CN115594862A - Method and equipment for preparing humic acid calcium magnesium chelating liquid by using ammonia-soda alkaline residue - Google Patents
Method and equipment for preparing humic acid calcium magnesium chelating liquid by using ammonia-soda alkaline residue Download PDFInfo
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- CN115594862A CN115594862A CN202211029323.4A CN202211029323A CN115594862A CN 115594862 A CN115594862 A CN 115594862A CN 202211029323 A CN202211029323 A CN 202211029323A CN 115594862 A CN115594862 A CN 115594862A
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- ammonia
- humic acid
- filtrate
- dioxide gas
- filter cake
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000004021 humic acid Substances 0.000 title claims abstract description 43
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000007789 gas Substances 0.000 claims abstract description 63
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 52
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 36
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 26
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 claims abstract description 20
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000012267 brine Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000011591 potassium Substances 0.000 claims abstract description 8
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims description 46
- 239000000706 filtrate Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 30
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 3
- 239000011575 calcium Substances 0.000 claims 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- 239000011777 magnesium Substances 0.000 claims 2
- 229910052749 magnesium Inorganic materials 0.000 claims 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 1
- 229910001424 calcium ion Inorganic materials 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 239000003518 caustics Substances 0.000 description 6
- 239000010802 sludge Substances 0.000 description 6
- 238000009621 Solvay process Methods 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1418—Recovery of products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1475—Removing carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1493—Selection of liquid materials for use as absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
- B01D2252/50—Combinations of absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
Abstract
The invention relates to a method and equipment for preparing a calcium magnesium humate chelating liquid by using ammonia-soda alkaline residues, belongs to the technical field of ammonia-soda alkaline residue treatment and recycling, and particularly relates to a method for industrially producing the calcium magnesium humate chelating liquid by using waste acid, alkali and ammonia-soda alkaline residues. According to the method, ammonia-soda residue, nitric acid, humic acid, sodium carbonate and potassium hydroxide are used as raw materials, and the humic acid calcium magnesium chelate liquid is obtained through mixing and filtering, so that the process is simple and easy to implement, and can be applied in batch production; the by-product can be used as calcium sulfate whisker; the generated carbon dioxide gas and nitrogen dioxide gas are collected in a mixture containing potassium humate and ammonia water to carry out four-stage circulation, the nitrogen dioxide gas is absorbed, and the carbon dioxide gas enters a kiln gas washing tower to be used in an ammonia brine carbonation section.
Description
Technical Field
The invention relates to a method and equipment for preparing calcium magnesium humate chelating liquid by using ammonia-soda alkaline residues, belongs to the technical field of ammonia-soda alkaline residue treatment and recycling, and particularly relates to a method for industrially producing the calcium magnesium humate chelating liquid by using waste acid, alkali and ammonia-soda alkaline residues.
Background
The production capacity of the enterprises for producing the soda ash by the ammonia-soda process accounts for 46 percent of the whole country (about 1000 ten thousand tons per year), and a large amount of caustic sludge and waste liquid are discharged every year, thereby seriously polluting the environment and damaging the growth of crops. Aiming at the practical problem, the enterprises for producing soda ash by the ammonia-soda process adopt a series of solutions, such as: building cofferdam, repairing dam, changing equipment and adjusting process, but the discharge scale of waste liquid and waste caustic sludge can not be changed fundamentally. The reason for this is that the "ammonia-soda process" needs to discharge 10 tons of waste liquid and waste caustic sludge for each ton of soda ash produced. The price of soda is only about 2000 yuan per ton, and the high cost for treating 10 cubic meters of waste liquid and waste caustic sludge cannot be borne. In ammonia-soda production enterprises, the comprehensive utilization of caustic sludge is a problem to be solved urgently.
The Shandong building materials academy and the Shandong ocean chemical group soda manufacturing company cooperate together, special calcium carbonate is successfully extracted from secondary salt slurry, the special calcium carbonate is identified by provincial technology, mass production and market release are performed, research on extracting light magnesium oxide from primary salt slurry is successful in laboratory expansion experiments, pilot-scale production is prepared, residues of the light magnesium oxide are extracted from the primary salt slurry, and development and research for manufacturing cement or building cementing materials are greatly advanced.
The project of Xinjiang Tianye (group) Tianneng chemical industry limited company for preparing ceramsite by taking alkaline residue as a raw material is in a pilot-scale test stage, and the ceramsite can be widely used in the aspects of building heat preservation, building material production, water treatment filter materials, soilless culture base materials and the like.
However, how to comprehensively utilize various components of the caustic sludge is still an unsolved technical problem in the field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method and equipment for preparing a humic acid calcium magnesium chelating solution by utilizing ammonia alkaline residue, which comprehensively utilize various components of the alkaline residue, change waste into valuable, achieve zero emission and solve the problem of environmental pollution caused by the alkaline residue.
