CN113087430A - Ammonia extraction desulfurization gypsum and disposal and utilization method thereof - Google Patents
Ammonia extraction desulfurization gypsum and disposal and utilization method thereof Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 126
- 239000010440 gypsum Substances 0.000 title claims abstract description 126
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 88
- 238000000605 extraction Methods 0.000 title claims abstract description 66
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 49
- 230000023556 desulfurization Effects 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004568 cement Substances 0.000 claims abstract description 45
- 239000008394 flocculating agent Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 239000002699 waste material Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 18
- 239000002910 solid waste Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 14
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical class [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 22
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 22
- 239000004571 lime Substances 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000008267 milk Substances 0.000 claims description 9
- 210000004080 milk Anatomy 0.000 claims description 9
- 235000013336 milk Nutrition 0.000 claims description 9
- 229920002401 polyacrylamide Polymers 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- -1 transition metal salt Chemical class 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Chemical class 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 229910052748 manganese Chemical class 0.000 claims description 3
- 239000011572 manganese Chemical class 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 230000002411 adverse Effects 0.000 abstract description 7
- 150000003624 transition metals Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
- C04B22/146—Calcium-sulfate other waste Ca-sulfate
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
Abstract
The invention discloses ammonia extraction desulfurization gypsum and a disposal and utilization method thereof, wherein the ammonia extraction desulfurization gypsum is prepared by taking a transition metal (nickel-cobalt-manganese) salt mixed solution as a raw material, taking an ammonia water solution as a complexing agent, controlling pH by an alkali liquor to realize coprecipitation reaction, treating and recycling solid waste generated during washing waste liquid, taking the solid waste as a cement gypsum retarder, and controlling the content of a flocculating agent in cement to be less than or equal to 0.01% by the mixing amount of the ammonia extraction desulfurization gypsum in the cement according to the content of the flocculating agent. The invention can use a large amount of industrial solid waste ammonia extraction desulfurized gypsum as the gypsum retarder required by cement production, and does not cause adverse effect on cement strength.
Description
Technical Field
The invention relates to the technical field of cement retarder production, and relates to ammonia extraction desulfurized gypsum and a disposal and utilization method thereof.
Background
The nickel-cobalt-manganese (NCM) ternary material is a composite oxide with multiple components, has excellent comprehensive performance and higher cost performance, such as high specific capacity, high standard voltage, higher compaction density and excellent low-temperature performance, and becomes a hotspot of commercialization of anode materials and a technical choice of power battery cores in the future. Eyes of a userThe most common synthesis method of the NCM ternary precursor is to use a transition metal salt mixed solution as a raw material, an ammonia water solution as a complexing agent and NaOH alkali liquor to control the pH value to realize coprecipitation reaction, so as to obtain the precursor. High concentration of Na is generated in the synthesis process2SO4When the sulfate waste liquid is equal, most NCM ternary precursor synthesis enterprises adopt the direct ammonia stripping and ammonia recovery of the waste liquid and the liquid evaporation and crystallization to generate Na2SO4The treatment is carried out, but Na is wasted2SO4It is not easy to handle and utilize. In order to reduce the energy consumption of waste liquid treatment, better treat the generated solid waste and simultaneously prepare alkali liquor, lime is added into the waste liquid for treatment, the generated industrial solid waste mainly containing dihydrate gypsum can be used as a cement gypsum retarder, then ammonia stripping is carried out to recover ammonia, and the generated clear liquid (NaOH alkali liquor) is recycled. The method can be directly used for preparing alkali liquor, but when the amount of polyacrylamide is too high, the fluidity and the consistency of cement, especially the strength, are greatly influenced due to the actions of particle agglomeration, air entrainment and the like when the flocculating agent polyacrylamide is added for accelerating the precipitation of precipitates in the lime adding process, so that the use of the flocculating agent as a cement gypsum retarder is influenced.
Disclosure of Invention
In order to solve the technical problems, the invention provides the ammonia extraction desulfurized gypsum and the disposal and utilization method thereof, the method can fully utilize the ammonia extraction desulfurized gypsum to replace natural gypsum or desulfurized gypsum to be used as a gypsum retarder for cement production, and the method does not cause negative influence on the strength of cement.
