JPS594165B2 - Biliyuushigiyoshiyuuhokakuhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for agglomerating and capturing colloidal fine particles in a dispersion using a thread-like polymer aggregating agent.

The dispersion of colloidal fine particles does not settle (and even if you try to filter it with a P cloth to remove it, phenomena such as passing through the grains of the cloth or clogging the cloth are observed, and the filtration performance is are often the cause of pollution.

For example, iron components produced during aluminum smelting are fine if they are dissolved in water as ions, but when they encounter large amounts of water or alkali, they become hydroxides and float in the water, causing red mud pollution.

Similar red mud pollution also occurs in metal cleaning factories and titanium factories.

Corrosion of water pipes due to limescale also causes water in domestic water supplies to become redundant, making ordinary households uncomfortable.

All of these are caused by fine particles of colloidal iron hydroxide.

In addition, colloidal starch is contained in wastewater from washing rice during the production of alcoholic beverages and rice crackers, as well as wastewater from noodle factories, which often increases BOD and causes pollution.

Attempts have been made to coagulate and precipitate such a dispersion of fine particles, but they cannot be said to be advantageous because the selection of a flocculant requires extensive equipment, and it is difficult to remove the fine particles with a simple operation. A method was needed.

In addition, laundry wastewater and latex wastewater contain proteins and rubber components dispersed in the water using surfactants, but it has not been possible to coagulate and precipitate them through simple operations.

The present inventors have discovered that fine particles floating in water, especially colloidal fine particles having, for example, oxygen, hydroxyl groups, amino groups, or carboxylic acid groups on their surfaces, are extremely easily captured by mountain bark; In addition, by adding a stringable polymer flocculant, the fine particles captured by the mountain bark can be flocculated to the extent that they can be passed through gauze of about 10 mesh.
It was found that precipitation occurs.

The present invention is based on what knowledge.

That is, the present invention is a method for agglomerating and capturing fine particles, which is characterized in that the fine particles are agglomerated and captured by adding a thread-like polymer flocculant to a dispersion of fine particles.

The colloidal fine particles of the present invention are water or organic solvents (e.g.
Fine particles that are insoluble (or poorly soluble) in alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, amides such as dimethylacetamide and dimethylformamide, and chlorinated solvents such as methylene chloride and trichlene. may be liquid or solid.

Specifically, for example, Al(OH)3, Fe(O
K ) a, In(OH) 3, Z n (OH) 2
, Mn5n(OH)a (Mn: Cu, Ni, Co,
Fe, Zn, Co1Ca, Mg, Mn), Te (OH
)a, NaSb(OH)a, e.g. Fed(OH), A10(OH), Mn0(OH)
), such as Mg(OR)(f(CO3), Mg(OH)3C1
・4H20, Cu2(0H)2Qll)3, Ca4(O
H)6So,,Cu2(OH)PO4,Pb(O
H)2(pbco3)2, Coco33Co(OH)2
Basic salts such as Fe[Fe(CN)a),
Ferrocyanate salts such as K2Co(CNS)4, rhodan salts such as AgC1, Bash4, etc., such as Fe2O3,13a 7I.

Light, various ferrites (oxides such as Al2O3), activated carbon, zeolite, inorganic fine particles such as silica gel:
For example, organic fine particles such as starch, cellulose, etc., which have hydroxyl groups in their molecules, proteins, etc., which have amine groups and carboxylic acid groups in their molecules, organic acid salts, such as calcium tartrate, tartarite, and latex. These include latex components in waste liquids, lanolin fats and oils in hair washing waste liquid, oil in car wash waste liquid, and grime in laundry waste liquid.

According to the present invention, colloidal (particle size: about Ionμ to 500mμ) fine particles, which are generally difficult to remove, can be easily removed.

The mountain bark used in the present invention is a general term for clay minerals having a large number of active hydroxyl groups on the surface, and is composed of hydrated magnesium silicate.
1icate) of sepiolite (5epiolite)
) ・hydrated magnesium alumina silitar) (i
drousmagnesium alu minimum
5ilicate)
pu1gite or palygorskite)
means.

It is commonly called mountain leather, mountain cork, mountain wood, etc.

Meerschaum, which is famous for pipes, is also one of this type.

