CN106883471B - A kind of white clay recycling method of comprehensive utilization - Google Patents
A kind of white clay recycling method of comprehensive utilization Download PDFInfo
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- CN106883471B CN106883471B CN201710281045.4A CN201710281045A CN106883471B CN 106883471 B CN106883471 B CN 106883471B CN 201710281045 A CN201710281045 A CN 201710281045A CN 106883471 B CN106883471 B CN 106883471B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
- C08K5/47—Thiazoles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
A kind of white clay recycling method of comprehensive utilization is directly mixed with papermaking recycling white clay using strong acid weak base salt, obtains the white clay powder of removal however, residual base after dry and ball milling.The powder prepares rubber or plastic composite as filler, can not only reduce the production cost of composite material, but also can improve product properties.The present invention directly uses the however, residual base of strong acid weak base salt removal white clay, instead of acid stronger inorganic acid and high-cost organic acid, can promote the whiteness of white clay, simplify treatment process, save processing cost, have good Social benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of recoverying and utilizing methods of gained by-product white clay in paper-making process, more particularly, to a kind of white
Mud recycles method of comprehensive utilization, belongs to rubber or filling plastic modification and resources circulation field of comprehensive utilization.
Background technique
White clay is the by-product of alkali collection stage generation during paper-making pulping, and main component is calcium carbonate, with residual
Remaining alkali belongs to secondary pollution.Currently, being mainly landfill method and calcination method to the processing method of white clay.Wherein landfill method is easy to make
At underground water pollution, calcination method investment is big, energy consumption is high, and while recycling is limited by silicone content in paper pulp.Therefore, white clay
Recycling comprehensive utilization has become paper industry urgent problem.In the recycling research of white clay, prepared using white clay
Environmentally friendly composite material is a kind of good comprehensive utilization technique.But due to white clay have however, residual base, pH higher,
The performance that is used for a long time that will affect product is directly used, and easily corrodes equipment during the preparation process.Therefore, white clay is being utilized
Prepare the however, residual base for needing to remove white clay before composite material.Chinese invention patent CN103754918A, CN102553890A,
CN105481294A, CN105504725A, CN105214471A, CN102786732A, CN104803406A and
It is white that CN106146937A is respectively adopted in water washing, inorganic acid and organic acid and/or is passed through in sour gas and wait modes to remove
The however, residual base of mud.Wherein, water washing will cause great lot of water resources waste and water pollution;Inorganic acid easily corrode equipment and
And additive amount is not easy to control;Organic acid higher cost and however, residual base cannot be completely removed;It is passed through sour gas and be easy to cause air
Pollution, equipment requirement are high.In addition, the mode operating process of above-mentioned removal white clay however, residual base is cumbersome, the comprehensive reutilization of white clay
Process is complicated.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome the deficiencies of the prior art and provide it is a kind of operation it is simpler, cost compared with
Low, the white clay small to equipment corrosion recycles method of comprehensive utilization.
The technical solution used to solve the technical problems of the present invention is that a kind of white clay recycling method of comprehensive utilization, including with
Lower step:
(1) strong acid weak base salt is directly mixed with the white clay that papermaking is recycled, adjusts the additional amount of strong acid weak base salt, so that mixed
The pH value for closing object is 6-8;
(2) by step (1) gained mixture drying 2-5h at 100-110 DEG C;
(3) by the mixture ball milling 0.5-2h after step (2) are dry, powder material is obtained.
(4) gained powder material can be used as filler and prepare rubber or plastic composite.
The strong acid weak base salt, one of preferably sulfuric acid zinc, aluminum sulfate, magnesium sulfate, zinc chloride, aluminium chloride, magnesium chloride
Or it is a variety of.
Rubber clone applied by the present invention treated white clay includes: nitrile rubber, butadiene-styrene rubber, butadiene rubber, day
At least one of right rubber, haloflex, bibasic ethylene propylene rubber, ethylene propylene diene rubber, epichlorohydrin rubber, neoprene.
Plastics variety applied by the present invention treated white clay includes: polyvinyl chloride, polypropylene, polyethylene, polyphenyl second
One of alkene, polycarbonate, polyamide are a variety of.
The invention has the advantages that directly using strong acid weak base salt (zinc sulfate, aluminum sulfate, magnesium sulfate, zinc chloride, aluminium chloride,
Magnesium chloride) remover as white clay however, residual base instead of acid stronger inorganic acid and high-cost organic acid simplifies preparation work
Skill, and white clay can be rationally utilized again, solve problem of environmental pollution.
