CN113666470A - Wastewater treatment agent and method for producing wastewater treatment agent - Google Patents
Wastewater treatment agent and method for producing wastewater treatment agent Download PDFInfo
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- CN113666470A CN113666470A CN202110516198.9A CN202110516198A CN113666470A CN 113666470 A CN113666470 A CN 113666470A CN 202110516198 A CN202110516198 A CN 202110516198A CN 113666470 A CN113666470 A CN 113666470A
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- wastewater treatment
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 79
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- 239000000701 coagulant Substances 0.000 claims abstract description 49
- 229920002301 cellulose acetate Polymers 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 39
- 238000001035 drying Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000004898 kneading Methods 0.000 claims description 17
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000008187 granular material Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 abstract description 9
- 239000001913 cellulose Substances 0.000 abstract description 8
- 239000000843 powder Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 20
- 239000002351 wastewater Substances 0.000 description 19
- 241000196324 Embryophyta Species 0.000 description 11
- 238000000926 separation method Methods 0.000 description 11
- 239000010802 sludge Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 238000011282 treatment Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010008 shearing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YVHUUEPYEDOELM-UHFFFAOYSA-N 2-ethylpropanedioic acid;piperidin-1-id-2-ylmethylazanide;platinum(2+) Chemical compound [Pt+2].[NH-]CC1CCCC[N-]1.CCC(C(O)=O)C(O)=O YVHUUEPYEDOELM-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000010805 inorganic waste Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000010206 Corchorus olitorius Nutrition 0.000 description 1
- 244000227473 Corchorus olitorius Species 0.000 description 1
- 244000146493 Cryptotaenia japonica Species 0.000 description 1
- 235000004035 Cryptotaenia japonica Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000005407 Nasturtium officinale Species 0.000 description 1
- 235000017879 Nasturtium officinale Nutrition 0.000 description 1
- 240000006915 Petasites Species 0.000 description 1
- 241000218689 Podocarpus Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 244000300264 Spinacia oleracea Species 0.000 description 1
- 235000009337 Spinacia oleracea Nutrition 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- -1 fluorine ions Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011802 pulverized particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
Abstract
The present invention aims to provide a wastewater treatment agent which contains a large amount of a component having poor fluidity such as cellulose, has excellent fluidity, and can prevent bridging or a rat hole from being generated in a hopper in an automatic supply system, and a method for producing the wastewater treatment agent. A wastewater treatment agent comprising particles containing cellulose acetate and a coagulant polymer, the angle of repose being 38 degrees or less.
Description
Technical Field
The present invention relates to a wastewater treatment agent and a method for producing a wastewater treatment agent.
Background
In recent years, in the production of various products in factories, a large amount of wastewater containing an environmentally-friendly substance such as metal ions or fluorine ions as inorganic ions is generated, and a wastewater treatment agent is used to purify the wastewater.
Since wastewater treatment itself is performed during passage through a plurality of water tanks, the chemical (wastewater treatment agent) supplied to each water tank is usually supplied in a liquid form, and a chemical of solid powder such as coagulant (flocculant) polymer is supplied to the treatment water tank after being made into a syrup-like aqueous solution using a dedicated dissolving apparatus. When the amount of wastewater to be treated is large or when the wastewater is treated by automatic operation, a device having a system for automatically supplying a chemical attached to the dissolving apparatus is often used. In this case, in order to obtain a solution having a constant concentration, a device having a mechanism for quantitatively supplying a drug as a solid powder by utilizing the self weight and fluidity of the drug is widely used. When the amount of wastewater is small or the fluctuation of wastewater to be treated is large, the dissolution may be performed by manually changing the conditions, but the above-described automatic supply system is often used because the field load such as an increase in the number of steps increases.
Among them, the lower the water content of the dewatered sludge produced after the dewatering treatment, the less the amount of waste to be treated, and the lower the treatment cost, and therefore, it is desired to perform a high-level dewatering treatment on the sludge.
Therefore, for example, an inorganic sludge dewatering agent for pressure filtration is proposed, which can reduce the water content of an inorganic sludge cake (sludge cake) by using an alkylene oxide (see, for example, patent document 1). Further, a sludge dewatering aid comprising a fibrous viscose rayon having a water content of 30 to 80 wt% has been proposed. Further, a method of dehydrating sludge in which a dehydration assistant and a polymer flocculant are added to an organic sludge, mixed, and then mechanically dehydrated has been proposed (for example, see patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6123158;
patent document 2: japanese patent No. 4817431.
