WO2024033276A1 - Amorphous non-nano silica spheres - Google Patents
Amorphous non-nano silica spheres Download PDFInfo
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- WO2024033276A1 WO2024033276A1 PCT/EP2023/071757 EP2023071757W WO2024033276A1 WO 2024033276 A1 WO2024033276 A1 WO 2024033276A1 EP 2023071757 W EP2023071757 W EP 2023071757W WO 2024033276 A1 WO2024033276 A1 WO 2024033276A1
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- Prior art keywords
- composition
- silicate
- silica gel
- personal care
- ash
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000000377 silicon dioxide Substances 0.000 title abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000741 silica gel Substances 0.000 claims description 22
- 229910002027 silica gel Inorganic materials 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 14
- 230000000035 biogenic effect Effects 0.000 claims description 12
- 239000002537 cosmetic Substances 0.000 claims description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 11
- 235000011149 sulphuric acid Nutrition 0.000 claims description 11
- 239000004115 Sodium Silicate Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000005022 packaging material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002910 solid waste Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- 240000000111 Saccharum officinarum Species 0.000 claims description 4
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 4
- 239000008188 pellet Substances 0.000 claims description 4
- 241000609240 Ambelania acida Species 0.000 claims description 3
- 239000010905 bagasse Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims 2
- 239000004744 fabric Substances 0.000 claims 2
- 238000001694 spray drying Methods 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- 239000002956 ash Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- -1 gravel Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000002918 Fraxinus excelsior Nutrition 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000426 Microplastic Polymers 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000012358 sourcing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/025—Explicitly spheroidal or spherical shape
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/25—Silicon; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
- C01B33/128—Preparation of silica of undetermined type by acidic treatment of aqueous silicate solutions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
Definitions
- Silicon dioxide also known as silica
- Silica is one of the most common minerals in the earth's crust.
- non-renewable resources such as sand, gravel, clay, granite, diatomaceous earth, and many other forms of rock.
- sourcing silica from sand by dredging requires significant energy consumption and emits large amounts of CO2.
- Silica is used widely in personal care products, including cosmetics, due to its multifunctioning nature, primarily as an absorbent powder and thickening agent in cosmetics. Silica employed in personal care products, however, are currently sized as nano material; /. ⁇ ?., having particle sizes in the range of 2 -50nm. Consumers and researchers are becoming increasing aware and concerned about interactions of biological systems (such as the skin) and nanomaterials.
- Evidence demonstrates what is disclosed herein to be superior to the silica obtained from sand and other non-renewable sources of silica in personal care products, particularly cosmetics.
- the following disclosure also offers an alternative to microplastics which are currently being phased out of many cosmetic products.
- the silica, methods, compositions of matter and articles thereof disclosed herein improve the properties of personal care products, particularly cosmetics, such as smoothness for spreadability, abrasiveness for cleansing and exfoliating, soft focus, soft scrub, matte finish, light deflection and oil absorption.
- the amorphous silica spheres disclosed herein also improve the even distribution of pigments in cosmetics, prevent setting thereof in applying makeup, and enhance the absorption by the skin of other ingredients.
- the disclosed amorphous silica spheres have unique sphericity, high oil absorption, particle size distribution and oil/water absorption ratio. These characteristics supply benefits such as sebum control, mattification, and anti-aging effects without drying the skin.
- the claimed invention relates to unique amorphous silica spheres consisting of amorphous spheres having particles with an average size between 1 to about 10 pm and methods for their manufacture. Additional embodiments of the invention relate to compositions of matter containing the amorphous silica spheres of the invention and a suitable carrier therefore adapted for admixture with personal care products; compositions of matter comprising a personal care product and product improving amounts of the above described amorphous silica spheres; compositions of matter comprising a personal care product and product improving amounts of the above described compositions containing the amorphous silica spheres and a carrier, and articles of manufacture, each comprising packaging material containing any of the above described products or compositions, wherein each packaging material contains instructions for the use thereof.
- Fig. l is a block diagram of an embodiment of the invention comprising a method of preparing the above-described amorphous silica spheres.
- Fig. 2 is a more detailed block diagram of Fig. 1.
- Fig. 3 is a block diagram of a metals mitigation method which may be incorporated into the methods depicted in Figs 1 and 2.
- the amorphous silica spheres disclosed herein differ from those currently manufactured in various respects, including size, composition, and methods of manufacture.