The technical scheme of the invention is as follows:
the ammonia extraction desulfurization gypsum is prepared by taking a transition metal salt mixed solution as a raw material, taking an ammonia water solution as a complexing agent and controlling pH by an alkali liquor to realize coprecipitation reaction, and solid wastes generated in the process of treating and recycling washing waste liquid when a nickel-cobalt-manganese (NCM) ternary material precursor is prepared.
The washing waste liquid contains a large amount of sulfate such as sodium sulfate and ammonium sulfate.
The solid waste is a precipitate which is mainly formed by adding lime or lime milk and a small amount of flocculant into waste liquid to react.
Preferably, the processes of preparing the nickel-cobalt-manganese (NCM) ternary material precursor and producing the ammonia extraction desulfurized gypsum are shown in fig. 1, a mixed salt solution of nickel, cobalt and manganese metals is complexed with ammonia water, and forms hydroxide precipitate with alkali, then the precipitate is centrifugally washed and dried to obtain the nickel-cobalt-manganese ternary material precursor, wherein the ammonia water complexation can reduce the nucleation rate in the precipitate crystallization process and improve the stacking density of the finished product, the washing waste liquid contains a large amount of soluble sulfate, the precipitate ammonia extraction desulfurized gypsum is produced by adding lime or lime milk and a flocculating agent for reaction, meanwhile, the supernatant is subjected to ammonia stripping by an ammonia stripping device to recover ammonia as a complexing agent for preparing the NCM ternary precursor, and an alkaline solution is recovered as an alkaline solution for preparing the NCM ternary precursor.
Further preferably, the lime or lime milk is added in an amount of 1.2 to 1.3 times the molar amount of sulfate.
Further preferably, the flocculant is polyacrylamide, and mainly has the functions of accelerating the precipitation of solid wastes and recovering NaOH clear solution as alkali liquor for preparing NCM ternary precursor.
Preferably, the addition amount of the flocculant in the process of treating and recycling the washing waste liquid is controlled to control the content of the flocculant in the ammonia extraction desulfurization gypsum to be less than or equal to 0.2 percent. Therefore, the ammonia-extracting desulfurized gypsum can be used for completely replacing paste materials such as natural gypsum or desulfurized gypsum and the like to be used as a cement retarder, and the full utilization of solid waste resources is realized.
According to the disposal and utilization method of the ammonia extraction desulfurization gypsum, the ammonia extraction desulfurization gypsum is used as a cement gypsum retarder, the mixing amount of the ammonia extraction desulfurization gypsum in cement is determined according to the content of a flocculating agent of the ammonia extraction desulfurization gypsum, so that the content of the flocculating agent in the cement is controlled to be less than or equal to 0.01%, and the cement strength can be prevented from being adversely affected.
Further preferably, if the content of the flocculating agent in the ammonia extraction desulfurization gypsum is more than 0.2%, 1-3% of alkaline high-valence cation salt solution is added into the ammonia extraction desulfurization gypsum, and the ammonia extraction desulfurization gypsum is heated for 2-5 h at 50-70 ℃, or is stacked for more than 5 months or stacked for not less than 2 months at the average daily temperature of not less than 25 ℃. The flocculant in the ammonia extraction desulfurization gypsum is fully hydrolyzed and salted, the adverse effect of the ammonia extraction desulfurization gypsum as a retarder on the cement strength can be reduced, and the utilization rate of the ammonia extraction desulfurization gypsum is improved.
More preferably, the alkaline high-valence cation salt solution is prepared by 92-97 wt% of saturated limewater and 8-3 wt% of high-valence cation soluble salt, the valence state of the high-valence cation is more than or equal to 2, and the high-valence cation comprises Ca2+、Mg2+And Al3+The main function of the cement retarder is to accelerate the hydrolysis and salt decomposition of the flocculant so as to reduce the adverse effect of the ammonia desulfurization gypsum used as the retarder on the strength of the cement.
The ammonia extraction desulfurized gypsum and the disposal and utilization method thereof provided by the invention can be used for largely utilizing industrial solid waste ammonia extraction desulfurized gypsum as a gypsum retarder required by cement production, and do not cause adverse effects on cement strength.