In order to realize the purpose, the invention provides a method for preparing humic acid calcium magnesium chelating liquid by utilizing ammonia-soda residue, and the method uses ammonia-soda residue, nitric acid, humic acid, sodium carbonate and potassium hydroxide as raw materials;
the humic acid is mineral source humic acid or plant source humic acid;
the method comprises the following steps:
firstly, mixing the ammonia-soda residue and sodium carbonate for 1-20min, filtering to obtain a first filtrate and a first filter cake, and separating the first filter cake from the first filtrate to obtain a second filter cake and a second filtrate; the mass of the sodium carbonate is 5-20% of the mass of the ammonia-soda alkali residue, and the obtained second filter cake mainly comprises calcium carbonate and calcium sulfate;
secondly, mixing the second filter cake obtained in the first step with nitric acid, filtering to obtain a third filtrate and a third filter cake, and separating the third filter cake from the third filtrate to obtain a fourth filter cake and a fourth filtrate; the mass of the nitric acid is 60-70% of that of the second filter cake;
thirdly, adding potassium hydroxide into the fourth filtrate obtained in the second step to adjust the pH value to 6.5-7 to obtain a mixed solution;
fourthly, adding humic acid into the mixed liquid obtained in the third step to obtain humic acid calcium magnesium chelate liquid, wherein the mass of the humic acid is 0.8-1.2 times, preferably 1 time of that of calcium magnesium ions in the mixed liquid;
the second filtrate obtained in the first step can be used as a solvent for preparing calcium sulfate whiskers; can also be used in the refining section of salt dissolving or brine in the ammonia-soda production process;
the fourth filter cake obtained in the second step can be used as calcium sulfate whisker;
and in the second step, carbon dioxide gas and nitrogen dioxide gas can be generated when the second filter cake is mixed with nitric acid, the generated carbon dioxide gas and nitrogen dioxide gas are collected in a mixture containing potassium humate and ammonia water to carry out four-stage circulation, the nitrogen dioxide gas is absorbed, and the carbon dioxide gas enters a kiln gas washing tower to be used in an ammonia brine carbonation section.
An apparatus for preparing humic acid calcium magnesium chelating liquid by ammonia-soda alkaline residue comprises a material mixer, a filter, a material collector, a gas collector, a four-stage circulator and a kiln gas washing tower;
the material mixer is used for mixing materials, such as ammonia-soda residue and sodium carbonate, mixing the fourth filtrate and potassium hydroxide, mixing the mixed solution and humic acid,
the filter is used for separating materials, such as filtrate and filter cake;
the material collector is used for collecting materials, for example, after the second filtrate is collected, the second filtrate is used as a solvent in the preparation of calcium sulfate whiskers; can also be used in the refining section of salt dissolving or brine in the ammonia-soda production process; a fourth filter cake can be collected and used as calcium sulfate whiskers;
the gas collector is used for collecting carbon dioxide gas and nitrogen dioxide gas;
the four-stage circulator is used for performing four-stage circulation on the mixture of potassium humate and ammonia water filled with carbon dioxide gas and nitrogen dioxide gas;
the kiln gas washing tower is used for collecting carbon dioxide gas, and the collected carbon dioxide gas is used in an ammonia salt water carbonation workshop section.
Advantageous effects
(1) According to the method, ammonia-soda residue, nitric acid, humic acid, sodium carbonate and potassium hydroxide are used as raw materials, and the humic acid calcium magnesium chelate liquid is obtained through mixing and filtering, so that the process is simple and easy to implement, and can be applied in batch production;
(2) In the method, the fourth filter cake as a byproduct can be used as calcium sulfate whiskers;
(3) In the method, the second filter cake as a byproduct and nitric acid can generate carbon dioxide gas and nitrogen dioxide gas when mixed, the generated carbon dioxide gas and nitrogen dioxide gas are collected in a mixture containing potassium humate and ammonia water to carry out four-stage circulation, the nitrogen dioxide gas is absorbed, and the carbon dioxide gas enters a kiln gas washing tower to be used in an ammonia brine carbonation section.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
The composition of the alkaline residue obtained by the ammonia-soda process of Sanyou chemical Co., ltd, tangshan is shown in Table 1 after being analyzed by the inspection center of Tianjin chemical research and design institute.