Studies have shown that the present invention uses zinc salt, aluminium salt, magnesium salts, the zinc hydroxide generated after reaction, aluminium hydroxide and hydrogen-oxygen
Changing magnesium is also a kind of rubber or plastic additive, can not only reduce the production cost of composite material, but also can improve product
Performance can further promote the comprehensive performance of rubber composite material or plastic composite.In addition to this, the present invention directly uses
The by-product white clay of paper technology, raw material sources are abundant, and treatment process is simple, can substantially reduce production cost, and can mention
The utilization of papermaking by-product-white clay is risen, there is preferable Social benefit and economic benefit.
During comprehensive reutilization white clay of the present invention, directly using the however, residual base of strong acid weak base salt removal white clay, with reality
Modes are now substituted in water washing in the prior art, inorganic acid and organic acid and/or be passed through in sour gas and wait, are removed white
The however, residual base of mud simplifies operating process, reduces production cost, efficiently using white clay and solves white clay problem of environmental pollution.This hair
The bright direct however, residual base using strong acid weak base salt removal white clay, instead of acid stronger inorganic acid and high-cost organic acid, energy
The whiteness of white clay is promoted, treatment process is simplified, saves processing cost, there is good Social benefit and economic benefit.
Specific embodiment
Below in conjunction with specific embodiment the present invention is explained in more detail.
In each embodiment and comparative example, butt (effective ingredient) weight ratio for the recycling white clay being added is 65wt%, aqueous
Amount is 35wt%.
The detection method standard of the tensile property of the rubber composite material is GB/T 528-2008 detection method.Hardness
Detection method standard is GB/T531-1999 detection method.
The detection method standard of the tensile property of the plastic composite is GB/T 16421-1996 detection method.It is curved
Bent method for testing performance standard is GB/T9341-2000 detection method.Impact property detection method standard is GB/T1043-1993
Detection method.
Comparative example 1: according to existing refining gluing method, by 100 parts of raw rubber, 5.0 parts of zinc oxide, 2.0 parts of stearic acid, rubber
1.5 parts of glue primary accelerator CZ, 2.5 parts of sulphur, not plus 50 parts of white clay of ball milling 1h of strong acid weak base salt processing (with dry basis
Meter), it is mixed with open mill to uniform;Finally rubber compound is vulcanized at 150 DEG C with vulcanizing press according to a conventional method, point
White clay/nitile-butadiene rubber composite material and white clay/styrene-butadiene rubber composite material are not prepared.
Comparative example 2: according to existing melt-blending process, by 100 parts of polyvinyl chloride, 7 parts of lead barium stabilizer, stearic acid 0.6
Part, 1 part of paraffin, not plus strong acid weak base salt processing ball milling 1h 50 parts of white clay (with butt restatement), using double screw extruder
Extrusion granulation, each zone temperatures are between 140-185 DEG C in extrusion process, 8 Hz of screw speed.Polyvinyl chloride-white clay is compound
Material pellet injection molding prepares polyvinyl chloride-white clay composite material, is molded each zone temperatures between 140-185 DEG C.
Comparative example 3: according to existing melt-blending process, by 100 parts of polypropylene, not plus strong acid weak base salt processing ball milling 1h
50 parts of white clay (with butt restatement), using double screw extruder extrusion granulation, each zone temperatures are in 150-190 in extrusion process
Between DEG C, 8 Hz of screw speed.By polypropylene-white clay composite material pellet injection molding, polypropylene-white clay composite wood is prepared
Material, is molded each zone temperatures between 150-190 DEG C.
Embodiment 1: the removal of white clay however, residual base
Under room temperature, the white clay (with water-containing material restatement) and 25 grams of strong acid weak base salts for weighing 500 grams of papermaking recycling (divide
Also known as take white vitriol, aluminum sulfate octadecahydrate, Aluminum Chloride Hexahydrate or magnesium chloride hexahydrate), white vitriol, 18 water sulphur is added
The pH value of mixed material is respectively 6,7,7,8 after sour aluminium, Aluminum Chloride Hexahydrate or magnesium chloride hexahydrate, 105 after mechanical mixture is uniform
Dry 2h at DEG C, then by the mixture ball milling 1h after drying, obtain the white clay of removal however, residual base.The pH value of gained white clay after processing
1 is shown in Table with whiteness:
Embodiment 2: according to existing refining gluing method, by 100 parts of nitrile rubber, 5.0 parts of zinc oxide, 2.0 parts of stearic acid, rubber
1.5 parts of glue primary accelerator CZ, 2.5 parts of sulphur, treated in embodiment 1 50 parts of white clay (in terms of butt), it is mixed with open mill
It is bonded to uniformly;Finally rubber compound is vulcanized at 150 DEG C with vulcanizing press according to a conventional method, prepares white clay/butyronitrile
Rubber composite material.Utilize white clay/nitile-butadiene rubber composite material mechanics of different strong acid weak base salts treated white clay preparation
Performance is shown in Table 2:
Embodiment 3: according to existing refining gluing method, by 100 parts of butadiene-styrene rubber, 5.0 parts of zinc oxide, 2.0 parts of stearic acid, rubber
1.5 parts of glue primary accelerator CZ, 2.5 parts of sulphur, treated in embodiment 1 50 parts of white clay (in terms of butt), it is mixed with open mill
It is bonded to uniformly;Finally rubber compound is vulcanized at 150 DEG C with vulcanizing press according to a conventional method, prepares white clay/butylbenzene
Rubber composite material.Utilize white clay/styrene-butadiene rubber composite material mechanics of different strong acid weak base salts treated white clay preparation
Performance is shown in Table 3:
Embodiment 4: polyvinyl chloride-white clay composite material
(1) according to existing melt-blending process, by 100 parts of polyvinyl chloride, 7 parts of lead barium stabilizer, 0.6 part of stearic acid, stone
1 part of wax, treated in embodiment 1 50 parts of white clay (in terms of butt), using double screw extruder extrusion granulation, in extrusion process
Each zone temperatures are between 140-185 DEG C, 8 Hz of screw speed.
