CN110903045A - Industrial waste residue natural stone imitation paste and preparation method and application thereof - Google Patents
Industrial waste residue natural stone imitation paste and preparation method and application thereof Download PDFInfo
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- CN110903045A CN110903045A CN201911250141.8A CN201911250141A CN110903045A CN 110903045 A CN110903045 A CN 110903045A CN 201911250141 A CN201911250141 A CN 201911250141A CN 110903045 A CN110903045 A CN 110903045A
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- waste residue
- gypsum
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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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides an industrial waste residue natural-imitated gypsum, a preparation method and application thereof, and belongs to the technical field of building materials. The preparation raw materials of the industrial waste residue imitating natural gypsum provided by the invention comprise fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue. The method takes the manganese sulfate waste residue, the sodium sulfate waste residue and other industrial waste residues as raw materials, has wide raw material sources, greatly improves the resource utilization rate of the industrial waste residues, reduces a large amount of resources occupied by landfill of the industrial waste residues, has low cost and does not generate secondary pollution; the manganese sulfate waste residue and the fluorgypsum are matched for use, so that the cost for treating high external moisture of the manganese sulfate waste residue is obviously reduced; the sodium sulfate in the sodium sulfate waste residue is used as an additive, so that the crystallization speed of the fluorgypsum is increased, and all technical indexes of the obtained industrial waste residue imitating natural gypsum reach the national standard value of natural gypsum for cement.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to an industrial waste residue natural-imitated gypsum and a preparation method and application thereof.
Background
Fluorgypsum is a major byproduct of hydrofluoric acid and sodium fluoroaluminate production processes, and is mainly derived from inorganic fluoride, organic fluoride and hydrofluoric acid production processes, and about 3.6 tons of anhydrous fluorgypsum are produced per ton of hydrofluoric acid produced. The main component of the fluorgypsum is calcium sulfate, and the fluorgypsum contains partial calcium fluoride and other fluoride, H2SO4High content of fluorine to be dischargedThe gypsum is acidic and belongs to strong corrosive toxic and harmful wastes, and untreated fluorgypsum cannot be directly discarded and is difficult to be utilized. At present, the utilization rate of the fluorgypsum is low, most of the fluorgypsum is stockpiled as solid waste, not only occupies the land, but also harmful substances in the fluorgypsum pollute the water body and threaten the natural environment.
Manganese sulfate is an important chemical product, and can be widely applied to industrial and agricultural production. The fertilizer is an important microelement fertilizer in agriculture, is a catalyst for synthesizing the chlorophyll by plants, and can ensure that various economic crops grow well and increase the yield by spraying manganese sulfate; it can also be used as feed additive. The manganese sulfate is used for producing and preparing various manganese salts in the inorganic industry, and is used for producing a drier, linseed oil manganese sulfate and the like in the coating industry. The main production process of manganese sulfate is a pyrolusite method, and the flow is as follows: ore dressing, reduction roasting, cooling, acidolysis, filter pressing, filtering, concentration crystallization, separation and drying, wherein manganese sulfate waste residues are generated in the filter pressing and filtering processes, namely residues left after the processed manganese ore powder is dissolved by sulfuric acid. The manganese sulfate waste residue contains a large number of heavy metals, and particularly the total manganese content is up to 15.83 wt%. Under the long-term weathering leaching action of a large amount of manganese sulfate waste residues, heavy metal elements such as manganese and the like are migrated and released to surrounding soil, earth surface and underground water, and the absorption of manganese and compounds thereof by a human body can cause chronic poisoning and generate central nervous system symptoms. At present, manganese sulfate waste residue is mainly treated by landfill, which not only occupies a large amount of land resources, but also causes the waste of a large amount of manganese resources. Therefore, how to realize the comprehensive utilization of industrial waste residue resources such as fluorgypsum, manganese sulfate waste residue and the like is a very urgent problem.
The crystal water, the external moisture and the sulfur trioxide in the gypsum used for cement production are main quality indexes, if no crystal water exists in the gypsum, the use performance of the cement is influenced, the unstable sulfur trioxide seriously influences the quality of the cement, and after the external moisture content exceeds 10 wt%, the cement cannot be normally produced. The content of sulfur trioxide in the manganese sulfate waste residue is 25-30 wt%, and the sulfur trioxide is unstable; a water of crystallization content of about 15 wt%, an external moisture content of about 40 wt%; the content of sulfur trioxide in the fluorgypsum reaches 53 percent, and the fluorgypsum does not contain crystal water. Therefore, manganese sulfate waste and fluorgypsum cannot be directly applied to the preparation of gypsum for cement. The existing method for reducing the high-content external moisture of the manganese sulfate waste residue is to reduce the external moisture content to about 18 wt% by drying with heat energy, and the cost is about 40 yuan/ton. The existing disposal method has high cost and can not solve the problems of unstable sulfur trioxide, ultrahigh water content and the like in the manganese sulfate waste residue.