The mountain bark used in the present invention can be used in any form, such as powdered mined raw stones, dispersed in water or organic solvents, paste, or paper. However, water and organic solvents (e.g. alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, amides such as dimethayatamide and dimethylformamide, and chlorinated solvents such as methylene chloride and trichlene), etc. Dispersion is preferred.

Usually, an aqueous dispersion of mountain bark is used, but the concentration of mountain bark is approximately 0. OO1% to 50% by weight, preferably 5% or less.

When making an aqueous dispersion of mountain bark, the particle size of mountain bark is usually about Lon.
A value of μ~5 is used.

This aqueous dispersion, like other clays, can be obtained by simply placing mountain bark in water and stirring and mixing using appropriate means.
If a polyhydric alcohol such as sugar is applied to mountain bark in advance, it can be easily dispersed in water.

Dispersion can be accelerated by using hot water instead of water, or alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate may be added. .

Any mixing method may be used for dispersion, but
A dispersion having a mountain bark concentration of about 1% or less can be pulverized and dispersed using, for example, a high-speed mixer.

For highly concentrated liquids, for example, a three-roll method can be applied.

For medium dispersions of 1 to 5%, dispersion methods that involve simultaneous stirring and kneading, such as a papermaking clay dispersion machine, or a dispersion method using a dispersion method in which stirring and kneading are performed at the same time, such as a papermaking clay dispersion machine, or a dispersion method using a dispersion method using a dispersion method that involves stirring and kneading at the same time, such as a papermaking clay dispersion machine, or a dispersion method that is carried out between two rotating grindstones, are used.
Speed line mills and agitators that can be passed through are used.

In addition, when dispersing, for example, Li+, Na'', K+
, NH4+, Rb+, C8+, TI+, Ag+: e.g. Mg2+, Ca2+, Sr"
Divalent metal ions such as +, Ba, Ni2+, Co2+, Fe2+, Mn2+, Zn", Cd2+, Pb2+; trivalent metal ions such as Fe", A13+, T13+; e.g. TiO"+, ZrO2
Metal oxycations such as +, CIO, '10; y10 e.g. Fe (CH) , Alx (OH) y+X
3X7 3℃ (X: Q integer of 3 or less; y: integer of 8 or less; metal hydroxy cation; for example, halogen, halogen acid, sulfuric acid, selenic acid, chromic acid, molybdic acid, tungstic acid, vanadate) One or more cations or anions soluble in water or organic solvents may be present, such as phosphoric acid, stannic acid, manganic acid, cyanide, rhodan, ferrocyan, nickel cyanide, and the like.

Furthermore, activated carbon, zeolite, clay, silica gel,
A water-insoluble adsorbent such as alumina gene or activated clay may be co-dispersed.

Further, a known surfactant or peptizer can also be used together.

The amount of mountain skin added (dry mountain skin weight) varies depending on the shape and size of the fine particles in the dispersion liquid, the degree of pulverization of the mountain skin, etc., but is about 1/100 to 10 of the weight of all the fine particles in the system. It's double.

The stringable polymer flocculant used in the present invention includes anionic polymers (e.g., sodium polyacrylate, partial hydrolyzate salts of polyacrylamide (e.g., Na, K,
, ...), salts of maleic acid copolymers, etc.), cationic polymers (e.g., polyvinylpyridine hydrochloride, salts of vinylpyridine copolymers, partial hydrolysates of polyacrylamide, etc.) ), nonionic polymers (e.g., diallyldimethylammonium chloride polymers, polyacrylamide, polyethylene oxide, polyvinyl alcohol, etc.), or natural stringiness, such as natto mucilage, egg white, yellow mallow, and okra fruit mucilage. Polymers can also be mentioned.

When these are dissolved in water or an organic solvent to form a liquid, they need only be viscous enough to draw strings, and their molecular weight is about 5,000 or more, preferably about 10,000 to 500X.
10'.

Among these, particularly preferred are anionic polymers such as sodium acrylate, nonionic polymers such as polyethylene oxide, and black mallow.

The amount of stringable polymer flocculant added is approximately 0 of the dry weight of mountain bark.
．． 0001% to 50%.

The stringable polymer flocculant may be in the form of a powder, or may be in the form of a solution preliminarily dissolved in the above-mentioned organic solvent.

In this case, additives may be added as necessary to make it easier to dissolve in the solvent.

