CN108821309B - Method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide from industrial waste liquid - Google Patents

Method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide from industrial waste liquid Download PDF

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CN108821309B
CN108821309B CN201811030838.XA CN201811030838A CN108821309B CN 108821309 B CN108821309 B CN 108821309B CN 201811030838 A CN201811030838 A CN 201811030838A CN 108821309 B CN108821309 B CN 108821309B
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filter cake
ammonium nitrate
filtrate
waste liquid
product
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CN108821309A (en
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宋雪雪
李丽娟
聂锋
宋富根
时东
姬连敏
刘志启
曾忠民
彭小五
张利诚
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Qinghai Institute of Salt Lakes Research of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/18—Nitrates of ammonium
    • C01C1/185—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/14—Magnesium hydroxide
    • C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
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Abstract

The invention provides a method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by using industrial waste liquid, which adopts a reasonable process path and takes the industrial waste liquid as a raw material to recover more than 95 percent of ammonium nitrate and more than 95 percent of magnesium hydroxide, thereby realizing the purposes of changing waste into valuable, reducing pollution and improving efficiency, reducing production cost for production enterprises, greatly reducing the discharge amount of waste water, enabling the enterprises to more easily meet the environmental protection requirement and realizing the purposes of energy conservation and emission reduction for the enterprises. Meanwhile, the ammonium nitrate product and the hexagonal flaky magnesium hydroxide product which are co-produced and prepared by the method have regular shapes and good dispersibility, and have good market application prospects.

Description

Method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide from industrial waste liquid
Technical Field
The invention belongs to the technical field of industrial waste liquid treatment, and particularly relates to a method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by using industrial waste liquid.
Background
Chemistry has permeated into the aspects of human life, relates to various fields, has complex and various chemical components, is a substance which pollutes the environment and is harmful to human bodies, and if the waste liquid generated in the production process is discharged into a living area, the life of the human bodies can be threatened, thus bringing harm to the human bodies and the environment; some production waste liquid has certain economic value, in order to improve the comprehensive utilization rate of resources and strive to realize clean production, certain measures are taken to purify the waste liquid and recycle useful components before the waste liquid is discharged, and the environmental protection and the effective utilization of resources can be realized.
At present, domestic enterprises can generate various production waste liquids in the process of developing phosphorite, wherein one waste liquid basically comprises the following components: 4 mol/L-7 mol/L NH4 +、0.4mol/L～1mol/L Mg2+、5mol/L～10mol/LNO3 -And a small amount of Ca2+、Na+、K+、SO4 2-、PO4 3-、F-、SiO3 2-And other ions. It can be seen that the waste liquid contains a large amount of NH4 +And Mg2+If the waste liquid can be recycled, the pollution of the waste liquid can be reduced, and the resource utilization rate can be improved.
Ammonium nitrate is a substance which is widely available, has low detonation properties, is smokeless or smokeless during combustion, has wide application, can be used as a fertilizer, an analytical reagent, an oxidant, a pesticide, a refrigerant, and can be used for producing laughing gas, fireworks, explosives and the like. Ammonium nitrate is produced by two methods, namely a conversion method and a neutralization method. The conversion method is to utilize the byproduct calcium nitrate tetrahydrate in the production process of the nitrophosphate fertilizer as a raw material to react with an ammonium carbonate solution to generate ammonium nitrate and calcium carbonate precipitates, and the ammonium nitrate and the calcium carbonate precipitates are filtered to obtain a filtrate which is processed into an ammonium nitrate product or returned to the nitrophosphate fertilizer production system. The neutralization reaction of the neutralization method may be carried out under normal pressure, pressure or vacuum. In the industry, nitric acid with the concentration of 50-60% and ammonia are mostly used for neutralizing under the pressurizing condition of 0.4-0.5 MPa to obtain ammonium nitrate solution with the concentration of 80-87%, then the ammonium nitrate solution is concentrated to 95-99% by a vacuum evaporation or falling film evaporation method, and finally granulation is carried out by different methods.
Magnesium hydroxide is taken as a novel high-efficiency, superior and environment-friendly additive inorganic flame retardant, and is increasingly emphasized at home and abroad, so that the magnesium hydroxide is greatly developed in the field of inorganic flame retardants. The flame retardant, smoke abatement, drip resistance, filling and other multiple functions are widely applied to the polymer material industry. With the continuous progress of society, the requirements of people on new materials are continuously improved, the quality index of magnesium hydroxide products not only stays at the original product purity, but also puts higher requirements on the product form and the particle size distribution. Mg (OH)2The production process of the magnesium hydroxide is various, the precipitation method is the main method for producing the magnesium hydroxide at present, and the methods for preparing the magnesium hydroxide by the precipitation method reported at present mainly comprise a direct precipitation method, a hydrothermal reaction method, a uniform precipitation method, a reversed-phase precipitation method, a homogeneous fluid method and the like. Because magnesium hydroxide with special morphology and uniform particle size distribution shows excellent performance in the application field, the research content at present mostly focuses on the ultra-fining of particles and the preparation of magnesium hydroxide with special morphology.