- the amorphous silica spheres of the claimed invention are between 1 to 10 pm in size - significantly larger that the nano-particles employed in traditional articles of manufacture.
- the claimed invention derives from the unexpected discovery that amorphous silica spheres of the above particle size range perform unexpectedly superior to traditional silica, particularly in personal care products, such as cosmetics, for example.
- the amorphous silica spheres of the present invention are prepared by reacting a biogenic ash; e.g. sugarcane bagasse ash (SCBA) with a base to form a silicate, although it will be understood by those skilled in the art that any suitable biogenic ash may be employed in the practice of the invention.
- a biogenic ash e.g. sugarcane bagasse ash (SCBA)
- SCBA sugarcane bagasse ash
- any suitable biogenic ash may be employed in the practice of the invention.
- NaOH sodium hydroxide
- any suitable base may be employed including, but not limited to lithium hydroxide (LiOH), potassium hydroxide (KOH) and the like.
- the silicate is solubilized and then acidified to yield precipitated amorphous silica.
- sulfuric acid H2SO4
- any suitable acid may be employed.
- amorphous silica is then homogenized to form particles of essentially uniform size and spray dried to produce the desired non-nano amorphous spheres.
- milling is described in the examples, it will be understood by those skilled in the art that any suitable homogenization method may be employed.
- the sphericity and size of the ultimate non-nano amorphous silica spheres is dependent on the size of the SiCh particles fed to the spray dryer.
- a SiCh feed to the spray drier having a particle size of 0.1 - 1 micron ultimately yielded non-nano amorphous silica spheres having a particle size of from about 1 to about 10 microns.
- acid concentration, % silica, and temperature during the neutralization/precipitation step determine the oil absorption/density of the final product.
- the ash was separated from impurities such as sand, for example in the Siever 1 and conveyed to Heating Mix Reactor 2 where it was mixed with a 50% NaOH solution and allowed to react at 350°C for 20 minutes to produce sodium silicate [Na2SiOs], which was then conveyed to Filter Press 3 where the silicate solution was separated from solid waste.
- impurities such as sand
- Heating Mix Reactor 2 where it was mixed with a 50% NaOH solution and allowed to react at 350°C for 20 minutes to produce sodium silicate [Na2SiOs], which was then conveyed to Filter Press 3 where the silicate solution was separated from solid waste.
- silicate solution was conveyed to Mixer 4 to which was added H2SO4 [10% (v/v) or 17.26% (w/w)] to promote silica gel formation by precipitation.
- Liquid waste was drained from the mixer and the silicate solution sent to Filter Press 5 where water was added and, after filtration to remove liquid waste, a silica gel in the form of a wet cake remained.
- the wet cake was slurried in water in Mixer 6 where it was homogenized as described further below.
- the homogenized solution was then fed to Spray dryer 7 to produce the final non-nano amorphous silica spheres product having an average particle size ranging between 1 to 10 microns.
- Fig. 2 illustrates in greater detail the method carried out in the system depicted in Fig. 1. Examples of raw materials used in Fig. 2 are shown below in Table 1.
- Table 1 As described in further detail below, the final product of the method illustrated in Fig. 2 are amorphous silica spheres, with a particle size between 2-8 microns. Furthermore, the feed composition using the method illustrated in Fig. 2 include: Ashes/NaOH 1 kg sifted ash: 1.5 kg NaOH (dw). Exemplary storage and temperature conditions are shown below in Table 2.
- raw sugar cane fly ash was sieved through a 100 mesh screen (Siever) as in Example 1 to produce a dry biogenic ash essentially free of large particles and non- biogenic silica such as quartz and field sand, for example. While not shown in Fig. 2, dry biogenic ash can be sifted through 100 - 120 mesh screens. The expected yield is 50 - 60% through the 100 mesh screen shown in Fig. 2.
- the ash may be pretreated with acid (2a) as described below to remove metal impurities that may be present.
- the ash was conveyed to the mix reactor to which a 50% solution of sodium hydroxide was added. Reaction was allowed to proceed at the depicted temperature and time:
- the reactions produce amorphous sodium silicate (Na 2 SiO 3 ). Optimally, the reaction takes place at 185 - 350 °C (just above NaOH pellets 318 °C, melting point). According to certain embodiments disclosed herein, the mass ratio of 1.5 : 1 (NaOH: ash) is the optimized ratio. Further options include:
- the ash material may form large solids that require milling to allow for the material to be solubilized after the reaction. The material needs to be put into solution prior to filtration.