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made to solve the above-described problems of the related art and to achieve the following object. That is, the present invention aims to: a waste water treating agent which contains a large amount of a component having poor fluidity such as cellulose, has excellent fluidity and can prevent the generation of bridges or rat holes (rat holes) in a hopper of an automatic supply system, and a method for producing the waste water treating agent are provided.
Means for solving the problems
In the prior art, a wastewater treatment agent has been proposed which combines a cellulose having excellent water-repellent properties and a flocculant polymer and has both a water content reduction effect of sludge and high flocculation properties, but such a wastewater treatment agent contains a considerable amount of a cellulose having poor fluidity and poor affinity for water as one of the raw materials, and therefore, it is difficult to form a granular state having good fluidity by being bonded to and integrated with the flocculant polymer, and there is a problem that the fluidity of the granulated substance or the mixture is easily deteriorated.
Means for solving the above problems are as follows. That is to say that the first and second electrodes,
the wastewater treatment agent is characterized in that:
comprising particles comprising Cellulose acetate and a coagulant polymer,
the angle of repose is 38 degrees or less.
<2> the wastewater treatment agent according to <1>, wherein the bulk density of the wastewater treatment agent is 0.46g/mL or more.
<3> the wastewater treatment agent according to any one of <1> to <2>, wherein the angle of repose of the wastewater treatment agent is 37 degrees or less.
<4> the wastewater treatment agent according to any one of <1> to <3>, wherein the mass ratio of the cellulose acetate to the coagulant polymer (cellulose acetate: coagulant polymer) is 40%: 60% -60%: 40 percent.
[ claim 5 ] A method for producing a wastewater treatment agent, comprising the steps of:
a kneaded material preparation step of adding water to and kneading cellulose acetate and a coagulant polymer using a pressure kneader to prepare a kneaded material; and
and an extrusion molding step of subjecting the kneaded product to extrusion molding using a biaxial screw molding machine to obtain a molded product.
<6> the method for producing a wastewater treatment agent <5> comprising the steps of:
a primary drying step of drying the molded product to a moisture content of 14 to 22% to obtain a primary dried product;
a granulation step of crushing the primary dried product to obtain granules; and
and a secondary drying step of drying the granules.
<7>As described above<6>The method for producing a wastewater treatment agent, wherein in the granulating step, the particle diameter is less than 250%μThe production rate of the fine particles of m is 19 mass% or less based on the total particles.
Effects of the invention
The present invention solves the above-described problems of the prior art, and provides a wastewater treatment agent which contains a large amount of a component having poor fluidity, such as cellulose, but has excellent fluidity and can prevent the generation of bridges or rat holes in a hopper in an automatic supply system, and a method for producing the wastewater treatment agent.
Detailed Description
(wastewater treatment agent)
The wastewater treatment agent of the present invention comprises particles containing cellulose acetate and a coagulant polymer, and further contains other components as required.
The angle of repose of the wastewater treatment agent is 38 degrees or less (less than 38.5 degrees in consideration of decimal 1 st position), and preferably 37 degrees or less. When the angle of repose is 38 degrees or less, the fluidity of the wastewater treatment agent is improved, and bridging or a rat hole can be prevented from being generated in the hopper of the automatic supply system.
The angle of repose of the wastewater treatment agent can be measured, for example, by using a powder tester PT-X (manufactured by Hosokawa Micron corporation), and the wastewater treatment agent to be measured is dropped onto a circular support table through a funnel, and the angle formed by the inclined surface and the horizontal surface when a layer is formed on a mountain shape (angle material) is measured.
The wastewater treatment agent of the present invention is produced by the method for producing a wastewater treatment agent of the present invention described later, and is formed in the form of particles obtained by integrating the cellulose acetate and the coagulant polymer, and has an angle of repose of 38 degrees or less.
< particles >
The particles contain the cellulose acetate and the coagulant polymer, and if necessary, other components.