Most of the ammonium nitrate and the magnesium hydroxide are prepared by the method, so that if the waste liquid generated in the process of developing the phosphorite to be discharged can be recycled, the comprehensive utilization rate of resources is improved, the harm to the environment is reduced, a preparation path of the ammonium nitrate and/or the magnesium hydroxide is provided, and the preparation cost is reduced.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by using industrial waste liquid, which takes the industrial waste liquid as a raw material, and can recover more than 95% of ammonium nitrate and more than 95% of magnesium hydroxide by process design, thereby realizing the purposes of changing waste into valuable, reducing pollution and improving efficiency.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by using industrial waste liquid comprises the following steps:
s1, evaporating and concentrating the industrial waste liquid at 50-90 ℃ for 1-10 h, and coolingCrystallizing and filtering to obtain a first filter cake and a first filtrate; wherein, in the industrial waste liquid, NH4 +Has a concentration of 4mol/L to 7mol/L, Mg2+The concentration of (A) is 0.4mol/L to 1mol/L, NO3 -The concentration of (A) is 5-10 mol/L;
s2, preparing an ammonium nitrate product, comprising the following steps:
s21, placing the first filter cake into a prepared ammonium nitrate saturated solution, dispersing, washing and filtering to obtain a second filter cake;
s22, dissolving the second filter cake in deionized water according to the mass ratio of 1.5: 1-2.5: 1 at room temperature to obtain an ammonium nitrate solution; wherein the mass percent of water in the ammonium nitrate solution is 29-40%;
s23, evaporating and concentrating the ammonium nitrate solution at 50-90 ℃ to remove 15-35% of water, cooling and crystallizing, and filtering to obtain a third filter cake;
s24, drying the third filter cake to obtain the ammonium nitrate product;
s3, preparing a hexagonal flaky magnesium hydroxide product, comprising the following steps:
s31, heating the first filtrate to 30-80 ℃ under the condition of stirring, adding 2-14 mol/L alkali liquor into the first filtrate at the feeding speed of 1-20 mL/min, and aging for 10-60 min to obtain a first suspension;
s32, filtering the first suspension to obtain a fourth filter cake;
s33, washing the fourth filter cake, dispersing the fourth filter cake in a hydrothermal medium, and carrying out hydrothermal reaction at the temperature of 120-200 ℃ for 1-48 h to obtain a second suspension;
s34, filtering the second suspension to obtain a fifth filter cake;
and S35, washing the fifth filter cake until no hydrothermal medium is carried, and drying to obtain the hexagonal flaky magnesium hydroxide product.
Further, in the step S1, the industrial waste liquid is derived from a production waste liquid generated when the phosphorus concentrate, the phosphoric acid and the salt thereof and/or the elemental phosphorus product are produced from the medium-low grade phosphorus ore.
Further, in the step S33, the hydrothermal medium is deionized water, or a sodium hydroxide solution or a potassium hydroxide solution having a concentration of not more than 6 mol/L.
Further, in the step S23, a third filtrate corresponding to the third filter cake is also obtained; the third filtrate is returned to the step S21 to replace the saturated solution of ammonium nitrate.
Further, in the step S21, a second filtrate corresponding to the second filter cake is also obtained; and returning the second filtrate to the step S1 to be evaporated and concentrated together with the industrial waste liquid.
Further, in the step S32, a fourth filtrate corresponding to the fourth filter cake is also obtained; and returning the fourth filtrate to the step S1 to be evaporated and concentrated together with the industrial waste liquid.
Further, in the step S34, a fifth filtrate corresponding to the fifth filter cake is also obtained; and returning the fifth filtrate to the step S33 to replace part of the hydrothermal medium, mixing the washed fourth filter cake and the hydrothermal medium, and performing hydrothermal reaction.
Further, in step S35, a washing liquid is also generated after washing the fifth filter cake to be free of the entrained hydrothermal medium; the washing liquid is used for preparing the hydrothermal medium.
Further, in the step S24, drying the third filter cake at 30-80 ℃ for 1-10 h to obtain the ammonium nitrate product; and/or, in the step S35, drying the washed fifth filter cake at 80-120 ℃ for 5-10 h to obtain the hexagonal flaky magnesium hydroxide product.
The invention realizes the purposes of changing waste into valuable, reducing pollution and improving efficiency by taking industrial waste liquid as a raw material and recycling more than 95 percent of ammonium nitrate and more than 95 percent of magnesium hydroxide through a reasonable process path, can reduce the production cost for production enterprises, greatly reduces the discharge amount of waste water, enables the enterprises to more easily meet the environmental protection requirement, and realizes the purposes of energy conservation and emission reduction for the enterprises. The ammonium nitrate product and the hexagonal flaky magnesium hydroxide product obtained by co-production are regular in shape and good in dispersity, and have good market application prospects.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a process flow diagram of a process for co-producing ammonium nitrate and hexagonal flake magnesium hydroxide from industrial waste streams in accordance with the present invention;
figure 2 is an XRD picture of a powdered ammonium nitrate product made in accordance with example 1 of the present invention;
figure 3 is a partial camera photograph of a powdered ammonium nitrate product made in accordance with example 1 of the present invention;
FIG. 4 is an XRD picture of a hexagonal flake magnesium hydroxide product according to example 1 of the present invention;
FIGS. 5 and 6 are SEM pictures of hexagonal flaky magnesium hydroxide products prepared according to example 1 of the present invention at different magnifications;
figure 7 is an XRD picture of the acicular ammonium nitrate product produced according to example 2 of the present invention;
FIG. 8 is a partial camera photograph of an acicular ammonium nitrate product made according to example 2 of the present invention;
FIGS. 9 and 10 are SEM pictures of hexagonal flaky magnesium hydroxide products prepared according to example 2 of the present invention at different magnifications;
FIG. 11 is a particle size distribution diagram of a hexagonal flaky magnesium hydroxide product according to example 2 of the present invention;
FIG. 12 is an XRD picture of a rod-shaped ammonium nitrate product produced according to example 3 of the present invention;
FIG. 13 is a partial camera photograph of a rod-shaped ammonium nitrate product produced in accordance with example 3 of the present invention;
FIGS. 14 and 15 are SEM pictures of hexagonal flaky magnesium hydroxide products prepared according to example 3 of the present invention at different magnifications;
FIG. 16 is a particle size distribution diagram of a hexagonal flaky magnesium hydroxide product prepared according to example 3 of the present invention;
FIG. 17 is an XRD picture of a rod-shaped ammonium nitrate product made in accordance with example 4 of the present invention;
FIG. 18 is a partial camera photograph of a rod-shaped ammonium nitrate product made in accordance with example 4 of the present invention;
FIG. 19 is an XRD picture of hexagonal flaky magnesium hydroxide products prepared according to example 4 of the present invention;
FIGS. 20 and 21 are SEM pictures of hexagonal flaky magnesium hydroxide products prepared according to example 4 of the present invention at different magnifications;
FIG. 22 is an XRD picture of hexagonal flaky magnesium hydroxide products prepared according to example 5 of the present invention;
fig. 23 and 24 are SEM pictures of hexagonal flaky magnesium hydroxide products manufactured according to example 5 of the present invention at different magnifications.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
It will be understood that, although the terms "first," "second," etc. may be used herein to describe various substances, these substances should not be limited by these terms. These terms are only used to distinguish one substance from another.
