Classifications

• • 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
  • C01B33/20—Silicates
  • C01B33/32—Alkali metal silicates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
  • B01D61/44—Ion-selective electrodialysis
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K17/00—Soil-conditioning materials or soil-stabilising materials
  • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
  • C09K17/12—Water-soluble silicates, e.g. waterglass
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F1/00—Treatment of water, waste water, or sewage
  • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
  • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S106/00—Compositions: coating or plastic
  • Y10S106/90—Soil stabilization

Definitions

• the present invention the molar ratio (Si0 2 / (A 2 0 + B) (A: alkali metal, B: NH 3)), a high alkali silicate aqueous solution of Anion activation degree of Kei element content Rapi, a method of manufacturing the same And how to use it.
• Aqueous silicate solution called water glass contains a relatively large amount of silicate in order to maintain the solution state, so the molar ratio of silicon to silicate
• silica sol and colloidal silica have no surface area and no crystalline part, and these are dispersed in an alkaline medium.
• Alkali reacts with the silica surface to create a negative charge on the alkali surface, and the silica particles have a negative charge and are stabilized by the repulsive force of the negative charges among the particles.
• silanol groups Si-OH
• silica colloid material there are many silanol groups (Si-OH) on the surface of silica colloid material in addition to silicate, which forms negative charge, so that the amount of negative charge is small and zeta potential Is in the range of 25 ⁇ — 38MV.
• Silica sol is obtained by dealkalization of water glass, but a stable intermediate between water glass and silicate sol has not been obtained. That is, the molar ratio increases with the progress of dealkalization, and the water glass cannot be maintained in a solution state. In general, when the molar ratio is 4.2 or more, precipitation of silica occurs, and the water glass cannot maintain a solution state.
• colloidal silica is also concentrated by an ultrafiltration method (see, for example, US Pat. No. 3,969,266, British Patent No. 1,148,950, and JP-A-58D15022).
• Colloidal silica with silica particles grown can be sufficiently concentrated by ultrafiltration, but water glass has many low molecular weight components such as ions, and the yield by ultrafiltration is low.
• the loss of ions is large, the anion activity inherent in water glass is also lost.
• the present invention has an intermediate characteristics between water glass and colloidal silica, the molar ratio (SiO 2 / (A 2 0 + B) (A: alkali metal, B: NH 3)) and Kei-containing high content Moreover It is an object of the present invention to provide an alkali silicate aqueous solution having a high anion activation degree, a method for producing the same, and a method for using the same. Disclosure of the invention
• Such an aqueous alkali silicate solution of the present invention preferably satisfies at least one of the following properties (C) to (F) in addition to the properties (A) and (B).
• Molar ratio (SiO 2 / (A 2 O + B) (A: alkali metal, B: NH 3)) is less than 4, in terms of oxide concentration Kei element (S i 0 2 concentration) 2.0: 12.0 by weight It is characterized in that an alkali silicate aqueous solution of 10% is dealkalized by an electrodialysis device. In the first production method, the obtained dealkalized solution is preferably concentrated by a reverse osmosis membrane method.
• the raw material silicate aqueous solution of less than 4 is removed by an electrodialysis device,
• the reverse osmosis is preferably performed using an alkali-resistant composite membrane having a molecular weight cutoff of 100 to 20,000.
• the obtained aqueous alkali silicate solution may be further subjected to a contact treatment with a cation exchange resin after electrodialysis and after Z or reverse osmosis.
• the aqueous alkali silicate solution according to the present invention is particularly preferably used as a main agent of a ground consolidating agent.
• Alkali silicate solution according to the invention has intermediate characteristics between water glass and colloidal silica, the molar ratio (Si0 2 / (A 2 0 + B) (A: alkali metal, B: NH 3)) Oyo It has a high silicon content and a high degree of anion activation.
• the alkali silicate aqueous solution according to the present invention has a feature that the content of silicon with respect to alkali is higher than that of ordinary water glass.
• lithium, lithium, sodium, potassium, ammonium, etc. are used as the alkali, most commonly sodium.
• the molar ratio of Kei element and Al force Li (A) (Si0 2 / ( A 2 0 + B) (A: alkali metal, B: NH 3)) is 4 30, preferably 9 to 26, more preferably 12 to 21.
• the alkali is lithium, sodium, potassium, or the like
• the molar ratio is a value calculated in terms of oxide (A 20 , where A is an alkali metal), and when the alkali is ammonia. , Is a value calculated on the basis of ammonia.
• an alkali metal and ammonium may be used in combination.
