WO2004014789A1 - Percarbonate de sodium revetu et son procede de preparation et son utilisation - Google Patents
Percarbonate de sodium revetu et son procede de preparation et son utilisation Download PDFInfo
- Publication number
- WO2004014789A1 WO2004014789A1 PCT/CN2002/000558 CN0200558W WO2004014789A1 WO 2004014789 A1 WO2004014789 A1 WO 2004014789A1 CN 0200558 W CN0200558 W CN 0200558W WO 2004014789 A1 WO2004014789 A1 WO 2004014789A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sodium percarbonate
- product
- aqueous solution
- hydrogen peroxide
- coated
- Prior art date
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- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 title claims abstract description 104
- 229940045872 sodium percarbonate Drugs 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 75
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000003381 stabilizer Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 26
- 239000003599 detergent Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000007844 bleaching agent Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000009472 formulation Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 13
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000004061 bleaching Methods 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 238000007689 inspection Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 2
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 claims 1
- 238000012216 screening Methods 0.000 claims 1
- 239000012459 cleaning agent Substances 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 32
- 238000000354 decomposition reaction Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 16
- 238000000576 coating method Methods 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 229910001385 heavy metal Inorganic materials 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- -1 papermaking Substances 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005243 fluidization Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 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 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000000022 bacteriostatic agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/055—Peroxyhydrates; Peroxyacids or salts thereof
- C01B15/10—Peroxyhydrates; Peroxyacids or salts thereof containing carbon
- C01B15/106—Stabilisation of the solid compounds, subsequent to the preparation or to the crystallisation, by additives or by coating
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-compounds
Definitions
- the invention relates to a coated sodium percarbonate, a method for preparing the coated sodium percarbonate, and an application of the coated sodium percarbonate as a bleaching component in a detergent, detergent and bleach formulation.
- the international patent classification number belongs to the field of C11D3 / 39 detergent. Background technique
- Sodium percarbonate has excellent bleaching and sterilization functions because it can decompose and release active oxygen. It is widely used in washing, printing and dyeing, textile, papermaking, medicine and health, etc., China's detergent industry is the largest coated sodium percarbonate. Potential market, compared with traditional chlorine bleach, phosphorus detergent builder and sodium perborate, it is regarded as the ideal detergent builder. In recent years, it has been widely used in foreign detergent industries. At present, the domestic sodium percarbonate cannot fully meet the use requirements in terms of stability and other aspects, which greatly limits the promotion and application of sodium percarbonate in the detergent industry. With the improvement of people's living standards and the strengthening of environmental protection awareness, low-phosphorus and non-phosphorus laundry powders will gradually replace phosphorus-containing laundry powders. At present, China's annual output of laundry powder is about 2 million tons. Based on the calculation that the amount of sodium percarbonate is 8%, the market demand for sodium percarbonate will reach nearly 200,000 tons.
- the dry method is to spray a sodium carbonate aqueous solution and a high-concentration hydrogen peroxide aqueous solution on a sodium percarbonate seed in a flowing air stream, dry and grow the crystal, or add a high-concentration hydrogen peroxide to the sodium carbonate particles.
- the dry method is to spray a sodium carbonate aqueous solution and a high-concentration hydrogen peroxide aqueous solution on a sodium percarbonate seed in a flowing air stream, dry and grow the crystal, or add a high-concentration hydrogen peroxide to the sodium carbonate particles.
- Its advantages are no filtration, short process and high yield, but there is a large amount of mixed heat and poor heat exchange effect during the reaction, large amount of dust, demanding equipment and process conditions, and high concentration of hydrogen peroxide, except for a few Outside the country, less used.
- the wet method is the reaction of hydrogen peroxide and sodium carbonate aqueous solution at a certain temperature, crystallization, and then drying to obtain the finished product. Because the materials can be fully mixed and easy to exchange heat, the process equipment is simple, the investment is small, the mother liquor can be recovered, Apply. At present, most of the domestic and foreign countries adopt the wet process. Japan first put it into industrial production in 1969, and now has a production capacity of more than 100,000 tons per year, and more than 60. 0% is used for detergent additives. At present, more than one million tons of sodium percarbonate are required worldwide, and the maximum single-set production capacity is 20,000 tons.
- Sodium percarbonate is a new type of multi-purpose fine chemical product with active oxygen content of 15.3%. It is known as solid hydrogen peroxide. It has strong bleaching, stain removal, sterilization and other functions. The main purpose is to be used as an auxiliary for detergents. It is also widely used as dyeing agent, bleaching agent, color developer, preservative, bacteriostatic agent and oxygen supply agent in the fields of textile, papermaking, food, medical and health. China began to research and produce sodium percarbonate in the early 1980s, and a large number of literatures have reported its preparation process research.
- the major domestic manufacturers include Yangzhou Pesticide Factory, Zhejiang Shangyu Inorganic Salt Factory, Jilin Chemical Industry Company, Tianjin Chemical Plant, and Guangzhou Jinzhujiang Chemical Co., Ltd., etc. Most of them use the wet process to produce sodium percarbonate.
- Sodium percarbonate (2N C03, 3H 2 0 2 ) can be used as the active oxygen component in detergents, cleaning agents and bleaching agents. Because sodium percarbonate has insufficient storage stability in a hot and humid environment and in the presence of various detergent and cleaning agent components, the stability of sodium percarbonate must be improved to reduce the loss of active oxygen.
- a basic principle for stabilizing is to coat the small particles of sodium percarbonate by forming a coating with the stabilizing components.
- GB174 891 has disclosed a method for spraying a sodium water glass solution onto a compound containing active oxygen for subsequent storage stability in order to improve storage stability.
- the sodium percarbonate particles obtained by crystallization are coated with sufficient silicate to stabilize the sodium percarbonate.
- a method for stabilizing granular sodium percarbonate is known from DE-OS 2417 572 and DE-PS 26 22610, one of which is a mixture formed by crystallization of sodium carbonate and other mineral salts such as sodium bicarbonate and I or sodium sulfate, or A mixture of sodium carbonate, sodium sulfate and sodium silicate is used as the coating substance.
- an aqueous solution of the coating material component is sprayed onto the sodium percarbonate particles while maintaining the fluidized bed temperature at 30-80 ° C, and the water added thereto is evaporated to form a strong coating.
- Another coating component is known from U.S. Patent 4,325,933: Stabilization by treating sodium percarbonate with an aqueous solution of an alkaline earth metal salt, magnesium sulfate or magnesium chloride. When the sodium percarbonate particles are treated, an alkaline earth metal carbonate layer is formed on the surface, which will reduce the water absorption of sodium percarbonate and improve its stability. However, it was shown that such stabilized products still do not have sufficient storage stability.
- the composition of sodium percarbonate has higher reliability; according to this embodiment, the composition contains Compounds of the inorganic magnesium compound series also contain alkali metal carbonates.
- the composition does not involve sodium percarbonate particles with a homogeneous coating tightly adhered to their core, but rather a mixture that is also granular. It can be determined in the post-processing of the method for preparing the composition described in the document that such a composition has insufficient storage stability in a humid and hot environment in the presence of detergent powder.