Disclosure of Invention
In view of the above, the invention aims to provide the industrial waste residue natural imitating gypsum and the preparation method and the application thereof, all technical indexes of the industrial waste residue natural imitating gypsum provided by the invention reach the national standard value of natural gypsum for cement, and the industrial waste residue is used as a raw material, so that the resource utilization rate is greatly improved.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an industrial waste residue natural-imitating gypsum, and the preparation raw materials comprise fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue.
Preferably, the content of sulfur trioxide in the industrial waste residue imitated natural gypsum is more than or equal to 35 wt%, the content of crystal water is more than or equal to 10 wt%, and the content of external moisture is less than 10 wt%.
Preferably, the granularity of the industrial waste residue imitating natural gypsum is 20-80 mm.
Preferably, the mass ratio of the fluorgypsum to the manganese sulfate waste residue to the sodium sulfate waste residue is 1: (1-4): (0.2-0.8).
Preferably, the content of sulfur trioxide in the manganese sulfate waste residue is 25-30 wt%, the content of crystal water is 8-10 wt%, and the content of external water is 8-10 wt%.
Preferably, the sodium content in the sodium sulfate waste residue is 4-6 wt%.
The invention provides a preparation method of the industrial waste residue imitated natural gypsum, which comprises the following steps:
mixing fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue, and carrying out industrial crystallization reaction to obtain industrial waste residue natural-imitated gypsum;
the temperature of the industrial crystallization reaction is <65 ℃.
Preferably, the industrial crystallization reaction is carried out under stirring conditions; the temperature of the industrial crystallization reaction is 50-60 ℃, and the time is 4-6 days.
Preferably, the industrial crystallization reaction is completed, and then the obtained gypsum crude product is crushed, so that the industrial waste residue is imitated natural gypsum.
The invention also provides application of the industrial waste residue natural-imitated gypsum prepared by the technical scheme or the industrial waste residue natural-imitated gypsum prepared by the preparation method in the technical scheme in preparation of cement.
The invention provides an industrial waste residue natural-imitating gypsum, and the preparation raw materials comprise fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue. The method takes the manganese sulfate waste residue, the sodium sulfate waste residue and other industrial waste residues as raw materials, has wide raw material sources, greatly improves the resource utilization rate of the industrial waste residues, reduces a large amount of resources occupied by landfill of the industrial waste residues, has low cost and does not generate secondary pollution; the manganese sulfate waste residue and the fluorgypsum are matched for use, so that the cost of reducing the high-content external moisture contained in the manganese sulfate waste residue to meet the external moisture content of the gypsum during treatment is obviously reduced; the sodium sulfate in the sodium sulfate waste residue is used as an additive, so that the crystallization speed of the fluorgypsum is increased, and all technical indexes of the obtained industrial waste residue imitating natural gypsum reach the national standard value of natural gypsum for cement. As shown in the results of the examples, the industrial waste residue imitating the natural gypsum prepared by the invention has the advantages of 35-38 wt% of sulfur trioxide, 10 wt% of crystal water and 9 wt% of external moisture, and has good economic and social benefits.
The preparation method provided by the invention is simple to operate and suitable for large-scale production.
Detailed Description
The invention provides an industrial waste residue natural-imitating gypsum, and the preparation raw materials comprise fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue.
In the invention, the content of sulfur trioxide in the manganese sulfate waste residue is preferably 25-30 wt%, and more preferably 28-30 wt%; the content of crystal water is preferably 10 wt%, more preferably 15 wt%; the external moisture content is preferably 40 wt%, more preferably 40 wt%. In the invention, the manganese sulfate waste residue is preferably electrolytic manganese sulfate waste residue. The granularity of the manganese sulfate waste residue is not particularly limited, and the granularity of the manganese sulfate waste residue known in the field can be adopted, and is specifically 10-20 mm.
In the invention, the granularity of the industrial waste residue natural imitating gypsum is preferably 20-80 mm, more preferably 40-80 mm, and most preferably 40-50 mm, and the granularity of the industrial waste residue natural imitating gypsum is controlled within the range, so that the industrial waste residue natural imitating gypsum can be fully and uniformly dispersed with other raw materials in the cement production process, and the use performance of cement can be improved.
In the invention, the content of sodium in the sodium sulfate waste residue is preferably 4-6 wt%, and more preferably 5 wt%. The source of the sodium sulfate waste residue is not particularly limited, and the sodium sulfate waste residue known in the field can be adopted.