The invention provides a method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by taking industrial waste liquid, particularly production waste liquid generated in the production of phosphate concentrate, phosphoric acid and salts thereof and/or elemental phosphorus products from medium-low grade phosphate ores as a raw material, based on the industrial waste liquid.
In the above industrial waste liquid, the basic composition thereof is: 4mol/L to 7mol/L NH4 +0.4mol/L to 1mol/L of Mg2+5 to 10mol/L of NO3 -(ii) a And when the method is specifically limited to production waste liquid generated in the production of phosphate concentrate, phosphoric acid and salts thereof and/or elemental phosphorus products from medium-low grade phosphate ores, a small amount of Ca is also contained in the production waste liquid2+、Na+、K+、SO4 2-、PO4 3-、F-、SiO3 2-Other ions, however, do not significantly affect the process disclosed herein.
Specifically, referring to fig. 1, the method comprises the steps of:
in step S1, the industrial waste liquid is evaporated and concentrated for 1h to 10h at 50 ℃ to 90 ℃, then cooled and crystallized, and filtered to obtain a first filter cake and a first filtrate.
In step S2, an ammonium nitrate product is prepared.
The following steps are specifically referred to:
s21, the first filter cake is placed in a prepared ammonium nitrate saturated solution, and the first filter cake is dispersedly washed and filtered to obtain a second filter cake and a second filtrate.
The second filtrate obtained will have a portion of the first filtrate component entrained with the first filter cake, but still be a saturated solution of ammonium nitrate, so it is preferred to return the second filtrate to step S1 for combining with the industrial waste stream for evaporative concentration.
S22, dissolving the second filter cake in deionized water according to the mass ratio of 1.5: 1-2.5: 1 at room temperature to obtain an ammonium nitrate solution.
Thus, the mass percent of water in the obtained ammonium nitrate solution is controlled to be 29-40%.
S23, evaporating and concentrating the ammonium nitrate solution at 50-90 ℃ to remove 15-35% of water, cooling and crystallizing, and filtering to obtain a third filter cake and a third filtrate.
The main component in the obtained third filtrate is saturated ammonium nitrate solution, which is similar to the ammonium nitrate saturated solution prepared in the step S21; as such, it is preferably returned to step S21 in place of the pre-prepared ammonium nitrate saturated solution to subject the first filter cake to a dispersion wash; therefore, on one hand, the recovery rate of the ammonium nitrate can be gradually improved in the process of gradual cyclic utilization, on the other hand, a saturated ammonium nitrate solution is not required to be prepared additionally to dispersedly wash the first filter cake, and the treatment cost of the industrial waste liquid is also reduced. In other words, when the process is started for the first time, a certain amount of ammonium nitrate saturated solution (i.e., the above-mentioned ammonium nitrate saturated solution) needs to be prepared in advance for dispersedly washing the first filter cake, but after the final ammonium nitrate product is produced, the third filtrate produced at this time can be recycled.
And S24, drying the third filter cake to obtain an ammonium nitrate product.
The specific drying method is preferably drying the third filter cake for 1-10 h at 30-80 ℃.
In step S3, a hexagonal flake magnesium hydroxide product is prepared.
The following steps are specifically referred to:
s31, heating the first filtrate to 30-80 ℃ under the stirring condition, adding 2-14 mol/L alkali liquor into the first filtrate at the feeding speed of 1-20 mL/min, and aging for 10-60 min to obtain a first suspension.
Specifically, the first filtrate is placed in a reactor, and is heated to 30-80 ℃ under the condition of stirring; and meanwhile, preparing 2-14 mol/L alkali liquor by using deionized water, adding the alkali liquor into the heated first filtrate at the feeding speed of 1-20 mL/min for synthesis reaction, and then aging for 10-60 min to obtain the first suspension.
S32, filtering the first suspension to obtain a fourth filter cake and a fourth filtrate.
The fourth filtrate is obtained with a main component of Mg in the first filtrate which is not completely reacted2+A large amount of original ammonium nitrate and ammonium nitrate newly produced by the secondary decomposition reaction when magnesium hydroxide in the fourth filter cake is produced, so that the ammonium nitrate is returned to the step S1 to be evaporated and concentrated together with the industrial waste liquid, which is effective for increasing NH in the industrial waste liquid4 +And Mg2+Recovery of (b) is very critical.
And S33, washing the fourth filter cake, dispersing the fourth filter cake in a hydrothermal medium, and carrying out hydrothermal reaction at the temperature of between 120 and 200 ℃ for 1 to 48 hours to obtain a second suspension.