TABLE 1 alkaline residue composition analysis
Alkaline residue composition | Sample 1% by weight | Sample 2% by weight | Sample 3% by weight | Sample 4% by weight |
Calcium sulfate | 17.3 | 3 | 15 | 3 |
Calcium carbonate | 21.2 | 64 | 20 | 64 |
Calcium oxide | 5.7 | 8 | 8 | |
Calcium chloride | 22.5 | 6 | 3 | 6 |
Sodium chloride | 3.1 | 4 | 10 | 4 |
Calcium hydroxide | 6.5 | 10 | 5 | 10 |
Magnesium hydroxide | 8.9 | 27 | ||
Silicon dioxide | 8.0 | 3 | 6 | 3 |
Alumina oxide | 2.5 | 2 | 2 | 2 |
Iron oxide | 1 | |||
Acid insoluble substance | 4.3 | 8 | 2 | 8 |
The method comprehensively utilizes the alkaline residue of the ammonia-soda process, completely recycles the alkaline residue and the wastewater for conveying the alkaline residue, has no pollutant discharge in the whole process, and can realize automatic control and continuous production.
Examples
A method for preparing humic acid calcium magnesium chelate liquid by ammonia-soda alkaline residue uses raw materials of ammonia-soda alkaline residue, nitric acid, humic acid, sodium carbonate and potassium hydroxide;
the humic acid is mineral source humic acid or plant source humic acid;
the method comprises the following steps:
firstly, mixing ammonia-soda residue and a sodium carbonate aqueous solution with the mass concentration of 15% at room temperature for 15min, filtering to obtain a first filtrate and a first filter cake, and separating the first filter cake from the first filtrate to obtain a second filter cake and a second filtrate; crushing the second filter cake to obtain a second filter cake mainly comprising calcium carbonate and calcium sulfate; washing the filter cake to ensure that the chlorine content in the second filter cake is lower than 3 percent; the mass of the sodium carbonate is 15 percent of the mass of the ammonia-soda alkaline residue;
secondly, mixing the second filter cake obtained in the first step with nitric acid with the mass concentration of 50%, filtering to obtain a third filtrate and a third filter cake, and separating the third filter cake from the third filtrate to obtain a fourth filter cake and a fourth filtrate; the mass of the nitric acid is 50% of the mass of the second filter cake;
step three, adding potassium hydroxide into the fourth filtrate obtained in the step two to adjust the pH value to 7.0, so as to obtain a mixed solution;
fourthly, adding humic acid into the mixed liquid obtained in the third step to obtain humic acid calcium magnesium chelating liquid, wherein the mass of the humic acid is 3 times of that of calcium magnesium ions in the mixed liquid;
the second filtrate obtained in the first step can be used as a solvent for preparing calcium sulfate whiskers; can also be used in the refining section of salt dissolving or brine in the ammonia-soda production process;
the fourth filter cake obtained in the second step can be used as calcium sulfate whisker;
and in the second step, carbon dioxide gas and nitrogen dioxide gas can be generated when the second filter cake is mixed with nitric acid, the generated carbon dioxide gas and nitrogen dioxide gas are collected in a mixture containing potassium humate and ammonia water to carry out four-stage circulation, the nitrogen dioxide gas is absorbed, and the carbon dioxide gas enters a kiln gas washing tower to be used in an ammonia brine carbonation section.
The obtained compound amino acid calcium magnesium chelating liquid meets the standard of calcium magnesium humate fertilizer.
An apparatus for preparing humic acid calcium magnesium chelate liquid by ammonia-soda alkaline residue comprises a material mixer, a filter, a material collector, a gas collector, a four-stage circulator and a kiln gas washing tower;
the material mixer is used for mixing materials, such as ammonia-soda residue and sodium carbonate, mixing the fourth filtrate and potassium hydroxide, mixing the mixed solution and humic acid,
the filter is used for separating materials, such as filtrate and filter cake;
the material collector is used for collecting materials, for example, after collecting the second filtrate, the second filtrate is used as a solvent in the preparation of the calcium sulfate whisker; can also be used in the refining section of salt dissolving or brine in the ammonia-soda production process; a fourth filter cake can be collected and used as calcium sulfate whiskers;
the gas collector is used for collecting carbon dioxide gas and nitrogen dioxide gas;
the four-stage circulator is used for performing four-stage circulation on the mixture of potassium humate and ammonia water filled with carbon dioxide gas and nitrogen dioxide gas;
the kiln gas washing tower is used for collecting carbon dioxide gas, and the collected carbon dioxide gas is used in an ammonia salt water carbonation workshop section.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explaining the principles of the invention and are not to be construed as limiting the invention. Therefore, any modification, equivalent replacement, improvement and the like made without departing from the spirit and scope of the present invention should be included in the protection scope of the present invention. Further, it is intended that the appended claims cover all such variations and modifications as fall within the scope and boundaries of the appended claims or the equivalents of such scope and boundaries.
