WO2023148365A1 - A composition for reducing the amount of sodium hydroaluminosilicate desposits and a method for obtaining the composition - Google Patents
A composition for reducing the amount of sodium hydroaluminosilicate desposits and a method for obtaining the composition Download PDFInfo
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- WO2023148365A1 WO2023148365A1 PCT/EP2023/052774 EP2023052774W WO2023148365A1 WO 2023148365 A1 WO2023148365 A1 WO 2023148365A1 EP 2023052774 W EP2023052774 W EP 2023052774W WO 2023148365 A1 WO2023148365 A1 WO 2023148365A1
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- composition
- hydrotrope
- chelating agent
- promoter
- mixture
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000011734 sodium Substances 0.000 title claims description 15
- 229910052708 sodium Inorganic materials 0.000 title claims description 13
- 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 title claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 75
- 239000002738 chelating agent Substances 0.000 claims description 43
- 230000002209 hydrophobic effect Effects 0.000 claims description 39
- -1 glycidyl ester Chemical class 0.000 claims description 37
- 239000002270 dispersing agent Substances 0.000 claims description 36
- 239000003752 hydrotrope Substances 0.000 claims description 36
- QUCDWLYKDRVKMI-UHFFFAOYSA-M sodium;3,4-dimethylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1C QUCDWLYKDRVKMI-UHFFFAOYSA-M 0.000 claims description 28
- 239000002318 adhesion promoter Substances 0.000 claims description 23
- 239000002798 polar solvent Substances 0.000 claims description 19
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 18
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 17
- 229920000570 polyether Polymers 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 230000001588 bifunctional effect Effects 0.000 claims description 13
- 150000001282 organosilanes Chemical class 0.000 claims description 13
- 229920000768 polyamine Polymers 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 239000003093 cationic surfactant Substances 0.000 claims description 10
- 239000002736 nonionic surfactant Substances 0.000 claims description 10
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 6
- 150000002118 epoxides Chemical class 0.000 claims description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000004131 Bayer process Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 5
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005065 mining Methods 0.000 abstract description 3
- 239000012716 precipitator Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000003623 enhancer Substances 0.000 description 6
- 229910052665 sodalite Inorganic materials 0.000 description 6
- 150000004645 aluminates Chemical class 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000012545 processing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002455 scale inhibitor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QQWAKSKPSOFJFF-UHFFFAOYSA-N oxiran-2-ylmethyl 2,2-dimethyloctanoate Chemical compound CCCCCCC(C)(C)C(=O)OCC1CO1 QQWAKSKPSOFJFF-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000003940 butylamines Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052663 cancrinite Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229940031728 cocamidopropylamine oxide Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229940048866 lauramine oxide Drugs 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052662 nosean Inorganic materials 0.000 description 1
- NNONYLAVTYBWGW-UHFFFAOYSA-N pentadecane-1,3-diamine Chemical compound CCCCCCCCCCCCC(N)CCN NNONYLAVTYBWGW-UHFFFAOYSA-N 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical class CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical compound CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Definitions
- the present invention relates to the mining industry, namely to the methods of obtaining materials and reagents that are used in the technological process of alumina production based on the Bayer method.
- the world alumina production is based predominantly on the processing of high-quality bauxite.
- the process of obtaining AI2O3 with a relatively low content of SiCh includes the following stages: autoclave leaching using a caustic soda solution; separating the aluminate solution from the red mud; decomposition of aluminate solution to obtain a caustic solution known as “spent liquor” (C(Na2O) ⁇ 150 g/dm 3 ) and aluminium hydroxide; calcination of A1(OH) 3 .
- scale As the weakly concentrated spent liquor is reheated on the heating surfaces, scale is formed, which is represented mainly in the form «Na2O-A12O3’(l,4-2)SiO2-xH2O and is defined as sodium hydroaluminosilicate (or SHAS).
- the scale formation leads to disruptions in the operation of evaporating equipment, namely: increased fuel and energy consumptions and costs; increased alkali consumption to support the caustic module of the circulating solution; reduced throughput of the devices.
- the overall throughput of evaporators is reduced, leading to a decrease in alumina production and increased costs.
- the chemical composition of SHAS is not constant and changes under the influence of several factors: temperature, composition and concentration of spent liquor.
- the sodium hydroaluminosilicate is comparable with a natural mineral called sodalite - 7(Na2O-A12O3’SiO2)-2NaAlO2-wH2O.
- the composition of SHAS released the from industrial solutions is much more diverse because in addition to the sodium aluminate, caustic soda and sodium silicate, it may also include sulphates, carbonate or sodium chloride, as well as other compounds depending on the raw materials.
- scale with anionic composition which includes ions Cl’, CCh 2 ’ and SCU 2 ’ indicates that the scale also has the presence of sodalite 3(Na2O-A12O3-2SiO2)-2NaCl, cancrinite 3(Na2O-A12O3-2SiO2)-Na2CO3 and nosean 3(Na2O-A12O3-2SiO2)-Na2SO4.
- a method that became widespread recently is one where a special chemical reagent is added, which is absorbed on the heating surface of the equipment and thus prevents it from scaling.
- MAX HTTM Sodalite Scale Inhibitor Plant Experience and Impact on the Process, by Donald Spitzer et. al., Pages 57-62, Light Metals 2008, (2008)]
- MAX HTTM Sodalite Scale Inhibitor Plant Experience and Impact on the Process, by Donald Spitzer et. al., Pages 57-62, Light Metals 2008, (2008)
- R can be H, C1-C3 alkyl or Na - attached to a broad class of polymers.
- Using this material at a dose of 2CH40 ppm minimises scaling on the surface of the heat exchangers.
- the disadvantages of the reagent include the inability to modify the heating surface to give it hydrophobic properties.
- US14/151,368 discloses a composition that inhibits sodalite scaling, which has no disadvantage of kinematic viscosity.