Specifically, the hydrothermal medium can be water or alkali liquor with the concentration not more than 6mol/L and the like which can help magnesium hydroxide to realize dissolution and recrystallization; the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution.
In the step, the fourth filter cake is washed without a large amount of water, only slight washing is needed, and preferably deionized water with the volume 2-3 times that of the fourth filter cake is used for washing for 2 times; and a large amount of water is not needed for the washing operation of the fourth filter cake, so that the washing water can be greatly saved, and the separation cost is further reduced.
S34, filtering the second suspension to obtain a fifth filter cake and a fifth filtrate.
The main component of the obtained fifth filtrate is similar to the hydrothermal medium, and therefore, the fifth filtrate is returned to step S43 instead of a part of the hydrothermal medium being mixed with the washed fourth cake and the hydrothermal medium to perform hydrothermal reaction.
And S35, washing the fifth filter cake until no hydrothermal medium is carried, and drying to obtain a hexagonal flaky magnesium hydroxide product.
Preferably, after the fifth filter cake is washed to have no entrained hydrothermal medium, the fifth filter cake is dried for 5 to 10 hours at the temperature of between 80 and 120 ℃, and then the hexagonal flaky magnesium hydroxide product can be obtained.
And washing liquid is also generated after the fifth filter cake is washed to the non-entrained hydrothermal medium, and a small amount of effective components of the hydrothermal medium still exist in the washing liquid, so that the effective components can be recycled and used for preparing the hydrothermal medium.
Therefore, the method provided by the invention has the advantages that through a reasonable process path, more than 95% of ammonium nitrate and more than 95% of magnesium hydroxide are recovered by taking industrial waste liquid as a raw material, the purposes of changing waste into valuable and reducing pollution and improving efficiency are realized, the production cost of production enterprises can be reduced, the discharge amount of waste water is greatly reduced, the enterprises can more easily meet the environmental protection requirements, and the purposes of saving energy and reducing emission are realized for the enterprises. Meanwhile, the ammonium nitrate product and the hexagonal flaky magnesium hydroxide product obtained by co-production are regular in shape and good in dispersity, and have good market application prospects.
It is worth noting that in the process design of the method of the present invention, there are several technical problems described below and eventually overcome, resulting in the above-described method of the present invention.
1) The main components of the industrial waste liquid based on the invention are ammonium nitrate and magnesium nitrate, but the inventor finds that the process path of firstly precipitating magnesium and separating by directly adding ammonia water or strong alkali is not feasible, even if 20-30 times of Mg is added into the industrial waste liquid2+When the ammonia water with the amount of the substances does not generate any precipitate, but when a large amount of strong alkali solution is added into the waste liquid, only a small amount of precipitate is generated, and through careful analysis and research, the reason is found to be a large amount of NH4 +The presence of (2) has OH-buffering effect, and can inhibit ionization of ammonia water. Based on the above, the invention provides a large amount of experiments, and a large amount of precipitates can be generated when the liquid (namely the first filtrate) obtained by evaporation concentration-cooling crystallization and filtration operation is added with ammonia water; the process path of the method proposed by the present invention is therefore finally determined as: firstly, evaporating, concentrating, cooling, crystallizing and filtering to obtain ammonium nitrate, and then adding ammonia water into the first filtrate to prepare magnesium hydroxide.
2) Evaporating and concentrating the industrial waste liquid at 50-90 ℃, cooling and crystallizing, and filtering to obtain a first filter cake with the main component of ammonium nitrate, wherein the first filter cake contains Mg2+、Ca2+、NO3 -And in order to improve the washing efficiency, the first filter cake obtained by filtering is transferred into a prefabricated ammonium nitrate saturated solution to be stirred and washed, so that most of impurities are removed, a small amount of residual impurities are further removed by redissolving, evaporation concentration, cooling crystallization and filtering operation, a high-purity ammonium nitrate product is prepared, and the third filtrate obtained by filtering can be used for washing the first filter cake due to low impurity content.
3) The inventor of the invention finds that the fourth filter cake contains a small amount of impurities, is yellowish instead of the white of magnesium hydroxide, and cannot be washed to be white no matter how much deionized water is used for washing, so the reason for the analysis is probably that magnesium hydroxide synthesized under normal pressure has strong surface polarity and is easy to agglomerate, and a small amount of other impurities are carried in the magnesium hydroxide, so the magnesium hydroxide synthesized under normal pressure needs to be subjected to hydrothermal modification, and magnesium hydroxide with small surface polarity, difficult agglomeration and good dispersibility is obtained through a dissolving and recrystallizing process.
4) Ammonium nitrate is stable at normal temperature, but explodes when heated sharply under high temperature and pressure and subjected to strong vibration. Both solid ammonium nitrate and ammonium nitrate solutions have severe explosiveness, and researches show that the explosion temperature of an ammonium nitrate aqueous solution containing a small amount of potassium chloride and with the mass fraction of 80 percent is only 220 ℃. In consideration of the safety problem of experimental work, the inventor of the invention does not directly carry out hydrothermal modification on the first suspension in the design of the process route, but firstly filters the first suspension to obtain a fourth filter cake, and then adds the fourth filter cake into a hydrothermal medium to be uniformly dispersed for hydrothermal modification.
The method for co-producing ammonium nitrate and hexagonal flake magnesium hydroxide from industrial waste liquid according to the present invention will be described below by way of specific examples, but the method is not limited to the parameters listed in the following examples, and the following parameters are only specific examples of the above method.
