gypsum partition board, fibrous plaster, gypsum block, gypsum plaster, building standard brick, sintering energy-saving tile, non-burning brick and decoration acoustic absorption etc.);
C, production industrial chemicals or industrial filler (ammonium sulfate, potassium sulfate, thiocarbamide and calcium carbonate);
D, be used as improvement soil agent (being mainly used in alkaline soil);
E, as roadbed.
In the field of building material, the utilization ratio of phosphogypsum is always lower, for cement setting retarder, the practical efficiency of phosphogypsum is no more than 7%, namely the cement setting retarder of 1 ton only can utilize the phosphogypsum of 0.07 ton, due to the heavy metal that exists in it and related impurities, too much adds the serious performance affecting cement setting retarder, and cannot be used in general building field.Producing, the utilization ratio in industrial chemicals/filler and as the agent of improvement soil is then lower.Also be difficult to avoid pollution of waterhead problem in the application being used as roadbed.The conclusion of present situation be phosphogypsum effectively utilize field few and effective rate of utilization is very low.Therefore, the stacking problem of quick solution phosphogypsum, the problem widening phosphogypsum application is extremely urgent.
The problem that China runs into separately is not only in the accumulation of phosphogypsum, and have at least in the whole world more than 50 country the same with China, face identical problem, current, the phosphogypsum accumulating amount in the whole world has reached 6,000,000,000 tons, and annual growth by 1.1 hundred million ~ 1.5 hundred million tons.The problem that phosphogypsum is piled up throughout the year is never effectively solved, and the improvement of phosphogypsum has become the global huge problem faced.Problem and the huge economical load such as its environmental pollution caused, allowed more country that phosphogypsum comprehensive utilization is classified as key research projects.
No matter be domestic or external, phosphogypsum recycling situation is all unsatisfactory.The effective rate of utilization of whole world phosphogypsum is only about 4.5%, and the phosphogypsum that is whole world obtains fully utilizing every year only has 12.6Mt.The utilization ratio of developed country's phosphogypsums such as Japan, Korea S and Germany is relative higher.For Japan, owing to lacking plaster of paris resource in Japan, phosphogypsum effective rate of utilization reaches more than 90%, and wherein about 75% for the production of gesso and plasterboard.The utilization ratio of other under-developed country's phosphogypsums is relatively very low, generally directly to discharge (abandoning).
To the end of the year 2011, China is accumulative will have piled up more than 300,000,000 tons of phosphogypsums.And the effective rate of utilization of Chinese phosphogypsum is less than 10%, the target reaching 60% apart from national Eleventh Five-Year Plan percentage of industrial solid waste that is comprehensively utilized still has larger gap.Be mainly used in the aspects such as building material made, soil improvement agent, cement setting retarder, industrial chemicals.
2013, National Development and Reform Committee was the target that the comprehensive utilization of phosphogypsum proposes that comprehensive utilization ratio in 2015 reaches 30%; In " industry by-product gypsum comprehensive utilization instruction ", the Ministry of Industry and Information Technology then proposed for the end of the year 2015, and phosphogypsum comprehensive utilization ratio brings up to 40% by current 20%.
Therefore, the utilization ratio problem that a kind of new solution effectively can solve phosphogypsum is proposed, very necessary.
[summary of the invention]
For overcoming current phosphogypsum land occupation resource, the problems such as seriously polluted and utilization ratio is low, the invention provides a kind of phosphogypsum composite material and its manufacture method, thus improve phosphogypsum utilization ratio, fundamentally solve phosphogypsum land occupation resource, with serious pollution problem.
The technical scheme that the present invention solves the problems of the technologies described above is: provide a kind of phosphogypsum composite material, and this matrix material comprises a sheet substrate layer, and this substrate layer is made up of inorganic component modified ardealite and organic constituent polyethylene.
Preferably, this substrate layer is by following weight proportion: modified ardealite 10-85 part, polyethylene 15-90 part.
Preferably, this phosphogypsum film comprises a coating layer further, and the coating of this coating layer is formed on substrate layer.