In the above particles, the cellulose acetate is integrated with the coagulant polymer. When the cellulose acetate is formed integrally with the coagulant polymer, the fluidity of the wastewater treatment agent is improved, and bridging or a rat hole can be prevented from being generated in a hopper in an automatic supply system.
The shape of the particles is not particularly limited as long as the angle of repose of the wastewater treatment agent is 38 degrees or less, and may be appropriately selected according to the purpose, and examples thereof include: approximately spherical, acicular, non-spherical, etc. Among these, an approximately spherical shape is also preferable from the viewpoint of having high fluidity.
Cellulose acetate-
The cellulose acetate is a cellulose ester obtained by esterifying cellulose by substituting a part of hydrogen of the cellulose with an acetate group.
The commercially available cellulose acetate is mainly in the form of a film or a fiber, and the powdered form is relatively small. However, in order to produce the wastewater treatment agent of the present invention, it is essential that the form is powdery and the particle size is 1.5mm or less (preferably 0.355mm or less). In addition, since the material itself has a low true specific gravity, the angle of repose of the cellulose acetate powder that can be obtained is 48 degrees or more and 58 degrees or less.
The weight average molecular weight of the cellulose acetate is preferably 100,000 or more, more preferably 150,000 or more. The higher the weight average molecular weight, the more the effect of reducing the water content of the sludge can be improved.
The weight average molecular weight of the cellulose acetate is, for example, a value obtained by converting a measurement value by gel permeation chromatography into a molecular weight of standard polymethyl methacrylate.
The above-mentioned cellulose acetate as one of the starting materials is preferably in the form of powder or granules.
The particle size of the cellulose acetate is preferably 1,500 from the viewpoint of the restriction on the production processμm is less than or equal to, more preferably 1,000μm is less than or equal to, more preferably 710μm is 355 or less, most preferably from the viewpoint of product characteristicsμm is less than or equal to m. If the above particle size is 1,500μWhen m is less, the water content of the sludge can be reduced.
The content of the cellulose acetate may be appropriately selected according to the purpose, and is preferably 40% by mass or more and 60% by mass or less with respect to the wastewater treatment agent.
Coagulant polymers
The flocculant polymer may be appropriately selected depending on the purpose as long as it exhibits an effect of removing inorganic waste in wastewater and is completely water-soluble, and for example, an acrylic acid/acrylamide copolymer (generally referred to as PAM) is preferable.
Examples of the PAM include: PAM having a carboxylate to have an anionic property.
As the PAM, commercially available products can be used, and as the commercially available products, for example: flopan AN913 (PAM having carboxylate in side chain) (both manufactured by SNF corporation) and the like.
The above-mentioned coagulant polymers available on the market are mostly excellent in fluidity, and their angle of repose is mostly 40 degrees or less. This is because manufacturers of the coagulant polymer control their physical properties (bulk density and particle size) to ensure good fluidity. Therefore, there are many commercially available coagulant polymers usable as the raw material of the present invention, and the angle of repose of the coagulant polymer used for the study was 37 degrees.
The content of the flocculant polymer is not particularly limited and may be appropriately selected according to the purpose, and is preferably 40% by mass or more and 60% by mass or less with respect to the wastewater treatment agent.
The mass ratio of the cellulose acetate to the coagulant polymer (cellulose acetate: coagulant polymer) is preferably 40%: 60% -60%: 40%, more preferably 50%: 50 percent. If the mass ratio is 40%: 60% -60%: 40%, both high cohesiveness and water content reduction effect can be obtained.
Other ingredients-
The other components are not particularly limited and may be appropriately selected according to the purpose, and examples thereof include: plant powder, and the like.
The plant powder is obtained by powdering a plant.
The plant is not particularly limited as long as it is a plant capable of aggregating and separating inorganic substances (nickel, copper, fluorine, etc.) in wastewater, and may be appropriately selected according to the purpose, and examples thereof include: hastellia (Corchorus olitorius), Egyptian Petasites (molokheiya), Podocarpus, Cryptotaenia japonica, watercress, spinach, etc. Among these, preferred are zafirluo and egyptian king vegetable.
Examples of the parts of the plants include: leaves, bark, stems, roots, etc., of which leaves and bark are preferred.
The angle of repose of the plant powder is not particularly limited and may be appropriately selected according to the purpose, and is preferably 47 degrees or more and 57 degrees or less.