Example 1
The specific composition of the industrial waste liquid is shown in table 1, and the industrial waste liquid is produced by phosphate ore concentrate, phosphoric acid and salts thereof and/or elemental phosphorus products in certain phosphate ore factory in Guizhou province.
TABLE 1 Main composition of Industrial waste streams
Unit: g/L
Figure BDA0001789686700000091
Specifically, the industrial waste liquid is used as a raw material to co-produce an ammonium nitrate product and a hexagonal flaky magnesium hydroxide product.
Firstly, evaporating and concentrating the industrial waste liquid at 80 ℃ for 8h under the condition of stirring, cooling, crystallizing and filtering to obtain a first filter cake and a first filtrate.
Secondly, the first filter cake is used as a raw material to prepare an ammonium nitrate product.
Specifically, the method comprises the steps of 1) adding a first filter cake into a prepared ammonium nitrate saturated solution containing trace impurities under the condition of stirring, washing and filtering to obtain a second filter cake and a second filtrate; 2) dissolving the second filter cake in deionized water according to the mass ratio of 2:1 to obtain an ammonium nitrate solution, heating the ammonium nitrate solution to 90 ℃ under the condition of stirring, evaporating and concentrating 30% of water, then forcibly cooling by using cooling water, and filtering to obtain a third filter cake and a third filtrate; 3) and drying the third filter cake at 50 ℃ for 5h to obtain a powdery ammonium nitrate product.
In the embodiment, the second filtrate is returned to the next circulation to be combined with the industrial waste liquid for evaporation and concentration; and the third filtrate is returned to the next cycle to replace the pre-made saturated solution of ammonium nitrate.
Carrying out X-ray diffraction test (hereinafter referred to as XRD) on the product obtained in the step, and photographing the apparent morphology of the product; the pictures and photographs are shown in fig. 2 and 3, respectively. Figures 2 and 3 confirm that the resulting product is a powdered ammonium nitrate product.
It is to be noted that in the camera photograph of the ammonium nitrate product of the present example, the prepared ammonium nitrate product was photographed in a watch glass; in addition, in order to more clearly express the appearance, the partial screenshot of the complete picture is displayed. The same applies to the camera photographs in the following embodiments.
And finally, preparing the hexagonal flaky magnesium hydroxide product by taking the first filtrate as a raw material.
Specifically, 1) heating the first filtrate to 60 ℃ under the condition of stirring, adding 14mol/L ammonia water into the first filtrate at the speed of 5mL/min for synthetic reaction, and aging for 15min to obtain a first suspension; 2) filtering the first suspension to obtain a fourth filter cake and a fourth filtrate; 3) washing the fourth filter cake, adding the fourth filter cake into 4mol/L sodium hydroxide solution, uniformly stirring, adding the fourth filter cake into a high-pressure reaction kettle, and carrying out hydrothermal reaction for 3 hours at the temperature of 150 ℃ at 300r/min to obtain second suspension; 4) filtering the second suspension to obtain a fifth filter cake and a fifth filtrate; 5) and washing the fifth filter cake until no hydrothermal medium is carried, drying for 10 hours at 105 ℃, and screening to obtain the hexagonal flaky magnesium hydroxide product with good dispersibility, regular appearance and uniform particle size distribution.
In the embodiment, the fourth filtrate is returned to the next cycle to be combined with the industrial waste liquid for evaporation and concentration; returning the fifth filtrate to the next cycle to replace part of the sodium hydroxide solution as a hydrothermal medium, and mixing the fifth filtrate with the washed fourth filter cake and the sodium hydroxide solution for hydrothermal reaction; and returning a washing liquid generated after washing the fifth filter cake to a subsequent circulation process for preparing the hydrothermal medium.
Sequentially carrying out XRD test and scanning electron microscope test (hereinafter referred to as SEM) under different multiplying powers on the product obtained in the step; the pictures are shown in fig. 4, fig. 5 and fig. 6 respectively. Fig. 4 to 6 confirm that the resulting product is a hexagonal flaky magnesium hydroxide product.
Example 2
The specific composition of the industrial waste liquid is shown in table 2, and the industrial waste liquid is produced by phosphate ore concentrate, phosphoric acid and its salt and/or elemental phosphorus product in certain phosphate ore factory in Guizhou province.
TABLE 2 Main composition of the Industrial waste streams
Unit: g/L
Figure BDA0001789686700000101
Specifically, the industrial waste liquid is used as a raw material to co-produce an ammonium nitrate product and a hexagonal flaky magnesium hydroxide product.
Firstly, evaporating and concentrating the industrial waste liquid at 60 ℃ for 10 hours under the condition of stirring, cooling, crystallizing and filtering to obtain a first filter cake and a first filtrate.
Secondly, the first filter cake is used as a raw material to prepare an ammonium nitrate product.
Specifically, the method comprises the steps of 1) adding a first filter cake into a prepared ammonium nitrate saturated solution containing trace impurities under the condition of stirring, washing and filtering to obtain a second filter cake and a second filtrate; 2) dissolving the second filter cake in deionized water according to the mass ratio of 2:1 to obtain an ammonium nitrate solution, heating the ammonium nitrate solution to 80 ℃ under the condition of stirring, evaporating and concentrating 20% of water, then forcibly cooling by using cooling water under the condition of slight stirring, and filtering to obtain a third filter cake and a third filtrate; 3) and drying the third filter cake at 50 ℃ for 5 hours to obtain a needle-shaped ammonium nitrate product.
In the embodiment, the second filtrate is returned to the next circulation to be combined with the industrial waste liquid for evaporation and concentration; and the third filtrate is returned to the next cycle to replace the pre-made saturated solution of ammonium nitrate.
