WO2024074005A1 - Wet-process phosphoric acid scale-dissolving agent, preparation method therefor, and use thereof - Google Patents
Wet-process phosphoric acid scale-dissolving agent, preparation method therefor, and use thereof Download PDFInfo
- Publication number
- WO2024074005A1 WO2024074005A1 PCT/CN2023/077170 CN2023077170W WO2024074005A1 WO 2024074005 A1 WO2024074005 A1 WO 2024074005A1 CN 2023077170 W CN2023077170 W CN 2023077170W WO 2024074005 A1 WO2024074005 A1 WO 2024074005A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- wet
- phosphoric acid
- process phosphoric
- agent
- acid
- Prior art date
Links
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 27
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 230000007797 corrosion Effects 0.000 claims abstract description 17
- 238000005260 corrosion Methods 0.000 claims abstract description 17
- 239000003112 inhibitor Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 229920000805 Polyaspartic acid Polymers 0.000 claims abstract description 10
- 108010064470 polyaspartate Proteins 0.000 claims abstract description 10
- 229920001529 polyepoxysuccinic acid Polymers 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical group NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 3
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims description 2
- ZQLBQWDYEGOYSW-UHFFFAOYSA-L copper;disulfamate Chemical compound [Cu+2].NS([O-])(=O)=O.NS([O-])(=O)=O ZQLBQWDYEGOYSW-UHFFFAOYSA-L 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- BTAAXEFROUUDIL-UHFFFAOYSA-M potassium;sulfamate Chemical compound [K+].NS([O-])(=O)=O BTAAXEFROUUDIL-UHFFFAOYSA-M 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- QDWYPRSFEZRKDK-UHFFFAOYSA-M sodium;sulfamate Chemical compound [Na+].NS([O-])(=O)=O QDWYPRSFEZRKDK-UHFFFAOYSA-M 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- GWTCIAGIKURVBJ-UHFFFAOYSA-L dipotassium;dodecyl phosphate Chemical compound [K+].[K+].CCCCCCCCCCCCOP([O-])([O-])=O GWTCIAGIKURVBJ-UHFFFAOYSA-L 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 159000000000 sodium salts Chemical class 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical group NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 abstract 1
- -1 potassium fluorosilicate Chemical compound 0.000 description 15
- 239000013078 crystal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000001506 calcium phosphate Substances 0.000 description 4
- 229910000389 calcium phosphate Inorganic materials 0.000 description 4
- 235000011010 calcium phosphates Nutrition 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 239000002455 scale inhibitor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- 159000000007 calcium salts Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CGORERCPVAYUAZ-UHFFFAOYSA-N P(=O)(O)(O)O.C(CCCCCCCCCCC)[K] Chemical compound P(=O)(O)(O)O.C(CCCCCCCCCCC)[K] CGORERCPVAYUAZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000668 effect on calcium Effects 0.000 description 1
- 229940104869 fluorosilicate Drugs 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000141 poly(maleic anhydride) Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
- B08B9/027—Cleaning the internal surfaces; Removal of blockages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto
- B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
- B08B9/027—Cleaning the internal surfaces; Removal of blockages
- B08B9/032—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing
- B08B9/0321—Cleaning the internal surfaces; Removal of blockages by the mechanical action of a moving fluid, e.g. by flushing using pressurised, pulsating or purging fluid
Definitions
- the present application relates to the technical field of anti-scaling, and in particular to a wet-process phosphoric acid scale dissolving agent and a preparation method and application thereof.
- wet phosphoric acid scaling mainly includes calcium salts (calcium sulfate, calcium carbonate, calcium phosphate) and fluorosilicates (such as potassium fluorosilicate, sodium fluorosilicate).
- calcium salts calcium sulfate, calcium carbonate, calcium phosphate
- fluorosilicates such as potassium fluorosilicate, sodium fluorosilicate.
- the prior art discloses a scale inhibitor for wet-process phosphoric acid production, which is composed of an organic phosphorus scale inhibitor, a polymer scale inhibitor dispersant and a bactericide and algaecide.
- the scale inhibitor has a certain scale inhibition effect on calcium sulfate, calcium carbonate and calcium phosphate produced in the production of wet-process phosphoric acid, but has a poor scale inhibition effect on fluorosilicate scale.
- the prior art also discloses a wet-process phosphoric acid anti-deposition agent and a preparation method thereof, which is prepared by compounding an acrylic acid multi-polymer, 2-phosphoryl-1,2,4-tricarboxylic acid butane and polymaleic anhydride, but its scale inhibition rate for sodium silicofluoride and potassium silicofluoride is still low and cannot meet the actual production and use requirements.
- the purpose of the present application is to overcome the defect of low descaling efficiency of wet-process phosphoric acid descaling agents in the prior art, and to provide a wet-process phosphoric acid descaling agent.
- the wet-process phosphoric acid descaling agent of the present application is compounded with a specific descaling agent, a dispersant and a penetrant, a corrosion inhibitor and a surfactant, and can efficiently dissolve and remove scales such as potassium fluorosilicate, sodium silicofluoride and calcium sulfate generated in the production process of wet-process phosphoric acid, and has low corrosiveness to wet-process phosphoric acid production equipment and does not damage the production equipment.
- Another object of the present application is to provide a method for preparing the above-mentioned wet-process phosphoric acid scale dissolving agent.
- Another object of the present application is to provide an application of the wet-process phosphoric acid descaling agent.
- the present application provides a wet-process phosphoric acid scale remover, comprising the following components in weight percentage:
- Descaling agent 5% to 15%, dispersant 8% to 13%, penetrant 0.5% to 1%, corrosion inhibitor 0.1% to 0.5%, surfactant 0.3% to 0.8%, and the balance is water;
- the descaling agent is aminosulfonate
- the dispersant is a mixture of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
- the scales produced during the production of wet-process phosphoric acid are mainly potassium fluorosilicate, sodium fluorosilicate and calcium sulfate.
- This application uses aminosulfonates as descaling agents. Aminosulfonates have high solubility for calcium salt scales and can effectively dissolve calcium sulfate, calcium phosphate and other substances. At the same time, compared with aminosulfonic acid, aminosulfonates are not highly acidic and will not cause corrosive damage to wet-process phosphoric acid equipment, nor will they have a negative impact on the production of phosphoric acid.