- the product of nonpolymerization reaction of a number of substances is used as an inhibitor, namely: low molecular weight binding amine; substances with one amine-reactive functional group and another silane-reactive functional group -Si(OR)3 - where R is H, C1-C12 alkyl, aryl, Na, K, Li or NH4; hydrophobic impurities with molecular weight of at least 500 Da from a group of halogenoalkanes C3-C22, phenol glycidyl and C3-C22 glycidyl ether, C3-C22 esters of sulphuric acid or a combination of these compounds.
- RU2678269 discloses a method of obtaining a surfactant to reduce aluminosilicate deposits by adding a non-polymeric product to the spent liquor, obtained by reacting an amine- binding surfactant, selected from linear, branched, aliphatic or cycloaliphatic monoamines, diamines, triamines, butylamines, pentylamines, dodecyl-1,3- propanediamine and also glycidoxy alkyltrimethoxy silane.
- an amine- binding surfactant selected from linear, branched, aliphatic or cycloaliphatic monoamines, diamines, triamines, butylamines, pentylamines, dodecyl-1,3- propanediamine and also glycidoxy alkyltrimethoxy silane.
- US 2014/071798 discloses a method of obtaining a composition of the inhibitor. It includes a surface promoter in the form of unmodified branched polyamine, bifunctional organosilane adhesion enhancer with reactive organic epoxide and hydrolysable inorganic methoxysilyl groups and glycidyl ether as a hydrophobic agent.
- this patent document discloses in full the ways to reduce the possibility of sodalite formation, namely the pre-treatment of heating surfaces with specialized siliconate-type polymers.
- the main disadvantage of this method is the condition of using the composition on pre-descaled surfaces, which requires treating the surfaces of heat exchangers with a composition that inhibits the formation of solid sediments before the surface comes into contact with the spent liquor flow based on the Bayer process.
- An aspect of the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, consisting of (in wt. %)
- surface promoter 7,0 18,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- hydrophobic agent 1,0 6,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents 1,0 10,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent 0,5 3,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
- Another aspect of the present invention provides a method of obtaining a composition for reducing the amount of sodium hydroaluminosilicate desposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid
- non-ionic surfactants C4-C12 alkylpolyglucosides
- cationic surfactants Cio-Cis alkyldimethylaminoxides
- chelating agent selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 % adhesion promoter: 3,0 8,0 %
- the term “at least one” means “one or more” and also encompasses the terms “at least two”, “at least three”, “at least four”, etc.
- the term "q.s. ad" refers to addition of a sufficient quantity of that material / compound to bring the final composition to the specified volume.
- the present invention aims to develop more efficient composition and a method for obtaining thereof, which would provide not only protection of heat exchanger surfaces of evaporators from precipitators from the spent liquor with high content of CCh 2 ' and SC 2 ', and solids (aluminium hydrate, red mud), but could also be used in the current technological flow of the Bayer process for washing heating surfaces on the go.
- An aspect of the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, comprising (in wt. %) or consisting of (in wt. %)
- surface promoter 7,0 18,0 %, preferably 9,0 - 11,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter 3,0 8,0 %, preferably 4,0 - 6,0 %,
- hydrophobic agent 1,0 6,0 %, preferably 2,0 to 4,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid
- hydrotrope and dispersant agents 1,0 10,0 %, preferably 5,0 - 8,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent 0,5 3,0 %, preferably 1,0 - 2,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
- the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, consisting of (in wt. %)
- surface promoter 7,0 18,0 %, preferably 9,0 - 11,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter 3,0 8,0 %, preferably 4,0 - 6,0 %
- hydrophobic agent 1,0 6,0 %, preferably 2,0 - 4,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents 1,0 10,0 %, preferably 5,0 - 8,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent 0,5 3,0 %, preferably 1,0 - 2,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
- the bifunctional organosilane adhesion promoter comprises or consists of reactive organic epoxide and hydrolysable inorganic methoxysilyl groups.
- Another aspect of the present invention provides a method for obtaining the composition of the invention for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method comprises or consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group comprising or consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid
- non-ionic surfactants C4-C12 alkylpolyglucosides
- cationic surfactants Cio-Cis alkyldimethylaminoxides
- the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %, hydrophobic agent: 1,0 6,0 %, preferably 2,0 - 4,0 %,
- hydrotrope and dispersant agents 1,0 10,0 %, preferably 5,0 - 8,0 %,
- - chelating agent 0,5 3,0 %, preferably 1,0 - 2,0 %,
- the present invention provides a method for obtaining the composition of the invention for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- hydrophobic agent glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid
- non-ionic surfactants C4-C12 alkylpolyglucosides
- cationic surfactants Cio-Cis alkyldimethylaminoxides
- chelating agent selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %, hydrophobic agent: 1,0 6,0 %, preferably 2,0 - 4,0 %,
- hydrotrope and dispersant agents 1,0 10,0 %, preferably 5,0 - 8,0 %,
- - chelating agent 0,5 3,0 %, preferably 1,0 - 2,0 %,
- the mixture of surface promoter, adhesion promoter and hydrophobic agent is pre-thermostated (pre-heated) for 6 to 10 hours (i.e. during minimum 6 hours to maximum 10 hours) at 60°C to 80°C (temperature selected between 60° to 80°C), preferably for 8 hours at 70°C, before adding into said mixture hydrotrope and dispersant agents and chelating agent.
- pre-thermostated typically means "preheated” and refers to the mixture that is heated beforehand during desired time at desired temperature, wherein the desired temperature is regulated by a thermostat.
- the mixture of surface promoter and adhesion promoter is pre-thermostated (pre-heated) for 10 to 14 hours (i.e. during minimum 10 hours to maximum 14 hours) at 40°C to 60°C (temperature selected between 40°C to 60°C), preferably for 12 hours at 50°C, before adding into said mixture hydrophobic agent, hydrotrope and dispersant agents, and chelating agent.