Carrying out XRD test on the product obtained in the step, and taking a picture of the apparent morphology of the product; the pictures and photographs are shown in fig. 7 and 8, respectively. Figures 7 and 8 confirm that the resulting product is a needle ammonium nitrate product.
And finally, preparing the hexagonal flaky magnesium hydroxide product by taking the first filtrate as a raw material.
Specifically, 1) heating the first filtrate to 60 ℃ under the condition of stirring, adding 14mol/L ammonia water into the first filtrate at the speed of 2.5mL/min for synthetic reaction, and aging for 15min to obtain a first suspension; 2) filtering the first suspension to obtain a fourth filter cake and a fourth filtrate; 3) washing the fourth filter cake, adding the fourth filter cake into 4mol/L sodium hydroxide solution, uniformly stirring, adding the fourth filter cake into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a constant temperature box, and carrying out hydrothermal reaction for 20 hours at 160 ℃ to obtain a second suspension; 4) filtering the second suspension to obtain a fifth filter cake and a fifth filtrate; 5) and washing the fifth filter cake until no hydrothermal medium is carried, drying for 10 hours at 105 ℃, and screening to obtain the hexagonal flaky magnesium hydroxide product with good dispersibility, regular appearance and uniform particle size distribution.
In the embodiment, the fourth filtrate is returned to the next cycle to be combined with the industrial waste liquid for evaporation and concentration; returning the fifth filtrate to the next cycle to replace part of the sodium hydroxide solution as a hydrothermal medium, and mixing the fifth filtrate with the washed fourth filter cake and the sodium hydroxide solution for hydrothermal reaction; and returning a washing liquid generated after washing the fifth filter cake to a subsequent circulation process for preparing the hydrothermal medium.
SEM tests are carried out on the product obtained in the step under different multiplying powers; the pictures are shown in fig. 9 and 10, respectively. Fig. 9 and 10 confirm that the obtained product is a hexagonal flaky magnesium hydroxide product.
Meanwhile, the particle size distribution of the hexagonal flaky magnesium hydroxide product obtained in this example was tested, wherein D is101.849 μm, D50Is 3.405 μm, D906.436 μm, as shown in FIG. 11. It can be seen that the magnesium hydroxide obtained in this example has a uniform particle size distribution with a particle size of 3.4 μm.
Example 3
The specific composition of the industrial waste liquid is shown in table 3, which takes the production waste liquid generated in the production of phosphate concentrate, phosphoric acid and its salt and/or phosphorus simple substance products in certain phosphate ore factory in Guizhou as the raw material of the industrial waste liquid.
TABLE 3 Main composition of the Industrial waste streams
Unit: g/L
Figure BDA0001789686700000121
Specifically, the industrial waste liquid is used as a raw material to co-produce an ammonium nitrate product and a hexagonal flaky magnesium hydroxide product.
Firstly, evaporating and concentrating the industrial waste liquid at 60 ℃ for 10 hours under the condition of stirring, cooling, crystallizing and filtering to obtain a first filter cake and a first filtrate.
Secondly, the first filter cake is used as a raw material to prepare an ammonium nitrate product.
Specifically, the method comprises the steps of 1) adding a first filter cake into a prepared ammonium nitrate saturated solution containing trace impurities under the condition of stirring, washing and filtering to obtain a second filter cake and a second filtrate; 2) dissolving the second filter cake in deionized water according to the mass ratio of 2:1 to obtain an ammonium nitrate solution, heating the ammonium nitrate solution to 70 ℃ under the condition of stirring, evaporating and concentrating 15% of water, forcibly cooling by using cooling water, and filtering to obtain a third filter cake and a third filtrate; 3) and drying the third filter cake for 5 hours at the temperature of 50 ℃ to obtain a rod-shaped ammonium nitrate product.
In the embodiment, the second filtrate is returned to the next circulation to be combined with the industrial waste liquid for evaporation and concentration; and the third filtrate is returned to the next cycle to replace the pre-made saturated solution of ammonium nitrate.
Carrying out XRD test on the product obtained in the step, and taking a picture of the apparent morphology of the product; the pictures and photographs thereof are shown in fig. 12 and 13, respectively. Figures 12 and 13 confirm that the resulting product is a rod ammonium nitrate product.
And finally, preparing the hexagonal flaky magnesium hydroxide product by taking the first filtrate as a raw material.
Specifically, 1) heating the first filtrate to 60 ℃ under the condition of stirring, adding 4mol/L ammonia water into the first filtrate at the speed of 5mL/min for synthetic reaction, and aging for 15min to obtain a first suspension; 2) filtering the first suspension to obtain a fourth filter cake and a fourth filtrate; 3) washing the fourth filter cake, adding the fourth filter cake into 4mol/L sodium hydroxide solution, uniformly stirring, adding the fourth filter cake into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a constant temperature box, and carrying out hydrothermal reaction for 20 hours at 160 ℃ to obtain a second suspension; 4) filtering the second suspension to obtain a fifth filter cake and a fifth filtrate; 5) and washing the fifth filter cake until no hydrothermal medium is carried, drying for 10 hours at 110 ℃, and screening to obtain the hexagonal flaky magnesium hydroxide product with good dispersibility, regular appearance and uniform particle size distribution.
In the embodiment, the fourth filtrate is returned to the next cycle to be combined with the industrial waste liquid for evaporation and concentration; returning the fifth filtrate to the next cycle to replace part of the sodium hydroxide solution as a hydrothermal medium, and mixing the fifth filtrate with the washed fourth filter cake and the sodium hydroxide solution for hydrothermal reaction; and returning a washing liquid generated after washing the fifth filter cake to a subsequent circulation process for preparing the hydrothermal medium.