- the methods disclosed herein may further optimize water quantity by using higher values. Further alternatives include speeding up the sludge removal at the filtration unit. Moreover, during scaleup the water content can be adjusted depending on the mixer conditions (open or closed) and filtration system.
- the sodium silicate solution was next filtered in the filter press 1 to remove all insoluble material and produce a clear/clean sodium silicate filtrate.
- a filter press rated at 0.3-3 cfm or pore size 0.5 - 5 pm is preferably used for this separation.
- filter aids may be employed (e.g., AC) and/or filtration with a tighter membrane may be used to remove fine suspensions. It will be understood by those skilled in the art that any suitable means may be employed to separate unwanted materials.
- Vacuum filtration tends to produce high tension and sludge may break through the filter paper. Often, pore size is a limiting factor and not the membrane material (e.g., a material that must be resistant to the pressure and high pH). Furthermore, with respect to the vacuum filtration, independent of the water added and the final solution, the remaining sludge has a viscosity of 50 cP and a density of 1.32 (room temperature). The resulting product of these vacuum filtration methods is a transparent yellow to brown solution with a pH of 11 to 12. Wastes produced include a black sludge rich in sodium hydroxide, minerals (mainly sodium, potassium, iron and calcium) and residual sodium silicate (pH 11 - 12).
- acid is next added to the clear sodium silicate filtrate stream to promote silica gel formation by precipitation.
- sulfuric acid 10-30% solution
- the precipitation temperature should preferably be lower than 30 °C (see Table 4).
- a pH potentiometer may be employed to monitor the addition of acid and the decrease in pH. The reaction produces a precipitated amorphous silica gel and sodium sulphate as residue, according to the equation: Na 2 SiO 3 + H2SO4 SiO 2 + Na 2 SO 4 + H 2 O
- Table 4 shown below, illustrates the impact of precipitation temperature on final product density and oil absorption.
- the product is filtered to remove amorphous silica gel [typically a 20 - 30% solid wet cake].
- the wet cake may be contaminated with metal impurities such as Al, Fe, and Cr, which are removed by be re-slurrying the wet cake in water and acid washing with an either an inorganic acid at a pH of less than 0.95 or an organic acid with chelating functionalities at pH 2-3 (see Example 3).
- the acid washed silica solution is next filtered, preferably through a filter press using filter press media rated at 3 cfm or pore size 0.5 - 5 pm. It will be understood by those skilled in the art that any suitable type of filter may be employed to isolate the wet cake which is used for the next step in the process.
- the sodium silicate produced by the filter press was conveyed to the neutralization mixer to which H2SO4 [10% (v/v) or 17.26% (w/w)] was next added to achieve a pH of 7 to promote silica gel formation by precipitation.
- H2SO4 10% (v/v) or 17.26% (w/w)
- any suitable inorganic or organic acid may be employed.
- the precipitated silica gel was removed and optionally acid washed at pH of 0.9 before being sent to the filter press rated at 3 cfm or pore size .5 - 5 , wherein liquid waste and soluble materials were removed to produce a silica gel in the form of a wet cake. It will be understood by those skilled in the art that any suitable separation means may be employed in this step.
- the wet cake was slurried in water (e.g., RO water) in the mixer to form a 5-7% solution at a pH of 5.5 - 8.5.
- the slurried wet cake was transported to the homogenizer/mill where it was resuspended in water and homogenized/milled at high pressure e.g., 3,000, 5,000 psi, 6,000 psi, etc.) for 1 - 2 passes to reduce the particle size thereof to below 1 micron.
- the silica gel can be subjected to an acid wash to remove metals.
- the main metal impurities in silica are Al, Fe and Cr, which can be mitigated by using inorganic acids at pH lower than 0.95 or using organic acids with chelating functionalities at pH 2-3.
- the method illustrated in Fig. 2 was modified as follows:
- Step 5a Use of sulfuric acid for acid wash on silica gel:
- Step 5b Use of citric acid for acid wash on silica gel:
- TDS ⁇ XX or Conductivity ⁇ 100 Micro Siemens Table 5 shown below, illustrates the estimated metal levels of final product after acid wash on dry basis silica (indicated by an asterisk (*)) or on wet basis silica (indicated by underlined text).