- the dispersant is a mixture of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
- Polyaspartic acid contains more carboxylic acid groups.
- the carboxylic acid is partially ionized to produce negatively charged anions, which can be adsorbed to the active growth points of the scaling crystals, thereby destroying potassium fluorosilicate,
- the crystal structure of sodium fluorosilicate and calcium sulfate causes lattice distortion; and the dispersant is adsorbed onto the surface of the scaling crystal particles, so that the surface of the scaling crystals carries the same negative charge, and mutual repulsion is generated between the crystal particles, thereby effectively dispersing the scaling crystals and making it difficult to aggregate.
- the polyepoxysuccinic acid in the dispersant can increase the surface free energy of potassium fluorosilicate and sodium fluorosilicate during crystallization, and further inhibit the crystallization of potassium fluorosilicate and sodium fluorosilicate.
- Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer can dissolve calcium salts well, especially calcium phosphate scale, which is easily formed into dispersed crystals under the action of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, so as to be removed.
- the scaling crystals are suspended in the solution and are evenly dispersed without aggregation.
- the number of scaling crystals is increased and the average particle size is reduced, making them easier to dissolve and remove.
- the penetrant and the surfactant act synergistically to enhance the scale dissolving agent's destruction of the interior of the scale crystals and accelerate the dissolution efficiency; the use of the corrosion inhibitor reduces the corrosion of the wet-process phosphoric acid scale dissolving agent on the production equipment and reduces the damage of the wet-process phosphoric acid scale dissolving agent to the production equipment.
- the wet-process phosphoric acid descaling agent includes the following components in weight percentage:
- the wet-process phosphoric acid scale dissolving agent has the above-mentioned component ratio, the synergistic effect between the components is better, and the dissolution rate of the wet-process phosphoric acid scale is faster.
- the aminosulfonate is at least one of sodium aminosulfonate, potassium aminosulfonate, and copper aminosulfonate.
- the dispersant contains polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-
- the weight ratio of the methylpropanesulfonic acid copolymer is (9-11):(1.5-3):1.
- the weight ratio of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer in the dispersant is 10:2:1.
- the wet-process phosphoric acid scale dissolving agent of the present application has higher scale dissolving efficiency.
- the penetrant is at least one of dioctyl sulfonate succinate sodium salt, ethanolamine, and decyl sulfonate succinate.
- the penetrant is dioctyl sulfonate sodium salt.
- the corrosion inhibitor is benzotriazole and/or mercaptobenzothiazole.
- the surfactant is at least one of dodecylbenzene sulfonate, dodecyl potassium phosphate, ⁇ -olefin sulfonate, polyoxyethylene ether phosphate, and alkyl alcohol amide phosphate.
- the surfactant is dodecylbenzene sulfonate.
- the present application provides a method for preparing the wet-process phosphoric acid scale dissolving agent, comprising the following steps:
- the wet-process phosphoric acid scale remover is obtained by adding a descaling agent, a dispersant, a penetrant, a corrosion inhibitor and a surfactant into water and mixing them evenly.
- the mixing condition is stirring at a temperature of 40 to 50°C.
- each component can be well dissolved in water and dispersed evenly, which helps to achieve better synergy between the components.
- the method for preparing the wet-process phosphoric acid scale remover comprises the following steps:
- the descaling agent, dispersant, penetrant, corrosion inhibitor and surfactant are sequentially added into water, stirred at 40-50° C. until the mixture is uniform, cooled and filtered to obtain the wet-process phosphoric acid descaling agent.
- the present application provides the above-mentioned wet-process phosphoric acid descaling agent for dissolving scales in wet-process phosphoric acid production. Application in.
- the wet-process phosphoric acid scale dissolving agent described in this application is diluted 5 to 10 times with water to control the concentration of the effective substance therein to be about 5%.
- the diluted wet-process phosphoric acid scale dissolving agent is circulated or soaked in the pipeline to be cleaned for 2 to 4 hours using a circulation pump to dissolve the scale formed in the production of wet-process phosphoric acid.
- the present application develops a wet-process phosphoric acid descaling agent, which is compounded with a specific descaling agent, a dispersant and a penetrant, a corrosion inhibitor and a surfactant to efficiently dissolve and remove scales such as potassium fluorosilicate, sodium fluorosilicate and calcium sulfate generated in the production process of wet-process phosphoric acid.
- scales such as potassium fluorosilicate, sodium fluorosilicate and calcium sulfate generated in the production process of wet-process phosphoric acid.
- the dissolution rate of the scale is ⁇ 45% in 0.5 hours and ⁇ 80% in 4 hours.
- the present application will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present application in any form.
- the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the art.
- the reagents and materials used in the present application are commercially available.
- Examples 1 to 16 provide a wet-process phosphoric acid scale dissolving agent, and the component contents are shown in Table 1.
- the preparation method of the wet-process phosphoric acid scale dissolving agent of Examples 1 to 16 is as follows:
- Comparative Examples 1 to 8 provide a wet-process phosphoric acid scale dissolving agent, and the component contents are shown in Table 2.
- the preparation methods of the wet-process phosphoric acid scale dissolving agents of Comparative Examples 1 to 8 are as follows:
- Scaling materials in a wet-process phosphoric acid filtration system of a phosphorus chemical industry in Yichang, Hubei province were taken as scale samples; the scale samples were added to the wet-process phosphoric acid scale dissolving agents prepared in the embodiments and comparative examples, respectively, with 2 g of the scale sample added to every 100 ml of the wet-process phosphoric acid scale dissolving agent, and the scale samples were soaked at 60° C. for 4 h, and the dissolution rates of the scale samples were detected at 0.5, 1, 2, and 4 h, respectively; the higher the dissolution rate, the better the scale dissolving efficiency of the wet-process phosphoric acid scale dissolving agent.
- m1 is the mass of the scale sample before dissolution
- m2 is the mass of the scale sample after dissolution and drying.