SEM tests are carried out on the product obtained in the step under different multiplying powers; the pictures are shown in fig. 14 and 15, respectively. Fig. 14 and 15 confirm that the obtained product is a hexagonal flaky magnesium hydroxide product.
Meanwhile, the particle size distribution of the hexagonal flaky magnesium hydroxide product obtained in this example was tested, wherein D is100.145 μm, D501.795 μm, D904.767 μm, as shown in FIG. 16. It can be seen that the magnesium hydroxide obtained in this example has a uniform particle size distribution with a particle size of 1.8 μm.
Example 4
The specific composition of the industrial waste liquid is shown in table 4, which is the production waste liquid generated in a certain phosphate ore factory in Guizhou when producing phosphate concentrate, phosphoric acid and salts thereof and/or elemental phosphorus products.
TABLE 4 Main composition of Industrial waste streams
Unit: g/L
Figure BDA0001789686700000131
Specifically, the industrial waste liquid is used as a raw material to co-produce an ammonium nitrate product and a hexagonal flaky magnesium hydroxide product.
Firstly, evaporating and concentrating the industrial waste liquid at 90 ℃ for 8h under the condition of stirring, cooling, crystallizing and filtering to obtain a first filter cake and a first filtrate.
Secondly, the first filter cake is used as a raw material to prepare an ammonium nitrate product.
Specifically, the method comprises the steps of 1) adding a first filter cake into a prepared ammonium nitrate saturated solution containing trace impurities under the condition of stirring, washing and filtering to obtain a second filter cake and a second filtrate; 2) dissolving the second filter cake in deionized water according to the mass ratio of 2:1 to obtain an ammonium nitrate solution, heating the ammonium nitrate solution to 50 ℃ under the condition of stirring, evaporating and concentrating 15% of water, naturally cooling, and filtering to obtain a third filter cake and a third filtrate; 3) and drying the third filter cake for 5 hours at the temperature of 50 ℃ to obtain a rod-shaped ammonium nitrate product.
In the embodiment, the second filtrate is returned to the next circulation to be combined with the industrial waste liquid for evaporation and concentration; and the third filtrate is returned to the next cycle to replace the pre-made saturated solution of ammonium nitrate.
Carrying out XRD test on the product obtained in the step, and taking a picture of the apparent morphology of the product; the pictures and photographs thereof are shown in fig. 17 and 18, respectively. Fig. 17 and 18 confirm that the resulting product is a rod-shaped ammonium nitrate product.
And finally, preparing the hexagonal flaky magnesium hydroxide product by taking the first filtrate as a raw material.
Specifically, 1) heating the first filtrate to 60 ℃ under the condition of stirring, adding 4mol/L ammonia water into the first filtrate at the speed of 15mL/min for synthetic reaction, and aging for 15min to obtain a first suspension; 2) filtering the first suspension to obtain a fourth filter cake and a fourth filtrate; 3) washing the fourth filter cake, adding the fourth filter cake into deionized water, stirring uniformly, adding the deionized water into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a constant temperature box, and carrying out hydrothermal reaction for 40 hours at 180 ℃ to obtain a second suspension; 4) filtering the second suspension to obtain a fifth filter cake and a fifth filtrate; 5) and washing the fifth filter cake until no hydrothermal medium is carried, drying for 10 hours at 105 ℃, and screening to obtain the hexagonal flaky magnesium hydroxide product with good dispersibility, regular appearance and uniform particle size distribution.
In this example, the fourth filtrate was returned to the next cycle and combined with the industrial waste liquid for the evaporation and concentration operation.
Sequentially carrying out XRD test and SEM test under different magnifications on the product obtained in the step; the pictures are shown in fig. 19, fig. 20 and fig. 21, respectively. Fig. 19 to 21 confirm that the resulting product is a hexagonal flaky magnesium hydroxide product.
Example 5
The specific composition of the industrial waste liquid is shown in table 5, which is the production waste liquid generated in a certain phosphate ore factory in Guizhou when producing phosphate concentrate, phosphoric acid and salts thereof and/or elemental phosphorus products.
TABLE 5 major composition of the Industrial waste streams
Unit: g/L
Figure BDA0001789686700000141
Specifically, the industrial waste liquid is used as a raw material to co-produce an ammonium nitrate product and a hexagonal flaky magnesium hydroxide product.
Firstly, evaporating and concentrating the industrial waste liquid at 90 ℃ for 8h under the condition of stirring, cooling, crystallizing and filtering to obtain a first filter cake and a first filtrate.
Secondly, the first filter cake is used as a raw material to prepare an ammonium nitrate product.
Specifically, the method comprises the steps of 1) adding a first filter cake into a prepared ammonium nitrate saturated solution containing trace impurities under the condition of stirring, washing and filtering to obtain a second filter cake and a second filtrate; 2) dissolving the second filter cake in deionized water according to the mass ratio of 2:1 to obtain an ammonium nitrate solution, heating the ammonium nitrate solution to 50 ℃ under the condition of stirring, evaporating and concentrating 15% of water, naturally cooling, and filtering to obtain a third filter cake and a third filtrate; 3) and drying the third filter cake for 5 hours at the temperature of 50 ℃ to obtain a rod-shaped ammonium nitrate product.
In the embodiment, the second filtrate is returned to the next circulation to be combined with the industrial waste liquid for evaporation and concentration; and the third filtrate is returned to the next cycle to replace the pre-made saturated solution of ammonium nitrate.
And finally, preparing the hexagonal flaky magnesium hydroxide product by taking the first filtrate as a raw material.