- pre-thermostated typically means “pre-heated” and refers to the mixture that is heated beforehand during desired time, at desired temperature, wherein the desired temperature is regulated by a thermostat.
- "surfaces of equipment” are surfaces inside of heat exchangers which are in contact with spent liquor.
- the polar solvent is a solvent that contains partial positive or negative charges, such as water, aqueous solutions of alkalis and acids, etc., in which the interaction between the solvent and the dissolved component does not lead to chemical changes in the molecular particles of the latter.
- the polar solvent is selected from the group comprising water, dimethylformamide (DMF), dimelthylsulfoxide (DMSO), and isopropanol. Most preferably, the polar solvent is water.
- the conditions of normal pressure and temperature are typically 22°C to 25°C and 0,9 bar to 1,1 bar.
- the surface promoter is mixture of linear and branched modified and unmodified polyethyleneimine with molecular weight from 500 to 2 000 000 Da, such as polyethyleneimine (EPOMIN TM).
- the bifunctional organosilane adhesion promoter is selected from the group comprising 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltriethoxysilane, [2-(3,4-epoxycyclohexy)ethyl]trimethoxysilane.
- the hydrophobic agent is glycidyl ester of synthetic saturated monocarboxylic acid of highly branched CIO isomers; preferably the hydrophobic agent is CarduraTM E10P.
- Cardura E10P monomer is the glycidyl ester of neodecanoic acid (VersaticTM Acid 10), a highly branched carboxylic acid containing 10 carbon atoms.
- the hydrotrope agent is selected from the group comprising C4-C12 alkylpolyglucosides, such as decyl octyl glycosides (example, GlucoponTM 100DK, GlucoponTM 225DK, GlucoponTM 215UP) and the dispersant agent is selected from the group comprising Cio-Cis alkyldimethylaminoxides, such as lauramine oxide, cocamidopropyl amine oxide (example, EMPIGEN® OB, EMPIGEN® OS/A).
- the hydrotrope agent is C4-C12 alkylpolyglucoside.
- the dispersant agent is Cio-Cis alkyldimethylaminoxide.
- the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid).
- the present invention provides a method of synthesis a composition for reducing sodium hydroaluminosilicate deposits on the surfaces of the Bayer process equipment (such as surfaces inside of heat exchangers which are in contact with spent liquor) in production alumina, which consists essentially of mixing and dissolving in a polar solvent of surface promoter, which is a complex mixture of modified and not modified branched polyamines, adhesion promoter, such as bifunctional organosilane with reactive organic epoxide and hydrolysable inorganic methoxysilyl groups, hydrophobic agent (hydrophobisier) such as glycidyl ester of synthetic saturated monocarboxylic acid, hydrotrope and dispersant agents such as non-ionic surfactants, from group C4-C12 alkylpolyglycosides, and cationic surfactants, from group Cio-Cis alkyldimethylaminoxides (alkyl dimethyl oxides with Cio-Cis compounds), and chelating agent such as poly
- the mixture of the surface promoter, adhesion promoter and hydrophobic agent is prethermostated for 8 hours at 70°C, before adding the hydrotrope and dispersant agents and a chelating agent.
- the mixture of the surface promoter and adhesion promoter is pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent and hydrophobic agent is added to them.
- Distinctive features of the composition of the present invention and the method of the present invention are the use of surface promoter as complex mixture of modified and not modified branched polyamines and glycidyl ester of synthetic saturated monocarboxylic acid as hydrophobic agent (hydrophobisier). Also, the presence of new components - mixture of non- ionic surfactants from group C4-C12 alkylpolyglycosides, and cationic surfactants from group C10-C18 alkyldimethylaminoxides, which are used as hydrotrope and dispersant agents, as well as polyamino polyether methylene phosphonic acid used as chelating agent in following proportion of compounds, weight % (wt. %) (mass.
- composition and the method for obtaining the composition has a different set of suitable components (substances) in a specific ratio, which are mixed together in a certain sequence, and special processing.
- the mixture of the surface promoter, adhesion enhancer and hydrophobic agent is pre-thermostated for 8 hours at 70°C, before adding the hydrotrope and dispersant agents and the chelating agent.
- the mixture of the surface promoter and adhesion enhancer is pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent and hydrophobic agent is added to them.
- the ratio of components in the composition ensures the stability and efficiency of the process of evaporation of the spent liquor of the Bayer process in a significantly wider range of concentrations of pollutants.
- each individual feature and the set of features of the proposed composition is aimed at solving the problem of creating effective protection of heat exchange surfaces of evaporators in the technological processes of alumina production.
- the composition was obtained as follows: The components were selected based on the inventors' knowledge, mixed and subjected to thermostating (a procedure, which involves maintaining a constant temperature for some time to increase the reaction rate). Then the selected components were added and mixed again, after which the total obtained new mixture was dissolved in a polar solvent (these are solvents that contain partial positive or negative charges, such as water, aqueous solutions of alkalis and acids, etc., in which the interaction between the solvent and the dissolved component does not lead to chemical changes in the molecular particles of the latter). The solvent was added after mixing all the components.
- a composition was prepared according to a similar method of the prior art.
- the composition was obtained as follows. The mixture of the surface promoter, adhesion enhancer and hydrophobic agent was pre-thermostated for 8 hours at 70°C, after which a mixture of hydrotrope and dispersant agents and a chelating agent were added in and dissolved. The amount of additives was added so that the mixture of alkylpolyglucoside, alkyldimethylaminoxide and polyamino polyether methylene phosphonic acid was 5%, 3% and 1% by weight respectively. Afterwards, dissolution was performed. The resulting composition was added to spent liquor with dosage of 5- ⁇ 20 ppm for the industrial production of alumina.