- An object of the present invention is to provide a coated sodium percarbonate having high stability, and the storage stability of the coated sodium percarbonate is superior to that of the prior art coated sodium percarbonate.
- Another object of the present invention is to provide a method for preparing coated sodium percarbonate which is particularly stable for storage.
- Sodium percarbonate is an adduct of sodium carbonate and hydrogen peroxide. This adduct is unstable. Under the influence of heat and moisture, hydrogen peroxide will be released. Hydrogen peroxide will decompose to generate water and oxygen:
- the decomposition mechanism of hydrogen peroxide is the process of electron transfer and radical reaction, and heavy metal ions, such as iron and copper, accidentally carried in the raw materials or during the synthesis process, catalyze the decomposition of H 2 0 2 and accelerate Decomposition of sodium percarbonate. Therefore, moisture, moisture, heat, and heavy metal ions are the main factors affecting the stability of sodium percarbonate. Therefore, the key to the preparation of stable sodium percarbonate is:
- the moisture content of the product must be less than 2%.
- the wet product is required to be easily filtered, which can reduce the moisture content of the centrifuged material to be low, loose, and non-agglomerated.
- the wet material that has entered the vibrating fluidized drying bed has good fluidization performance. — Drying in the temperature range of 115 ° C can reduce the loss of product's available oxygen, and can produce products with high active oxygen content.
- the particle size of the product cannot be too small, the particle size is too small, the specific surface area is large, it is easy to absorb moisture, and cause product decomposition.
- a crystal assisting agent is added at the beginning of the synthesis reaction, and the reaction temperature and the stirring speed are adjusted in combination to make the wet product easy to shake and filter, and the product particles above 95.0% can be controlled within the range of 80-10 mesh particle size.
- the stabilizer solution and the coating agent solution are atomized and sprayed separately.
- the sprayed stabilizer is also composed of a heavy metal ion complexing agent and a free radical inhibitor.
- the stabilizer is called an external stabilizer.
- the purpose of the coating agent is to form a very thin organic polymer film on the surface of sodium percarbonate, to prevent contact with moisture, but not too much, otherwise it will affect the dissolution rate of sodium percarbonate and limit the performance of product bleaching and oxidation.
- the inventor conducted a pilot test of coated sodium percarbonate in a 500 liter kettle through a small test, added heavy metal ion complexing agents, free radical inhibitor species and their ratios to the reaction materials, and added crystal assistants in the synthesis The amount, mixing ratio and addition time, the different mixing speeds and temperatures at different times in the synthesis have an impact on the product yield and product particle size.
- sodium percarbonate is dried, the stabilizers and film-forming agents have been screened and mixed for hundreds of years. This test determined the optimal process conditions and was successfully used in a 3000 liter synthetic kettle. The main points are as follows:
- the raw material sodium carbonate be recrystallized, which has a good effect, but the energy and material consumption are too high, which has no industrial significance.
- Adding a stabilizer to the reaction raw material liquid can complex heavy metal ions, and the organic amine EDTA can both complex heavy metal ions and act as a free radical inhibitor.
- the added internal stabilizer can enter the interior of the product particles, which can achieve "internal stability""
- the effect is that too little addition does not provide stability, too much addition adds cost, and even makes the wet product into agglomerates, and the filterability is not good.
- the "internal stabilizer" of the present invention is determined through a small test and a pilot test and verified by production, and proves that the formula is reasonable, economical and practical.
- the crystal flow aid sodium polyacrylate and / or polyamide is added at a fine flow rate, and the sodium polyacrylate and / or polyamide are formulated into a 5-30% (weight) aqueous solution by using the product amount 0-1.
- the stirring speed is adjusted by frequency conversion to adjust the stirring speed 10rpm-90rpm and the reaction temperature is adjusted 14 ° C -25V, so that the product particle size is 95.0% or more control It is in the range of 80 mesh to 10 mesh, and it is white spherical, and the wet product can be easily filtered.
- the moisture content of the wet product after the filtering aid is added is about 6.0%, and the imported hot air can be reduced to about 105 ° C during drying, and the fluidization condition is good, which can ensure the product effective oxygen 13.0% or more .
- Produce The yield is over 90 ⁇ . 0% by sodium carbonate.
- the external stabilizer composition is: Na 2 Si0 3 , MgS0 4 , triethanolamine
- the coating agent is composed of a polymer film-forming agent.
- the film agent is: any one of polyethylene glycol, hydroxyethyl cellulose or acrylic acid-maleic acid copolymer, which is formulated into an aqueous solution with a solid content of 5% -30%, and the amount is 0. 02% -0. 5%.
- the organic amine triethanolamine used is tertiary amine, LD 50 > 5000mg / Kg, basically non-toxic, it can inhibit the generation of 3 ⁇ 4 0 2 radicals, and can also complex heavy metal ions.
- the boiling point is 360 ° C .
- the drying loss is small, the price is 10 yuan / kg, it is economical and practical, and the compatibility is good.
- the coating agent and stabilizer formulation of the invention has characteristics and the coating process effect. Good, 80 seconds or so to dissolve the product, the product does not affect the bleaching effect, a vibration fluidized bed dryer for drying at the time of stabilization, coating with.
- the product meets the requirements of the enterprise standard Q / YT001-2000, with a stability of> 95. 0%, and a particle size above 95.0% after sieving is 20-50 mesh, and the particle size distribution range is relatively small.
- the water content is as large as 7. 0-8. 0%.
- sodium percarbonate is used in laundry powder additives to decompose the active oxygen quickly and lose its use value.
- 0% Made of laundry made by the inventors of coated and uncoated sodium percarbonate according to the formula of "China Chemical Product Manual Vol. Rc007 Color Bleaching Laundry Detergent" The powder moisture content was 6.5%, and a stability test was performed.
- the coating sodium percarbonate of the present invention is synthesized using 27.5% hydrogen peroxide, industrial sodium carbonate as the main raw material, and is produced by a wet process, and the product is coated.
- the process is as follows: industrial sodium carbonate and industrial refined salt are added at a ratio of 4: 1 by weight, and a slurrying kettle in which a predetermined amount of mother liquor has been placed is added under stirring, and an internal stabilizer is added to beat the metered 27.5% hydrogen peroxide into the hydrogen peroxide.
- the internal stabilizer is added under stirring, and the slurry and hydrogen peroxide are cooled to 14-16 ° C with a cold brine jacket, while being added to the metered mother liquid while stirring, and stirred to cool to the specified temperature of 14-16 ° C.
- the rate of the two materials is controlled.
- the crystal growth aid sodium polyacrylate and / or polyamide is added dropwise, the reaction temperature is controlled at 16-25 ° C, and the stirring speed range is adjusted to 10 rpm.
- the main material consumption per ton of product is as follows: 27.5% hydrogen peroxide 1080 kg, industrial sodium carbonate 750 kg, refined industrial salt sodium chloride 200 kg, coal 160 kg, electricity 260 kWh.