- the wet-process phosphoric acid scale dissolving agent prepared in each embodiment of the present application has a high dissolution rate for scale deposits. At 0.5 h, the dissolution rate is ⁇ 45%, and at 4 h, the dissolution rate is ⁇ 80%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present application provides a wet-process phosphoric acid scale-dissolving agent, a preparation method therefor, and use thereof, and relates to the technical field of scale prevention. The wet-process phosphoric acid scale-dissolving agent of the present application comprises the following components in percentage by weight: 5%-15% of a descaling agent, 8%-13% of a dispersing agent, 0.5%-1% of a permeating agent, 0.1%-0.5% of a corrosion inhibitor, 0.3%-0.8% of a surfactant, and the balance of water. The descaling agent is sulfamate. The dispersing agent is a mixture of polyepoxysuccinic acid, polyaspartic acid and an acrylic acid-2-acrylamido-2-methylpropane sulfonic acid copolymer. According to the present application, the specific descaling agent, the dispersing agent, the permeating agent, the corrosion inhibitor and the surfactant are used and compounded, such that potassium fluosilicate, sodium silicofluoride, calcium sulfate and other scaling substances generated in the wet-process phosphoric acid production process are efficiently dissolved and removed, the dissolution rate of the scaling substances is greater than or equal to 45% at the time of 0.5 h, and the dissolution rate of the scaling substances is greater than or equal to 80% at the time of 4 h.
Description
本申请涉及防垢技术领域，尤其是一种湿法磷酸溶垢剂及其制备方法和应用。The present application relates to the technical field of anti-scaling, and in particular to a wet-process phosphoric acid scale dissolving agent and a preparation method and application thereof.
在湿法磷酸工业生产时，反应、过滤、浓缩、储存等工艺环节都有结垢现象，尤其在真空过滤系统中，结垢现象较严重，湿法磷酸结垢物主要包括钙盐类(硫酸钙、碳酸钙、磷酸钙)和氟硅酸盐类(如硅氟酸钾、氟硅酸钠)。近年来随着磷矿品位的降低，湿法磷酸生产装置堵塞速度加快，清理频繁，且堵塞无坚硬，清理难度大，清理时间长达12h以上，工人劳动强度大，降低了开车率及年产量。因此需要一种快速清除结垢的方法。In the industrial production of wet phosphoric acid, scaling occurs in the reaction, filtration, concentration, storage and other process links, especially in the vacuum filtration system, where scaling is more serious. Wet phosphoric acid scaling mainly includes calcium salts (calcium sulfate, calcium carbonate, calcium phosphate) and fluorosilicates (such as potassium fluorosilicate, sodium fluorosilicate). In recent years, with the reduction of phosphate ore grade, the clogging speed of wet phosphoric acid production equipment has accelerated, and the cleaning is frequent. The blockage is not hard, the cleaning is difficult, and the cleaning time is as long as 12 hours or more. The labor intensity of workers is high, which reduces the start-up rate and annual output. Therefore, a method for quickly removing scaling is needed.
现有技术公开了一种湿法磷酸生产用阻垢剂，由有机磷类阻垢缓蚀剂、聚合物类阻垢分散剂和杀菌灭藻剂组合而成。该阻垢剂对于湿法磷酸生产中产生的硫酸钙、碳酸钙、磷酸钙具有一定的阻垢效果，但是对氟硅酸盐结垢物的阻垢效果差。还有现有技术公开了一种湿法磷酸抗沉积剂及其制备方法，该抗沉积剂由丙烯酸多元共聚物、2-磷酸基-1，2，4-三羧酸丁烷、聚马来酸酐复配制成，但是其对硅氟酸钠、硅氟酸钾的阻垢率仍较低，无法满足实际生产使用要求。The prior art discloses a scale inhibitor for wet-process phosphoric acid production, which is composed of an organic phosphorus scale inhibitor, a polymer scale inhibitor dispersant and a bactericide and algaecide. The scale inhibitor has a certain scale inhibition effect on calcium sulfate, calcium carbonate and calcium phosphate produced in the production of wet-process phosphoric acid, but has a poor scale inhibition effect on fluorosilicate scale. The prior art also discloses a wet-process phosphoric acid anti-deposition agent and a preparation method thereof, which is prepared by compounding an acrylic acid multi-polymer, 2-phosphoryl-1,2,4-tricarboxylic acid butane and polymaleic anhydride, but its scale inhibition rate for sodium silicofluoride and potassium silicofluoride is still low and cannot meet the actual production and use requirements.
因此，需要提供一种除垢效率高的湿法磷酸溶垢剂。Therefore, it is necessary to provide a wet-process phosphoric acid descaling agent with high descaling efficiency.
发明内容Summary of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
本申请的目的在于，克服现有技术中湿法磷酸溶垢剂除垢效率低的缺陷，提供一种湿法磷酸溶垢剂。本申请的湿法磷酸溶垢剂通过采用特定的除垢剂、分散剂与渗透剂、缓蚀剂和表面活性剂进行复配，可以高效溶解并去除湿法磷酸生产过程中产生的氟硅酸钾、硅氟酸钠和硫酸钙等结垢物，且对湿法磷酸生产设备的腐蚀性小，不损伤生产设备。The purpose of the present application is to overcome the defect of low descaling efficiency of wet-process phosphoric acid descaling agents in the prior art, and to provide a wet-process phosphoric acid descaling agent. The wet-process phosphoric acid descaling agent of the present application is compounded with a specific descaling agent, a dispersant and a penetrant, a corrosion inhibitor and a surfactant, and can efficiently dissolve and remove scales such as potassium fluorosilicate, sodium silicofluoride and calcium sulfate generated in the production process of wet-process phosphoric acid, and has low corrosiveness to wet-process phosphoric acid production equipment and does not damage the production equipment.
本申请的另一目的在于提供上述湿法磷酸溶垢剂的制备方法。Another object of the present application is to provide a method for preparing the above-mentioned wet-process phosphoric acid scale dissolving agent.
本申请的另一目的在于提供上述湿法磷酸溶垢剂的应用。Another object of the present application is to provide an application of the wet-process phosphoric acid descaling agent.