- the acid e.g., citric acid
- SCBA sifted ash
- Optional step 2a Use of Citric acid for acid wash on sifted ash (SCBA): • Citric acid concentration 7 wt% and pH of the silica solution between 2-3
- Acid choice may vary based on the disclosed methods and equipment employed; however, H2SO4 or citric acid is preferred since HC1 is not compatible with stainless reactors.
- An acid wash e.g., citric acid
Abstract
Disclosed herein are non-nano amorphous silica spheres and methods for manufacturing silica using renewable resources. Embodiments of the disclosed non-nano amorphous silica spheres have an average particle size ranging between 1 µm and 10 µm. Also disclosed are compositions containing same and methods for the preparation and use thereof.
Description
AMORPHOUS NON-NANO SILICA SPHERES
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority to U.S. Provisional Patent Application No. 63/370,684, filed on August 8, 2022, which is herein incorporated by reference in its entirety.
BACKGROUND
Silicon dioxide (also known as silica) is one of the most common minerals in the earth's crust. Conventionally, silica is sourced from non-renewable resources (such as sand, gravel, clay, granite, diatomaceous earth, and many other forms of rock) using environmentally harmful methods. For example, sourcing silica from sand by dredging requires significant energy consumption and emits large amounts of CO2.
Silica is used widely in personal care products, including cosmetics, due to its multifunctioning nature, primarily as an absorbent powder and thickening agent in cosmetics. Silica employed in personal care products, however, are currently sized as nano material; /.<?., having particle sizes in the range of 2 -50nm. Consumers and researchers are becoming increasing aware and concerned about interactions of biological systems (such as the skin) and nanomaterials.
What is needed is a renewable, environmentally responsible form of silica in a non-nano size to address the unmet needs of the industry.
SUMMARY
Disclosed herein are methods of deriving silica from biological materials, compositions of such matter, articles of manufacture and amorphous silica spheres. Evidence demonstrates what is disclosed herein to be superior to the silica obtained from sand and other non-renewable sources of silica in personal care products, particularly cosmetics. The following disclosure also offers an alternative to microplastics which are currently being phased out of many cosmetic products.
For example, the silica, methods, compositions of matter and articles thereof disclosed herein improve the properties of personal care products, particularly cosmetics, such as smoothness for spreadability, abrasiveness for cleansing and exfoliating, soft focus, soft scrub,
matte finish, light deflection and oil absorption. Furthermore, the amorphous silica spheres disclosed herein also improve the even distribution of pigments in cosmetics, prevent setting thereof in applying makeup, and enhance the absorption by the skin of other ingredients. For example, the disclosed amorphous silica spheres have unique sphericity, high oil absorption, particle size distribution and oil/water absorption ratio. These characteristics supply benefits such as sebum control, mattification, and anti-aging effects without drying the skin.
As described in further detail below, the claimed invention relates to unique amorphous silica spheres consisting of amorphous spheres having particles with an average size between 1 to about 10 pm and methods for their manufacture. Additional embodiments of the invention relate to compositions of matter containing the amorphous silica spheres of the invention and a suitable carrier therefore adapted for admixture with personal care products; compositions of matter comprising a personal care product and product improving amounts of the above described amorphous silica spheres; compositions of matter comprising a personal care product and product improving amounts of the above described compositions containing the amorphous silica spheres and a carrier, and articles of manufacture, each comprising packaging material containing any of the above described products or compositions, wherein each packaging material contains instructions for the use thereof.
DESCRIPTION OF DRAWINGS
Fig. l is a block diagram of an embodiment of the invention comprising a method of preparing the above-described amorphous silica spheres.
Fig. 2 is a more detailed block diagram of Fig. 1.
Fig. 3 is a block diagram of a metals mitigation method which may be incorporated into the methods depicted in Figs 1 and 2.
DETAILED DESCRIPTION
The amorphous silica spheres disclosed herein differ from those currently manufactured in various respects, including size, composition, and methods of manufacture. For example, the amorphous silica spheres of the claimed invention are between 1 to 10 pm in size - significantly larger that the nano-particles employed in traditional articles of manufacture. Moreover, the
claimed invention derives from the unexpected discovery that amorphous silica spheres of the above particle size range perform unexpectedly superior to traditional silica, particularly in personal care products, such as cosmetics, for example.