- the purpose of adding the crystal-assisting agent is to obtain a product with an appropriate particle size.
- the crystal-assisting agent still has a "flocculation" effect, which can increase the yield.
- the filterability is easy to “dry out”.
- the outer stabilizer is composed of Na4Si0 3 and MgS.0. 4.
- the coating agent is composed of any one of the polymer film-forming agent polyethylene glycol, hydroxyethyl cellulose or acrylic acid-maleic acid copolymer, and the solid content of the aqueous solution is 5%. — 30%, the amount is based on the weight of the product sodium percarbonate: 0. 02%-0.5%, the total amount is 3% of the product sodium percarbonate.
- the stability and product stability of the sodium percarbonate treated by the coating are significantly improved.
- the above three measures have been applied to the production of 2000 tons / year coated sodium percarbonate with good results.
- the main mechanism is that the decomposition of sodium percarbonate first releases H 2 0 2 , while the decomposition mechanism of H 2 0 2 is the process of electron transfer and radical reaction.
- the metal impurities such as copper and iron in the raw material decompose H 2 0 2 Catalysis, the effect of adding an internal stabilizer to the reaction material is to make the material
- Metal ions are precipitated or complexed by organic amine EDTA, and organic amine EDTA is a free radical absorbent like organic phenol, which can inhibit the decomposition of 3 ⁇ 40 2 .
- Silicate and magnesium salts added as external stabilizers can further complex metal ions, while organic amine triethanolamine is a high boiling point substance with a boiling point of 36CTC and low toxicity.
- LD 50 > 5000mg / kg can both complex metal ions and Inhibit the generation of free radicals, improve the stability of the product, and the price is low.
- the compatibility with the product is good.
- the high-molecular film-forming agent can make the external stabilizer better adhere to the surface of sodium percarbonate particles, but the film-forming dose is too large. Affects the solubility of sodium percarbonate, affects the bleaching and sterilization.
- added stabilizers can be reduced by the above two complex metal ions or products, or radical generated by absorption of the decomposition of H 2 0 2, to suppress the decomposition of H 2 0 2, i.e. inhibiting sodium percarbonate Decomposition.
- Sodium percarbonate is a heat-sensitive substance.
- the higher the reaction temperature the higher the decomposition rate of the sodium percarbonate synthesized and the lower the relative yield.
- the reaction temperature is too low, which affects the product results and leads to a decrease in yield.
- the process of the present invention generally controls the reaction temperature between 18-25 ° C, the temperature is too low, the energy consumption is too large, and it is uneconomical.
- the stability of the product is significantly improved, and the product can be guaranteed while improving the stability of the product. It has a moderate dissolution rate and active oxygen release rate and has a builder function, which can improve the performance of the product.
- the stability of the product was measured according to the Q7 YT001-2000 standard. The stability of six samples was measured, and the average particle size was 35 mesh. The results are listed in the table below:
- the coated sodium percarbonate is mainly used in laundry detergent as an additive to make a so-called color bleaching powder to improve the stain removal function of the detergent and make the fabric being washed bright and beautiful. Due to the high moisture content of 7-8% of domestic detergent, the added sodium percarbonate easily decomposes and loses the significance of adding sodium percarbonate.
- the present inventors took part of the same batch of sodium percarbonate produced by themselves without coating treatment, and the other part was subjected to coating treatment. According to 10 kg of domestic washing powder, the moisture content is 6.5%, 3 kg is divided into 6 groups of 500 g each, 3 groups are added with 10% uncoated sodium percarbonate, and the other three groups are coated with percarbonate. Sodium 10%, put the test product in a polyethylene bag, and seal it. After placing it in a natural ventilation place for three months from August 05, 2000 to November 07, 2000, the active oxygen was tested, and the result was converted. See the following table:
- the decomposition of coated sodium percarbonate in the added laundry powder is much lower than that of uncoated sodium percarbonate, that is, it is much more stable.
- the decomposition rate in the table it is inferred that the uncoated carbonic acid for more than half a year
- the decomposition of sodium is close to 40%, and its active oxygen will be less than 8%.
- Sodium percarbonate has more than 8% active oxygen before it has value.
- the decomposition rate is less than 10%, and its active oxygen will still be Above 12%, it is still above the range of practical value.
- the invention has no waste gas and waste residue, and only mother liquor containing sodium carbonate and sodium chloride is generated.
- the mother liquor can be recovered and applied.
- the mother liquor is zero-emission and has no pollution to the environment.
- This project requires fans and centrifuges, and low-noise models are selected and arranged. Noise-proof treatment indoors or walls. '
- the invention belongs to the production of inorganic chemicals, and the main equipment is produced under normal pressure. No flammable gas or liquid exists. Electrical equipment can be installed in accordance with non-explosion requirements.
- the main road of the factory is used for the entrance of the factory building, and the fire trucks can come and go freely. There are fire extinguishers, fire extinguishers and fire hydrants in the workshop.
- Hydrogen peroxide is a strong oxidizing agent.
- the labor protection supplies necessary for production work such as work clothes, rubber gloves and shoes, masks, protective glasses, etc. have been provided.
- the workshop has been equipped with flushing facilities and simple health care medicines.
- Figure 1 is a schematic diagram of the process flow of the present invention.
- FIG. 2 is a schematic diagram showing the change of the yield a of sodium percarbonate with the concentration X of 3 ⁇ 4 2 (specific embodiments
- Crystallizer Sodium polyacrylate 3. Add 25 kg of water to 25 kg.
- Coating agent Polyethylene glycol 1.5 kg water and 10 kg.
- the reaction is completed for another 5-15 minutes.
- the material is stirred and shaken in a shaker centrifuge.
- the mother liquid enters the mother liquid pool for recovery and application.
- the wet material enters a relatively small size through a vibrating feeder 4Mpa ⁇
- the first vibrating fluidized bed in the middle of the fluidized bed at a pressure of 0. 4Mpa sprayed into the prepared external stabilizer aqueous solution, in the rear section of the fluidized bed at 0. 4Mpa of Atomizing force into the prepared aqueous coating agent, the coated treated product enters the second vibration fluidized bed dryer and dried, the product after sieving into the hopper, inspection is finished packaging.
- the obtained product had an active oxygen content of 14.2%, a water content of 1.4%, and a stability of 98.4%.
- Example 1 The crystal assisting agent in Example 1 was changed to polyamide 3.25 kg and 15 kg of water, and the coating agent was hydroxyethyl cellulose 1.5 kg and 10 kg of water, and the other ingredients were unchanged. According to the production process of Example 1, the To get the same effect.