(2) by polyvinyl chloride-white clay composite material pellet injection molding, polyvinyl chloride-each area of white clay composite material is prepared
Duan Wendu is between 140-185 DEG C.Utilize polyvinyl chloride-white clay composite wood of different strong acid weak base salts treated white clay preparation
The mechanical property of material is shown in Table 4:
Embodiment 5: polypropylene-white clay composite material
(1) according to existing melt-blending process, by 100 parts of polypropylene, treated in embodiment 1 50 parts of white clay is (with dry
Base meter), using double screw extruder extrusion granulation, each zone temperatures are between 150-190 DEG C in extrusion process, screw speed 8
Hz。
(2) by polypropylene-white clay composite material pellet injection molding, polypropylene-white clay composite material, each section temperature are prepared
Degree is between 150-190 DEG C.Utilize polypropylene-white clay composite material power of different strong acid weak base salts treated white clay preparation
It learns performance and is shown in Table 5:
Claims (3)
1. a kind of white clay recycles method of comprehensive utilization, which is characterized in that first with the white clay of strong acid weak base salt and papermaking recycling
It directly mixes, obtains powder material after dry and ball milling, recycle that the powder material prepares rubber as filler or plastics are compound
Material;
Specifically includes the following steps:
(1) strong acid weak base salt is directly mixed with the white clay that papermaking is recycled, the additional amount of strong acid weak base salt is adjusted, so that mixture
PH value be 6-8;
(2) by step (1) gained mixture drying 2-5h at 100-110 DEG C;
(3) by the mixture ball milling 0.5-2h after step (2) are dry, powder material is obtained;
(4) gained powder material can be used as filler and prepare rubber or plastic composite;
The strong acid weak base salt is one of zinc sulfate, aluminum sulfate, magnesium sulfate, zinc chloride, aluminium chloride, magnesium chloride or a variety of.
2. white clay according to claim 1 recycles method of comprehensive utilization, which is characterized in that applied by gained powder material
Rubber clone includes: nitrile rubber, butadiene-styrene rubber, butadiene rubber, natural rubber, haloflex, bibasic ethylene propylene rubber, ternary
At least one of EP rubbers, epichlorohydrin rubber, neoprene.
3. white clay according to claim 1 or 2 recycles method of comprehensive utilization, which is characterized in that gained powder material is answered
Plastics variety includes: one of polyvinyl chloride, polypropylene, polyethylene, polystyrene, polycarbonate, polyamide or more
Kind.
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Publication number | Priority date | Publication date | Assignee | Title |
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CN1208377C (en) * | 2002-08-21 | 2005-06-29 | 上海挪亚环境资源开发有限公司 | Water-proofing roll material using paper-making waste mud as filling agent |
CN1587508A (en) * | 2004-09-23 | 2005-03-02 | 崔木春 | Method for producing light calcium carbonate product with white mud |
CN101391794B (en) * | 2008-10-24 | 2010-06-09 | 魏湘 | Novel method for preparing light calcium carbonate by recovering solid white slime through alkaline pulping |
CN101700901A (en) * | 2009-11-25 | 2010-05-05 | 王冬生 | Novel method for producing light calcium carbonate (CaCO3) from white clay generated from alkali recovering in paper-making industry |
CN102553890A (en) * | 2012-01-18 | 2012-07-11 | 牟作峰 | White mud recycling method |
CN102786732B (en) * | 2012-09-07 | 2014-07-23 | 上海第二工业大学 | Method for producing plastic filling master batch through papermaking waste white mud |
CN103708522A (en) * | 2014-01-03 | 2014-04-09 | 三三环保科技(北京)有限公司 | Causticization method for producing high-quality calcium carbonate by recycling green liquor by alkali |
CN106146937A (en) * | 2015-03-24 | 2016-11-23 | 湖南师范大学 | A kind of wet method modifies the method that white clay prepares rubber master batches |
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