• (Si0 2 / (A 2 O + B) (A: NH 3): Al force Li metal, B) may be abbreviated as simply "molar ratio" a.
• the silicon concentration in terms of oxide, S i 0 2 concentration (B) force is S 6.8-30 wt%, preferably 8 to 26, rather more preferably is 14 to 22.
• Such an alkali silicate aqueous solution according to the present invention has a silicon concentration approximately equal to that of a silicate sol or colloidal silica.
• the aqueous alkali silicate solution of the present invention preferably satisfies at least one of the following properties (C) to (F) in addition to the properties (A) and (B).
• the degree of anion activation is evaluated by the zeta potential.
• the zeta potential (C) is preferably from 140 MV to 180 MV, more preferably from 150 MV to 180 MV, particularly preferably from 1 MV to 180 MV. It ranges from 58 MV to one 80 MV.
• Zeta potential is a parameter involved in particle dispersion and aggregation. If the same type of particles are dispersed in the liquid, each particle will have the same charge. And the higher the charge, the more they repel each other and stay stable for a long time without agglomeration. Conversely, if there is no charge, or if substances with the opposite sign are mixed, the particles immediately aggregate and precipitate. The charge of these particles also depends on the pH of the solution.
• the zirconium silicate aqueous solution of the present invention has a high anion activity since the zeta potential is negative and contains many anionic molecules as described above.
• the anionic molecules contained in the aqueous alkali silicate solution of the present invention are extremely small, and are smaller than colloids such as colloidal silica. Therefore, in the present invention, even when the aionic particles are present, no sol-like behavior is observed, and the particles can be practically handled as a solution. This is supported by the transmittance described later.
• silica silicate Although the form of existence of the anionic particles is not always clear, the surface has Si It seems to exist as ultra-fine particles of the order of nanometers.
• the structure of silica silicate is variously known as follows, but the aqueous solution of silica silicate according to the present invention belongs to a mono- or bifunctional linear polymer or polycyclic silica. It is thought that there are few of them and many trifunctional Q3x, trifunctional Q3y and tetrafunctional Q4 are contained.
• the alkali silicate aqueous solution according to the present invention has a high anion activity, a papermaking retention agent, a heat-resistant binder, a catalyst, an inorganic coating agent, a reinforcing agent, Applications such as lubricating agents, adhesives, porous materials, and insulating materials can be expected.
• the peak area at the chemical shift of one 100-1 120ppm, chemical shift -100 ⁇ water glass was 29 Si_NMR measured under the same conditions - preferably 1.35 times or more of the peak area of 120ppm More preferably, it is 1.35 to 2.5 times, and the chemical shift of colloidal silica measured by 29 Si-NMR under the same conditions is 1.20 times or more, more preferably 1.20 to 1.33 times the peak area at 100 120 ppm.
• the silicate solution of the present invention has a small number of monofunctional or bifunctional ones belonging to a linear polymer or a polycyclic silicate anion, and has a trifunctional Q3x, a trifunctional Q3y, and a trifunctional Q3y. It can be seen that a large amount of the functional Q4 is contained.
• the peak area is calculated from the area surrounded by the vertical axis at 100 ppm, the vertical axis at 120 ppm, and the spectrum curve after baseline correction.
• the aqueous alkali silicate solution of the present invention preferably has a transmittance (E) in the wavelength region of 1000 to 200 nm in the spectrophotometric method of 90 to 100%, more preferably 95 to 100%.
• E transmittance
• the transmittance of ordinary water glass is the same as above, but the transmittance of colloidal silica is extremely low at 10 to 0% below 200 to 380 nm. As a result, it is found that the aqueous alkali silicate solution of the present invention has characteristics close to those of water glass.
• the aqueous alkali silicate solution of the present invention has an electric conductivity (F) of preferably 2.1 to 35 mS / cm, more preferably 2.1 to 16 mS / cm, and particularly preferably 5.0 to 11.0 mS / cm. cm.
• F electric conductivity
• the aqueous alkali silicate solution of the present invention is a highly desalted solution because of its high electrical conductivity, and is a solution that maintains stability without aggregation by silicate anion.
• Such an aqueous solution of silica silicate according to the present invention comprises water glass and colloidal silica. It has intermediate properties with power, has a high molar ratio and a high silicon content, and has a high degree of anion activation.
• Molar ratio (Si0 2 / (A 2 O + B) (A: alkali metal, B: NH 3)) is less than 4, in terms of oxide concentration Kei element (S i 0 2 concentration) 2.0: 12 by weight It is characterized in that an alkali silicate aqueous solution of 10% is dealkalized by an electrodialysis device.