为实现上述目的，本申请采用如下技术方案：To achieve the above objectives, this application adopts the following technical solutions:
第一方面，本申请提供了一种湿法磷酸溶垢剂，包括如下重量百分比的组分：In a first aspect, the present application provides a wet-process phosphoric acid scale remover, comprising the following components in weight percentage:
除垢剂5％～15％，分散剂8％～13％，渗透剂0.5％～1％，缓蚀剂0.1％～0.5％，表面活性剂0.3％～0.8％，余量为水；Descaling agent 5% to 15%, dispersant 8% to 13%, penetrant 0.5% to 1%, corrosion inhibitor 0.1% to 0.5%, surfactant 0.3% to 0.8%, and the balance is water;
所述除垢剂为氨基磺酸盐，所述分散剂为聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的混合物。The descaling agent is aminosulfonate, and the dispersant is a mixture of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
湿法磷酸生产过程中所产生的结垢物主要为氟硅酸钾、氟硅酸钠和硫酸钙。本申请采用氨基磺酸盐作为除垢剂，氨基磺酸盐对于钙盐类结垢物有较高的溶解性，可以有效溶解硫酸钙、磷酸钙等物质。同时，相比于氨基磺酸，氨基磺酸盐的酸性不强，不会造成湿法磷酸设备的腐蚀性损坏，也不会对磷酸的生产产生负面影响。The scales produced during the production of wet-process phosphoric acid are mainly potassium fluorosilicate, sodium fluorosilicate and calcium sulfate. This application uses aminosulfonates as descaling agents. Aminosulfonates have high solubility for calcium salt scales and can effectively dissolve calcium sulfate, calcium phosphate and other substances. At the same time, compared with aminosulfonic acid, aminosulfonates are not highly acidic and will not cause corrosive damage to wet-process phosphoric acid equipment, nor will they have a negative impact on the production of phosphoric acid.
本申请的湿法磷酸溶垢剂中，分散剂采用聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的混合物。In the wet-process phosphoric acid scale dissolving agent of the present application, the dispersant is a mixture of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
聚天冬氨酸含有较多羧酸基团，在除垢过程中羧酸发生部分电离，产生带负电的阴离子，能够吸附至结垢物晶体的活性增长点上，从而破坏了氟硅酸钾、
氟硅酸钠和硫酸钙的晶体结构，使其发生晶格畸变；并且分散剂吸附至结垢物晶体颗粒表面，使得结垢物晶体表面带有相同的负电荷，晶体颗粒间产生相互排斥力，从而有效分散结垢物晶体，使其难以聚集。Polyaspartic acid contains more carboxylic acid groups. During the descaling process, the carboxylic acid is partially ionized to produce negatively charged anions, which can be adsorbed to the active growth points of the scaling crystals, thereby destroying potassium fluorosilicate, The crystal structure of sodium fluorosilicate and calcium sulfate causes lattice distortion; and the dispersant is adsorbed onto the surface of the scaling crystal particles, so that the surface of the scaling crystals carries the same negative charge, and mutual repulsion is generated between the crystal particles, thereby effectively dispersing the scaling crystals and making it difficult to aggregate.
分散剂中的聚环氧琥珀酸可以提高氟硅酸钾和氟硅酸钠结晶时的表面自由能，进一步抑制氟硅酸钾和氟硅酸钠结晶。The polyepoxysuccinic acid in the dispersant can increase the surface free energy of potassium fluorosilicate and sodium fluorosilicate during crystallization, and further inhibit the crystallization of potassium fluorosilicate and sodium fluorosilicate.
丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物可以良好溶解钙盐，特别是磷酸钙结垢，在丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的作用下易于形成分散的晶体，从而被去除。Acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer can dissolve calcium salts well, especially calcium phosphate scale, which is easily formed into dispersed crystals under the action of acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer, so as to be removed.
通过除垢剂和分散剂的协同作用，一方面使得结垢物晶体悬浮于溶液中，且均匀分散、不聚集，另一方面还使得结垢物晶体的晶粒数增加、平均粒径减小，易于溶解去除。Through the synergistic effect of the descaling agent and the dispersant, on the one hand, the scaling crystals are suspended in the solution and are evenly dispersed without aggregation. On the other hand, the number of scaling crystals is increased and the average particle size is reduced, making them easier to dissolve and remove.
在本申请的湿法磷酸溶垢剂中，渗透剂和表面活性剂通过协同作用，增强了溶垢剂对于结垢物晶体内部的破坏，加速了溶解效率；缓蚀剂的使用，减缓了湿法磷酸溶垢剂对生产设备的腐蚀性，减弱了湿法磷酸溶垢剂对生产设备的破坏。In the wet-process phosphoric acid scale dissolving agent of the present application, the penetrant and the surfactant act synergistically to enhance the scale dissolving agent's destruction of the interior of the scale crystals and accelerate the dissolution efficiency; the use of the corrosion inhibitor reduces the corrosion of the wet-process phosphoric acid scale dissolving agent on the production equipment and reduces the damage of the wet-process phosphoric acid scale dissolving agent to the production equipment.
可选地，湿法磷酸溶垢剂包括如下重量百分比的组分：Optionally, the wet-process phosphoric acid descaling agent includes the following components in weight percentage:
除垢剂10％～15％，分散剂10％～13％，渗透剂0.5％～0.8％，缓蚀剂0.3％～0.5％，表面活性剂0.3％～0.5％，余量为水。Descaling agent 10%-15%, dispersant 10%-13%, penetrant 0.5%-0.8%, corrosion inhibitor 0.3%-0.5%, surfactant 0.3%-0.5%, and the balance is water.
当湿法磷酸溶垢剂为上述组分配比时，各组分间的协同增效作用更优，对于湿法磷酸结垢物的溶解速率更快。When the wet-process phosphoric acid scale dissolving agent has the above-mentioned component ratio, the synergistic effect between the components is better, and the dissolution rate of the wet-process phosphoric acid scale is faster.
可选地，所述氨基磺酸盐为氨基磺酸钠、氨基磺酸钾、氨基磺酸铜中的至少一种。Optionally, the aminosulfonate is at least one of sodium aminosulfonate, potassium aminosulfonate, and copper aminosulfonate.
可选地，所述分散剂中聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-
甲基丙磺酸共聚物的重量比为(9～11)∶(1.5～3)∶1。Optionally, the dispersant contains polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2- The weight ratio of the methylpropanesulfonic acid copolymer is (9-11):(1.5-3):1.
可选地，所述分散剂中聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的重量比为10∶2∶1。Optionally, the weight ratio of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer in the dispersant is 10:2:1.
发明人研究发现，当聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的重量比满足上述比例范围时，本申请的湿法磷酸溶垢剂的溶垢效率更高。The inventors have found that when the weight ratio of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer meets the above ratio range, the wet-process phosphoric acid scale dissolving agent of the present application has higher scale dissolving efficiency.
