CN107459806A - Tea saponin modification desulfurization ash and its with waste or used plastics made of composite floor brick - Google Patents

Tea saponin modification desulfurization ash and its with waste or used plastics made of composite floor brick Download PDF

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Publication number
CN107459806A
CN107459806A CN201710387387.4A CN201710387387A CN107459806A CN 107459806 A CN107459806 A CN 107459806A CN 201710387387 A CN201710387387 A CN 201710387387A CN 107459806 A CN107459806 A CN 107459806A
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tea saponin
desulfurization ash
waste
product
composite floor
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刘彤
张龙
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Guizhou University
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Guizhou University
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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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00—Flooring
    • E04F15/02—Flooring or floor layers composed of a number of similar elements
    • E04F15/10—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials
    • E04F15/105—Flooring or floor layers composed of a number of similar elements of other materials, e.g. fibrous or chipped materials, organic plastics, magnesite tiles, hardboard, or with a top layer of other materials of organic plastics with or without reinforcements or filling materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Road Paving Structures (AREA)
  • Floor Finish (AREA)

Abstract

The invention discloses a kind of tea saponin modification desulfurization ash, by 6~10wt% Tea Saponins, forms with 90%~94wt% desulfurization ash, makes in the steps below：60 DEG C are added to desulfurization ash and Tea Saponin in high-speed mixer, stir 6~8 minutes, obtain tea saponin modification desulfurization ash.Its composite floor brick made of with waste and old Polyethylene terephthalate plastic, is prepared from the following raw materials in parts by weight：Waste and old 16~27 parts of Polyethylene terephthalate plastic, 73~84 parts of tea saponin modification desulfurization ash, through drying, stir, plasticate in flakes, molding, cutting cut-parts form.Desulfurization ash surface nature is changed as lipophile by the present invention using Tea Saponin by hydrophily, its comixing compatibility with waste and old Polyethylene terephthalate, associativity is set to be greatly improved, the larger performance for improving composite floor brick, the filling number of desulfurization ash in composite floor brick is added simultaneously, effectively reduces the cost of product.