An example of this is, for example, treating polyethylene oxide with an alcohol such as isopropanol to make it easier to dissolve in water, and then dissolving it in water.

Examples of methods for coagulating and capturing fine particles include (1) a method in which a mountain bark is added to a dispersion of fine particles to capture the fine particles on the surface of the mountain bark, and then a stringable polymer flocculant is added to coagulate and precipitate the fine particles.

■ When dispersing the above-mentioned mountain bark, the above-mentioned cations or anions are added to the aqueous dispersion of mountain bark containing cations or anions that are soluble in water or organic solvents that may be present in the form of fine particles. Compound (e.g., in the case of Ni+2, N
a 2 S n (OH) a, etc.) to form fine particles on the mountain bark, and then a stringable polymer flocculant is added to coagulate and precipitate them.

■ An aqueous solution containing cations or anions is added to a mountain bark dispersion in which a compound that can form fine particles of cations or anions shown in ■ is dissolved in advance to form fine particles on the mountain bark. A method of coagulating and precipitating by adding a filamentous polymer flocculant.

■ After adding the fine particles captured or generated on the mountain skin in the above ■, ■, and ■ to water or an organic solvent solution (including waste liquid, etc.) containing cations or anions to form new fine particles, A method of coagulating and precipitating by adding a stringable polymer flocculant.

etc. can be mentioned.

Specific examples of making cations or anions soluble in water or organic solvents into fine particles by methods (1) and (2) above include the following.

Method (2) is a method in which fine particles captured on the surface of the mountain bark are reacted with ions in water or an organic solvent to produce more stable fine particles in the coexistence of the mountain bark.

For example, mountain skin aggregates that capture iron rust capture and aggregate tumble blue and Prussian blue through the following reaction with ferrocyan ions and cyanide ions.

Such a reaction can be easily confirmed by a change in the color of the aggregates (from red to blue).

In addition, the following reaction can be carried out in the same way with mountain bark containing red lead, and this can be applied to chromic acid wastewater from plating factories, etc.

Furthermore, regarding cations, silver ions can be recovered by the following reaction.

When using ion exchange in this way, finely powdered zeolite or ion exchanger can also be used.

The flocculated precipitate thus generated is, for example,
It can be easily washed off with a cloth, sponge, etc.

The grain size of the mountain bark varies depending on the particle size of the mountain bark, the method of adding the stringable polymer flocculant, etc., but it is usually passed through a coarse mesh of 10 to 200 mesh by methods such as natural filtration, centrifugal filtration, and vacuum r-filtration. Ru.

When flocculation and sedimentation occurs in the best condition, the flocculates can be squeezed out using a compressor or the like after being filtered through about 10 mesh gauze.

The aggregates thus obtained are white or colored fibers or sheets, and by drying them, they can be used as flame-retardant fibers (or paper) or non-combustible fibers (or paper).

Next, examples will be given as specific examples of the method of the present invention.

Example 1 Tap water containing red rust was collected in a 1 ton tank.

When a portion of this was analyzed by atomic absorption spectroscopy, the results shown in the upper part of the table below were obtained.

Add 300cc of 5% mountain bark aqueous dispersion and mix with a stirrer for approx.
After about 5 minutes of stirring, the mountain crust that had caught the rust began to settle.

At this time, polyethylene oxide (molecular weight 250 x 10
When a 1% aqueous solution IQcc of ', trade name Alcox E100 (manufactured by Meisei Chemical Industry Co., Ltd.) was added and stirred for 30 seconds, sedimentation started one second later.

The bottom row of the table below shows the results of an atomic absorption spectrometry analysis of water that was drained with a gauze cloth attached to the water outlet.

The mountain skin attached to the gauze was reddish brown, and the sheet obtained by drying this had a weight of 38.2 gr.

As a result, the mountain bark was purified to less than 1/100 of the rust in the water, and 23.2g of iron hydroxide was captured.

Example 2 Add tap water to 20g of basic iron acetate to make 21.

After stirring - Take only the upper part of the colloid that does not settle after being left to stand day and night, and use this as highly concentrated red mud (sample stock solution)
.

Take 100 grams of this sample stock solution, add 20 cc of a 2.34% coarse dispersion of mountain bark (water), and stir for 1 minute. Iron rust captured on the surface of the mountain bark was observed under a microscope. Ta.