Preferably, the thickness of substrate layer is 0.02-2mm.
Preferably, the order number of modified ardealite is 800-2000.
Preferably, coating layer weight proportion is as follows: poly(lactic acid)/18-24 part; Zinc sulfide white/18-24 part; Deionized water/42-48 part; Ammoniacal liquor/2-2.5 part; Static inhibitor/0.2-0.24 part.
Preferably, the ratio of phosphogypsum composite material machine direction tensile strength and cross direction tensile strength is 1.12:1 to 1:1.15, and the ratio of its machine direction tear and cross direction tear strength is 1:1.05 to 1:1.18.
Preferably, in substrate layer, modified ardealite and poly proportioning are 35-75:30-35.
The another technical scheme that the present invention solves the problems of the technologies described above is: a kind of making method of phosphogypsum composite material, and this phosphogypsum composite material comprises a substrate layer, and the making method of this phosphogypsum composite material comprises the following steps: 1). prepare a substrate layer; It comprises S1. and prepares modified ardealite: be transported to by industrial residue phosphogypsum on high temperature stove, toasts 5-25min to obtain the modified ardealite of stable in properties under the condition of 150-250 DEG C; S2. be 800-2000 order powder by modified ardealite milled processed; S3. inorganic component modified ardealite and organic constituent polyethylene are stirred; compound is sent in Banbury mixer again after carrying out banburying synthesis process and carry out granulation by banburying synthetic material feeding tablets press; particle granulation formed is sent in rolling press and is extruded; finally adopted by extruded stock drawing machine to carry out stretch processing, obtain the roughening treatment that thickness is 0.02-2mm substrate layer and S4. substrate layer.
Preferably, the making method of this phosphogypsum composite material comprises the following steps: 2). prepare a coating layer; It comprises with step: loaded by deionized water in container, poly(lactic acid) is heated to 40-60 DEG C and dissolves in deionized water; Once in the deionized water being dissolved with poly(lactic acid), add ammoniacal liquor and zinc sulfide white, add static inhibitor after stirring and make coating medium; The single or double more obtained coating medium being coated substrate layer forms coating layer.
Compared with prior art, the phosphogypsum composite material that inventing provides adopts modified ardealite to be made, because this phosphogypsum composite material has waterproof fireproofing, antifog, grease proofing, insect protected and resistance toly to tear, folding, the advantage such as printable, its use range is very wide, traditional paper and polymer thin film can be substituted, in phosphogypsum composite material provided by the invention makes, modified ardealite can reach the proportion of 85%, in the production process of that is 100 tons of films, the modified ardealite up to 85 tons can be used, in only paper annual production just more than China of 100,000,000 tons, use this phosphogypsum composite material to substitute traditional paper both the phosphogypsum stacked in a large number to be disposed within several years, traditional paper can be avoided again to fall trees in process of production brought various environmental problems.The polyethylene that existing film uses polyreaction to produce usually is made, and relative to traditional film, and phosphogypsum composite material composition of the present invention is mainly phosphogypsum, greatly reduces poly usage ratio like this, has saved industrial cost.Phosphogypsum is the solid slag produced in Industrial processes, use it as the raw material making phosphogypsum composite material, be turn waste into wealth, the present invention can solve whole world phosphogypsum faced for a long time and pile up and the problem utilized, and the production of phosphogypsum composite material fundamentally can solve the accumulation problem of phosphogypsum.
[embodiment]
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
First embodiment of the invention phosphogypsum composite material comprises a substrate layer, and this substrate layer is sheet structure, and its thickness is at 0.02-2mm.This substrate layer is made up of inorganic component and organic constituent proportioning, the proportioning of inorganic component and organic constituent is 10-85:15-90, and wherein inorganic component is the modified ardealite that industrial residue phosphogypsum modification obtains, and organic constituent is polyethylene, therefore the weight proportion of phosphogypsum composite material is as follows:
Modified ardealite 10-85 part
Polyethylene 15-90 part
The order number of this modified ardealite is at 800-2000, and the main component of modified ardealite more than 95% is calcium sulfate and calcium carbonate, and wherein the proportioning of calcium sulfate and calcium carbonate is 1:1 to 1:5.