Specifically, 1) heating the first filtrate to 60 ℃ under the condition of stirring, adding 4mol/L ammonia water into the first filtrate at the speed of 15mL/min for synthetic reaction, and aging for 15min to obtain a first suspension; 2) filtering the first suspension to obtain a fourth filter cake and a fourth filtrate; 3) washing the fourth filter cake, adding the fourth filter cake into deionized water, stirring uniformly, adding the deionized water into a high-pressure reaction kettle, placing the high-pressure reaction kettle into a constant temperature box, and carrying out hydrothermal reaction for 20 hours at 180 ℃ to obtain a second suspension; 4) filtering the second suspension to obtain a fifth filter cake and a fifth filtrate; 5) and washing the fifth filter cake until no hydrothermal medium is carried, drying for 10 hours at 110 ℃, and screening to obtain the hexagonal flaky magnesium hydroxide product with good dispersibility, regular appearance and uniform particle size distribution.
In the embodiment, the fourth filtrate is returned to the next cycle to be combined with the industrial waste liquid for evaporation and concentration; returning the fifth filtrate to the next cycle to replace part of the sodium hydroxide solution as a hydrothermal medium, and mixing the fifth filtrate with the washed fourth filter cake and the sodium hydroxide solution for hydrothermal reaction; and returning a washing liquid generated after washing the fifth filter cake to a subsequent circulation process for preparing the hydrothermal medium.
Sequentially carrying out XRD test and SEM test under different magnifications on the product obtained in the step; the pictures are shown in fig. 22, fig. 23 and fig. 24. Fig. 22 to 24 confirm that the resulting product is a hexagonal flaky magnesium hydroxide product.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.

Claims (9)

1. A method for co-producing ammonium nitrate and hexagonal flaky magnesium hydroxide by using industrial waste liquid is characterized by comprising the following steps:
s1, evaporating and concentrating the industrial waste liquid at 50-90 ℃ for 1-10 h, cooling and crystallizing, and filtering to obtain a first filter cake and a first filtrate; wherein, in the industrial waste liquid, NH4 +Has a concentration of 4mol/L to 7mol/L, Mg2+The concentration of (A) is 0.4mol/L to 1mol/L, NO3 -The concentration of (A) is 5-10 mol/L;
s2, preparing an ammonium nitrate product, comprising the following steps:
s21, placing the first filter cake into a prepared ammonium nitrate saturated solution, dispersing, washing and filtering to obtain a second filter cake;
s22, dissolving the second filter cake in deionized water according to the mass ratio of 1.5: 1-2.5: 1 at room temperature to obtain an ammonium nitrate solution; wherein the mass percent of water in the ammonium nitrate solution is 29-40%;
s23, evaporating and concentrating the ammonium nitrate solution at 50-90 ℃ to remove 15-35% of water, cooling and crystallizing, and filtering to obtain a third filter cake;
s24, drying the third filter cake to obtain the ammonium nitrate product;
s3, preparing a hexagonal flaky magnesium hydroxide product, comprising the following steps:
s31, heating the first filtrate to 30-80 ℃ under the condition of stirring, adding 2-14 mol/L alkali liquor into the first filtrate at the feeding speed of 1-20 mL/min, and aging for 10-60 min to obtain a first suspension;
s32, filtering the first suspension to obtain a fourth filter cake;
s33, washing the fourth filter cake, dispersing the fourth filter cake in a hydrothermal medium, and carrying out hydrothermal reaction at the temperature of 120-200 ℃ for 1-48 h to obtain a second suspension;
s34, filtering the second suspension to obtain a fifth filter cake;
and S35, washing the fifth filter cake until no hydrothermal medium is carried, and drying to obtain the hexagonal flaky magnesium hydroxide product.
2. The method of claim 1, wherein in the step S1, the industrial waste liquid is derived from production waste liquid generated in production of phosphate concentrate, phosphoric acid and its salt and/or elemental phosphorus product from medium-low grade phosphate ore.
3. The method as claimed in claim 1, wherein in the step S33, the hydrothermal medium is deionized water, or a sodium hydroxide solution with a concentration of not more than 6mol/L, or a potassium hydroxide solution with a concentration of not more than 6 mol/L.
4. The method according to any one of claims 1 to 3, wherein in the step S23, a third filtrate corresponding to the third filter cake is also obtained; the third filtrate is returned to the step S21 to replace the saturated solution of ammonium nitrate.
5. The method according to any one of claims 1 to 3, wherein in the step S21, a second filtrate corresponding to the second filter cake is also obtained; and returning the second filtrate to the step S1 to be evaporated and concentrated together with the industrial waste liquid.
6. The method according to any one of claims 1 to 3, wherein in the step S32, a fourth filtrate corresponding to the fourth filter cake is also obtained; and returning the fourth filtrate to the step S1 to be evaporated and concentrated together with the industrial waste liquid.
7. The method according to any one of claims 1 to 3, wherein in the step S34, a fifth filtrate corresponding to the fifth filter cake is also obtained; and returning the fifth filtrate to the step S33 to replace part of the hydrothermal medium, mixing the washed fourth filter cake and the hydrothermal medium, and performing hydrothermal reaction.
8. The method according to any one of claims 1 to 3, wherein in step S35, a wash liquid is also generated after washing the fifth filter cake to the absence of entrained hydrothermal medium; the washing liquid is used for preparing the hydrothermal medium.
9. The method according to any one of claims 1 to 3, wherein in step S24, the third filter cake is dried at 30 to 80 ℃ for 1 to 10 hours to obtain the ammonium nitrate product; and/or, in the step S35, drying the washed fifth filter cake at 80-120 ℃ for 5-10 h to obtain the hexagonal flaky magnesium hydroxide product.
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