• Silicate and Al force in the starting alkali silicate aqueous Li (alkali as defined above), the molar ratio (Si0 2 / (A 2 0 + B) (A: alkali metal, B: NH 3)) force less than 4, preferably 1.5 to 4.0, more preferably about 2.8 to 3.5 is suitable.
• the electrodialysis device has a cation exchange membrane 1 and an anion exchange membrane 2 alternately arranged between an anode and a cathode, and a desalination chamber 3 and a concentration chamber 4 alternately. Is formed.
• a conventionally known device can be used without any particular limitation. That is, the electrodes, ion-exchange membranes, and other necessary members constituting such an electrodialysis apparatus are not particularly limited and known ones are used.
• ion exchange membranes are generally made of a styrene-dibutylbenzene copolymer material with a cation exchange group of a sulfonic acid group and an anion exchange group of a quaternary ammonium group using a reinforcing material.
• Hydrocarbon cation and anion exchange membranes are also used industrially. It is also possible to use a fluorinated ion exchange membrane in which the material of the ion exchange membrane is a fluoropolymer. it can.
• an ion-exchange membrane that is resistant to alkaline in order to concentrate (generate) caustic alkali while the aqueous alkali silicate solution used for electrodialysis is alkaline.
• the raw silicate aqueous solution is supplied to the desalting chamber 3 of the electrodialyzer, and water or a dilute caustic aqueous solution is supplied to the concentration chamber 4 for electrodialysis.
• alkali metal ions for example, Na +
• hydroxide ions OH ⁇
• the water is transferred to the enrichment room side 4 for desalination.
• the concentration chamber 4 the metal ions and hydroxide ions transferred from the desalting chamber 3 are concentrated to obtain a caustic aqueous solution.
• the operating conditions of the electrodialysis machine vary depending on the size of the machine, the concentration of the raw material aqueous alkali silicate solution, etc.
• a supply speed of about 3.1 littorno is appropriate.
• Water or dilute caustic aqueous solution is supplied to the enrichment chamber at a rate of about 3.1 liter Z minutes.
• an alkali silicate aqueous solution (dealkalized solution) having a reduced alkali concentration is obtained by dealtering.
• Molar ratio (SiO 2 / (A 2 0 + B)) while increasing, and the molar ratio of the order, silicate Al Chikarari water obtained from the desalting chamber 3 which inhibit precipitation of silica solids is preferably 4.0 to
• the force S is preferably adjusted to 30, more preferably 9 to 26, particularly preferably about 12 to 21.
• Electrodialysis conditions by particularly selecting the electrical conductivity appropriate, it is possible to adjust the molar balance of the alkali silicate aqueous solution (Si0 2 / (A 2 0 + B)).
• Si0 2 / (A 2 0 + B) when the electric conductivity is high, if the Si0 2 / (A 2 0 + B) is lowered, also low electrical conductivity, SiO 2 / (A 20 + B) tends to be high.
• the use of a relatively high Keimoto concentration, Quai I oxygen partial concentration of the resulting silicate al Chikarari aqueous solution, S i 0 2 conversion Preferably 6.8 to: 12% by weight, more preferably about 6.8 to 9% by weight.
• a caustic aqueous solution is obtained from the concentration chamber 4.
• silicic acid migrates through the ion-exchange membrane during the dialysis process, and a small amount of silicic acid of about 0.1 to 1% by weight may be mixed in.
• mixing of a small amount of silicic acid does not matter.
• an alkali source for preparing an aqueous solution of an alkali silicate which is a starting material for the production of a silica sol, for example, it can be recycled as it is.
• the S i 0 2 / A 2 0 ratio lower JIS 1 No. 2 No. alkali silicate, sodium metasilicate, it is possible to use in the production of Orutokei oxygen Ichida.
• a reverse osmosis membrane method is used to further concentrate the dealkalized solution (aqueous solution of alkali silicate) obtained from the desalting chamber. ,. Since the alkali removal solution contains a trace amount of alkali, it is desirable to use an alkali-resistant composite membrane as the reverse osmosis membrane.
• the reverse osmosis membrane preferably has a molecular weight cut-off of 100 to 20,000, more preferably 100 to 1,000, and most preferably 100 to 800.
• a feature of the reverse osmosis membrane method is that water is removed without evaporating water and energy consumption is reduced, and the recovery of valuable resources (here, silica silicate) is concentrated stably and efficiently in the form of a solution.