The invention has the following advantages and effects:
1. by reasonably controlling the addition amount of the flocculating agent in the washing waste liquid, the settling speed of solid waste precipitates (ammonia extraction desulfurization gypsum) can be ensured on one hand, and the strength of cement is not negatively influenced when the ammonia extraction desulfurization gypsum is used as a retarder on the other hand.
2. When the addition amount of the flocculating agent in the washing waste liquid is slightly fluctuated and the flocculating agent in the ammonia extraction desulfurization gypsum exceeds 0.2%, 1-3% of alkaline high-valence cation salt solution is added into the ammonia extraction desulfurization gypsum, and the ammonia extraction desulfurization gypsum is heated for 2h-5h at 50-70 ℃ or is stacked for more than 5 months or stacked for not less than 2 months at the daily average temperature of not less than 25 ℃, so that the flocculating agent in the ammonia extraction desulfurization gypsum is fully hydrolyzed and salted out, the adverse effect of the ammonia extraction desulfurization gypsum as a retarder on the cement strength can be reduced, and the utilization rate of the ammonia extraction desulfurization gypsum is improved.
3. The technology of the invention can fully utilize the ammonia extraction desulfurized gypsum to replace desulfurized gypsum or natural gypsum to be used as a cement retarder in various large cement production enterprises, the effective disposal and the utilization rate of the ammonia extraction desulfurized gypsum used as the cement retarder are greatly improved, the negative effects of land occupation and underground water source pollution of the ammonia extraction desulfurized gypsum stacking can be further reduced, and the environmental protection benefit is remarkable.
Drawings
FIG. 1 is a diagram of the production process of a nickel-cobalt-manganese (NCM) ternary material precursor and the production process of ammonia extraction desulfurization gypsum.
Detailed Description
The invention is further illustrated by the following examples, but the scope of the invention as claimed is not limited to the scope of the examples.
An ammonia extraction desulfurization gypsum is prepared by taking a transition metal salt mixed solution as a raw material, taking an ammonia water solution as a complexing agent, and controlling pH by using an alkali liquor to realize a coprecipitation reaction to prepare a nickel-cobalt-manganese (NCM) ternary material precursor (the specific process can refer to the research on synthesis optimization and modification of a high-nickel ternary cathode material of Zhang super-Johnson university, Qingdao science and technology university, 2020), and solid waste generated during washing waste liquid recovery is treated.
The washing waste liquid contains a large amount of sulfate such as sodium sulfate and ammonium sulfate.
The solid waste is a precipitate which is mainly formed by adding lime or lime milk and a small amount of flocculant into waste liquid to react.
Preferably, the processes of preparing the nickel-cobalt-manganese (NCM) ternary material precursor and producing the ammonia extraction desulfurized gypsum are shown in fig. 1, a mixed salt solution of nickel, cobalt and manganese metals is complexed with ammonia water, and forms hydroxide precipitate with alkali, then the precipitate is centrifugally washed and dried to obtain the nickel-cobalt-manganese ternary material precursor, wherein the ammonia water complexation can reduce the nucleation rate in the precipitate crystallization process and improve the stacking density of the finished product, the washing waste liquid contains a large amount of soluble sulfate, the precipitate ammonia extraction desulfurized gypsum is produced by adding lime or lime milk and a flocculating agent for reaction, meanwhile, the supernatant is subjected to ammonia stripping by an ammonia stripping device to recover ammonia as a complexing agent for preparing the NCM ternary precursor, and an alkaline solution is recovered as an alkaline solution for preparing the NCM ternary precursor.
Further preferably, the lime or lime milk is added in an amount of 1.2 times the molar amount of sulfate.
Further preferably, the flocculant is polyacrylamide, and mainly has the functions of accelerating the precipitation of solid wastes and recovering NaOH clear solution as alkali liquor for preparing NCM ternary precursor.
According to the disposal and utilization method of the ammonia extraction desulfurization gypsum, the ammonia extraction desulfurization gypsum is used as a cement gypsum retarder, the mixing amount of the ammonia extraction desulfurization gypsum in cement is determined according to the content of a flocculating agent of the ammonia extraction desulfurization gypsum, so that the content of the flocculating agent in the cement is controlled to be less than or equal to 0.01%, and the cement strength can be prevented from being adversely affected.