Best, in substrate layer, modified ardealite and poly proportioning are 60-85:30-40, when meeting this proportioning, substrate layer can form the sheet phosphogypsum composite material that has certain toughness, its tensile strength is up to 4 × 10-2N/m, wherein the ratio of machine direction tensile strength and cross direction tensile strength is 1.12:1 to 1:1.15, and the ratio of its machine direction tear and cross direction tear strength is 1:1.05 to 1:1.18.Especially, in substrate layer, modified ardealite and poly proportioning are 68-75:30-35, and now, phosphogypsum composite bed has best tensile strength and tear strength.
The substrate layer of phosphogypsum composite material of the present invention can form coating layer by single or double coating composition as required, and the weight proportion of this coating is as follows:
In the present embodiment, the preparation method of phosphogypsum composite material is as follows:
1). prepare phosphogypsum substrate layer
1. prepare modified ardealite: be transported to by industrial residue phosphogypsum on high temperature stove, by high temperature stove, phosphogypsum is dried, be under the condition of 150-250 DEG C again in temperature by the phosphogypsum after oven dry, high temperature stove carries out baking 5-25min, impurity in phosphogypsum is removed in the mode of baking, to obtain the modified ardealite of stable in properties;
2. grind modified ardealite: used by modified ardealite shredder to carry out milled processed, make the granularity of modified ardealite be 800-2000 order;
3. prepare substrate layer: mixed with organic constituent polyethylene by inorganic component modified ardealite; and stir; compound is sent in Banbury mixer again after carrying out banburying synthesis process and carry out granulation by banburying synthetic material feeding tablets press; particle granulation formed is sent in rolling press and is extruded; finally adopted by extruded stock drawing machine to carry out stretch processing, obtaining thickness is 0.02-2mm substrate layer.
4. the roughening treatment of substrate layer: carry out corona treatment to the substrate layer made, makes the surface of substrate layer have certain roughness, makes the surface of substrate layer have good tack;
The substrate layer of phosphogypsum composite material of the present invention can form coating layer by single or double coating composition as required, and the technique of making of coating layer comprises further on above-mentioned basis of preparing substrate layer:
2). the coating of substrate layer
Deionized water is loaded in container, poly(lactic acid) is heated to 40-60 DEG C and dissolves in deionized water; Once in the deionized water being dissolved with poly(lactic acid), add ammoniacal liquor and zinc sulfide white, add static inhibitor after stirring and make coating medium; Again obtained coating medium is coated on substrate layer and form coating layer.
The making of phosphogypsum composite material all completes, this phosphogypsum composite material made is applicable to doing the products such as various packing bag, wrapping paper, shopping bag, handbag, it has the advantages such as waterproof, fire prevention, antifog, grease proofing, insect protected, and have in physical property resistance toly to tear, folding resistance.This film can be used for printing, its blotting jail, ink-jet printing can not be etched, also waterproof, reason is that it is made up of nano level modified ardealite, makes without fiber, after ink-jet printing, sharpness is up to arriving 2880dpi tolerance range, coating layer/film can not be covered in its surface, therefore with ink, chemical action can not occur, and causes colour cast, decolouring phenomenon.