The content of the plant powder is not particularly limited and may be appropriately selected according to the purpose, and is preferably 0 mass% to 10 mass% with respect to the wastewater treatment agent. When the content is 0% by mass or more, coagulation of the micro-flocs is promoted by the components contained in the plant powder, and coagulation and precipitation are achieved in a short time. On the other hand, if the content of the plant powder is too high, the content of the flocculant polymer component necessary for flocculation is reduced, and the blend balance of the components is deteriorated, so that the content is preferably 10% by mass or less.
The size of the particles of the above wastewater treatment agent needs to be controlled to 150μA particle size of m or more and 1mm or less to ensure high fluidity and solubility in use. The particle size distribution is more preferably 250μm is more than or equal to 850μm is less than or equal to m.
The particle size distribution of the wastewater treatment agent is preferably determined dry in principle, and may be determined by using, for example, Morphogi G3 (manufactured by Malvern).
The bulk density of the wastewater treatment agent is not particularly limited and may be appropriately selected according to the purpose, and is preferably 0.46g/mL or more, more preferably 0.51g/mL or more. When the bulk density is 0.46g/mL or more, the facilities for dissolving the coagulant polymer have hitherto been able to be used without modification, and therefore the initial cost required for introducing the wastewater treatment agent of the present invention can be saved.
The bulk density of the wastewater treatment agent can be measured by using a powder tester PT-X (manufactured by Hosokawa Micron Co., Ltd.) or the like as an industrial standard, and 100cc of the wastewater treatment agent is gently charged into a 100cc stainless steel cup, and the bulk density of the wastewater treatment agent at this time is measured.
The CA separation rate (cellulose acetate separation rate) is preferably 10% or less, more preferably 5% or less. When the CA separation ratio is 10% or less, the amount of cellulose acetate powder integrated with the coagulant polymer is small, and a wastewater treatment agent having a small variation in angle of repose or bulk density can be realized.
Here, the CA separation ratio can be obtained as follows.
[ CA separation Rate ]
7g of a wastewater treatment agent as a measurement sample was put into 350g of acetone, and dissolved in an ultrasonic washer at 28kHz, 30 ℃ to 40 ℃ and 10 minutes to obtain a solution. Next, qualitative filter paper (retained particle diameter: 6) was usedμm) the resulting solution was filtered to obtain a residue. The obtained residue was dried at 80 ℃ for 30 minutes or more to completely evaporate/remove acetone in the residue, and then the mass x (g) of the dried residue was measured. The measurement method is a measurement method using the following 2-point properties: while cellulose acetate is soluble in acetone, the coagulant polymer or other ingredients are insoluble in acetone; and cellulose acetate separated from other components such as a coagulant polymer are preferentially dissolved in acetone. Thus, the CA separation ratio can be obtained according to the following calculation formula.
CA separation rate (%) = (7-X)/7X 100
(method for producing wastewater treatment agent)
The method for producing a wastewater treatment agent of the present invention includes a kneaded product preparation step and an extrusion molding step, and preferably includes a primary drying step, a granulation step, a secondary drying step, and other steps as necessary. The method for producing a wastewater treatment agent of the present invention can be suitably used for producing a wastewater treatment agent of the present invention.
< preparation of kneaded product >
The step of preparing a kneaded product is a step of kneading the cellulose acetate powder and the coagulant polymer with water using a pressure kneader to prepare a kneaded product. In the kneaded material preparation step, a high shearing force can be applied to the kneaded material by using a pressure kneader, and as a result, it is realized that heterogeneous and weak affinity materials such as the cellulose acetate powder and the coagulant polymer are bonded and integrated with each other.
Specifically, the water fed to the kneading equipment is preferentially absorbed only by the coagulant polymer, and is not absorbed at all by the water-repellent cellulose acetate powder. Here, the water absorbed in the coagulant polymer is forcibly and uniformly permeated into the entire coagulant polymer by the high shearing force of the pressure kneader, and the whole coagulant polymer is in a half-dissolved state. By making the coagulant polymer as a solid powder into a semi-dissolved state, the above coagulant polymer becomes a state such as a high viscosity binder as if it were made into a state in which the cellulose acetate powder is dispersed in a high viscosity liquid such as a coagulant polymer. By further kneading, the water-repellent and water-insoluble cellulose acetate powder is forcibly bonded to the coagulant polymer. Thus, cellulose acetate which is originally poor in affinity is strongly bonded to and integrated with the coagulant polymer.