Preferably, the addition amount of the flocculating agent in the process of treating and recycling the waste liquid is controlled to be less than or equal to 0.2 percent of the flocculating agent content in the ammonia extraction desulfurization gypsum.
Example 1
Taking the control of the content of a flocculating agent in ammonia extraction desulfurization gypsum as an example, the ammonia extraction desulfurization gypsum and the disposal and utilization method thereof comprise the following specific steps:
1) in the figure 1, excessive lime and a proper amount of flocculating agent polyacrylamide are added into the washing waste liquid, the mass proportion of the polyacrylamide in the precipitate (ammonia-extracting desulfurized gypsum) is controlled to be 0.15%, and the precipitate is stored for 10 days at the daily average temperature of 15-20 ℃;
2) the ammonia-extracting desulfurized gypsum (designated as ammonia-extracting desulfurized gypsum A) obtained above was used as cement retarders of 32.5 grade, 42.5 grade and 52.5 grade, and the doping amount was 5%, and the concrete test and comparison results are shown in Table 1, wherein the doping amounts were 5% desulfurized gypsum, 5% natural gypsum, 5% ammonia-extracting desulfurized gypsum B (flocculant content 0.3%, storage time 10 days at daily average temperature 15-20 ℃), 5% ammonia-extracting desulfurized gypsum C (flocculant content 0.4%, storage time 10 days at daily average temperature 15-20 ℃), 2% natural gypsum + 3% ammonia-extracting desulfurized gypsum B and 3% desulfurized gypsum + 2% ammonia-extracting desulfurized gypsum C, respectively, as comparative examples.
Table 1 shows the comparison of cement performance between the ammonia-extracting desulfurized gypsum and other gypsum used as retarders
As can be seen from the data in Table 1, when the ammonia-containing desulfurized gypsum A (the content of the flocculant is controlled within 0.2%) is used as a cement retarder, the setting time of the cement of each strength grade is close to that of desulfurized gypsum and natural gypsum, and the ammonia-containing desulfurized gypsum A can completely replace desulfurized gypsum or natural gypsum. And the ammonia extraction desulfurized gypsum B and the ammonia extraction desulfurized gypsum C completely replace desulfurized gypsum or natural gypsum in the cement by 5 percent of dosage because the content of the flocculating agent exceeds 0.2 percent, so that the compression strength of the cement is obviously reduced by 3d and 28 d. When the mixing amount of the ammonia extraction desulfurized gypsum B and the ammonia extraction desulfurized gypsum C is respectively reduced to 3 percent and 2 percent, and the content of the flocculating agent in the cement is controlled within 0.01 percent, the flocculating agent has no negative effect on the strength of the cement, but can only replace part of desulfurized gypsum or natural gypsum.
Example 2
Taking the control of pretreatment and stacking conditions of ammonia extraction desulfurization gypsum as an example, an ammonia extraction desulfurization gypsum and a disposal and utilization method thereof are provided, which comprises the following specific steps:
1) in the figure 1, excessive lime and polyacrylamide serving as a flocculating agent are added into the washing waste liquid to obtain a precipitate (ammonia-extracting desulfurized gypsum), wherein the mass ratio of polyacrylamide to the precipitate is more than 0.2% and is 0.4%;
2) stacking the above precipitates at a daily average temperature of less than 25 deg.C for half a year, stacking at a high temperature season (daily average temperature of NO less than 25 deg.C) for 2 months, and adding 2% alkaline high valence cation salt solution (95% saturated limewater + 5% Mg (NO)3)2) Heating at 60 ℃ for 3h to obtain ammonia extraction desulfurized gypsum D, ammonia extraction desulfurized gypsum E and ammonia extraction desulfurized gypsum F;
3) the ammonia-extracting desulfurized gypsum D, E and the ammonia-extracting desulfurized gypsum F obtained above were used as cement retarders of 32.5 grade, 42.5 grade and 52.5 grade, respectively, and the mixing amounts were 5%, and the concrete test results are shown in Table 2, and the comparative examples are 5% desulfurized gypsum, 5% natural gypsum and 5% ammonia-extracting desulfurized gypsum C (flocculant content 0.4%, storage time 10 days at a daily average temperature of 15-20 ℃ C.) in Table 1.