可选地，所述渗透剂为磺化琥珀酸二辛酯钠盐、乙醇胺、磺化琥珀酸癸酯中的至少一种。Optionally, the penetrant is at least one of dioctyl sulfonate succinate sodium salt, ethanolamine, and decyl sulfonate succinate.
可选地，所述渗透剂为磺化琥珀酸二辛酯钠盐。Optionally, the penetrant is dioctyl sulfonate sodium salt.
可选地，所述缓蚀剂为苯并三唑和/或巯基苯并噻唑。Optionally, the corrosion inhibitor is benzotriazole and/or mercaptobenzothiazole.
可选地，所述表面活性剂为十二烷基苯磺酸盐、十二烷基磷酸酯钾盐、α-烯烃磺酸盐、聚氧乙烯醚磷酸酯盐、烷基醇酰胺磷酸酯中的至少一种。Optionally, the surfactant is at least one of dodecylbenzene sulfonate, dodecyl potassium phosphate, α-olefin sulfonate, polyoxyethylene ether phosphate, and alkyl alcohol amide phosphate.
可选地，所述表面活性剂为十二烷基苯磺酸盐。Optionally, the surfactant is dodecylbenzene sulfonate.
第二方面，本申请提供了上述湿法磷酸溶垢剂的制备方法，包括如下步骤：In a second aspect, the present application provides a method for preparing the wet-process phosphoric acid scale dissolving agent, comprising the following steps:
将除垢剂、分散剂、渗透剂、缓蚀剂和表面活性剂加至水中，混合均匀后，即得所述湿法磷酸溶垢剂。The wet-process phosphoric acid scale remover is obtained by adding a descaling agent, a dispersant, a penetrant, a corrosion inhibitor and a surfactant into water and mixing them evenly.
可选地，所述混合的条件为40～50℃温度下搅拌。Optionally, the mixing condition is stirring at a temperature of 40 to 50°C.
在40～50℃下，各组分可以良好溶于水中，且分散均匀，有助于组分间的协同作用更好。At 40-50°C, each component can be well dissolved in water and dispersed evenly, which helps to achieve better synergy between the components.
可选地，所述湿法磷酸溶垢剂的制备方法，包括如下步骤：Optionally, the method for preparing the wet-process phosphoric acid scale remover comprises the following steps:
将除垢剂、分散剂、渗透剂、缓蚀剂和表面活性剂依次加至水中，在40～50℃条件下搅拌至混合均匀，冷却后过滤，即得所述湿法磷酸溶垢剂。The descaling agent, dispersant, penetrant, corrosion inhibitor and surfactant are sequentially added into water, stirred at 40-50° C. until the mixture is uniform, cooled and filtered to obtain the wet-process phosphoric acid descaling agent.
第三方面，本申请提供了上述湿法磷酸溶垢剂在溶解湿法磷酸生产结垢物
中的应用。In a third aspect, the present application provides the above-mentioned wet-process phosphoric acid descaling agent for dissolving scales in wet-process phosphoric acid production. Application in.
在设备检修或管道清洗的过程中，使用水将本申请所述湿法磷酸溶垢剂稀释5～10倍，控制其中有效物质的浓度在5％左右。运用循环泵将稀释好的湿法磷酸溶垢剂在需要清洗的管道进行循环或浸泡2～4h，即可实现溶解湿法磷酸生产结垢物的作用。During equipment maintenance or pipeline cleaning, the wet-process phosphoric acid scale dissolving agent described in this application is diluted 5 to 10 times with water to control the concentration of the effective substance therein to be about 5%. The diluted wet-process phosphoric acid scale dissolving agent is circulated or soaked in the pipeline to be cleaned for 2 to 4 hours using a circulation pump to dissolve the scale formed in the production of wet-process phosphoric acid.
与现有技术相比，本申请的有益效果是：Compared with the prior art, the beneficial effects of this application are:
本申请开发了一种湿法磷酸溶垢剂，通过采用特定的除垢剂、分散剂与渗透剂、缓蚀剂和表面活性剂进行复配，高效溶解并去除湿法磷酸生产过程中产生的氟硅酸钾、硅氟酸钠和硫酸钙等结垢物，在0.5h时结垢物的溶解率≥45％，4h时结垢物的溶解率≥80％。The present application develops a wet-process phosphoric acid descaling agent, which is compounded with a specific descaling agent, a dispersant and a penetrant, a corrosion inhibitor and a surfactant to efficiently dissolve and remove scales such as potassium fluorosilicate, sodium fluorosilicate and calcium sulfate generated in the production process of wet-process phosphoric acid. The dissolution rate of the scale is ≥45% in 0.5 hours and ≥80% in 4 hours.
在阅读并理解了详细描述后，可以明白其他方面。Still other aspects will be apparent upon reading and understanding the detailed description.
为更好的说明本申请的目的、技术方案和优点，下面将结合具体实施例来进一步说明本申请，但实施例并不对本申请做任何形式的限定。除非特别说明，本申请采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。除非特别说明，本申请所用试剂和材料均为市购。In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present application in any form. Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the art. Unless otherwise specified, the reagents and materials used in the present application are commercially available.
实施例1～16Examples 1 to 16
实施例1～16提供一种湿法磷酸溶垢剂，组分含量见表1。实施例1～16的湿法磷酸溶垢剂的制备方法如下：Examples 1 to 16 provide a wet-process phosphoric acid scale dissolving agent, and the component contents are shown in Table 1. The preparation method of the wet-process phosphoric acid scale dissolving agent of Examples 1 to 16 is as follows:
按照表1的组分含量，在40～50℃下，依次将除垢剂、分散剂、渗透剂、缓蚀剂和表面活性剂加至水中，保持在40～50℃恒温搅拌至各组分混合均匀，冷却至25℃后过滤，即得湿法磷酸溶垢剂。According to the component contents in Table 1, at 40-50°C, add the descaling agent, dispersant, penetrant, corrosion inhibitor and surfactant to water in sequence, maintain the constant temperature at 40-50°C and stir until the components are evenly mixed, cool to 25°C and filter to obtain the wet-process phosphoric acid descaling agent.