In the present invention, in order to obtain a high shear force, a pressure kneader using 2 blades was investigated, and desired results were obtained. On the other hand, in the case of a kneader having a blade specification for increasing the shearing force such as 3 blades, for example, it is possible to obtain the same high shearing force without applying pressure, and it can be easily estimated that the same result can be obtained if such a kneader having an increased number of blades is used.
The number of blades of the pressure kneader is not particularly limited, and may be appropriately selected according to the purpose, and if the number of blades is increased and the shearing force is excessively increased, the state of over kneading may occur, and the quality of the product may be impaired, and therefore, 2 blades are preferable in consideration of the balance thereof.
The pressure cover of the pressure kneader is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include: a pressurizing cover or the like that pressurizes with an air cylinder (air cylinder) may be used. By providing the pressure kneader with a pressure-applying cover, a shearing force can be uniformly applied to the kneaded mixture, and scattering of dust generated during kneading with water can be suppressed. The pressure of the pressurizing cover is preferably 0.6MPa or more.
The temperature during the water-addition kneading is preferably 15 ℃ to 40 ℃ inclusive in order to suppress thermal deterioration or changes in mechanical properties of the raw materials to be kneaded.
The amount of water added in the water-added kneading is a factor that affects not only the kneading step but also the subsequent extrusion molding step or drying step, and therefore needs to be controlled to an optimum value. Specifically, the mass ratio is preferably about 72% by mass of the total mass of the cellulose acetate powder, the coagulant polymer and the raw materials thereof.
The number of rotations of the blade during the water-addition kneading is in the range of 10 to 40 rpm. The time for the water-addition kneading is preferably, for example, 3 to 8 minutes. Although high shear force and mixing by the shear force are necessary, if the shear force is too high or the mixing time is too long, the coagulant polymer deteriorates and the quality of the product deteriorates, and therefore the number of revolutions of the blades and the mixing time need to be controlled to an optimum value.
< extrusion Molding Process >
The extrusion molding step is a step of obtaining a molded product by extrusion-molding the kneaded product using a twin-screw molding machine. In the extrusion molding step, the kneaded product is extrusion molded while being pressurized by using a biaxial screw molding machine, whereby the densification of the kneaded product is promoted and the true specific gravity of the molded product is increased. According to this effect, the bulk density of the finished product can be increased, and the above-mentioned wastewater treatment agent having high fluidity can be realized. Further, by continuously cutting the molded article into pellets immediately after extrusion, densification and granulation of the kneaded product can be simultaneously performed, and the efficiency of the drying step (primary drying step and secondary drying step) and the granulation step, which will be described later, can be improved, and the yield of the above-mentioned wastewater treatment agent can be improved.
The twin screw molding machine described above requires attention because the material suitable for the screw changes depending on the shape of the screw blade. Further, since the degree of densification and the yield greatly vary depending on the shape of the holes (the diameter of the holes, the number of holes, and the arrangement of the holes) of the die for extruding the kneaded material, it is necessary to optimize the degree of densification and the yield depending on the physical property values of the kneaded material to be charged. In the present invention, a twin screw extruder designed for producing pellets for tire rubber is used, and the die has a bore diameter ofϕ3.5mm。
The temperature in the extrusion molding is preferably 15 ℃ to 40 ℃, for example.
The number of rotations of the twin-screw in the extrusion molding is preferably, for example, 10rpm to 36 rpm. If the rotation speed is 40rpm or more, kneading in the twin-screw is accelerated to cause excessive kneading, which may deteriorate the quality of the finished product.
< Primary drying step >
The primary drying step is a step of drying the molded product to a water content of 14% to 22% to obtain a primary dried product. Since the molded product has flexibility by drying the molded product so that the water content thereof is 14% to 22%, physical damage to the primary dried product in the granulating step described later can be suppressed, and generation of fine powder in the granulating step can be suppressed.