• valuable resources here, silica silicate
• the point that can be raised For example, in the conventional method of concentrating colloidal silica, evaporating and concentrating by raising the temperature to 100 ° C., which is the boiling point of water, and depressurizing distillation by lowering the boiling point of water under reduced pressure, Since the colloidal silica particles are grown under heating conditions, the activity is easily lost even if there is only a small amount of silicate on the particle surface.
• the ultrafiltration membrane method in which water is removed using an organic thin film such as polysulfone, polyatalylonitrile, cellulose acetate, etrocellulose, or cellulose under pressure, is an energy aspect and condition control. It is generally used because of its simplicity (see US Patent No. 3,969,266, British Patent No. 1,148,950, and Japanese Patent Publication No. 58-15022).
• the ultrafiltration membrane method has a drawback that it removes the effective and highly active silicate anion generated by electrodialysis.
• the reverse osmosis membrane method in which a stable organic thin film is formed in a strong alkaline aqueous solution as a module with excellent volumetric efficiency, is compact, energy-saving, easy to control conditions, and saves valuable resources without applying heat. It is a method that can be concentrated and recovered without deteriorating.
• the pressure during reverse osmosis is preferably 4.0 MPa or less (at the entrance to the reverse osmosis module), and more preferably it is preferably adjusted to about 3.2 to 3.8 MPa.
• silicate alkali aqueous solution obtained through the electrodialysis can be further concentrated, the Kei oxygen partial concentration, preferably in S I_ ⁇ 2 conversion 3.0-30.0 % By weight, more preferably about 6.5 to 30% by weight.
• the raw material alkali silicate aqueous solution having a molar ratio (SiO 2 / A 20 ) of less than 4 is dealt with using an electrodialyzer,
• the solution is characterized in that the solution is concentrated by a reverse osmosis membrane method.
• Silicate and Al force Li in the raw material silicate al Chikarari solution (Al force Li is as defined above), the molar ratio (Si0 2 / (A 2 O + B)) force less than 4, preferably 1.5 to 4.0, still more preferably Or 2.8 to 3.5 is appropriate.
• the oxide concentration in terms of Kei element (S i 0 2 concentration) is not particularly limited, 2.0 to 12.0 wt%, preferably from 3.0 to 12.0% by weight, preferably in the et suitably about 4.5 to 12.0 wt% It is.
• the equipment and conditions used for electrodialysis are the same as in the first production method.
• the molar ratio (SiO 2 / (a 2 0 + B)) is preferably 4.0 to 30, preferably to further 9-26, particularly preferably desirable to have adjusted to about 12 to 21 New
• Kei oxygen partial concentration of the dealkalized solution in the second manufacturing method preferably 3.0 to 10.0% by weight S i 0 2 conversion, more preferably be kept adjusted to degrees about 4.0 to 8.0 wt% desirable.
• the dealkalized solution obtained from the desalting chamber is concentrated by a reverse osmosis membrane method.
• Reverse osmosis is performed as described above.
• the concentration of alkali metal (in terms of oxide) of the active silica silicate aqueous solution having a high molar ratio obtained by the present invention is reduced to 0.4% by weight or less, but if necessary, it may be replaced with a positive ion exchange resin. By performing the contact treatment, the alkali concentration can be further reduced.
• the ion-exchange resin, R- S_ ⁇ 3 H type, R- COOH type, R- OH-type cation exchange resin is used without being particularly limited.
• the contact treatment with the ion exchange resin may be performed after electrodialysis or after reverse osmosis.
• Desalting proceeds in an alkaline solution by directly contacting an aqueous solution of activated silica silicate with a high molar ratio with the cation exchange membrane by electrodialysis and reverse osmosis membrane method. and, further the molar ratio (Si0 2 / (a 2 0 + B)) it is possible to increase adjusted.
• Contact with the cation exchange resin can, for example, in a column tower 200 to 1000 cm 3, packed with a cation exchange resin of 240 ⁇ 530Cm 3, washed with water PH5.0 ⁇ 6.0, silicate at a flow rate 4 ⁇ 25Ml / sec It is carried out by passing an aqueous solution.
• the high-molar-ratio active silica silicate aqueous solution of the present invention as described above is widely used for various applications, but is useful as a ground consolidating agent because of its low alkali content.
• the ground consolidation agent is injected into the ground to give the ground strength and durability, for example, when performing construction work on soft ground. If the soil consolidation agent contains Algarium, it may contaminate soil and groundwater. However, according to the present invention, the alkali content can be extremely low, so that it can be used without fear of contamination.