When 0.0005 gr of the polyethylene oxide powder used in Example 1 is added to this and slowly stirred, a completely transparent supernatant remains and fibrous aggregates settle.

The aggregate is filtered through a 20-mesh wire mesh and dried to yield red nonflammable paper.

Comparative example) Take 100g of this sample stock solution, add 0.5g of Aerosil 2000 (fine powder silica manufactured by Nippon Aerosil Co., Ltd.) to it instead of mountain bark, and stir for 1 hour, and you will notice some changes in the sample stock solution.

When 0.05g of the polyethylene oxide powder used in Example 1 was added to this and slowly stirred, a slightly reddish supernatant liquid was observed, but it could not be easily filtered out using plain paper.

(2) Take 100g of sample stock solution and add 0.5g to it.
The polyethylene oxide used in Example 1 was added, slowly stirred, and no coagulation and precipitation of iron hydroxide was observed even when the mixture was left to stand for about one week.

It passed through a 100-mesh wire mesh, but it passed through the mesh.

Also, with the second paper, it got clogged and I couldn't get through it.

A small amount of tear fluid collected in Comparative Example (2) and Example 2
The results of atomic absorption spectrometry analysis of tear fluid are shown below.

Example 3 Dried mountain bark aggregate containing iron rust obtained in Example 1 30
Take gr and put it in 300 cc of 1N hydrochloric acid (while stirring).

The pH of this solution was y3.

When the above-mentioned mountain bark aggregate was added to wastewater 2001 containing 65 ppm of CN- and stirred, the mountain bark was dyed blue.

After stirring for about 1 hour, if you leave it for a while, the blue mountain crust will begin to settle.

When 2 CC of the 1% aqueous solution of polyethylene oxide used in Example 1 is added and slowly stirred, a blue fibrous sediment is obtained.

The liquid obtained by filtering the sediment through a 20-mesh wire mesh was colorless and transparent, and when the amount of CN was measured using CN-T (manufactured by Wako Pharmaceutical Co., Ltd., a pollution analysis reagent for total cyanide), it was so large that it could not be measured. There weren't many.

On the other hand, when examined by X-ray powder diffraction of the blue mountain skin sediment,
X-ray diffraction pattern peculiar to mountain skin and Fe (Fe (CN)
6]·H2O characteristic broad X-ray diffraction pattern overlap was obtained.

Example 4 12.48gt of copper sulfate and 10g of mountain bark were added to water in Step 11 and mixed in a high-speed rotating mixer (stir and mix to obtain a green thixotropic liquid.

Prepare 200 cc of IN- caustic soda and drop it into the M copper mine bark liquid while stirring until the pH of the liquid is 8.5.
If the solution is dropped until the concentration reaches about 90%, green-blue colored mountain bark containing basic copper sulfate will be obtained.

If you stop stirring and let it stand for a while, a clear liquid will be obtained at the top.

Polyethylene oxide (product name (PolyoxWS)
RN-750) ; Union carbide
Add 0 or 1 gr (manufactured by Seiko Co., Ltd.) and stir slowly with a glass rod to obtain a blue precipitate.

Clear water was obtained by squeezing the precipitate with gauze, and no Cu2+ was detected in it.

The squeezed blue sediment was spread out into a sheet, a portion was cut, and a piece of unglazed pottery was heated with lees placed over the top of the boxwood and baked at 1,230 degrees Celsius, producing Oribe-style pottery.

Example 5 Solution 1 13.34g of sodium sousnate and 10g of mountain skin
When you add it to the water from Step 1 and stir it well, it becomes a slightly cloudy, chicken-tropic liquid.

Solution 2: When 13.34 g of IJum (1-) alone is dissolved in water from Step 11, a clear liquid is obtained.

Separately, Ni2+ 1N solution (A solution), Cu2+ 1N solution (B solution), Fe2+ 1N solution (C solution), Zn2+ 1N solution (D solution), Mn2+ 1N solution (E solution) , Co2
0.1 gr of the polyethylene oxide used in Example 1 was dissolved in each 11 normal solution (F solution).

When the following test was carried out by combining Solutions A to F and Solution 1 or 2 under stirring, the results shown in the table below were obtained.

Test 1 Filter the solution through a 100-mesh wire mesh, and analyze the transition metals and Sn in the filtered solution.