In the primary drying step, the molded articles (pellets) need to be dried so that they do not bind to each other to form a large lump and the moisture content of the molded articles is 14 to 22%. Therefore, in the present invention, drying is performed by continuous treatment using a vibrating flow dryer. The drying conditions in this case are such that the treatment is carried out at a hot air temperature of 80 ℃ or lower for a drying time (residence time in the dryer) of 5 to 10 minutes.
< granulation step >
The granulating step is a step of pulverizing the primary dried product to obtain granules, and the granule size is preferably less than 250μThe production rate of the fine particles of m is 19 mass% or less based on the total particles.
As the granulating step, it is necessary to pulverize particles having a size of several mm into 250 pieces by 1 treatmentμm～850μm is selected from the group consisting of sodium hydroxide, sodium hydroxide and potassium hydroxide. Further, since the suitable pulverization method differs depending on the hardness of the particles and the constituent material, it is necessary to select a pulverizer having both necessary treatment capacity and workability.
In the present invention, a combination of a multiple bladed shredder and an air delivery system continuously feeds a quantity of particles to the shredder for shredding.
< Secondary drying step >
The secondary drying step is a step of drying the pulverized particles until the water content is 6% or less.
In the secondary drying step, the temperature of the product in the dryer must be constantly measured and monitored, and the product temperature must be controlled so as not to rise to 80 ℃ or higher by controlling the hot air temperature and the drying time. Therefore, in the present invention, a fluidized bed dryer and an air delivery system are combined, and hot air of about 100 ℃ is delivered to 4kg to 5kg of products each time, and drying treatment is performed so that the product temperature is 80 ℃ or lower. The drying time in this case is 10 to 15 minutes.
< other Process >
Examples of the other steps include: a classification step, and the like.
In the classification step, the dried granules are preferably classified by a classifier such as a vibratory screening machine or a drum screening machine so that the particle diameter of the good product becomes 250μm is more than or equal to 850μm is less than or equal to m.
(method of Using wastewater treatment agent)
As a method of using the above-mentioned wastewater treatment agent, the wastewater treatment agent of the present invention is dissolved in water at a predetermined concentration, and the resulting aqueous solution is supplied to wastewater to which an inorganic flocculant is added, whereby fine particles of inorganic unnecessary substances in the wastewater are flocculated/precipitated and removed from the wastewater.
Examples of the inorganic unnecessary substance include: and inorganic wastes containing at least one of nickel, fluorine, iron, copper, zinc, chromium, arsenic, cadmium, tin, and lead.
The water purification method of the present invention will be specifically explained.
The inorganic-based unwanted materials (nickel, chromium, copper, zinc, fluorine, etc.) to be removed are generally dissolved in the wastewater in the form of ions. Therefore, the above-mentioned treatment for solidifying the ions is first performed using a neutralizing agent, a coagulant, or the like corresponding to each component, and micro-flocs are formed. Next, an inorganic flocculant such as PAC (polyaluminium chloride) is added to improve the surface potential balance of the above microflocs, thereby promoting coagulation and increasing the size. However, since the flocs cannot be increased to a size that allows the flocs to be coagulated/precipitated in a short time by only adding the inorganic coagulant, a proper amount of the wastewater treatment agent-dissolved solution of the present invention, which has formed an aqueous solution of 0.1 to 0.2 mass%, is added thereto. As a result, the microfloc particles grow to a size capable of coagulation/sedimentation in a short time, and only the sediment is separated/recovered, whereby useless substances existing in the wastewater are removed, and purified wastewater is obtained.
In the above-described wastewater treatment, the amount of the chemical agent (neutralizing agent, inorganic flocculant, wastewater treatment agent of the present invention) to be used greatly varies depending on the concentration of each component in the wastewater, the initial pH, the amount of the wastewater, and the like, and the amount to be added needs to be adjusted for each wastewater. However, since increasing the amount of the chemical agent directly increases the cost of wastewater treatment, it is preferable to use a smaller amount of the chemical agent.
Examples
The present invention will be described with reference to examples, but the present invention is not limited to these examples.