Claims (9)
1. A method for preparing humic acid calcium magnesium chelate liquid by ammonia-soda alkaline residue is characterized in that the raw materials used in the method are ammonia-soda alkaline residue, nitric acid, humic acid, sodium carbonate and potassium hydroxide;
the humic acid is mineral source humic acid or plant source humic acid;
the method comprises the following steps:
firstly, mixing the ammonia-soda residue and sodium carbonate for 1-20min, filtering to obtain a first filtrate and a first filter cake, and separating the first filter cake from the first filtrate to obtain a second filter cake and a second filtrate; the mass of the sodium carbonate is 5-20% of the mass of the ammonia-soda alkaline residue;
secondly, mixing the second filter cake obtained in the first step with nitric acid, filtering to obtain a third filtrate and a third filter cake, and separating the third filter cake from the third filtrate to obtain a fourth filter cake and a fourth filtrate; the mass of the nitric acid is 60-70% of that of the second filter cake;
thirdly, adding potassium hydroxide into the fourth filtrate obtained in the second step to adjust the pH value to 6.5-7 to obtain a mixed solution;
and step four, adding humic acid into the mixed liquid obtained in the step three to obtain humic acid calcium magnesium chelate liquid, wherein the mass of the humic acid is 0.8-1.2 times of the mass of calcium magnesium ions in the mixed liquid.
2. The method for preparing the humic acid calcium magnesium chelating solution by using the ammonia-soda alkaline residue as claimed in claim 1, which is characterized in that:
in the first step, the obtained second filtrate is used as a solvent for preparing the calcium sulfate whiskers or used in a refining section of salt dissolving or brine in an ammonia-soda production process.
3. The method for preparing the humic acid calcium magnesium chelating solution by using the ammonia-soda alkaline residue according to claim 1, which is characterized by comprising the following steps of:
and in the second step, the obtained fourth filter cake is used as calcium sulfate whiskers.
4. The method for preparing the humic acid calcium magnesium chelating solution by using the ammonia-soda alkaline residue as claimed in claim 1, which is characterized in that:
and in the second step, carbon dioxide gas and nitrogen dioxide gas can be generated when the second filter cake is mixed with nitric acid, the generated carbon dioxide gas and nitrogen dioxide gas are collected in a mixture containing potassium humate and ammonia water to carry out four-stage circulation, the nitrogen dioxide gas is absorbed, and the carbon dioxide gas enters a kiln gas washing tower to be used in an ammonia brine carbonation section.
5. The method for preparing the humic acid calcium magnesium chelating solution by using the ammonia-soda residue as claimed in any one of claims 1 to 4, which is characterized in that:
in the third step, the mass of humic acid is 1 time of the mass of calcium and magnesium ions in the mixed solution.
6. The equipment for preparing the humic acid calcium magnesium chelate liquid by utilizing the ammonia-soda alkaline residue is characterized by comprising the following steps of:
the equipment comprises a material mixer, a filter, a material collector, a gas collector, a four-stage circulator and a kiln gas washing tower;
the material mixer is used for mixing materials;
the filter is used for separating materials;
the material collector is used for collecting materials;
the gas collector is used for collecting carbon dioxide gas and nitrogen dioxide gas;
the four-stage circulator is used for performing four-stage circulation on the mixture of potassium humate and ammonia water filled with carbon dioxide gas and nitrogen dioxide gas;
the kiln gas washing tower is used for collecting carbon dioxide gas, and the collected carbon dioxide gas is used in an ammonia salt water carbonation workshop section.
7. The apparatus for preparing the chelated calcium and magnesium humate solution by using the ammonia-soda alkaline residue as claimed in claim 6, is characterized in that:
the material mixer is used for mixing ammonia-soda residue and sodium carbonate;
the filter is used for separating the filtrate from the filter cake;
and the material collector is used for collecting the second filtrate and using the second filtrate as a solvent for preparing the calcium sulfate whiskers.
8. The equipment for preparing the humic acid calcium magnesium chelating solution by using the ammonia-soda alkaline residue according to claim 6, which is characterized in that:
the material mixer is used for mixing the fourth filtrate with potassium hydroxide;
the filter is used for separating the filtrate from the filter cake;
the material collector is used for collecting the second filtrate and then using the second filtrate in a refining section of salt dissolving or brine of the ammonia-soda production process.
9. The apparatus for preparing the chelated calcium and magnesium humate solution by using the ammonia-soda alkaline residue as claimed in claim 6, is characterized in that:
the material mixer is used for mixing humic acid and the mixed liquid;
the filter is used for separating the filtrate from the filter cake;
and the material collector is used for collecting the fourth filter cake and using the collected fourth filter cake as calcium sulfate whiskers.
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