Test 2 After spreading the sediment on a 100-mesh wire mesh onto plain paper, a dry sheet was prepared using a photographic Ferro board.

Example 6 20 J of a 2% aqueous dispersion of mountain bark is added to 2 tons of cloudy waste water obtained by washing a large amount of polished rice, and the mixture is stirred for about 5 to 10 minutes.

If you leave it for a while, the top will become transparent. When about 5 QCC of the 3% aqueous solution of polyethylene oxide used in Example 1 was added and slowly stirred, fibrous pure white aggregates precipitated.

The top part will be completely transparent.

If a 60-mesh wire mesh is connected to the drain hole and the water is drained, a sticky aggregate will be obtained on the wire mesh.

The cloudy waste liquid contained 0.4% solids, but the water from the drain after the mountain bark-polyethylene oxide treatment contained less than 5 pI)m of solids.

When the sticky condensate was left to stand after being steamed for about 10 minutes, blue mold grew.

Example 7 Add 300 cc of 1% mountain bark to 151 ml of cloudy wastewater from a laundry shop.
After adding and stirring, 5g of activated carbon (fine powder of 80 mesh or less) was added and stirred, and 3% sodium polyacrylate (Aron A-2op; manufactured by Toagosei Kagaku Kogyo KK) 2
When CC was added, gray activated carbon and aggregates of mountain bark adsorbing dirt and other substances settled out.

The upper part of the wastewater was a colorless and transparent liquid with no foaming.

When filtered through a soft urethane foam, a sheet of aggregate was formed on the soft urethane foam.

When this is dried, a gray, soapy-smelling sheet is obtained.

When this sheet was roasted over a gas fire, it emitted the characteristic odor of protein and turned into a black sheet.

Example 8 Add 20 cc of a mixture of 200 cc of 1% mountain skin and 10 cc of 50% aluminum biphosphate (A 1 (H2PO4) 3) liquid to white latex waste liquid containing 5% rubber component and stir well. The waste liquid then becomes clear immediately.

When about 0.5 CC of aqueous polyethylene oxide used in Example 1 is added to this and stirred with a glass rod, fibrous white aggregates float up.

Strain the aggregate through gauze to obtain a completely clear liquid.

Even when only polyethylene oxide was added to the latex waste liquid, no flocculation occurred.

Further, even when aluminum diphosphate and polyethylene oxide were added to the latex waste liquid, no aggregates that could be easily passed through were obtained.

Example 9 200C containing 30 gr ZrOCl2-8H20 under stirring in 5 oocc aqueous solution containing 64 gr H3PO4
When 4N hydrochloride of C is slowly added dropwise, a very fine powder of Zr(HPO4)2.H2O is produced.

This is milky and cannot be washed away with regular R paper.

When a 10% aqueous dispersion of mountain bark IQcc is added and stirred uniformly, Z r (HPo 4 ) 2 is deposited on the surface of mountain bark.
・H2O is captured and a small amount of transparent supernatant (if left for a while) forms a slightly transparent supernatant.

Add 10% of the polyethylene oxide used in Example 1 to this.
When 0 m9 is added and stirred, it aggregates to a volume of 100 cc or less.

After removing most of the water by decantation, drain with gauze.

By the way, even if only polyethylene oxide is added to zr(HPO4)2.H2O, it will not coagulate.

Next, 500 cc of an aqueous solution containing NaCllgr was prepared, the above aggregates were added thereto, and after leaving it for about an hour, the aggregates were removed with gauze, and an aqueous solution of KSb(OH) 6 was dropped into the aqueous solution, but it did not become cloudy. .

Next, prepare 500 cc of an aqueous solution containing 22 gr of AgNO, add the aggregates that captured Na+ to this, leave it for about an hour, remove the aggregates with gauze, and add a small amount of HCI to the solution.
was added dropwise, but no precipitation of AgC1 occurred.

When an aqueous solution of KSb(OH)a was added to this liquid, it became cloudy.

This shows that the aggregate expelled Na+ and captured Ag+.

Claims (1)

[Claims] 1. A method for agglomerating and capturing fine particles, which comprises adding mountain bark and a stringable polymer flocculant to a dispersion of colloidal fine particles having a particle size of approximately 10 mμ to 500 mμ to agglomerate and capture the fine particles.