(example 1)
-water addition mixing process
50% by mass of cellulose acetate (median position)Diameter: 200μm～330μm, weight average molecular weight (Mw): 170,000, manufactured by china) and 50 mass% of a coagulant polymer (polyacrylamide, Flopan AN 926, manufactured by SNF) to obtain a mixture, and then 72 mass% of water was added to the obtained mixture, followed by kneading with water for 5 minutes using a 2-blade pressure kneader to obtain a kneaded product.
Extrusion Molding Process
Extruding the resulting kneaded mixture using a twin-screw extruder designed to produce pellets for tire rubber, and subjecting the resultant kneaded mixture to extrusion molding to obtain a rubber composition having a specific particle size of (A), (B), (C)ϕ) The molded product extruded through the 3.5mm die hole was cut to a length (L) of 5mm or less with a rotary knife.
Primary drying process
The obtained molded product was dried continuously while controlling the molded products (granular) so as not to be bonded to each other to form a large lump during drying using a vibration flow dryer manufactured by Dulton corporation, to obtain a primary dried product. When the moisture content of the obtained primary dried product is measured by an infrared moisture meter, the moisture content is 14 to 22%.
-granulation procedure-
The obtained primary dried product was pulverized using a multi-blade chopper manufactured by Horai to obtain granules. The particle size of the pulverized material is less than 250μThe production rate of the fine particles m is 12 to 19 mass% based on the total particles.
Secondary drying process-
The resulting granules were subjected to secondary drying using a fluidized bed dryer manufactured by the company Dulton to remove adhesion/cohesion of the granules to each other. In this case, in order to prevent the product temperature from rising to 80 ℃ or higher, a temperature sensor is inserted into the dryer, and the batch process is performed while measuring the product temperature. When the water content of the obtained secondary dried product was measured by an infrared ray type moisture meter, the water content was 6% or less.
-a classification procedure-
The obtained wastewater treatment agent has particle size of above 850μParticles of m pass through a nominal mesh 850μm (sieve size 20) and particle size less than 250μThe particles of m pass through a nominal mesh 250μRemoving m (sieve number 60) to obtain a product with a particle size of 250μm is more than or equal to 850μAnd m is less than the water treatment agent.
(example 2)
In example 1, the content of cellulose acetate was changed from 50 mass% to 47.5 mass%, the content of the coagulant polymer was changed from 50 mass% to 47.5 mass%, the entire part of the molokhia was dried by solar drying or the like until the water content was 10% or less, and then 5 mass% of cellulose acetate was added and pulverized by a chopper or the like until the particle size distribution was 50μm～710μA wastewater treatment agent was obtained in the same manner as in example 1 except that the plant powder obtained in m was used.
Comparative example 1
40% by mass of cellulose acetate (median diameter: 200)μm～330μm, weight average molecular weight (Mw): 170,000, manufactured by china) and 60 mass% of a coagulant polymer (polyacrylamide, Flopan AN 926, manufactured by SNF) were put into a plastic bag, and then mixed by shaking manually for 5 minutes or more to obtain a wastewater treatment agent.
Comparative example 2
A wastewater treatment agent was obtained in the same manner as in comparative example 1, except that the content of cellulose acetate was changed to 50 mass% and the content of the flocculant polymer was changed to 50 mass% in comparative example 1.
Comparative example 3
A wastewater treatment agent was obtained in the same manner as in comparative example 1, except that the content of cellulose acetate in comparative example 1 was changed to 60 mass% and the content of the coagulant polymer was changed to 40 mass%.
Comparative example 4
50% by mass of cellulose acetate (median diameter: 200) was carried out using a planetary mixerμm～330μm, weight average molecular weight (Mw): 170,000, manufactured by china) and 50 mass% of a coagulant polymer (polyacrylamide, Flopan AN 926, manufactured by SNF), and a kneading step (about 180% of the amount of water based on the weight of the raw material mixture, and a kneading time of about 20 minutes). Next, the kneaded mixture was chargedThe molded article was put into a rectangular box, a press cover was placed thereon, and pressure molding was performed for about 1 minute under a pressure of 0.5MPa to obtain a block-shaped molded article. The molded article was cut into pieces of about 15cm square, and the cut pieces were stretched one by a stretcher (45 t presser, manufactured by Mitsuki Kaisha) to obtain a sheet-like molded article having a thickness of 6 mm.