- the composition was obtained as follows. The mixture of the surface promoter and adhesion enhancer was pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent was added to them. The amount of additives (hydrotrope and dispersant agents and chelating agent) was added so that the mixture of alkylpolyglucoside, alkyldimethylaminoxide and polyamino polyether methylene phosphonic acid was 5%, 3% and 1% by weight respectively. Then the hydrophobic agent was added in an amount corresponding to the content of glycidyl ester of synthetic saturated monocarboxylic acid - 1% by weight. This specific technological operation allows to modify the entire surface of the formed branched molecule. Afterwards, dissolution was performed. The resulting composition was added to spent liquor with dosage of 5- ⁇ 20 ppm for the industrial production of alumina.
- the efficiency of the obtained composition was evaluated by the results of industrial comparative tests in the technological process of alumina production based on the Bayer process, where the quantitative criterion was chosen to be an interval (duration) between cleaning evaporators, steam pressure and a heat transfer coefficient (HTC).
- the results of the composition obtained by the method of the present invention were compared to the prior art.
- Table 1 The interval between cleaning based on the condition of adding the proposed composition to the spent liquor in the technological process of alumina production based on the Bayer process (dose 20 ppm).
- composition obtained by the invention allows to increase the interval between cleaning procedures from 120 to 165 days, increase production capacity by 7%, reduce the specific energy consumption for evaporation of excess water from the spent liquor by 9% and also increase the concentration of the mother liquor by Na?O by about 2,5%.
- composition obtained by the method of the present invention can be used on known and widespread equipment in the mining industry using proven technologies and using materials that are not scarce or difficult to access.
Abstract
The present invention relates to the mining industry, namely to the methods of obtaining materials and reagents that are used in the technological process of alumina production based on the Bayer method. The invention provides a composition and a method for obtaining more efficient composition, which would provide not only protection of heat exchanger surfaces of evaporators from precipitators from the spent liquor with high content of CO3 2- and SO4 2-, and solids (aluminium hydrate, red mud, etc.), but could also be used in the current technological flow of the Bayer process for washing heating surfaces on the go.
Description
A COMPOSITION FOR REDUCING THE AMOUNT OF SODIUM HYDROALUMINOSILICATE DESPOSITS AND A METHOD FOR OBTAINING
THE COMPOSITION
FIELD OF THE INVENTION
The present invention relates to the mining industry, namely to the methods of obtaining materials and reagents that are used in the technological process of alumina production based on the Bayer method.
BACKGROUND OF THE INVENTION
The world alumina production is based predominantly on the processing of high-quality bauxite. The process of obtaining AI2O3 with a relatively low content of SiCh includes the following stages: autoclave leaching using a caustic soda solution; separating the aluminate solution from the red mud; decomposition of aluminate solution to obtain a caustic solution known as “spent liquor” (C(Na2O) ~ 150 g/dm3) and aluminium hydroxide; calcination of A1(OH)3.
As the weakly concentrated spent liquor is reheated on the heating surfaces, scale is formed, which is represented mainly in the form «Na2O-A12O3’(l,4-2)SiO2-xH2O and is defined as sodium hydroaluminosilicate (or SHAS). Over time, the scale formation leads to disruptions in the operation of evaporating equipment, namely: increased fuel and energy consumptions and costs; increased alkali consumption to support the caustic module of the circulating solution; reduced throughput of the devices. As a result, the overall throughput of evaporators is reduced, leading to a decrease in alumina production and increased costs.
The chemical composition of SHAS is not constant and changes under the influence of several factors: temperature, composition and concentration of spent liquor. In its composition, the sodium hydroaluminosilicate is comparable with a natural mineral called sodalite - 7(Na2O-A12O3’SiO2)-2NaAlO2-wH2O. The composition of SHAS released the from industrial solutions is much more diverse because in addition to the sodium aluminate, caustic soda and sodium silicate, it may also include sulphates, carbonate or sodium chloride, as well as other compounds depending on the raw materials. The formation of scale with anionic composition which includes ions Cl’, CCh2’ and SCU2’ indicates that the scale also has the
presence of sodalite 3(Na2O-A12O3-2SiO2)-2NaCl, cancrinite 3(Na2O-A12O3-2SiO2)-Na2CO3 and nosean 3(Na2O-A12O3-2SiO2)-Na2SO4.
Currently, there are several common ways to restore and sustainably operate evaporating equipment. One of the most common methods is chemical and mechanical cleaning of heat exchange surfaces from scale [Schmidt, R. L., and Featherstone, R. H., 1969, Cleaning Evaporator Tubes, US Patent 3,443,992], However, besides the labour intensity and safety questions associated with this method, it does not prevent the problem but only deals with its consequences. In addition to the method mentioned, there is also an option to apply protective polymer coating on the surface of the heat exchange tubes. However, this method is not practical because any coating thick enough to maintain mechanical integrity would itself significantly reduce the heat transfer [Kazakov V., Potapov N. & Bobrov A. (1979) “Heating and evaporation of silica-containing aluminate liquors”, Tsvetnye Met., no.10, pp. 45-48.; Kazakov V. & Potapov N. (1982) “Use of an organosilicone inhibitor in the evaporation step of aluminate liquors”, Tsvetnye Met., no. 8, pp. 39-41],
A method that became widespread recently is one where a special chemical reagent is added, which is absorbed on the heating surface of the equipment and thus prevents it from scaling.
One of the most popular is reagent MAX HT™ produced by Cytec Industries Inc. [MAX HT™ Sodalite Scale Inhibitor: Plant Experience and Impact on the Process, by Donald Spitzer et. al., Pages 57-62, Light Metals 2008, (2008)], which is a substance consisting of silane functional groups: -Si(OR)3 - where R can be H, C1-C3 alkyl or Na - attached to a broad class of polymers. Using this material at a dose of 2CH40 ppm minimises scaling on the surface of the heat exchangers. The disadvantages of the reagent include the inability to modify the heating surface to give it hydrophobic properties.