• the aqueous solution of activated silica silicate having a high molar ratio of the present invention also has a function as a precursor of colloidal silica.
• the concentration of alkali silicate or other salts is adjusted to maintain stability.
• the salt-free colloidal silica is used, and the amount of positive counterions that balance with the surface charge is widely distributed around the particles, and the particle growth is averaged. According to such a method, high-quality colloidal silica can be easily and inexpensively produced.
• the aqueous solution of active silica silicate having a high molar ratio of the present invention can be used in various fields in which silica fine particles have been conventionally used, for example, heat-resistant binders, catalysts, anti-skid wrapping paper, anti-slip matting, It can also be used as various coating agents, abrasives for polishing wafers, reinforcing agents, flocculants, and fixing agents for inkjet.
• the invention's effect can be used in various fields in which silica fine particles have been conventionally used, for example, heat-resistant binders, catalysts, anti-skid wrapping paper, anti-slip matting, It can also be used as various coating agents, abrasives for polishing wafers, reinforcing agents, flocculants, and fixing agents for inkjet.
• the specifications of the electrodialysis device and the reverse osmosis device used are as follows.
• Electrodialysis machine manufactured by Tokuyama Corporation
• Cation exchange membrane (12) CMB (trade name), manufactured by Tokuyama Corporation
• Electrode material Ni plate
• Reverse osmosis membrane Mini spiral membrane (alkali resistant synthetic composite membrane: molecular weight cut off 200, membrane area 1.6m2, cp2.0x40L)
• aqueous alkali silicate solution was supplied to the desalting chamber of the electrodialyzer having the above specifications, and the concentrated caustic soda solution was supplied to the concentrating chamber.
• the dealkalized solution obtained from the desalting chamber is temperature-controlled to 30 to 40 ° C and supplied to the concentration tank of the reverse osmosis unit.
• the inlet flow rate is 10 LZ, the average pressure is 3.0 MPa, and the flux is )
• the mixture was concentrated at 35-28 kg / m3 ⁇ 4r to obtain the following raw material and aqueous solution of high molar sodium silicate.
• FIG. 2 shows a 29 Si-NMR spectrum of the following water glass colloidal silica measured under the same conditions.
• Water glass diluted No. 3 sodium silicate (Toso Sangyo Co., Ltd.)
• the peak area at 120 ppm is the peak area of water glass.
• FIG. 3 shows the results of UV-visible absorption spectroscopy.
• FIG. 3 shows the results of UV-visible absorption spectroscopy analysis of colloidal silica (SM manufactured by DuPont) and the following colloidal silica measured under the same conditions.
• aqueous alkali silicate solution was supplied to the desalting chamber of the electrodialyzer having the above specifications, and the concentrated caustic soda solution was supplied to the concentrating chamber.
• the desalting solution obtained from the desalting chamber was brought into contact with the ion exchange resin.
• Chi words, column tower (Cp2.8XH63 cm) in weakly acidic cation exchange resin Diaion WK40 (Japan ⁇ Ltd.) was 280 cm 3 filled in the washing after pH 5.79, de-alkaline aqueous solution 2000 ml It was introduced at a flow rate of 12.7 ml / sec and desalted.
• aqueous alkali silicate solution was supplied to the desalting chamber of the electrodialyzer having the above specifications, and the concentrated caustic soda solution was supplied to the concentrating chamber.
• the dealkalized solution obtained from the desalting chamber is controlled to a 30 ° C to 40 ° C, and fed to the concentration tank of the reverse osmosis unit. (° C)
• the solution was concentrated at 35 to 28 kg / m3 ⁇ 4r to obtain an aqueous sodium silicate solution having the following specific gravity and composition.
• the obtained aqueous sodium silicate solution was brought into contact with an ion exchange resin. That is, column tower (Cp2.8XH63 cm) in weakly acidic cation exchange resin Diaion WK40 (Nippon ⁇ water Ltd.) was 197 cm 3 filled in the washing after pH 5.60, the silicate al Chikarari solution 1000 ml It was introduced at a flow rate of 6.41 ml / sec and desalted.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Inorganic Chemistry (AREA)
• Water Supply & Treatment (AREA)
• Health & Medical Sciences (AREA)
• Soil Sciences (AREA)
• Materials Engineering (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Urology & Nephrology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Silicon Compounds (AREA)
• Separation Using Semi-Permeable Membranes (AREA)
• Water Treatment By Electricity Or Magnetism (AREA)

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• 2001
  • 2001-03-21 JP JP2001081298A patent/JP4290348B2/ja not_active Expired - Lifetime
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