The molded article was placed on a rack on which a net was laid, and dried by a hot air dryer (80 ℃ C., 20 hours or more) together with the rack. The dried cake having a water content of 6% or less was pulverized into a powder in 2 stages by a chopper. Finally, classification is carried out using a vibrating screen or the like so that the particle size distribution thereof is 250μm～850μAnd m, obtaining the wastewater treatment agent.
[ angle of repose ]
The angle of repose was measured using a PT-X type powder tester (manufactured by Hosokawa Micron Co., Ltd.).
A sample to be measured was dropped onto a circular support via a funnel, and the angle formed between the inclined surface and the horizontal surface when a layer was formed on a mountain (angle bar) was measured.
[ bulk Density ]
100cc of the wastewater treatment agent was gently charged into a 100cc stainless steel cup, and the density of the wastewater treatment agent at this time was measured using a PT-X type powder tester (manufactured by Hosokawa Micron Co., Ltd.).
[ cellulose acetate separation ratio (CA separation ratio) ]
7g of a wastewater treatment agent as a measurement sample was put into 350g of acetone, and dissolved in an ultrasonic washer at 28kHz, 30 ℃ to 40 ℃ and 10 minutes to obtain a solution. Next, qualitative filter paper (retained particle diameter: 6) was usedμm) the resulting solution was filtered to obtain a residue. The resulting residue was dried at 80 ℃ for 30 minutes or more to completely evaporate/remove acetone in the residue, and thereafter the mass x (g) of the dried residue was measured. The measurement method is a measurement method using the following 2-point properties: while cellulose acetate is soluble in acetone, the coagulant polymer or other ingredients are insoluble in acetone; and cellulose acetate separated from other components such as coagulant polymerIt is decomposed in acetone. Thus, the CA separation ratio can be obtained according to the following calculation formula.
CA separation rate (%) = (7-X)/7X 100
(evaluation)
< feed stability >
Each wastewater treatment agent was charged into a hopper having an angle of 60 degrees, and when automatically supplied to the dissolution tank, whether stable supply was possible was evaluated according to the following criteria.
Evaluation criteria-
A: no bridging or rat hole is generated, and stable supply can be continuously performed;
b: although the bridge or the rat hole is generated, the bridge or the rat hole disappears by applying vibration to the hopper, and the supply can be continuously carried out;
c: the bridging or the rat hole is generated, and even if the hopper is applied with vibration, the bridging or the rat hole can not be eliminated, and the stable supply can not be carried out.
< Manufacturing lead time >
The time required for the production (L/T for the production) was measured from the time point when the cellulose acetate and the coagulant polymer were weighed to the time point when the wastewater treatment agent was obtained.
< Manufacturing yield (Manufacturing yield) >
The production yield is a measurement of the finished product (weight)/the total input amount (weight) of the raw material.
[ Table 1]
Claims (7)
1. A wastewater treatment agent characterized by:
comprising particles comprising cellulose acetate and a coagulant polymer,
the angle of repose is 38 degrees or less.
2. The wastewater treatment agent according to claim 1, having a bulk density of 0.46g/mL or more.
3. The wastewater treatment agent according to any one of claims 1 to 2, which has an angle of repose of 37 degrees or less.
4. The wastewater treatment agent according to any one of claims 1 to 3, wherein a mass ratio of the cellulose acetate to the coagulant polymer is: coagulant polymer 40%: 60% -60%: 40 percent.
5. A method for producing a wastewater treatment agent, comprising the steps of:
a kneaded material preparation step of adding water to and kneading cellulose acetate and a coagulant polymer using a pressure kneader to prepare a kneaded material; and
and an extrusion molding step of subjecting the kneaded product to extrusion molding using a biaxial screw molding machine to obtain a molded product.
6. A process for producing a wastewater treatment agent according to claim 5, comprising the steps of:
a primary drying step of drying the molded product to a moisture content of 14 to 22% to obtain a primary dried product;
a granulation step of crushing the primary dried product to obtain granules; and
and a secondary drying step of drying the granules.
7. The method for producing a wastewater treatment agent according to claim 6, wherein in the granulating step, the particle size is less than 250%μThe production rate of the fine particles of m is 19 mass% or less based on the total particles.
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| TW202202456A (en) | 2022-01-16 |
| CN113666470B (en) | 2024-04-23 |
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