Heitner et al., 2014, Hydrophobically modified polyamine scale inhibitors, US 9,365,442 B2, discloses that the developers add new properties to sodalite scaling inhibitors by introducing into the structure a wide range of hydrophobicity modifiers that are attached to a reactive secondary nitrogen atom contained in the polymerization reaction product - branched polyamine. The main disadvantage of this disclosure is considered to be the increased kinematic viscosity of the reagent, which increases due to the use of polymerisation products
with a relatively high molecular weight during the synthesis of the final reagent. As a result, this leads to poor distribution of the reagent in aluminate solutions.
US14/151,368 discloses a composition that inhibits sodalite scaling, which has no disadvantage of kinematic viscosity. According to this patent document, the product of nonpolymerization reaction of a number of substances is used as an inhibitor, namely: low molecular weight binding amine; substances with one amine-reactive functional group and another silane-reactive functional group -Si(OR)3 - where R is H, C1-C12 alkyl, aryl, Na, K, Li or NH4; hydrophobic impurities with molecular weight of at least 500 Da from a group of halogenoalkanes C3-C22, phenol glycidyl and C3-C22 glycidyl ether, C3-C22 esters of sulphuric acid or a combination of these compounds. In addition to the advantage of decreasing kinematic viscosity, the authors argue that lower molecular weight provides faster diffusion of the inhibitor and the presence of more active inhibitory substances at the site of formation of SHAS crystals. One of the main disadvantages of this disclosure, as in previous cases, is the lack of efficiency of the reagent during the processing of low-quality bauxite.
RU2678269 discloses a method of obtaining a surfactant to reduce aluminosilicate deposits by adding a non-polymeric product to the spent liquor, obtained by reacting an amine- binding surfactant, selected from linear, branched, aliphatic or cycloaliphatic monoamines, diamines, triamines, butylamines, pentylamines, dodecyl-1,3- propanediamine and also glycidoxy alkyltrimethoxy silane.
However, it is known that in the processing of low-quality bauxite, limestone additions are used in technological processes that include a high share of impurities, which increases silicates, sulphates and carbonates in the spent liquor to values greater than 1.5 g/dm3 in terms of SiCh, 60 and 120 g/dm3, respectively. In addition, particles of aluminium hydrate and red mud residues may enter the technological streams, which in turn can act as centres of scale formation.
US 2014/071798 discloses a method of obtaining a composition of the inhibitor. It includes a surface promoter in the form of unmodified branched polyamine, bifunctional organosilane adhesion enhancer with reactive organic epoxide and hydrolysable inorganic methoxysilyl groups and glycidyl ether as a hydrophobic agent. In addition to the composition of the scale inhibitor, this patent document discloses in full the ways to reduce the possibility of sodalite
formation, namely the pre-treatment of heating surfaces with specialized siliconate-type polymers. The main disadvantage of this method is the condition of using the composition on pre-descaled surfaces, which requires treating the surfaces of heat exchangers with a composition that inhibits the formation of solid sediments before the surface comes into contact with the spent liquor flow based on the Bayer process.
Consequently, there is still a need for a method that allows obtaining more efficient composition, which would provide not only protection of heat exchanger surfaces of evaporators from precipitators from the spent liquor with high content of CCh2' and SCU2', and solids (aluminium hydrate, red mud), but could also be used in the current technological flow of the Bayer process for washing heating surfaces on the go.
SUMMARY OF THE INVENTION
An aspect of the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, consisting of (in wt. %)
• surface promoter: 7,0 18,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
• bifunctional organosilane adhesion promoter: 3,0 8,0 %,
• hydrophobic agent: 1,0 6,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
• hydrotrope and dispersant agents: 1,0 10,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
• chelating agent: 0,5 3,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
• polar solvent: q.s. ad 100%.
Another aspect of the present invention provides a method of obtaining a composition for reducing the amount of sodium hydroaluminosilicate desposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method
consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter,
- hydrophobic agent, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents in the form of non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 % adhesion promoter: 3,0 8,0 %
- hydrophobic agent: 1,0 6,0 %
- hydrotrope and dispersant agents: 1,0 10,0 %
- chelating agent: 0,5 3,0 %
- polar solvent: q.s. ad 100%.
DETAILED DESCRIPTION OF THE INVENTION
All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The publications and applications discussed herein are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the present invention is not entitled to antedate such publication by virtue of prior invention. In addition, the materials, methods, and examples are illustrative only and are not intended to be limiting.
In the case of conflict, the present specification, including definitions, will control. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in art to which the subject matter herein belongs. As used herein, the following definitions are supplied in order to facilitate the understanding of the present invention.
The term “comprise” is generally used in the sense of include, that is to say permitting the presence of one or more features or components. Also as used in the specification and claims, the language "comprising" can include analogous embodiments described in terms of "consisting of “ and/or "consisting essentially of’.
As used in the specification and claims, the singular form "a", "an" and "the" include plural references unless the context clearly dictates otherwise.
As used in the specification and claims, the term "and/or" used in a phrase such as "A and/or B" herein is intended to include "A and B", "A or B", "A", and "B".
As used herein, the term “at least one” means “one or more” and also encompasses the terms “at least two”, “at least three”, “at least four”, etc.
As used herein, the term "q.s. ad" refers to addition of a sufficient quantity of that material / compound to bring the final composition to the specified volume.
The present invention aims to develop more efficient composition and a method for obtaining thereof, which would provide not only protection of heat exchanger surfaces of evaporators from precipitators from the spent liquor with high content of CCh2' and SC 2', and solids (aluminium hydrate, red mud), but could also be used in the current technological flow of the Bayer process for washing heating surfaces on the go.