The amorphous silica spheres of the present invention are prepared by reacting a biogenic ash; e.g. sugarcane bagasse ash (SCBA) with a base to form a silicate, although it will be understood by those skilled in the art that any suitable biogenic ash may be employed in the practice of the invention. Although the invention is exemplified herein employing sodium hydroxide (NaOH) in pellet form or in aqueous solution to produce sodium silicate, it will be understood by those skilled in the art that any suitable base may be employed including, but not limited to lithium hydroxide (LiOH), potassium hydroxide (KOH) and the like.
The silicate is solubilized and then acidified to yield precipitated amorphous silica. Although the invention is exemplified herein employing sulfuric acid (H2SO4) to form the amorphous silica, it will be understood by those skilled in the art that any suitable acid may be employed.
The amorphous silica is then homogenized to form particles of essentially uniform size and spray dried to produce the desired non-nano amorphous spheres. Although milling is described in the examples, it will be understood by those skilled in the art that any suitable homogenization method may be employed.
Surprisingly, it has been found, as set forth in the following examples, that the sphericity and size of the ultimate non-nano amorphous silica spheres is dependent on the size of the SiCh particles fed to the spray dryer. Thus, a SiCh feed to the spray drier having a particle size of 0.1 - 1 micron ultimately yielded non-nano amorphous silica spheres having a particle size of from about 1 to about 10 microns. Moreover, as demonstrated in the Examples below, acid concentration, % silica, and temperature during the neutralization/precipitation step determine the oil absorption/density of the final product.
The foregoing description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the claimed invention, since the scope of the claimed invention is best defined by the appended claims.
Several methods of preparing amorphous silica sphere according to the claimed invention are described in the following examples. These examples are not to be taken in a limiting sense. Rather, these examples are provided merely for the purpose of illustrating the general principles
of the claimed invention, since the scope of the claimed invention is best defined by the appended claims.
EXAMPLES
EXAMPLE 1
Referring to FIG. 1, the ash was separated from impurities such as sand, for example in the Siever 1 and conveyed to Heating Mix Reactor 2 where it was mixed with a 50% NaOH solution and allowed to react at 350°C for 20 minutes to produce sodium silicate [Na2SiOs], which was then conveyed to Filter Press 3 where the silicate solution was separated from solid waste.
The silicate solution was conveyed to Mixer 4 to which was added H2SO4 [10% (v/v) or 17.26% (w/w)] to promote silica gel formation by precipitation. Liquid waste was drained from the mixer and the silicate solution sent to Filter Press 5 where water was added and, after filtration to remove liquid waste, a silica gel in the form of a wet cake remained.
The wet cake was slurried in water in Mixer 6 where it was homogenized as described further below.
The homogenized solution was then fed to Spray dryer 7 to produce the final non-nano amorphous silica spheres product having an average particle size ranging between 1 to 10 microns.
EXAMPLE 2
Fig. 2 illustrates in greater detail the method carried out in the system depicted in Fig. 1. Examples of raw materials used in Fig. 2 are shown below in Table 1.
Table 1
As described in further detail below, the final product of the method illustrated in Fig. 2 are amorphous silica spheres, with a particle size between 2-8 microns. Furthermore, the feed composition using the method illustrated in Fig. 2 include: Ashes/NaOH 1 kg sifted ash: 1.5 kg NaOH (dw). Exemplary storage and temperature conditions are shown below in Table 2.
Referring now to Fig. 2, the steps illustrated are summarized in Table 3 and described in further detail below.
As shown in Fig. 2, raw sugar cane fly ash was sieved through a 100 mesh screen (Siever) as in Example 1 to produce a dry biogenic ash essentially free of large particles and non- biogenic silica such as quartz and field sand, for example. While not shown in Fig. 2, dry biogenic ash can be sifted through 100 - 120 mesh screens. The expected yield is 50 - 60% through the 100 mesh screen shown in Fig. 2.
Optionally, the ash may be pretreated with acid (2a) as described below to remove metal impurities that may be present.
The ash was conveyed to the mix reactor to which a 50% solution of sodium hydroxide was added. Reaction was allowed to proceed at the depicted temperature and time:
2NaOH + SiO2 Na2SiO3 + H2O.
The reactions produce amorphous sodium silicate (Na2SiO3). Optimally, the reaction takes place at 185 - 350 °C (just above NaOH pellets 318 °C, melting point). According to certain embodiments disclosed herein, the mass ratio of 1.5 : 1 (NaOH: ash) is the optimized ratio. Further options include:
• Option 2.1 : Higher Temp (350 C), NaOH pellets, Shorter Time (2 hours)
• Option 2.2: Lower Temp (185 C), 50% NaOH, Longer Time (7 hours)
According to the foregoing, if reactor option 2.1 is chosen (Higher Temp / Shorter Time), the ash material may form large solids that require milling to allow for the material to be solubilized after the reaction. The material needs to be put into solution prior to filtration.