表1实施例1～16的湿法磷酸溶垢剂的组分含量(重量百分比)
Table 1 Component contents of wet-process phosphoric acid scale removers of Examples 1 to 16 (weight percentage)
Table 1 Component contents of wet-process phosphoric acid scale removers of Examples 1 to 16 (weight percentage)
对比例1～8Comparative Examples 1 to 8
对比例1～8提供一种湿法磷酸溶垢剂，组分含量见表2。对比例1～8湿法磷酸溶垢剂的制备方法如下：Comparative Examples 1 to 8 provide a wet-process phosphoric acid scale dissolving agent, and the component contents are shown in Table 2. The preparation methods of the wet-process phosphoric acid scale dissolving agents of Comparative Examples 1 to 8 are as follows:
按照表1的组分含量，在40～50℃下，依次将除垢剂、分散剂、渗透剂、缓蚀剂和表面活性剂加至水中，保持在40～50℃恒温搅拌至各组分混合均匀，冷却至25℃后过滤，即得湿法磷酸溶垢剂。According to the component contents in Table 1, at 40-50°C, add the descaling agent, dispersant, penetrant, corrosion inhibitor and surfactant to water in sequence, maintain the constant temperature at 40-50°C and stir until the components are evenly mixed, cool to 25°C and filter to obtain the wet-process phosphoric acid descaling agent.
表2对比例1～8的湿法磷酸溶垢剂的组分含量(重量百分比)
Table 2 Component contents of wet-process phosphoric acid scale removers of Comparative Examples 1 to 8 (weight percentage)
Table 2 Component contents of wet-process phosphoric acid scale removers of Comparative Examples 1 to 8 (weight percentage)
性能测试Performance Testing
对上述实施例和对比例得到的湿法磷酸溶垢剂的溶解结垢物的性能进行测试，具体测试方法如下：The performance of the wet-process phosphoric acid descaling agent obtained in the above examples and comparative examples in dissolving scale deposits was tested, and the specific test method is as follows:
取湖北宜昌某一磷化工湿法磷酸过滤系统中的结垢物，记为垢样；向实施例和对比例制得的湿法磷酸溶垢剂中分别加入垢样，每100ml湿法磷酸溶垢剂中垢样的加入量为2g，在60℃条件下浸泡4h，分别于0.5、1、2、4h检测垢样的溶解率；溶解率越高说明湿法磷酸溶垢剂的溶垢效率越好。Scaling materials in a wet-process phosphoric acid filtration system of a phosphorus chemical industry in Yichang, Hubei Province were taken as scale samples; the scale samples were added to the wet-process phosphoric acid scale dissolving agents prepared in the embodiments and comparative examples, respectively, with 2 g of the scale sample added to every 100 ml of the wet-process phosphoric acid scale dissolving agent, and the scale samples were soaked at 60° C. for 4 h, and the dissolution rates of the scale samples were detected at 0.5, 1, 2, and 4 h, respectively; the higher the dissolution rate, the better the scale dissolving efficiency of the wet-process phosphoric acid scale dissolving agent.
其中垢样的溶解率按照如下方法检测：称取一定质量的垢样，质量记为m1,置于湿法磷酸溶垢剂中4h，用蒸馏水清洗垢样三次，用中性滤纸过滤，烘干至恒重得垢样，质量记为m2；垢样的溶解率公式如下：w＝(m1-m2)/m1*100％；The dissolution rate of the scale sample is detected according to the following method: weigh a certain mass of the scale sample, the mass is recorded as m 1 , place it in a wet phosphoric acid scale dissolving agent for 4 hours, wash the scale sample three times with distilled water, filter it with neutral filter paper, and dry it to constant weight to obtain the scale sample, the mass is recorded as m 2 ; the dissolution rate formula of the scale sample is as follows: w = (m 1 -m 2 )/m 1 *100%;
m1为垢样溶解前质量， m1 is the mass of the scale sample before dissolution,
m2为垢样溶解后烘干质量。 m2 is the mass of the scale sample after dissolution and drying.
测试结果见表3。The test results are shown in Table 3.
表3
table 3
table 3
从表3的测试结果可以看出，本申请各实施例所制备的湿法磷酸溶垢剂对于结垢物具有高效的溶解率，在0.5h时，溶解率≥45％，4h时，溶解率≥80％。It can be seen from the test results in Table 3 that the wet-process phosphoric acid scale dissolving agent prepared in each embodiment of the present application has a high dissolution rate for scale deposits. At 0.5 h, the dissolution rate is ≥45%, and at 4 h, the dissolution rate is ≥80%.
根据实施例1～4，可以看出，当分散剂中聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的重量比满足(9～11)∶(1.5～3)∶1时，垢样的溶解率更高，说明湿法磷酸溶垢剂对结垢物的溶解速率更快。According to Examples 1 to 4, it can be seen that when the weight ratio of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer in the dispersant satisfies (9-11):(1.5-3):1, the dissolution rate of the scale sample is higher, indicating that the wet-process phosphoric acid scale dissolving agent has a faster dissolution rate for scale deposits.
根据对比例1～5的测试结果，可以看出在缺少了某一分散剂组分时，湿法磷酸溶垢剂的溶垢效果下降严重，即使增加其他分散剂组分的量，也难以达到各实施例的溶解率水平。由对比例6～8，在缺少除垢剂、渗透剂或表面活性剂
时，制得的湿法磷酸溶垢剂的组分间难以起到有效协同增效作用，使得其对结垢物的溶解率较低。According to the test results of Comparative Examples 1 to 5, it can be seen that when a certain dispersant component is missing, the scale dissolving effect of the wet-process phosphoric acid scale dissolving agent is seriously reduced. Even if the amount of other dispersant components is increased, it is difficult to reach the dissolution rate level of each embodiment. From Comparative Examples 6 to 8, in the absence of a descaling agent, a penetrant or a surfactant When the wet-process phosphoric acid scale dissolving agent is used, it is difficult for the components to play an effective synergistic role, resulting in a low dissolution rate of scale deposits.
最后所应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present application rather than to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, ordinary technicians in this field should understand that the technical solution of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present application.