An aspect of the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, comprising (in wt. %) or consisting of (in wt. %)
• surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
• bifunctional organosilane adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %,
• hydrophobic agent: 1,0 6,0 %, preferably 2,0 to 4,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
• hydrotrope and dispersant agents: 1,0 10,0 %, preferably 5,0 - 8,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
• chelating agent: 0,5 3,0 %, preferably 1,0 - 2,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
• polar solvent: q.s. ad 100%.
In a preferred embodiment, the present invention provides a composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, consisting of (in wt. %)
• surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
• bifunctional organosilane adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %
• hydrophobic agent: 1,0 6,0 %, preferably 2,0 - 4,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
• hydrotrope and dispersant agents: 1,0 10,0 %, preferably 5,0 - 8,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
• chelating agent: 0,5 3,0 %, preferably 1,0 - 2,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
• polar solvent: q.s. ad 100%.
According to an embodiment of the composition of the invention, the bifunctional organosilane adhesion promoter comprises or consists of reactive organic epoxide and hydrolysable inorganic methoxysilyl groups.
Another aspect of the present invention provides a method for obtaining the composition of the invention for reducing the amount of sodium hydroaluminosilicate deposits on the
surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method comprises or consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group comprising or consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter,
- hydrophobic agent, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents in the form of non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %, hydrophobic agent: 1,0 6,0 %, preferably 2,0 - 4,0 %,
- hydrotrope and dispersant agents: 1,0 10,0 %, preferably 5,0 - 8,0 %,
- chelating agent: 0,5 3,0 %, preferably 1,0 - 2,0 %,
- polar solvent: q.s. ad 100%.
In a preferred embodiment, the present invention provides a method for obtaining the composition of the invention for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, wherein the method consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, compounds selected from the group consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter,
- hydrophobic agent, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents in the form of non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent: wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), preferably the chelating agent is PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 %, preferably 9,0 - 11,0 %, adhesion promoter: 3,0 8,0 %, preferably 4,0 - 6,0 %, hydrophobic agent: 1,0 6,0 %, preferably 2,0 - 4,0 %,
- hydrotrope and dispersant agents: 1,0 10,0 %, preferably 5,0 - 8,0 %,
- chelating agent: 0,5 3,0 %, preferably 1,0 - 2,0 %,
- polar solvent: q.s. ad 100%.
In an embodiment of the method of the invention, the mixture of surface promoter, adhesion promoter and hydrophobic agent is pre-thermostated (pre-heated) for 6 to 10 hours (i.e. during minimum 6 hours to maximum 10 hours) at 60°C to 80°C (temperature selected between 60° to 80°C), preferably for 8 hours at 70°C, before adding into said mixture hydrotrope and dispersant agents and chelating agent. The term "pre-thermostated" typically means "preheated" and refers to the mixture that is heated beforehand during desired time at desired temperature, wherein the desired temperature is regulated by a thermostat.
In another embodiment of the method of the invention, the mixture of surface promoter and adhesion promoter is pre-thermostated (pre-heated) for 10 to 14 hours (i.e. during minimum 10 hours to maximum 14 hours) at 40°C to 60°C (temperature selected between 40°C to 60°C), preferably for 12 hours at 50°C, before adding into said mixture hydrophobic agent, hydrotrope and dispersant agents, and chelating agent. The term "pre-thermostated" typically means "pre-heated" and refers to the mixture that is heated beforehand during desired time, at desired temperature, wherein the desired temperature is regulated by a thermostat.
In some embodiments of the method of the invention, "surfaces of equipment" are surfaces inside of heat exchangers which are in contact with spent liquor.
In some embodiments of the composition of the invention and the method of the invention, the polar solvent is a solvent that contains partial positive or negative charges, such as water, aqueous solutions of alkalis and acids, etc., in which the interaction between the solvent and the dissolved component does not lead to chemical changes in the molecular particles of the latter. In some preferred embodiments, the polar solvent is selected from the group comprising water, dimethylformamide (DMF), dimelthylsulfoxide (DMSO), and isopropanol. Most preferably, the polar solvent is water.
In some other embodiments of the method of the invention, the conditions of normal pressure and temperature are typically 22°C to 25°C and 0,9 bar to 1,1 bar.
In some other embodiments of the composition of the invention and the method of the invention, the surface promoter is mixture of linear and branched modified and unmodified polyethyleneimine with molecular weight from 500 to 2 000 000 Da, such as polyethyleneimine (EPOMIN ™).
In some other embodiments of the composition of the invention and the method of the invention, the bifunctional organosilane adhesion promoter is selected from the group comprising 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4- epoxycyclohexyl)ethyltriethoxysilane, [2-(3,4-epoxycyclohexy)ethyl]trimethoxysilane.
In some other embodiments of the composition of the invention and the method of the invention, the hydrophobic agent is glycidyl ester of synthetic saturated monocarboxylic acid of highly branched CIO isomers; preferably the hydrophobic agent is Cardura™ E10P. Cardura E10P monomer is the glycidyl ester of neodecanoic acid (Versatic™ Acid 10), a highly branched carboxylic acid containing 10 carbon atoms.
In some other embodiments of the composition of the invention and the method of the invention, the hydrotrope agent is selected from the group comprising C4-C12 alkylpolyglucosides, such as decyl octyl glycosides (example, Glucopon™ 100DK, Glucopon™ 225DK, Glucopon™ 215UP) and the dispersant agent is selected from the group
comprising Cio-Cis alkyldimethylaminoxides, such as lauramine oxide, cocamidopropyl amine oxide (example, EMPIGEN® OB, EMPIGEN® OS/A). Preferably, the hydrotrope agent is C4-C12 alkylpolyglucoside. Preferably, the dispersant agent is Cio-Cis alkyldimethylaminoxide.