Compared with prior art, phosphogypsum composite material provided by the invention adopts modified ardealite to be made, because this phosphogypsum composite material has waterproof fireproofing, antifog, grease proofing, insect protected and resistance toly to tear, folding, the advantage such as printable, its use range is very wide, traditional paper and polymer thin film can be substituted, in phosphogypsum composite material provided by the invention makes, modified ardealite can reach the proportion of 85%, in the production process of that is 100 tons of films, the modified ardealite up to 85 tons can be used, in only paper annual production just more than China of 100,000,000 tons, use this phosphogypsum composite material to substitute traditional paper the phosphogypsum stacked in a large number can be realized to dispose within several years, it can avoid traditional paper to fall trees in process of production brought various environmental problems.The polyethylene that existing film uses polyreaction to produce usually is made, and relative to traditional film, and phosphogypsum composite material composition of the present invention is mainly phosphogypsum, greatly reduces poly usage ratio like this, has saved industrial cost.Phosphogypsum is the solid slag produced in Industrial processes, use it as the raw material making phosphogypsum composite material, be turn waste into wealth, the present invention can solve whole world phosphogypsum faced for a long time and pile up and the problem utilized, and the production of phosphogypsum composite material fundamentally can solve the accumulation problem of phosphogypsum.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within principle of the present invention, equivalent replacement and improvement etc. all should be included within protection scope of the present invention.
Claims (10)
1. a phosphogypsum composite material, this matrix material comprises a sheet substrate layer, it is characterized in that: this substrate layer is made up of inorganic component modified ardealite and organic constituent polyethylene.
2. phosphogypsum composite material as claimed in claim 1, is characterized in that: this substrate layer is by following weight proportion:
Modified ardealite 10-85 part
Polyethylene 15-90 part.
3. phosphogypsum composite material as claimed in claim 1, is characterized in that: comprise a coating layer further, and the coating of this coating layer is formed on substrate layer.
4. phosphogypsum composite material as claimed in claim 1, is characterized in that: the thickness of substrate layer is 0.02-2mm.
5. phosphogypsum composite material as claimed in claim 1, is characterized in that: the order number of modified ardealite is 800-2000.
6. phosphogypsum composite material as claimed in claim 3, is characterized in that: coating layer weight proportion is as follows:
7. phosphogypsum composite material as claimed in claim 1, it is characterized in that: the ratio of phosphogypsum composite material machine direction tensile strength and cross direction tensile strength is 1.12:1 to 1:1.15, the ratio of its machine direction tear and cross direction tear strength is 1:1.05 to 1:1.18.
8. phosphogypsum composite material as claimed in claim 1, is characterized in that: in substrate layer, modified ardealite and poly proportioning are 68-70:30-32.
9. a manufacture method for phosphogypsum composite material, this phosphogypsum composite material comprises a substrate layer, it is characterized in that: the making method of this phosphogypsum composite material comprises the following steps:
S1. prepare modified ardealite: be transported to by industrial residue phosphogypsum on high temperature stove, under the condition of 150-250 DEG C, toast 5-25min to obtain the modified ardealite of stable in properties;
S2. be 800-2000 order powder by modified ardealite milled processed;
S3. inorganic component modified ardealite and organic constituent polyethylene are stirred, compound is sent in Banbury mixer again after carrying out banburying synthesis process and carry out granulation by banburying synthetic material feeding tablets press, particle granulation formed is sent in rolling press and is extruded, finally adopted by extruded stock drawing machine to carry out stretch processing, obtaining thickness is 0.03-2mm substrate layer; And
S4. the roughening treatment of substrate layer.
10. the manufacture method of phosphogypsum composite material as claimed in claim 9, is characterized in that: the application step comprising substrate layer further: loaded by deionized water in container, poly(lactic acid) is heated to 40-60 DEG C and dissolves in deionized water; Once in the deionized water being dissolved with poly(lactic acid), add ammoniacal liquor and zinc sulfide white, add static inhibitor after stirring and make coating medium; The single or double more obtained coating medium being coated substrate layer forms coating layer.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109680574A (en) * | 2019-02-18 | 2019-04-26 | 胡瑾 | Modified ardealite roadbed |
| CN112063124A (en) * | 2020-07-21 | 2020-12-11 | 贵州大学 | Biodegradable polyester polymer/phosphogypsum composite material with high filling, low cost and controllable biodegradation and preparation method thereof |
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| CN112063124A (en) * | 2020-07-21 | 2020-12-11 | 贵州大学 | Biodegradable polyester polymer/phosphogypsum composite material with high filling, low cost and controllable biodegradation and preparation method thereof |
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Application publication date: 20160427 |