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Description
包膜过碳酸钠及其制备方法和应用 技术领域
本发明涉及包膜过碳酸钠、包膜过碳酸钠的制备方法及包膜过碳酸钠作为洗涤剂、清 洗剂和漂白剂配方中的漂白组分的应用。 国际专利分类号属于 C11D3 / 39洗涤剂领域。 背景技术
过碳酸钠由于能分解释放出活性氧而具备优良的漂白和杀菌消毒功能，被大量用于洗 涤、 印染、 紡织、 造纸、 医药卫生等领域中， 我国洗涤剂工业是包膜过碳酸钠最大的潜在 市场， 它与传统的氯系漂白剂、磷系洗涤剂助剂和过硼酸钠相比， 被视为理想的洗涤剂助 剂。近年来在国外洗涤剂工业中得到广泛的应用。由于目前国内过碳酸钠在稳定性等方面 尚不能完全满足使用需求，极大地限制了过碳酸钠在洗涤剂行业中的推广应用。随着我国 人民生活水平的提高和环保意识的加强， 低磷、无磷洗衣粉将逐步取代含磷洗衣粉。 目前 我国洗衣粉年产量约 200万吨， 按过碳酸钠加入量为 8 %计算， 过碳酸钠的市场需求将达 到近 20万吨。
制取过碳酸钠有干法和湿法二种。干法是在流动气流中将碳酸钠水溶液和高浓度的过 氧化氢水溶液雾化喷在过碳酸钠晶种上，干燥并使结晶成长，或者将高浓度过氧化氢添加 到碳酸钠颗粒上进行反应。其优点是不用过滤， 流程短、 产率高， 但存在反应时物料混合 放热量大及热交换效果差， 粉尘量大， 设备及工艺条件要求苛刻， 并要求高浓度的过氧化 氢，除少数国家外，较少采用。湿法则是由过氧化氢与碳酸钠水溶液在一定的温度下反应、 结晶， 再经干燥而得成品， 由于物料能进行充分混合及易于进行热交换， 工艺设备简单、 投资少、 母液可以回收、 套用。 目前国内外大多采用湿法工艺。 日本首先于 1969年投入 工业化生产， 现已超过 10万吨 /年生产能力， 60. 0%以上用于洗衣粉添加剂。 目前全球 需过碳酸钠 100余万吨， 最大单套生产能力为 2万吨。 我国 1983年开始研究开发， 目前 仍处于研究发展阶段， 国内年生产量不足 1万吨， 主要是物料消耗过高，碳酸钠使用率一 般只有 80. 0%左右 \双氧水使用率在 90. 0%以下， 产品贮存稳定性较差， 限制了产品 的贮存运输， 单套规模偏小， 未形成规模生产。 我国是个人口众多的国家， 洗衣粉年产量 200余万吨， 按洗衣粉年产量的 20. 0%制成彩漂粉， 每吨按 8. 0—10. 0 %添加过碳酸 钠，每年可消耗过碳酸钠 3. 2-4. 0万吨，还不包括其它工业领域及养殖等行业的使用量。 随着国民经济的发展， 国民购买力的提高， 彩漂洗衣粉在 3年之内必将大量进入家庭， 过 碳酸钠在我国发展余地很大。 中国化工报及其它化工刊物一直呼吁发展过碳酸钠的生产，
因为我国有几十万吨的双氧水及近百万吨的碳酸钠要增值，而用于生产过碳酸钠是较好的 选择， 目前我国发展过碳酸钠首先要优化工艺提高产品收率， 降低成本，提高产品的稳定 性， 便于贮运、 出口， 占领国内外市场。
过碳酸钠是一种新型、 多用途的精细化工产品， 活性氧含量达到 15. 3 % , 有固体双 氧水之称。 其具有很强的漂白、 去渍、 杀菌等功能。 主要用途是作洗涤剂的助剂， 同时在 纺织、 造纸、 食品、 医疗卫生等领域广泛用作整染剂、 漂白剂、 显色剂、 保鲜剂、 刹菌剂 和给氧剂。我国于八十年代初开始研究和生产过碳酸钠， 目前已有大量文献报道了其制备 工艺研究。 国内主要生产厂家有扬州农药厂、 浙江上虞市无机盐厂、 吉林化学工业公司、 天津化工厂和广州金珠江化学有限公司等， 大都采用湿法工艺生产过碳酸钠。
过碳酸钠 (2N C03，3H202)可用作洗涤剂、 清洗剂和漂白剂中的活性氧组分。 由于过 碳酸钠在湿热环境以及在各种洗涤剂和清洗剂组分的存在下贮存稳定性不够，必须提高过 碳酸钠的稳定性， 以降低活性氧的损失。进行稳定的一个基本原理是用起稳定作用的组分 形成涂层来裹覆过碳酸钠小粒子。
GB174 891 已公开了一种为了提高贮存稳定性而把钠水玻璃溶液喷涂到含活性氧的 化合物上并随后干燥的方法。在 DE-OS2652776公开的方法中是在结晶得到的过碳酸钠粒 子上涂覆足够的硅酸盐而使过碳酸钠稳定。足够的稳定性，尤其是在洗涤剂和清洗剂存在 时， 无法用上述方法得到。
从 DE-OS2417 572和 DE-PS 26 22610中已知使颗粒状过碳酸钠稳定的方法，其中一 种由碳酸钠和其它矿物盐如碳酸氢钠和 I或硫酸钠结晶形成的混合物，或一种碳酸钠、硫 酸钠和硅酸钠的混合物用作涂层物质。 在这些方法中， 保持流化床温度 30-80°C下把涂层 材料组份的水溶液喷涂到过碳酸钠颗粒上， 蒸去其中加入的水份而形成一层坚固的涂层。 尽管这样涂覆的过碳酸钠颗粒的稳定性大为提高，但在洗涤剂粉末存在下长期贮存时活性 氧含量仍下降过快。
已知有大量方法使用硼化合物诸如硼酸 (DE-PS 2800 916)、 硼酸盐 (DE-OS3321082)和 过硼酸盐 (DE-PS 2651 442和 DE-PS 28 10 379)有效稳定过碳酸钠。尽管某种程度上有很好 的稳定作用， 但市场上越来越对不含硼化合物的涂覆过碳酸钠感兴趣。
从美国专利 4， 325, 933中知道另一种涂层组分： 通过用碱土金属盐硫酸镁或氯化镁 的水溶液处理过碳酸钠进行稳定。在对过碳酸钠颗粒处理时，在表面形成碱土金属碳酸盐 层，这样会降低过碳酸钠的吸水性并提高其稳定性。然而表明，这类稳定化产物仍没有足 够的贮存稳定性。
从 EP-A0405797可知具有较高可靠性的过碳酸钠组成；按照这一实施方案，该组成含
无机镁化合物系列的化合物，此外还含有碱金属碳酸盐。在所述组成中不涉及在其核上紧 紧粘结有均匀涂层的过碳酸钠颗粒，而是涉及也呈颗粒状的混合物。在所述文件中说明的 用于制备所述组成的方法的后加工中可确定，这类组成在洗涤剂粉末存在下的湿热环境中 的贮存稳定性不足。 . 发明内容
本发明的目的在于提供一种有高稳定性的包膜过碳酸钠， 该包膜过碳酸钠的贮存稳 定性超过现有技术的包膜过碳酸钠。本发明的另一个目的是提供一种制备贮存特别稳定的 包膜过碳酸钠的方法。
实现本发明方案的基本原理及关键技术内容如下所述。
过碳酸钠的合成可以用下列反应式表示：
稳定剂
2Na2C03+3H202 2Na2C03 · 3Η202+ΔΗ
过碳酸钠为碳酸钠和双氧水的加合物， 这种加合物不稳定， 在热和湿气的影响下会 游离出过氧化氢， 过氧化氢再分解生成水和氧：
湿 · 2Na2C03+3H202 2 (Na2C03 · 3H20) +3H20+3/2 02个
"、、
2Na2C03+3H202 2Na2C03+3H20+3/2 02个