Since the theoretical solubility of sodium silicate is 22 g/100 ml water, the methods disclosed herein may further optimize water quantity by using higher values. Further alternatives include speeding up the sludge removal at the filtration unit. Moreover, during scaleup the water content can be adjusted depending on the mixer conditions (open or closed) and filtration system.
The sodium silicate solution was next filtered in the filter press 1 to remove all insoluble material and produce a clear/clean sodium silicate filtrate. For example, a filter press rated at 0.3-3 cfm or pore size 0.5 - 5 pm is preferably used for this separation. Furthermore, filter aids may be employed (e.g., AC) and/or filtration with a tighter membrane may be used to remove
fine suspensions. It will be understood by those skilled in the art that any suitable means may be employed to separate unwanted materials.
Although a filtration system comprising a filter press or modular filter is preferred, It will be understood by those skilled in the art that any suitable means may be employed to separate unwanted materials including, but not limited to vacuum filtration and the like. Vacuum filtration tends to produce high tension and sludge may break through the filter paper. Often, pore size is a limiting factor and not the membrane material (e.g., a material that must be resistant to the pressure and high pH). Furthermore, with respect to the vacuum filtration, independent of the water added and the final solution, the remaining sludge has a viscosity of 50 cP and a density of 1.32 (room temperature). The resulting product of these vacuum filtration methods is a transparent yellow to brown solution with a pH of 11 to 12. Wastes produced include a black sludge rich in sodium hydroxide, minerals (mainly sodium, potassium, iron and calcium) and residual sodium silicate (pH 11 - 12).
Returning to Fig. 2, acid is next added to the clear sodium silicate filtrate stream to promote silica gel formation by precipitation. Preferably, sulfuric acid [ 10-30% solution] is added to the sodium silicate solution in a mixed reactor until a pH of 6-7 is reached. To generate final product silica with controlled density and oil absorption, the precipitation temperature should preferably be lower than 30 °C (see Table 4). A pH potentiometer may be employed to monitor the addition of acid and the decrease in pH. The reaction produces a precipitated amorphous silica gel and sodium sulphate as residue, according to the equation: Na2SiO3 + H2SO4 SiO2 + Na2SO4 + H2O
Table 4, shown below, illustrates the impact of precipitation temperature on final product density and oil absorption.
The product is filtered to remove amorphous silica gel [typically a 20 - 30% solid wet cake]. The wet cake may be contaminated with metal impurities such as Al, Fe, and Cr, which are removed by be re-slurrying the wet cake in water and acid washing with an either an inorganic acid at a pH of less than 0.95 or an organic acid with chelating functionalities at pH 2-3 (see Example 3). As disclosed herein, the acid washed silica solution is next filtered, preferably through a filter press using filter press media rated at 3 cfm or pore size 0.5 - 5 pm. It will be understood by those skilled in the art that any suitable type of filter may be employed to isolate the wet cake which is used for the next step in the process.
For example, according to Fig. 2, the sodium silicate produced by the filter press was conveyed to the neutralization mixer to which H2SO4 [10% (v/v) or 17.26% (w/w)] was next added to achieve a pH of 7 to promote silica gel formation by precipitation. It will be understood by those skilled in the art that any suitable inorganic or organic acid may be employed.
The precipitated silica gel was removed and optionally acid washed at pH of 0.9 before being sent to the filter press rated at 3 cfm or pore size .5 - 5 , wherein liquid waste and soluble materials were removed to produce a silica gel in the form of a wet cake. It will be understood by those skilled in the art that any suitable separation means may be employed in this step.
The wet cake was slurried in water (e.g., RO water) in the mixer to form a 5-7% solution at a pH of 5.5 - 8.5. The slurried wet cake was transported to the homogenizer/mill where it was resuspended in water and homogenized/milled at high pressure e.g., 3,000, 5,000 psi, 6,000 psi, etc.) for 1 - 2 passes to reduce the particle size thereof to below 1 micron.
The homogenized solution was then fed to the spray dryer to produce the final non-nano amorphous silica spheres having a moisture of less than 5% (LOD) and an average particle size ranging between 1 to 10 microns.