In some other embodiments of the composition of the invention and the method of the invention, the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid).
The present invention provides a method of synthesis a composition for reducing sodium hydroaluminosilicate deposits on the surfaces of the Bayer process equipment (such as surfaces inside of heat exchangers which are in contact with spent liquor) in production alumina, which consists essentially of mixing and dissolving in a polar solvent of surface promoter, which is a complex mixture of modified and not modified branched polyamines, adhesion promoter, such as bifunctional organosilane with reactive organic epoxide and hydrolysable inorganic methoxysilyl groups, hydrophobic agent (hydrophobisier) such as glycidyl ester of synthetic saturated monocarboxylic acid, hydrotrope and dispersant agents such as non-ionic surfactants, from group C4-C12 alkylpolyglycosides, and cationic surfactants, from group Cio-Cis alkyldimethylaminoxides (alkyl dimethyl oxides with Cio-Cis compounds), and chelating agent such as polyamino polyether methylene phosphonic acid, in the following proportion of compounds, weight % (wt. %) (mass. %): surface promoter 7,0-48,0; adhesion promoter 3, 0^-8, 0; hydrophobic agent l,04>,0; hydrotrope and dispersant agents 1,0-40,0; chelating agent 0,543,0; polar solvent q.s. 100%. In an embodiment, the mixture of the surface promoter, adhesion promoter and hydrophobic agent is prethermostated for 8 hours at 70°C, before adding the hydrotrope and dispersant agents and a chelating agent. In another embodiment, the mixture of the surface promoter and adhesion promoter is pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent and hydrophobic agent is added to them.
Distinctive features of the composition of the present invention and the method of the present invention are the use of surface promoter as complex mixture of modified and not modified branched polyamines and glycidyl ester of synthetic saturated monocarboxylic acid as hydrophobic agent (hydrophobisier). Also, the presence of new components - mixture of non-
ionic surfactants from group C4-C12 alkylpolyglycosides, and cationic surfactants from group C10-C18 alkyldimethylaminoxides, which are used as hydrotrope and dispersant agents, as well as polyamino polyether methylene phosphonic acid used as chelating agent in following proportion of compounds, weight % (wt. %) (mass. %): surface promoter 7,0-48,0; adhesion enhancer 3, 0^-8, 0; hydrophobic agent 1, 045,0; hydrotrope and dispersant agents 1, 0-40, 0; chelating agent 0,543,0; polar solvent q.s. 100%. That is, a distinctive feature of the invention is that the composition and the method for obtaining the composition has a different set of suitable components (substances) in a specific ratio, which are mixed together in a certain sequence, and special processing. In an embodiment, the mixture of the surface promoter, adhesion enhancer and hydrophobic agent is pre-thermostated for 8 hours at 70°C, before adding the hydrotrope and dispersant agents and the chelating agent. In another embodiment, the mixture of the surface promoter and adhesion enhancer is pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent and hydrophobic agent is added to them.
The technical result and advantage of the composition of the present invention and of the method of the present invention is that the resulting synthesised composition of the invention and specific ratios of components, provide the lowest required dosage of the reagent, in other words results in greater efficiency of inhibition of scaling, unattainable with similar methods of the prior art.
The ratio of components in the composition ensures the stability and efficiency of the process of evaporation of the spent liquor of the Bayer process in a significantly wider range of concentrations of pollutants.
The introduction of a mixture of hydrotrope and dispersant agents and chelating agent increases the degree of inhibition of SHAS at high concentrations of solids in the spent liquor, and the specified amount of 5%, 3% and 1% by weight respectively, provide the highest efficiency with a minimum amount of reagent consumption.
Experiments have shown that the introduction of 10% of the mixture hydrotrope and dispersant agents with the addition of a chelating agent to the composition inhibits the formation of SHAS by an average of 964)8% while reducing costs by 3 5%. At the same time, its introduction in smaller quantities does not ensure the achievement of such indicators,
and its introduction in larger quantities practically does not increase this degree. The ratio of components in the composition (hydrotrope and dispersant agents, and chelating agents) ensures the stability and efficiency of the evaporation of the spent liquor in a much wider range of pollutant concentrations and facilitates the possibility of cleaning the heating surfaces process equipment in real time.
Thus, each individual feature and the set of features of the proposed composition is aimed at solving the problem of creating effective protection of heat exchange surfaces of evaporators in the technological processes of alumina production.
Comparative analysis of the present invention with the similar methods of the prior art allows to conclude that all of the key stated indicators are superior.
Those skilled in the art will appreciate that the invention described herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the invention includes all such variations and modifications without departing from the spirit or essential characteristics thereof. The invention also includes all of the steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features. The present disclosure is therefore to be considered as in all aspects illustrated and not restrictive, the scope of the invention being indicated by the appended claims, and all changes which come within the meaning and range of equivalency are intended to be embraced therein.
The foregoing description will be more fully understood with reference to the following Examples. Such Examples, are, however, exemplary of methods of practising the present invention and are not intended to limit the application and the scope of the invention.
EXAMPLES
Examples of obtaining the composition and its application.
The composition was obtained as follows: The components were selected based on the inventors' knowledge, mixed and subjected to thermostating (a procedure, which involves maintaining a constant temperature for some time to increase the reaction rate). Then the selected components were added and mixed again, after which the total obtained new mixture
was dissolved in a polar solvent (these are solvents that contain partial positive or negative charges, such as water, aqueous solutions of alkalis and acids, etc., in which the interaction between the solvent and the dissolved component does not lead to chemical changes in the molecular particles of the latter). The solvent was added after mixing all the components. Separately, for comparative tests, a composition was prepared according to a similar method of the prior art.