过氧化氢的分解机理为电子转移和游离基反应过程，而原料中或合成过程中不慎带入 的重金属离子如铁、铜等金属离子，对 H202的分解起催化作用， 加速了过碳酸钠的分解。 因此， 水份、 湿、 热、 重金属离子是影响过碳酸钠稳定的主要因素， 因此制备稳定过碳酸 钠关键在于：
(一)在过碳酸钠制备过程中， 要求产品水份要低于 2%。 在合成反应结束， 要求湿产 品易于甩滤， 可使经离心甩干的物料水份低、疏松、不结团块， 进入振动流化干燥床干燥 的湿物料的流化性能好， 可以在 105— 115°C温度范围内烘干， 减少产品有效氧的损失， 可制得活性氧含量高的产品。产品粒度不能太小， 粒度太小比表面积大， 易吸潮， 引起产 品分解。 为解决此问题在合成反应开始时加入助晶剂， 并结合调整反应温度及搅拌速度， 使湿产品易于甩滤， 产品 粒 95. 0%以上可控制在 80— 10目粒径范围以内。
(二)在参加反应的原料中加入稳定剂， 一是络合重金属离子，去除原料中的重金属离 子:稳定剂中的有机胺既可络合重金属离子，又可以渗入产品中起到游离基抑制剂的作用，
减缓过碳酸钠的分解， 在反应原料中加入的稳定剂又称内稳定剂。 内稳定剂-
Na2Si03:MgS04: EDTA=8: 3： 2， 配制成水溶液固体含量为 10%-60% (重)， 其用量为产 品重量的 0. 02%— 1. 0%。 本发明中如无特殊说明， 则所有助剂用量均为相对于产品的 重量比。
(三)在小型流化干燥床中后部分别雾化喷入稳定剂液和包膜剂液，雾化喷入的稳定剂 也由重金属离子络合剂和游离基抑制剂组成，这时的稳定剂称为外稳定剂。用包膜剂的目 的是在过碳酸钠表面形成很薄的有机高分子膜， 阻隔与湿气的接触， 但不能太多， 否则影 响过碳酸钠溶解速度， 限制产品漂白、 氧化性能的发挥。
本发明人通过小试再在 500升釜中进行包膜过碳酸钠中试， 在反应物料中添加重金 属离子络合剂、游离基抑制剂的品种及其配比，合成中助晶剂的添加量、配比及添加时间， 合成中不同时期不同搅拌速度和温度对产品收率、 产品粒度的影响， 在干燥过碳酸钠时， 稳定剂、 成膜剂筛选及配比作了近半年上百次试验， 确定了最佳工艺条件， 并成功用于 3000立升合成釜。 其要点如下：
(一)在碳酸钠浆料和双氧水中分别加入内稳定剂， 其主要成份为 Na2Si03、 MgS04、 EDTA。 其重量配比为 Na2Si03 : MgS04: EDTA=8: 3： 2， 配制成水溶液固体含量为 10 %-60% , 其用量为产品过碳酸钠重量的 0. 02 -1. 0%。 等分成两份分别加入衆料釜和 双氧水釜中。所使用原料在生产或贮运过程中不免要带入重金属离子，有人曾提出将原料 碳酸钠进行重结晶， 效果很好， 但能耗、 物耗过高， 没有工业化意义。 在反应原料液中加 入稳定剂可以络合重金属离子， 有机胺 EDTA既可络合重金属离子又可作为游离基抑制 剂， 此时加入的内稳定剂可进入产品颗粒内部， 可起到 "内稳定"作用， 加入量太少起不 到稳定作用， 加入太多成本增加， 甚至使湿产品结成团块， 过滤性不好。 本发明 "内稳定 剂"是通过小试、 中试试验确定并经生产验证， 证明配方合理、 经济实用。
(二)在合成反应开始时细流量加入助晶剂聚丙烯酸钠和 /或聚酰胺， 所说的聚丙烯酸 钠和 /或聚酰胺配制成 5-30% (重)的水溶液， 其用量为产品过碳酸钠重量的 0. 1 -1. 0 % , 并在不同的反应阶段通过变频调速调整搅拌速度 10rpm-90rpm及调整反应温度 14°C -25V , 使产品粒径 95. 0%以上控制在 80 目至 10目的范围内， 且为白色球状， 湿产品 易于甩滤。在中试中曾进行比较，如果反应中不在反应开始时加入助晶剂，物料很难甩滤， 甩滤后湿品部分出现团块，湿品水分髙达 10. 0—12. 0% ,产品收率按碳酸钠计只有 85. 0 %左右。湿品在振动流化+燥床中流化情况差， 必须提高进口热风温度至 130°C， 这就很 难保证产品有效氧大于 13. 0%。在反应开始时加入助晶剂甩滤后的湿品水份 6. 0%左右， 烘干时进口热风可降至 105°C左右， 流化状况良好， 能确保产品有效氧 13. 0%以上。 产
品收率按碳酸钠计达 90·. 0%以上。
(三)有文献报导将产品过碳酸钠溶解在有包膜剂的有机溶剂中， 搅拌浸泡一定时间去 除有机溶剂或将过碳酸钠与稳定剂、包膜剂混合液在双锥回转混合器中机械混合，前者效 果好， 但能耗、 物耗大， 工业化不可能。 后者包膜效„果欠佳， 不烘干水份偏大。 而本发明 工艺是在第一振动流化干燥床中段用约 0. 4Mpa压力雾化喷入外稳定剂液， 在后段用约 0. 4Mpa压力雾化喷入包膜剂液。 外稳定剂成份为： Na2Si03、 MgS04、 三乙醇胺， 外稳 定剂组成： Na2Si03: MgS04:三乙醇胺 =8 : 3： 1 ,配制成水溶液固体含量为 25 %-60 % (重)， 其用量为产品过碳酸钠重量的 0. 5 %-5. 0%。 包膜剂由高分子成膜剂组成， 包膜剂为： 聚乙二醇、羟乙基纤维素或丙烯酸一马来酸共聚物中任意一种， 配成水溶液固体含量为 5 %-30 % , 其用量为过碳钠产品重量的 0. 02%-0. 5 %。 使用的有机胺三乙醇胺为叔胺， LD50>5000mg/Kg, 基本无毒， 既能抑制 ¾02游离基的产生， 还能络合重金属离子， 沸点 360°C， 干燥损失小， 价格 10元 / kg, 经济实用， 相溶性好， 本发明的包膜剂、 稳定剂配 方有特色， 包膜工艺效果良好， 产品溶解时间 80秒左右， 不影响产品漂白功效， 在烘干 时于振动流化干燥床中进行稳定、 包膜处理。
(四)产品符合企业标准 Q / YT001-2000要求， 稳定度 >95. 0 % , 筛分后粒径 95. 0 %以上为 20-50目， 粒径分布范围比较小， 国产洗衣粉由于含水份较大达 7. 0-8. 0% , 一般过碳酸钠用于洗衣粉添加剂活性氧分解较快，而失去使用价值。本发明人曾将包膜处 理与不包膜处理的过碳酸钠按 "中国化工产品手册下册 Rc007彩漂洗衣粉" 的配方加入 量均为洗衣粉量的 10. 0 % , 制成的洗衣粉水份 6. 5 % , 进行稳定性试验， 结果表明使用 本发明人经包膜处理的过碳酸钠即使贮放半年后活性氧仍可达 12. 0 %以上， 使用未蒈包 膜处理的过碳酸钠半年后活性氧将低于 8. 0% , 而失去使用价值。 每吨产品耗用 27. 5 %双氧水 1080公斤： 双氧水使用率达 96. 0% (文献报导为 90. 0%左右)。 每吨产品耗 用碳酸钠 750公斤， 碳酸钠使用率为 90. 0% (文献报导为 85. 0 %), 物料消耗最低。