Claims (10)
- 一种湿法磷酸溶垢剂，其中，包括如下重量百分比的组分：A wet-process phosphoric acid descaling agent, comprising the following components in percentage by weight:除垢剂5％～15％，分散剂8％～13％，渗透剂0.5％～1％，缓蚀剂0.1％～0.5％，表面活性剂0.3％～0.8％，余量为水；Descaling agent 5% to 15%, dispersant 8% to 13%, penetrant 0.5% to 1%, corrosion inhibitor 0.1% to 0.5%, surfactant 0.3% to 0.8%, and the balance is water;所述除垢剂为氨基磺酸盐，所述分散剂为聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的混合物。The descaling agent is aminosulfonate, and the dispersant is a mixture of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，包括如下重量百分比的组分：The wet-process phosphoric acid descaling agent according to claim 1, wherein the components are as follows in weight percentage:除垢剂10％～15％，分散剂10％～13％，渗透剂0.5％～0.8％，缓蚀剂0.3％～0.5％，表面活性剂0.3％～0.5％，余量为水。Descaling agent 10%-15%, dispersant 10%-13%, penetrant 0.5%-0.8%, corrosion inhibitor 0.3%-0.5%, surfactant 0.3%-0.5%, and the balance is water.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，所述氨基磺酸盐为氨基磺酸钠、氨基磺酸钾、氨基磺酸铜中的至少一种。According to the wet-process phosphoric acid scale remover of claim 1, wherein the aminosulfonate is at least one of sodium aminosulfonate, potassium aminosulfonate, and copper aminosulfonate.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，所述分散剂中聚环氧琥珀酸、聚天冬氨酸和丙烯酸-2-丙烯酰胺-2-甲基丙磺酸共聚物的重量比为(9～11)∶(1.5～3)∶1。According to the wet-process phosphoric acid scale remover of claim 1, wherein the weight ratio of polyepoxysuccinic acid, polyaspartic acid and acrylic acid-2-acrylamide-2-methylpropanesulfonic acid copolymer in the dispersant is (9-11):(1.5-3):1.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，所述渗透剂为磺化琥珀酸二辛酯钠盐、乙醇胺、磺化琥珀酸癸酯中的至少一种。According to the wet-process phosphoric acid scale remover of claim 1, wherein the penetrant is at least one of sodium salt of dioctyl sulfonatesuccinate, ethanolamine, and decyl sulfonatesuccinate.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，所述缓蚀剂为苯并三唑和/或巯基苯并噻唑。According to the wet-process phosphoric acid scale remover of claim 1, wherein the corrosion inhibitor is benzotriazole and/or mercaptobenzothiazole.
- 根据权利要求1所述湿法磷酸溶垢剂，其中，所述表面活性剂为十二烷基苯磺酸盐、十二烷基磷酸酯钾盐、α-烯烃磺酸盐、聚氧乙烯醚磷酸酯盐、烷基醇酰胺磷酸酯中的至少一种。According to the wet-process phosphoric acid scale remover of claim 1, wherein the surfactant is at least one of dodecylbenzene sulfonate, dodecyl phosphate potassium salt, α-olefin sulfonate, polyoxyethylene ether phosphate salt, and alkyl alcohol amide phosphate.
- 权利要求1～7任一项所述湿法磷酸溶垢剂的制备方法，其中，包括如下步骤： The method for preparing the wet-process phosphoric acid scale remover according to any one of claims 1 to 7, comprising the following steps:将除垢剂、分散剂、渗透剂、缓蚀剂和表面活性剂加至水中，混合均匀后，即得所述湿法磷酸溶垢剂。The wet-process phosphoric acid scale remover is obtained by adding a descaling agent, a dispersant, a penetrant, a corrosion inhibitor and a surfactant into water and mixing them evenly.
- 根据权利要求8所述制备方法，其中，所述混合为在40～50℃温度下搅拌。The preparation method according to claim 8, wherein the mixing is stirring at a temperature of 40 to 50°C.
- 权利要求1～7任一项所述湿法磷酸溶垢剂在溶解湿法磷酸生产结垢物中的应用。 Use of the wet-process phosphoric acid scale dissolving agent according to any one of claims 1 to 7 in dissolving scale in wet-process phosphoric acid production.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211228836.8 | 2022-10-08 | ||
| CN202211228836.8A CN115571863B (en) | 2022-10-08 | 2022-10-08 | Wet phosphoric acid scale-dissolving agent and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024074005A1 true WO2024074005A1 (en) | 2024-04-11 |
Family
ID=84584394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2023/077170 WO2024074005A1 (en) | 2022-10-08 | 2023-02-20 | Wet-process phosphoric acid scale-dissolving agent, preparation method therefor, and use thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115571863B (en) |
| WO (1) | WO2024074005A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115571863B (en) * | 2022-10-08 | 2024-02-09 | 广东邦普循环科技有限公司 | Wet phosphoric acid scale-dissolving agent and preparation method and application thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004072327A1 (en) * | 2003-02-17 | 2004-08-26 | Exel, Hendrikus, Gerrit | Composition and method for removing and/or preventing scaling of elements in processing equipment |
| CN101967024A (en) * | 2010-06-04 | 2011-02-09 | 内蒙古天晨科技有限责任公司 | Phosphorus-free corrosion and scale inhibitor |
| CN102285723A (en) * | 2010-06-21 | 2011-12-21 | 北京市壹清利达水处理技术服务中心 | Dust deposition inhibitor for dedusting water system in steel plant |
| CN102583792A (en) * | 2012-04-06 | 2012-07-18 | 济南大学 | Method for preparing composite industrial circulating cooling water scale inhibitor |
| CN103449618A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Non-phosphorus composite corrosion and scale inhibitor suitable for industrial circulating cooling water |
| CN103740489A (en) * | 2014-02-12 | 2014-04-23 | 北京戴斯科技有限公司 | Pipeline cleaning agent |
| CN104058511A (en) * | 2014-06-16 | 2014-09-24 | 淄博海星环保科技有限公司 | Non-phosphorus composite corrosion and scale inhibitor used for circulating water |
| CN108033577A (en) * | 2017-12-01 | 2018-05-15 | 欣格瑞（山东）环境科技有限公司 | A kind of evaporation dirt dispersion agent for papermaking reducing rules waste liquid and preparation method thereof |
| CN108083457A (en) * | 2017-12-28 | 2018-05-29 | 新疆水处理工程技术研究中心有限公司 | A kind of low-phosphorus antiincrustation dispersant |
| CN109012211A (en) * | 2018-10-15 | 2018-12-18 | 河南永业环保工程有限公司 | A kind of reverse osmosis antisludging agent and its preparation process |
| CN111003822A (en) * | 2019-12-28 | 2020-04-14 | 珠海津环环保工程有限公司 | Modified non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN112725813A (en) * | 2020-12-25 | 2021-04-30 | 德蓝水技术股份有限公司 | Acidic cleaning agent and preparation method thereof |