EXAMPLE 3
The silica gel can be subjected to an acid wash to remove metals. The main metal impurities in silica are Al, Fe and Cr, which can be mitigated by using inorganic acids at pH lower than 0.95 or using organic acids with chelating functionalities at pH 2-3. The metals (Al, Fe and Cr) removal efficiency of acids from high to low are listed as below: HC1 > H2SO4 = Citric Acid > HNO3 > Acetic Acid. For example, the method illustrated in Fig. 2 was modified as follows:
Step 5a. Use of sulfuric acid for acid wash on silica gel:
• Concentration and pH: used 1 M H2SO4 with the pH of the silica solution lower than 0.95
• Reaction time: 5-14 hr
• Temp: 25 °C or higher
• Mixing: 200-300 rpm to make sure solution is well mixed
• Silica gel concentration: 5-7 wt%
• After acid wash, the silica cake was rinsed with ~3 B V DI water followed by weak NaOH (0.2 g/L) and DI water to bring the pH of rinse water back to 6.5
• TDS < XX or Conductivity < 100 Micro Siemens
Step 5b. Use of citric acid for acid wash on silica gel:
• Citric acid concentration 7 wt% (range 5-10 %) with the pH of the silica solution between 2-3
• Reaction time: 14 hr
• Temp: 25 °C or higher
• Mixing: 200-300 rpm to ensure the solution is well mixed
• Silica gel concentration: 5-7 wt%
• After acid wash, the silica cake was rinsed with ~3 B V DI water followed by weak NaOH (0.2 g/L) and DI water to bring the pH of the rinse water back to 6.5
• TDS < XX or Conductivity < 100 Micro Siemens
Table 5, shown below, illustrates the estimated metal levels of final product after acid wash on dry basis silica (indicated by an asterisk (*)) or on wet basis silica (indicated by underlined text).
As shown in Table 5, the following metal removal efficiencies are provided according to the methods disclosed herein: • Cr3 removal: HC1 (82%) > H2SO4 = Citric (40-50%) > HNO3 (29%) >Acetic acid (18%)
• Al/Fe removal: HC1 (88/76%) > H2SO4 >= Citric acid > HNO3 >Acetic acid
• Cr6 removal: Ascorbic acid can reduce Cr6 to Cr3 at low pH.
The results demonstrate that a citric acid/sulfuric acid washing of the silica gel or the sugarcane bagasse ash (SCBA) provides the most efficient metals mitigation.
In addition, as mentioned previously, the acid (e.g., citric acid) may be used as an acid wash on the sifted ash (SCBA). For example, the methods illustrated in Fig. 2 were modified as follows:
Optional step 2a. Use of Citric acid for acid wash on sifted ash (SCBA): • Citric acid concentration 7 wt% and pH of the silica solution between 2-3
• Reaction time: 14 hr
• Temperature: 25 °C or higher
• Ash concentration: 10 wt%
• After acid wash, the silica cake was rinsed with ~3 BV DI water followed by weak NaOH (0.2 g/L) and DI water to bring the pH of the rinse water back to 6.5
Exemplary results of optional step 2a described above and illustrated in Fig. 2 are shown below in Table 6.
Acid choice may vary based on the disclosed methods and equipment employed; however, H2SO4 or citric acid is preferred since HC1 is not compatible with stainless reactors. An acid wash (e.g., citric acid) may be performed on the sifted ash and thereby reduce >50% Cr, Fe and Al.
OTHER EMBODIMENTS
It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other aspects, advantages, and modifications are within the scope of the following claims.
Claims
1. Amorphous silica spheres having an average particle size between 1 pm and 10 pm.
2. A method of preparing the amorphous silica spheres of claim 1, comprising: reacting a biogenic ash with a base to produce a silicate; acidifying the silicate to produce a silica gel cake; suspending the silica gel cake in water; homogenizing the suspended silica gel cake in water; and spray drying the homogenized silica gel cake to produce the amorphous silica spheres.
3. The method of claim 2, wherein said biogenic ash is sugar cane bagasse ash.
4. The method of claim 2, wherein said base is sodium hydroxide and said silicate is sodium silicate.
5. The method of claim 2, wherein said silicate is acidified with H2SO4.
6. A composition of matter adapted for admixture with a personal care product comprising the amorphous silica spheres of claim 1, and a compatible carrier therefore.