本发明包膜过碳酸钠合成采用 27. 5 %双氧水， 工业碳酸钠为主要原料， 釆用湿法工 艺生产， 并对产品进行包膜处理。 其工艺过程为工业碳酸钠与工业精制盐按重量比为 4: 1的比例在搅拌下加入已放好定量母液的打浆釜内并加入内稳定剂打浆， 将计量的 27. 5 %双氧水加入双氧水釜， 在搅拌下加入内稳定剂， 浆液和双氧水均用冷盐水夹套冷却至 14一 16°C， 搅拌下同时加入到已放入计量母液开动搅拌并冷却至规定的温度 14-16°C的合 成釜内，控制二种物料的力 ή入速度，在反应开始时向合成釜滴加'助晶剂聚丙烯酸钠和 /或 聚酰胺， 控制反应温度在 16-25Ό , 调整搅拌速度范围 10rpm--90rpm， 使产品颗粒控制在 所需的范围内，加料结束，再反应 5— 15分钟，反应结束，搅拌下将物料放入离心机甩干，
母液进入母液池回收套用，湿物料经振动给料器进入振动流化干燥床，在振动流化干燥中、 后部分别压力雾化喷入外稳定剂液、 包膜剂液， 物料经初烘干， 包膜物料再第二次烘干， 筛分， 进入料仓、 检验合格， 包装即为成品， 参见图 1。
产品主要技术指标如下:
吨产品主要物料消耗如下： 27. 5 %双氧水 1080公斤， 工业碳酸钠 750公斤， 精制工 业盐氯化钠 200公斤， 煤 160公斤， 电 260千瓦时。
经小试和扩试业已证明在包膜过碳酸钠合成中：①在碳酸钠液和双氧水中同时加入内 稳定剂是必要的， 内稳定剂主要由 Na2Si03、 MgS04: 有机胺 EDTA=8: 3： 2组成， 加入 的目的是去除原料中的金属离子， 提高产品的稳定性。
②在反应液中加入助晶剂， 其组成为聚丙烯酸和 /或聚酰胺， 也可以为聚丙烯酸钠： 聚酰胺 =2:1，配制成 5 %-30% (重)的水溶液， 加入总量为产品过碳酸钠重量的 0. 1 %-1. 0 %。加入助晶剂的目的是制得合适粒度的产品，助晶剂尚有"絮凝"作用，可以增加产量。 另外加助晶剂产品在离心脱水时， 可过滤性， 好易于 "里干"。
③经离心甩干的过碳酸钠进入振动流化干燥床，在烘干床的中、后部分别压力雾化喷 洒外稳定剂液和包膜剂液， 外稳定剂由 Na4Si03、 MgS.04、 有机胺三乙醇胺组成； 包膜剂 由高分子成膜剂聚乙二醇、羟乙基纤维素或丙烯酸一马来酸共聚物中任意一种组成，其配 成水溶液固体含量为 5 %— 30%， 其用量为产品过碳酸钠重量的： 0. 02%-0. 5 % , 总量 为产品过碳酸钠的 3 %。 经稳定、 包膜处理的过碳酸钠， 产品稳定性得到显著提高。
上述三项措施， 用于 ,2000吨 /年包膜过碳酸钠生产收到很好效果。主要机理为过碳酸 钠的分解是先放出 H202， 而 H202的分解机理为电子转移和游离基反应过程， 原料中的杂 质铜铁等金属离子对 H202的分解起催化作用， 反应原料中加入内稳定剂的作用是使原料
中的金属离子被沉淀或被有机胺 EDTA络合， 而且有机胺 EDTA和有机酚一样又是游离 基吸收剂， 能起到抑制 ¾02分解的作用。 作为外稳定剂加入的硅酸盐和镁盐可进一步络 合金属离子，而有机胺三乙醇胺为高沸点物质，其沸点 36CTC低毒性， LD50>5000mg / kg, 既可络合金属离子又能抑制游离基的产生，提高产品的稳定性， 且价格低， 与产品的相溶 性好，高分子成膜剂可使外稳定剂更好地附着在过碳酸钠颗粒表面，但成膜剂量过大会影 响过碳酸钠溶解度， 影响漂白、 杀菌力的发挥。 因此， 通过上述两种方式添加的稳定剂能 减少或络合产品中的金属离子， 或通过吸收 H202的分解产生的游离基， 抑制 H202的分 解， 亦即抑制过碳酸钠的分解。
对整个反应体系而言， 所采用的过氧化氢浓度愈高， 相应带入反应体系的水分愈少， 即弃除的母液也愈少， 以碳酸钠和双氧水计算的反应收率都高 (参见图 2)。
考虑浓度不同双氧水的价格问题，以及双氧水生产厂家产品情况，本发明人选用 27. 5 %的双氧水， 可由江西氨厂供应。
过碳酸钠属热敏性物质， 反应温度愈高， 反应合成的过碳酸钠分解率也愈高， 相对收 率也愈低。反应温度过低， 影响产品结果并导致收率下降， 本发明工艺一般地将反应温度 控制在 18-25 °C之间， 温度过低， 能耗过大， 不经济。
通过采用含有机胺的复合内稳定剂和采用外稳定剂及含有机高分子成膜剂的包膜剂 对产品包膜处理，使产品的稳定显著提高，在提高产品稳定性的同时可保证产品具有适中 的溶解速度和活性氧释放速度并具有助洗功能， 可提高产品的使用性能。
产品稳定度的测定按 Q7 YT001-2000标准进行， 做了六个样品的稳定度测定， 平均 粒径 35目， 结果列于下表：
, 原活性氧 -稳定度检测活性氧
计算办法 稳定度 （％) = xlOO
原活性氧
上述稳定度的六个样 '品， 取 500克封于聚乙烯塑料袋内袋口热塑封死， 于 2000年 06 月 20日存放至 09月 21 日， 存放地为成品库阴凉通风处一小木架上， 2000年 09月 21 日 按 Q / YT001-2000标准检测结果列于下表：
从上述二表结果可以看出发明工艺产品稳定性很好。 Q/YT001-2000标准稳定度测定 方法与自然存放三个月的试样稳定性比较吻合 Q I YT001-2000标准稳定度测定。
包膜过碳酸钠主要用于洗衣洗粉作添加剂，制成所谓的彩漂粉， 以提高洗衣粉的去污 渍功能， 使被洗涤织物鲜艳亮丽。 国产洗衣粉由于水分偏高至 7-8 % , 容易引起所添加的 过碳酸钠较大量的分解， 而失去添加过碳酸钠意义。
本发明人由自己所生产的同一批量过碳酸钠取一部分不进行包膜处理，另一部分经包 膜处理。 按国内通用洗衣粉的 10公斤， 经检测水分为 6. 5 % , 取 3公斤分成 6组， 每组 500克， 3组加入未包膜过碳酸钠 10%， 另三组加入包膜过碳酸钠 10%，试品放入聚乙烯 袋内， 封口， 在 2000年 08月 05日至 2000年 11月 07日， 于自然通风处放置三个月后， 经检测活性氧， 并经换算其结果比照如下表：
*为未包膜的过碳酸钠。
从表中可以看出包膜过碳酸钠在所添加的洗衣粉中分解比未包膜过碳酸钠要低得多， 即稳定得多， 按表中的分解速度推论， 半年以上未包膜碳酸钠的分解平均接近 40%， 其 活性氧将低于 8 %， 过碳酸钠活性氧 8 %以上才有使用价值， 而包膜过碳酸钠半年之后分 解率为 10%以下， 其活性氧仍将在 12%以上， 仍处于有实用价值的范围之上。
本发明无废气、 废渣产生， 仅含有碳酸钠、 氯化钠的母液产生， 该母液可以回收、 套 用， 母液实行零排放， 对环境无污染。 本工程需用风机和离心机， 选用低噪声机种， 布置
于室内或围墙隔噪处理。'
本发明属于无机类化学品生产， 主要设备常压生产。 没有可燃性气体、 液体存在。 用 电设备可按非防爆要求安装。厂房门口用厂内交通要道， 消防车可以自由出入。厂房内备 有灭火器、 灭火筒及消防栓。
生产工人经过培训上岗， 每班均有兼职安全员， 就地进行安全检查。 双氧水是强氧 化剂， 一生产工作已配备所必须的劳保用品， 如工作服、 胶手套和胶鞋、 口罩、 防护眼镜 等。 车间内已配备冲水设施和简单的保健药品。