| CN113912195A (en) * | 2021-11-10 | 2022-01-11 | 山东天庆科技发展有限公司 | Non-phosphorus scale inhibitor for inhibiting silicon scale and preparation method thereof |
| CN115571863A (en) * | 2022-10-08 | 2023-01-06 | 广东邦普循环科技有限公司 | Wet-process phosphoric acid scale dissolver and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PE20121419A1 (en) * | 2009-09-25 | 2012-10-17 | Cytec Tech Corp | PREVENTION OR REDUCTION OF INCRUSTATIONS IN THE PRODUCTION OF PHOSPHORIC ACID BY WET VIA |
| JP6634294B2 (en) * | 2016-01-14 | 2020-01-22 | 株式会社ニイタカ | Descaler and scale removal method |
| CN113955866A (en) * | 2021-11-15 | 2022-01-21 | 新昌中国计量大学企业创新研究院有限公司 | Scale and corrosion inhibitor and preparation method thereof |
| CN114045188A (en) * | 2021-11-29 | 2022-02-15 | 胡翠华 | Neutral environment-friendly cleaning agent and preparation method and application thereof |
-
2022
- 2022-10-08 CN CN202211228836.8A patent/CN115571863B/en active Active
-
2023
- 2023-02-20 WO PCT/CN2023/077170 patent/WO2024074005A1/en unknown
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004072327A1 (en) * | 2003-02-17 | 2004-08-26 | Exel, Hendrikus, Gerrit | Composition and method for removing and/or preventing scaling of elements in processing equipment |
| CN101967024A (en) * | 2010-06-04 | 2011-02-09 | 内蒙古天晨科技有限责任公司 | Phosphorus-free corrosion and scale inhibitor |
| CN102285723A (en) * | 2010-06-21 | 2011-12-21 | 北京市壹清利达水处理技术服务中心 | Dust deposition inhibitor for dedusting water system in steel plant |
| CN102583792A (en) * | 2012-04-06 | 2012-07-18 | 济南大学 | Method for preparing composite industrial circulating cooling water scale inhibitor |
| CN103449618A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Non-phosphorus composite corrosion and scale inhibitor suitable for industrial circulating cooling water |
| CN103740489A (en) * | 2014-02-12 | 2014-04-23 | 北京戴斯科技有限公司 | Pipeline cleaning agent |
| CN104058511A (en) * | 2014-06-16 | 2014-09-24 | 淄博海星环保科技有限公司 | Non-phosphorus composite corrosion and scale inhibitor used for circulating water |
| CN108033577A (en) * | 2017-12-01 | 2018-05-15 | 欣格瑞（山东）环境科技有限公司 | A kind of evaporation dirt dispersion agent for papermaking reducing rules waste liquid and preparation method thereof |
| CN108083457A (en) * | 2017-12-28 | 2018-05-29 | 新疆水处理工程技术研究中心有限公司 | A kind of low-phosphorus antiincrustation dispersant |
| CN109012211A (en) * | 2018-10-15 | 2018-12-18 | 河南永业环保工程有限公司 | A kind of reverse osmosis antisludging agent and its preparation process |
| CN111003822A (en) * | 2019-12-28 | 2020-04-14 | 珠海津环环保工程有限公司 | Modified non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN112725813A (en) * | 2020-12-25 | 2021-04-30 | 德蓝水技术股份有限公司 | Acidic cleaning agent and preparation method thereof |
| CN113912195A (en) * | 2021-11-10 | 2022-01-11 | 山东天庆科技发展有限公司 | Non-phosphorus scale inhibitor for inhibiting silicon scale and preparation method thereof |
| CN115571863A (en) * | 2022-10-08 | 2023-01-06 | 广东邦普循环科技有限公司 | Wet-process phosphoric acid scale dissolver and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115571863B (en) | 2024-02-09 |
| CN115571863A (en) | 2023-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6156129A (en) | Liquid metal cleaner for aqueous system | |
| CN103409763B (en) | A kind of clean-out system composition and clean-out system and application thereof | |
| CN109576077B (en) | Optical glass cleaning agent | |
| JP4171329B2 (en) | Scale cleaner | |
| WO2024074005A1 (en) | Wet-process phosphoric acid scale-dissolving agent, preparation method therefor, and use thereof | |
| CN107674778B (en) | Chemical cleaning agent for removing hard scale of air preheater and preparation method thereof | |
| CN103469222A (en) | Descaling agent for water scale of condensing equipment and descaling method | |
| CN112725813A (en) | Acidic cleaning agent and preparation method thereof | |
| CN105400616A (en) | CIP alkaline cleaning agent with anti-freezing effect and preparation method therefor | |
| KR101956388B1 (en) | Cleaning solution composition for sapphire wafer | |
| CN101899667B (en) | Special cleaning agent for aluminium equipment | |
| CN114045188A (en) | Neutral environment-friendly cleaning agent and preparation method and application thereof | |
| CN101880885B (en) | Cleaning agent special for galvanizing equipment and using method thereof | |
| CN113862682A (en) | Cleaning agent, preparation method and cleaning method using cleaning agent | |
| CN111440679A (en) | Cleaning agent for cleaning high sulfate scale and preparation method and application thereof | |
| CN114504948B (en) | Reverse osmosis membrane silica scale cleaning agent and preparation method thereof | |
| CN113789227B (en) | Calcium sulfate scale cleaning agent suitable for aluminum alloy heat transfer tube and preparation method and application thereof | |
| CN113955868A (en) | Multifunctional scale and corrosion inhibitor and preparation method thereof | |
| CN102051628B (en) | Degradable environment-friendly dirt remover | |
| WO2016063881A1 (en) | Etching liquid for semiconductor substrate | |
| CN108085161B (en) | Hydrocyanic acid polymer cleaning reagent and method | |
| CN114350449B (en) | Cleaning agent and cleaning method for landfill leachate evaporator | |
| CN115323386B (en) | High-temperature-resistant corrosion-inhibition and scale-removal integrated agent for carbon steel equipment and preparation method thereof | |
| CN108911187A (en) | A kind of efficient prefilming agent and preparation method thereof | |
| JPH0892888A (en) | Scale preventing agent and prevention of scale in deinking process of wastepaper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23874200 Country of ref document: EP Kind code of ref document: A1 |