7. The composition of claim 6, wherein said personal care product is a cosmetic.
8. A composition of matter comprising a personal care product and the amorphous silica spheres of claim 1.
9. The composition of claim 8, wherein said personal care product is a cosmetic.
10. A composition of matter comprising a personal care product and the composition of claim 6.
11. The composition of claim 10, wherein said personal care product is a cosmetic.
12. A method of enhancing the properties of a personal care product comprising admixing therewith the amorphous silica spheres of claim 1.
13. The method of claim 12, wherein said personal care product is a cosmetic.
14. A method of enhancing the properties of a personal care product comprising admixing therewith a composition of claim 6.
15. The method of claim 14, wherein said personal care product is a cosmetic.
16. An article of manufacture comprising packaging material containing the amorphous silica spheres of claim 1, said packaging material containing instructions for the use thereof.
17. An article of manufacture comprising packaging material containing the composition of claim 6, said packaging material containing instructions for the use thereof.
18. An article of manufacture comprising packaging material containing the composition of claim 7, said packaging material containing instructions for the use thereof.
19. An article of manufacture comprising packaging material containing the composition of claim 9, said packaging material containing instructions for the use thereof.
20. The method of claim 2, including the step of removing metal impurities by washing either the biogenic ash or the silica gel with an acid.
21. The method of claim 2, further comprising a step of removing non-biogenic impurities from the ash prior to reaction with the base.
22. The method of claim 21, wherein said removal is effected with a si ever.
23. The method of claim 22, wherein said siever comprises a 100 to 120 mesh screen.
24. The method of claim 2, wherein the base: ash mass ratio is optimally 1.5 : 1.
25. The method of claim 4, wherein the reaction of biogenic ash with NaOH pellets is conducted at 350°C for about two hours.
26. The method of claim 4, wherein the reaction of biogenic ash with NaOH solution is conducted at 350°C for about two hours.
27. The method of claim 2, wherein the silica gel cake is precipitated at about 30 °C.
28. The method of claim 2, wherein the biogenic ash is reacted with an aqueous base to produce a silicate solution.
29. The method of claim 28, further comprising a step of separating the silicate from solid waste.
30. The method of claim 29, wherein the step of separating the silicate from solid waste is effected in a filter press.
31. The method of claim 30, wherein the filter press comprises a 0.3-3 cfm filter cloth.
32. The method of claim 29, wherein the step of separating the silicate from solid waste is effected by vacuum filtration.
33. The method of claim 2, further comprising a step of separating the precipitated silica gel from solid waste.
34. The method of claim 33, wherein the step of separating the silica gel from solid waste is effected in a filter press.
35. The method of claim 34, wherein the filter press comprises a 0.3-3 cfm filter cloth.
36. The method of claim 33, wherein the step of separating the silica gel from solid waste is effected by vacuum filtration.
37. The method of claim 2, wherein said silica gel is precipitated from said silicate by admixture with an acid.
38. The method of claim 37, wherein said acid is H2SO4.
39. The method of claim 38, wherein the concentration of TbSC is 10% (v/v) or 17.26% (w/w).
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WO1990005113A1 (en) * | 1988-11-09 | 1990-05-17 | J.M. Huber Corporation | Precipitated silicon dioxide abrasive compositions having superior compatibility with anti-plaque and therapeutic fluoride agents for dentifrice applications; dentifrice thereof; and method of making the same |
EP3162762A1 (en) * | 2014-06-30 | 2017-05-03 | JGC Catalysts and Chemicals Ltd. | Porous silica particles, method for producing same, and cosmetic compounded with same |
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WO1990005113A1 (en) * | 1988-11-09 | 1990-05-17 | J.M. Huber Corporation | Precipitated silicon dioxide abrasive compositions having superior compatibility with anti-plaque and therapeutic fluoride agents for dentifrice applications; dentifrice thereof; and method of making the same |
EP3162762A1 (en) * | 2014-06-30 | 2017-05-03 | JGC Catalysts and Chemicals Ltd. | Porous silica particles, method for producing same, and cosmetic compounded with same |
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SINGH JYOTI ET AL: "Utilization of secondary agricultural products for the preparation of value added silica materials and their important applications: a review", JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, SPRINGER, NEW YORK, NY, US, vol. 96, no. 1, 7 July 2020 (2020-07-07), pages 15 - 33, XP037243343, ISSN: 0928-0707, [retrieved on 20200707], DOI: 10.1007/S10971-020-05353-5 * |
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