我公司在国内率先提出了体现产品稳定性的稳定度指标。
如无特殊说明， 本发明中所用的百分数均为重量百分数。 附图说明
图 1是本发明工艺流程示意图。
图 2是过碳酸钠收率 a随 ¾02浓度 X的变化示意图 ( 具体实施方式
实施例 Γ
一， 原料配制
1. 工业碳酸钠： 400公斤
2. 工业精盐： ， 100公斤
3. 27. 5%双氧水： 700公斤
4. 内稳定剂： Na2SiO30. 8公斤、 MgSO40. 3公斤、 EDTA0. 2公斤加水 1. 3
公斤配制成水溶液并等分成两份。
5. 助晶剂： 聚丙烯酸钠 3. 25公斤加水 15公斤。
6. 外稳定剂： Na2Si0313公斤、 MgS045. 0公斤、 三乙醇胺 1. 6公斤加水 20公斤。
7. 包膜剂： 聚乙二醇 1. 5公斤加水 10公斤。
--. 生产过程
将工业碳酸钠与工业精盐按比例为 4: 1 的重量配比在搅拌下加入已放好定量母液的 浆料釜中打浆后加入备好的内稳定剂，将计量的双氧水加入双氧水高位槽中，在搅拌下加 入备好的内稳定剂， 浆料和双氧水均用冷却盐水夹套冷却至 14Ό一 16°C， 在搅拌下同时 加入到已放入计量母液并冷却到 14°C一 16°C的合成釜内并同时开始滴加助晶剂， 控制两 物料的加入速度， 控制反应温度在 16Ό-25Ό之间， 随着反应物料的逐渐增加逐步提高搅 拌速度以控制产品颗粒度， 控制加料反应时间为 90分钟， 加料结束， 再反应 5— 15分钟， 反应结束， 搅拌下将物料放入震动离心机中甩干， 母液进入母液池中回收套用，湿物料经 振动给料器进入相对小型第一振动流化床， 在该流化床中段以 0. 4Mpa的压力雾化喷入 已备好的外稳定剂水溶液， 在该流化床后段以 0. 4Mpa的压力雾化喷入已备好的包膜剂 水溶液， 经包膜处理的产品进入第二振动流化干燥床干燥， 产品经筛分后进入料仓， 检验 合格包装即为成品。 所得产品活性氧为 14. 2%、 水份为 1. 4%、 稳定度为 98. 4%。
实施例 2
将实施例 1中助晶剂换为聚酰胺 3. 25公斤加水 15公斤，包膜剂为羟乙基纤维素 1. 5 公斤加水 10公斤， 其它配料不变， 按实施例 1的生产工艺可得到相同的效果。
Claims
1.一种包膜过碳酸钠， 其特征在于： 将工业碳酸钠与工业精盐按比例为 4: 1 的重量 配比在搅拌下加入已放好定量母液的浆料釜中打浆后加入备好的内稳定剂，将计量的双氧 水加入双氧水高位槽中，在搅拌下加入备好的内稳定剂，浆料和双氧水均用冷却盐水夹套 冷却至 14°C一 16°C， 在搅拌下同时加入到已放入计量母液并冷却到 14°C一 16Ό的合成釜 内并同时开始滴加助晶剂， 控制两物料的加入速度， 控制反应温度在 16°C-25°C之间， 随 着反应物料的逐渐增加逐步提高搅拌速度以控制产品颗粒度， 控制加料反应时间为 90分 钟， 加料结束， 再反应 5— 15分钟， 反应结束， 搅拌下将物料放入震动离心机中甩干， 母 液进入母液池中回收套用，湿物料经振动给料器进入相对小型第一振动流化床，在该流化 床中段以 0. 4Mpa的压力雾化喷入已备好的外稳定剂水溶液，在该流化床后段以 0. 4Mpa 的压力雾化喷入已备好的包膜剂水溶液， 经包膜处理的产品进入第二振动流化干燥床干 燥， 产品经筛分后进入料仓， 检验合格包装即为成品。
2. 根据权利要求 1所述的包膜过碳酸钠， 其特征在于所述的工业精盐为氯化钠。
3. 根据权利要求 1所述的包膜过碳酸钠， 其特征在于所述的内稳定剂为 N¾Si03、 MgS04、 EDTA, 其组成重量配比为 Na2Si03 : MgS04: EDTA=8: 3： 2, 配制成水溶液固 体的重量百分数含量为 10%-60%， 其用量为产品过碳酸钠重量的 0. 02%-1. 0%。
4. 根据权利要求 1所述的包膜过碳酸钠， 其特征在于所述的双氧水浓度为 27. 5 %。
5. 根据权利要求 1所述的包膜过碳酸钠， 其特征在于所述的助晶剂为聚丙烯酸钠和 /或聚酰胺， 配制成重量百分数为 5-30%的水溶液， 其用量为产品过碳酸钠重量的 0. 1 %-1. 0 c
6. 根据权利要求 1 所述的包膜过碳酸钠， 其特征在于所述的外稳定剂成份为 Na2Si03，、 MgS04、 三乙醇胺， 其组成重量配比为 Na2Si03 : MgS04: 三乙醇胺 =8: 3： 1， 配制成水溶液固体的重量百分数含量为 25 %-60%， 其用量为产品过碳酸钠重量的 0. 5 %-5. 0%。
7， 根据权利要求 1所述的包膜过碳酸钠， 其特征在于所述的包膜剂选自聚乙二醇、 羟乙基纤维素或丙烯酸-马来酸共聚物， 配成水溶液固体含量为 5 %-30 ， 其用量为产品 过碳酸钠重量的 0. 02% -0. 5%。
8. 根据权利要求 1 所述的包膜过碳酸钠， 其特征在于所述的产品颗粒度为 80— 10 g。
9. 根据权利要求 1所述的包膜过碳酸钠， 其特征在于将工业碳酸钠 400公斤与工业
精盐 100公斤按比例为 4: 1的重量配比在搅拌下加入已放好定量母液的浆料釜中打浆后 加入备好的内稳定剂， 所述内稳定剂为 Na2SiO30. 8公斤， MgSO40. 3公斤， EDTA0. 2 公斤加水 1， 3公斤配制成水溶液并等分成两份： 将计量的浓度为 27. 5 %双氧水 700公 斤加入双氧水高位槽中，在搅拌下加入备好的内稳定剂，浆料和双氧水均用冷却盐水夹套 冷却致 14°C-16°C，在搅拌下同时加入到已放入计量母液并冷却到 14Ό一 16Ό的合成釜内 并同时开始滴加助晶剂， 所述的助晶剂为聚丙烯酸钠 3. 25公斤加水 15公斤， 控制两物 料的加入速度， 控制反应温度在 16°C-25°C之间， 随着反应物料的逐渐增加逐步提高搅拌 速度 lOrpm至 90rpm以控制产品颗粒 '度在 80-10目范围内，控制加料反应时间为 90分钟， 加料结束， 再反应 5— 15分钟， 反应结束， 搅拌下将物料放入震动离心机中甩千， 母液进 入母液池中回收套用，湿物料经振动给料器进入相对小型第一振动流化床，在该流化床中 段以 0. 4Mpa 的压力雾化喷入已备好的外稳定剂水溶液， 所述的外稳定剂水溶液为 Na2Si0313公斤， MgS045. 0公斤， 三乙醇胺 1. 6公斤加水 20公斤； 在该流化床后段以 0. 4Mpa的压力雾化喷入已备好的包膜剂水溶液， 所述的包膜剂为水溶液聚乙二醇 1. 5 公斤加水 10公斤； 经包膜处理的产品进入第二振动流化干燥床干燥， 产品经筛分后进入 料仓， 检验合格包装即为成品， 所得产品活性氧为 14. 2 % 水份为 1. 4%、 稳定度为 98. 4%。