Table 2 comparison of cement properties with different ammonia-extracting desulfurized gypsum as retarder
From the data in the table and comparison with table 1, it can be seen that although the flocculant content of the ammonia extracting desulfurized gypsum D, E and F is higher (0.4%), the negative effect on the cement strength can be reduced by the treatment means of prolonging the stacking time, adding alkaline high-valence soluble salt, increasing the material temperature and the like, and the proportion of the ammonia extracting desulfurized gypsum used in the cement is higher than that of the ammonia extracting desulfurized gypsum C, so that the desulfurized gypsum or natural gypsum can be completely replaced.
The above-described embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention is defined by the claims, and equivalents including technical features described in the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. An ammonia extraction desulfurization gypsum is characterized in that: the ammonia extraction desulfurization gypsum is prepared by taking a transition metal salt mixed solution as a raw material, taking an ammonia water solution as a complexing agent and controlling the pH value with an alkali liquor to realize coprecipitation reaction, and solid waste generated in the process of treating and recycling washing waste liquid when a nickel-cobalt-manganese (NCM) ternary material precursor is prepared.
2. The ammonia-extracting desulfurized gypsum according to claim 1, characterized in that: the washing waste liquid contains sodium sulfate, ammonium sulfate or other sulfates.
3. The ammonia-extracting desulfurized gypsum according to claim 1, characterized in that: the solid waste is a precipitate which is mainly formed by adding lime or lime milk and a flocculating agent into washing waste liquid and reacting.
4. The ammonia extraction desulfurization gypsum of claim 1, wherein the preparation of the nickel-cobalt-manganese (NCM) ternary material precursor and the production process of the ammonia extraction desulfurization gypsum are as follows: complexing the mixed solution of transition metal salts of nickel, cobalt and manganese with ammonia water, forming hydroxide precipitate with alkali, then centrifugally washing and drying to obtain a precursor of the nickel-cobalt-manganese ternary material, adding soluble sulfate in washing waste liquid, reacting by adding lime or lime milk and a flocculating agent to generate precipitate, extracting ammonia desulfurization gypsum, simultaneously recovering ammonia from supernatant through an ammonia stripping device to serve as a complexing agent for preparing the NCM ternary precursor, and recovering alkaline solution to serve as alkali liquor for preparing the NCM ternary precursor.
5. The ammonia extracting desulfurization gypsum according to claim 3, characterized in that: the flocculant is polyacrylamide.
6. The ammonia extracting desulfurization gypsum according to claim 5, characterized in that: the addition amount of the flocculant in the process of treating and recycling the washing waste liquid is controlled to control the content of the flocculant in the ammonia extraction desulfurization gypsum to be less than or equal to 0.2 percent.
7. The ammonia extracting desulfurization gypsum according to claim 3, characterized in that: the addition amount of the lime or lime milk is 1.2-1.3 times of the molar weight of the sulfate.
8. The method for treating and utilizing ammonia-extracting desulfurization gypsum according to any one of claims 1 to 7, characterized in that: the ammonia extraction desulfurized gypsum is used as a cement gypsum retarder, and the mixing amount of the ammonia extraction desulfurized gypsum in the cement is determined according to the content of a flocculating agent of the ammonia extraction desulfurized gypsum so as to control the content of the flocculating agent in the cement to be less than or equal to 0.01 percent.
9. The method of claim 8, wherein: if the content of the flocculant in the ammonia extraction desulfurization gypsum is more than 0.2 percent, adding 1 to 3 percent of alkaline high-valence cation salt solution into the ammonia extraction desulfurization gypsum, stirring and mixing uniformly, heating for 2 to 5 hours at the temperature of between 50 and 70 ℃, or stacking for more than 5 months or stacking for not less than 2 months at the average daily temperature of not less than 25 ℃.
10. The method of claim 9, wherein: the alkaline high-valence cation salt solution is prepared from 92-97 wt% of saturated limewater and 8-3 wt% of high-valence cation soluble salt, the valence of the high-valence cation is more than or equal to 2, and the high-valence cation comprises Ca2+、Mg2+And Al3+。
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