Example 1
The composition was obtained as follows. The mixture of the surface promoter, adhesion enhancer and hydrophobic agent was pre-thermostated for 8 hours at 70°C, after which a mixture of hydrotrope and dispersant agents and a chelating agent were added in and dissolved. The amount of additives was added so that the mixture of alkylpolyglucoside, alkyldimethylaminoxide and polyamino polyether methylene phosphonic acid was 5%, 3% and 1% by weight respectively. Afterwards, dissolution was performed. The resulting composition was added to spent liquor with dosage of 5-^20 ppm for the industrial production of alumina.
Example 2
The composition was obtained as follows. The mixture of the surface promoter and adhesion enhancer was pre-thermostated for 12 hours at 50°C, before the mixture of hydrotrope and dispersant agents, chelating agent was added to them. The amount of additives (hydrotrope and dispersant agents and chelating agent) was added so that the mixture of alkylpolyglucoside, alkyldimethylaminoxide and polyamino polyether methylene phosphonic acid was 5%, 3% and 1% by weight respectively. Then the hydrophobic agent was added in an amount corresponding to the content of glycidyl ester of synthetic saturated monocarboxylic acid - 1% by weight. This specific technological operation allows to modify the entire surface of the formed branched molecule. Afterwards, dissolution was performed. The resulting composition was added to spent liquor with dosage of 5-^20 ppm for the industrial production of alumina.
The efficiency of the obtained composition was evaluated by the results of industrial comparative tests in the technological process of alumina production based on the Bayer process, where the quantitative criterion was chosen to be an interval (duration) between cleaning evaporators, steam pressure and a heat transfer coefficient (HTC). The results of the
composition obtained by the method of the present invention were compared to the prior art.
The results obtained are shown in the Table 1 below.
Table 1. The interval between cleaning based on the condition of adding the proposed composition to the spent liquor in the technological process of alumina production based on the Bayer process (dose 20 ppm).
* The test period was completed when steam pressure reached 4,5 bar or HTC lower 1450 kcal/(m2xhxs).
The tests showed that the use of the composition obtained by the invention allows to increase the interval between cleaning procedures from 120 to 165 days, increase production capacity by 7%, reduce the specific energy consumption for evaporation of excess water from the spent liquor by 9% and also increase the concentration of the mother liquor by Na?O by about 2,5%.
Based on the above, it is possible to conclude that the composition obtained by the method of the present invention can be used on known and widespread equipment in the mining industry using proven technologies and using materials that are not scarce or difficult to access.
Claims
1. A composition, for reducing the amount of sodium hydroaluminosilicate deposits on the surfaces of equipment used in the process of alumina production based on the Bayer method, consisting of (in wt. %)
• surface promoter: 7,0 18,0 %, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
• bifunctional organosilane adhesion promoter: 3,0 8,0 %,
• hydrophobic agent: 1,0 6,0 %, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
• hydrotrope and dispersant agents: 1,0 10,0 %, wherein the hydrotrope and dispersant agents are non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
• chelating agent: 0,5 3,0 %, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid),
• polar solvent: q.s. ad 100%.
2. The composition of claim 1, wherein the bifunctional organosilane adhesion promoter comprises reactive organic epoxide and hydrolysable inorganic methoxysilyl groups.
3. A method for obtaining a composition of claims 1-2, wherein the method consists in mixing and dissolving in a polar solvent, while maintaining conditions of normal pressure and temperature, of compounds selected from the group consisting of surface promoter, wherein the surface promoter is a complex mixture of modified and unmodified branched polyamines,
- bifunctional organosilane adhesion promoter,
- hydrophobic agent, wherein the hydrophobic agent is glycidyl ester of synthetic saturated branched tertiary monocarboxylic acid,
- hydrotrope and dispersant agents in the form of non-ionic surfactants C4-C12 alkylpolyglucosides, and/or cationic surfactants Cio-Cis alkyldimethylaminoxides,
- chelating agent, wherein the chelating agent is selected from the group comprising HEDP (1-Hydroxy Ethylidene-l,l-Diphosphonic Acid), DETMPA (Diethylene Triamine Penta Methylene Phosphonic Acid), and PAPEMP (Polyamino Polyether Methylene Phosphonic Acid), wherein said compounds are added at the following ratio, weight %: surface promoter: 7,0 18,0 % adhesion promoter: 3,0 8,0 %
- hydrophobic agent: 1,0 6,0 %
- hydrotrope and dispersant agents: 1,0 10,0 %
- chelating agent: 0,5 3,0 %
- polar solvent: q.s. ad 100%.
4. The method of claim 3, wherein the mixture of surface promoter, adhesion promoter and hydrophobic agent is pre-thermostated for 6 to 10 hours at 60°C to 80°C, preferably 8 hours at 70°C, before adding into said mixture hydrotrope and dispersant agents and chelating agent.
5. The method of claim 3, wherein the mixture of surface promoter and adhesion promoter is pre-thermostated for 10 to 14 hours at 40°C to 60°C, preferably 12 hours at 50°C, before adding into said mixture hydrophobic agent, hydrotrope and dispersant agents, and chelating agent.
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| BR112023019597A BR112023019597A2 (en) | 2022-02-07 | 2023-02-06 | COMPOSITION FOR REDUCING THE AMOUNT OF SODIUM HYDROALUMINOSILICATE DEPOSITS ON EQUIPMENT SURFACES AND METHOD FOR OBTAINING A COMPOSITION |
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| UAA202200482A UA127639C2 (en) | 2022-02-07 | 2022-02-07 | COMPOSITION OF INHIBITOR OF SODIUM HYDROALUMOSILICATE DEPOSITS ON EQUIPMENT SURFACES IN THE PROCESS OF ALUMINUM PRODUCTION BY THE BAYER METHOD |
| UAA202200482 | 2022-02-07 | ||
| EP22173160 | 2022-05-13 | ||
| EP22173160.7 | 2022-05-13 |
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2023
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