In the invention, the content of sulfur trioxide in the fluorgypsum is preferably 50-55 wt%, and more preferably 53 wt%; the water of crystallization content is preferably 0 wt.%; no external moisture is contained. In the present invention, the source of the fluorgypsum is preferably a by-product of the preparation of hydrogen fluoride from sulfuric acid and fluorspar.
In the invention, the mass ratio of the fluorgypsum to the manganese sulfate waste residue to the sodium sulfate waste residue is preferably 1: (1-4): (0.2 to 0.8), more preferably 1: (1.2-3.5): (0.25-0.7).
In the invention, the content of sulfur trioxide in the industrial waste residue imitated natural gypsum is preferably more than or equal to 35 wt%, and more preferably 35-38 wt%; the crystal water content is preferably 10 wt.% or more, more preferably 10 wt.%; the external moisture content is preferably <10 wt.%, more preferably 9 wt.%.
The invention provides a preparation method of the industrial waste residue imitated natural gypsum, which comprises the following steps:
mixing fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue, and carrying out industrial crystallization reaction to obtain industrial waste residue natural-imitated gypsum;
the temperature of the industrial crystallization reaction is <65 ℃.
In the invention, the temperature of the industrial crystallization reaction is less than 65 ℃, more preferably 50-60 ℃, and most preferably 55-60 ℃. The invention controls the temperature of industrial crystallization reaction below 65 ℃, and can effectively control and prevent the crystal water from being converted into external moisture. In the invention, in the industrial crystallization reaction process, the fluorgypsum generates a crystallization reaction under the excitation of sodium sulfate, so that the external moisture is reduced and the crystal water is increased. The time of the industrial crystallization reaction is not particularly limited, and the external moisture content of the obtained industrial waste residue imitating natural gypsum can be ensured to meet the national standard (<10 wt%), specifically 4-6 days. In the present invention, the industrial crystallization reaction is preferably carried out under stirring conditions, and the stirring speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used.
After the industrial crystallization reaction is completed, the invention preferably further comprises crushing the obtained gypsum crude product to obtain the industrial waste residue imitated natural gypsum. The crushing mode is not particularly limited, and the grain size of the obtained natural gypsum imitation can meet the grain size requirement.
The preparation method provided by the invention is simple to operate and suitable for industrial production; the raw materials are wide in source and low in cost, and meanwhile, a large amount of land resources occupied by manganese sulfate waste residues and sodium sulfate waste residues are avoided being buried, and secondary pollution is avoided; the prepared industrial waste residue imitates natural gypsum, and each technical index meets the relevant national standard.
The invention also provides application of the industrial waste residue natural-imitated gypsum prepared by the technical scheme or the industrial waste residue natural-imitated gypsum prepared by the preparation method in the technical scheme in preparation of cement.
If the gypsum used for producing cement contains no crystal water, the service performance of the cement is affected; the unstable sulfur trioxide can seriously affect the quality of cement; and the cement cannot be normally produced if the external moisture content exceeds 10 wt%. The contents of sulfur trioxide, crystallized water and external water in the industrial waste residue imitation natural gypsum prepared by the invention meet the national standard value of the technical index of natural gypsum for cement, and the industrial waste residue imitation natural gypsum can be used for preparing cement.
The technical solution of the present invention will be clearly and completely described in the following with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
Uniformly stirring and mixing the fluorgypsum, the manganese sulfate waste residue and the sodium sulfate waste residue according to the mass ratio of 4:5:1, reacting at 60 ℃ until the external water content meets the national standard (<10 wt%), wherein the reaction time is 5 days, and crushing the obtained crude gypsum into particles (the particle size is 50mm), so as to obtain the industrial waste residue natural-imitated gypsum.
Example 2
Uniformly stirring and mixing the fluorgypsum, the manganese sulfate waste residue and the sodium sulfate waste residue according to the mass ratio of 2:7:1, reacting at 60 ℃ until the external water content meets the national standard (<10 wt%), wherein the reaction time is 5 days, and crushing the obtained crude gypsum into particles (the particle size is 40mm) to obtain the industrial waste residue natural-imitated gypsum.
Example 3
Uniformly stirring and mixing the fluorgypsum, the manganese sulfate waste residue and the sodium sulfate waste residue according to the mass ratio of 3:6:2, reacting at 60 ℃ until the external water content meets the national standard (<10 wt%), wherein the reaction time is 5 days, and crushing the obtained crude gypsum into particles (the particle size is 60mm) to obtain the industrial waste residue natural-imitated gypsum.
Comparative example 1
Uniformly stirring and mixing the fluorgypsum and the manganese sulfate waste residue according to the mass ratio of 4:6, reacting at 60 ℃ until the external water content meets the national standard (<10 wt%), wherein the reaction time is 80 days, and crushing the obtained crude gypsum into particles (the particle size is 50mm) to obtain the industrial waste residue natural-imitated gypsum.