10.权利要求 1 的包膜过碳酸钠作为洗涤剂、 清洗剂和漂白剂配方中的漂白组分的应 用。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2002/000558 WO2004014789A1 (fr) | 2002-08-12 | 2002-08-12 | Percarbonate de sodium revetu et son procede de preparation et son utilisation |
| AU2002327280A AU2002327280A1 (en) | 2002-08-12 | 2002-08-12 | Coated sodium percarbonate and the preparation process and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2002/000558 WO2004014789A1 (fr) | 2002-08-12 | 2002-08-12 | Percarbonate de sodium revetu et son procede de preparation et son utilisation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004014789A1 true WO2004014789A1 (fr) | 2004-02-19 |
Family
ID=31501656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2002/000558 WO2004014789A1 (fr) | 2002-08-12 | 2002-08-12 | Percarbonate de sodium revetu et son procede de preparation et son utilisation |
Country Status (2)
| Country | Link |
|---|---|
| AU (1) | AU2002327280A1 (zh) |
| WO (1) | WO2004014789A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1612186A1 (en) * | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them. |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112758897B (zh) * | 2021-01-26 | 2022-06-10 | 天津大学 | 一种过碳酸钠的制备方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089571A (zh) * | 1993-12-28 | 1994-07-20 | 山东大学 | 稳定过碳酸钠的制备方法 |
| US5603911A (en) * | 1992-09-07 | 1997-02-18 | Kemira Oy | Preparing a crystalline, stable sodium percarbonate |
| CN1156738A (zh) * | 1995-11-25 | 1997-08-13 | 黄明科 | 一种过碳酸钠稳定剂的配制方法 |
| JP2001302216A (ja) * | 2000-04-26 | 2001-10-31 | Oriental Chemical Ind | 洗剤用の粒状コーテッド過炭酸ナトリウム |
-
2002
- 2002-08-12 AU AU2002327280A patent/AU2002327280A1/en not_active Abandoned
- 2002-08-12 WO PCT/CN2002/000558 patent/WO2004014789A1/zh not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603911A (en) * | 1992-09-07 | 1997-02-18 | Kemira Oy | Preparing a crystalline, stable sodium percarbonate |
| CN1089571A (zh) * | 1993-12-28 | 1994-07-20 | 山东大学 | 稳定过碳酸钠的制备方法 |
| CN1156738A (zh) * | 1995-11-25 | 1997-08-13 | 黄明科 | 一种过碳酸钠稳定剂的配制方法 |
| JP2001302216A (ja) * | 2000-04-26 | 2001-10-31 | Oriental Chemical Ind | 洗剤用の粒状コーテッド過炭酸ナトリウム |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1612186A1 (en) * | 2004-06-29 | 2006-01-04 | SOLVAY (Société Anonyme) | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them. |
| WO2006003156A1 (en) * | 2004-06-29 | 2006-01-12 | Solvay (Societe Anonyme) | Sodium percarbonate particles, process for their production, their use and detergent compositions containing them |
| US8025972B2 (en) | 2004-06-29 | 2011-09-27 | SOLVAY (Société Anonyme | Coated sodium percarbonate particles having excellent long term stability, process for their production, their use and detergent compositions containing them |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2002327280A1 (en) | 2004-02-25 |
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