Comparative example 2
Uniformly stirring and mixing the fluorgypsum and the sodium sulfate waste residue according to the mass ratio of 4:6, reacting at 60 ℃ until the external water content meets the national standard (<10 wt%), wherein the reaction time is 8 days, and crushing the obtained crude gypsum into particles (the particle size is 50mm) to obtain the industrial waste residue natural imitating gypsum.
Test example
The testing temperature of the external moisture content of the industrial waste residue imitating the natural gypsum is 60 ℃; the contents of crystal water and sulfur trioxide were tested at 90 ℃.
TABLE 1 test results of properties of natural-like gypsum from industrial waste
As can be seen from Table 1, the addition of the sodium sulfate waste residue greatly saves the industrial crystallization reaction time, can greatly improve the production efficiency of preparing the industrial waste residue natural-like gypsum by using the industrial waste residue as a raw material, and reduces the energy consumption and time in the production process; after the temperature is controlled below 60 ℃, the crystal water can be effectively prevented from being converted into external moisture, the sulfur trioxide can be obtained by more than 35 wt%, the crystal water is more than 10 wt%, and the external moisture is less than 10 wt%, so that good economic benefit and social benefit are brought.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The natural-imitated gypsum is characterized in that preparation raw materials comprise fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue.
2. The natural-like gypsum produced from industrial waste residues as claimed in claim 1, wherein the content of sulfur trioxide in the natural-like gypsum produced from industrial waste residues is greater than or equal to 35 wt%, the content of crystal water is greater than or equal to 10 wt%, and the content of external moisture is less than 10 wt%.
3. The industrial waste residue natural imitating gypsum according to claim 1 or 2, wherein the granularity of the industrial waste residue natural imitating gypsum is 20-80 mm.
4. The natural-like gypsum produced from industrial waste residues as claimed in claim 1 or 2, wherein the mass ratio of the fluorgypsum to the manganese sulfate waste residues to the sodium sulfate waste residues is 1: (1-4): (0.2-0.8).
5. The industrial waste residue natural imitation gypsum according to claim 4, wherein the content of sulfur trioxide in the manganese sulfate waste residue is 25-30 wt%, the content of crystal water is 8-10 wt%, and the content of external moisture is 8-10 wt%.
6. The natural-like gypsum produced from industrial waste residues as claimed in claim 4, wherein the sodium content in the sodium sulfate waste residues is 4-6 wt%.
7. The method for preparing the natural stone-like plaster by using the industrial waste residue as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
mixing fluorgypsum, manganese sulfate waste residue and sodium sulfate waste residue, and carrying out industrial crystallization reaction to obtain industrial waste residue natural-imitated gypsum;
the temperature of the industrial crystallization reaction is <65 ℃.
8. The method according to claim 7, wherein the industrial crystallization reaction is carried out under stirring conditions; the time of the industrial crystallization reaction is 4-6 days.
9. The preparation method of claim 7, wherein the industrial crystallization reaction is completed, and the method further comprises crushing the obtained crude gypsum to obtain industrial waste residue imitating natural gypsum.
10. Use of the industrial waste residue imitated natural gypsum as defined in any one of claims 1 to 6 or the industrial waste residue imitated natural gypsum prepared by the preparation method as defined in any one of claims 7 to 9 in preparation of cement.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN111875269A (en) * | 2020-08-11 | 2020-11-03 | 汪文杰 | Calcium sulfate gypsum and preparation method thereof |
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CN101870494A (en) * | 2010-06-12 | 2010-10-27 | 上海大学 | Method for recrystallizing and purifying desulphurized gypsum |
CN103030180A (en) * | 2012-12-07 | 2013-04-10 | 中信大锰矿业有限责任公司 | Production method of high-purity manganese sulfate |
CN107352824A (en) * | 2017-08-22 | 2017-11-17 | 衡阳市仁义环保建材有限公司 | A kind of commercial synthesis sulphur gypsum and preparation method thereof |
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2019
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WO2006004561A1 (en) * | 2004-06-30 | 2006-01-12 | Krka, Tovarna Zdravil, D.D., Novo Mesto | Process for the preparation of gatifloxacin and regeneration of degradation products |
CN101870494A (en) * | 2010-06-12 | 2010-10-27 | 上海大学 | Method for recrystallizing and purifying desulphurized gypsum |
CN103030180A (en) * | 2012-12-07 | 2013-04-10 | 中信大锰矿业有限责任公司 | Production method of high-purity manganese sulfate |
CN107352824A (en) * | 2017-08-22 | 2017-11-17 | 衡阳市仁义环保建材有限公司 | A kind of commercial synthesis sulphur gypsum and preparation method thereof |
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