Description

Tea saponin modification desulfurization ash and its with waste or used plastics made of composite floor brick
Technical field
The invention belongs to building material field, changes more particularly to a kind of Tea Saponin as waste and old polydiphenyl ether plastics filler Property sulfate slag and its with waste and old polydiphenyl ether plastics made of composite floor brick.
Background technology
At present, the industrial residue sulfate slag that China's chemical industry is discharged every year increases year by year, these sulfate slags at present except Use to produce sulfate slag brick, outside cement, be also much stacked at the storage ash field of sulfate slag, not only occupied soil, can also make Into serious environmental pollution.It is in addition, growing with China's polydiphenyl ether plastics production capacity and consumption figure so that discarded polyphenylene oxide The plastic garbage yield that plastics are formed is more and more, causes serious " white pollution ".In addition, it is currently used in public place and family The floor tile of the local ground such as front yard house laying is mostly that clay, china clay, stone material are made, and its complex manufacturing, price is higher, production Product are in water-proof skid-proof, heat conduction is warming, still have certain defect in terms of sound absorption properties, comfortable foot feeling degree, suddenly treat a kind of twice laid, reduction The new material pollute, to economize on resources solves problem.On the other hand in waste and old polydiphenyl ether plastics and sulfate slag Blending Processes by In sulfate slag category polarity inorganic matter, hydrophily, and waste and old polydiphenyl ether plastics belongs to nonpolar organic matter, and lipophile, both are in thing Manage shape with it is far from it in chemical constitution, make to lack chemical bond force between the two, inorganic filler is above-mentioned when causing the two-phase to be blended Disperse uneven, two-phase poor compatibility in organic matter, so as to have influence on the performance of composite floor brick.
The content of the invention
The technical problem to be solved of the present invention be to provide a kind of tea saponin modification sulfate slag and its with waste and old polyphenyl Composite floor brick made of ether plastics, not only reduce dirt of waste and old polydiphenyl ether plastics and the industrial residue sulfate slag to environment Dye, while the composite floor brick has simple production process, cheap, water-proof skid-proof, heat conduction is warming, sound absorption properties are good, feel The advantages that comfort level is good.
The purpose of the present invention and solves its technical problem underlying using following technical scheme to realize：A kind of Tea Saponin Modified sulfate slag, it is characterised in that：By 5~8wt% Tea Saponins, 3~6wt%NaOH and 89%~92wt% sulfate slags form, Make in the steps below：
28 DEG C are added to sulfate slag and NaOH in high-speed mixer, and Tea Saponin is added again when stirring 5~7 minutes, 70 DEG C Heating stirring 4~5 minutes, obtains tea saponin modification sulfate slag；
Described Tea Saponin is a kind of candy glucoside compound by being extracted in tea tree seed, is a kind of day of good performance Right surfactant, the structure of Tea Saponin are as follows：
Described sulfate slag is that pyrite manufactures the waste residue discharged during sulfuric acid or sulfurous acid through broken, grinding, screening Gained afterwards, sulfate slag particle diameter≤350 μm.
Described tea saponin modification sulfate slag and composite floor brick made of waste or used plastics, by the raw material of following parts by weight It is made：
Waste and old 15~22 parts of polydiphenyl ether plastics,
78~85 parts of tea saponin modification sulfate slag；
Make in the steps below：
A, after waste and old polydiphenyl ether plastics is cleaned, 1.7h is dried at a temperature of 115 DEG C, then after being crushed to below 4mm, obtains A Product；
B, after A product and tea saponin modification sulfate slag being stirred with homogenizer, B product are obtained；
C, B product are placed on three-roller open mill and plasticated in flakes, 200~210 DEG C of temperature, piece 0.5~0.8mm of thickness, then sent Enter and be molded on hot press, 170 DEG C~180 DEG C of molding temperature, pressure 4.5MPa, 5~7 minutes time, obtain C product；
D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
The polyphenylene oxide product that the waste and old polydiphenyl ether plastics is industrial production and human lives are abandoned, selected from electronic apparatus Part, auto parts, household electrical appliance, office equipment, industrial machinery part, medical treatment and health leisure utensil, tubing, section bar, Sheet material.
The principle of the invention：The present invention utilizes the SiO containing 40~65wt% in sulfate slag2, its under strong basicity environment with NaOH generates sodium metasilicate, and acid-base reaction then occurs with the carboxyl in Tea Saponin molecule, generates coupled Tea Saponin silicic acid anhydride.
Specific reaction equation is as follows：
The first step：
Tea Saponin molecular structure：
It is reduced to：(HO)11-R-COOH；
Second step：
Glycosyl in coupled Tea Saponin silicic acid anhydride structure has preferable hydrophily, and sulfate slag can be modified, will Sulfate slag surface nature is changed as lipophile by hydrophily, and modified sulfate slag has good dispersive property in organic phase, Its comixing compatibility with waste and old polydiphenyl ether plastics, associativity is greatly improved, be added significantly to inorganic filler sulfuric acid The filling number of slag, effectively reduce the cost of product.Meanwhile the glycosyl institute hydroxyl of Tea Saponin silicic acid anhydride intramolecular has Activity, hydrogen bond easily occurs with elecrtonegativity oxygen in polyphenylene oxide and Van der Waals force is combined, so as to so that multiple polydiphenyl ether plastics point Son produces more effective absorption with Tea Saponin silicic acid anhydride, realizes the intensity increase of polydiphenyl ether plastics, improves composite floor brick Performance.Dependency structure is as follows：
The present invention has clear advantage and beneficial effect compared with prior art.From above technical scheme, this hair It is bright to have following characteristics：
(1) present invention is modified using Tea Saponin to sulfate slag first, using using contain 40 in sulfate slag~ 65wt% SiO2, it generates sodium metasilicate under strong basicity environment with NaOH, and acid then occurs with the carboxyl in Tea Saponin molecule Alkali reacts, and generates coupled Tea Saponin silicic acid anhydride.Glycosyl in the structure has preferable hydrophily, and sulfate slag can be changed Property, sulfate slag surface nature is changed as lipophile by hydrophily, modified sulfate slag has good disperse in organic phase Performance, its comixing compatibility with waste and old polydiphenyl ether plastics, associativity is greatly improved, be added significantly to inorganic filler The filling number of sulfate slag, effectively reduce the cost of product.Meanwhile the glycosyl institute hydroxyl of Tea Saponin silicic acid anhydride intramolecular It is active, hydrogen bond easily occurs with elecrtonegativity oxygen in polyphenylene oxide and Van der Waals force is combined, so as to so that multiple polyphenylene oxide are moulded Expect that molecule produces more effective absorption with Tea Saponin silicic acid anhydride, realize the intensity increase of polydiphenyl ether plastics, improve compoundly The performance of plate brick.
(2) present invention is using the waste and old polydiphenyl ether plastics that industrial production and human lives are abandoned and industrial residue sulfate slag For primary raw material, using suitable preparation method, composite floor brick is made, has both alleviated waste or used plastics with industrial residue to environment Pollution, add new material again for architectural engineering.
(3) composite floor brick that the present invention makes reaches the ground of the local ground laying such as state's public places in Nan Chong and home dwelling Plate brick standard, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry proposed standard (HG/T3747.1-2004), The coupling agents pair such as conventional silane coupler, titanate coupling agent, aluminate coupling agent, stearic acid are superior under the conditions of same recipe The modified effect of sulfate slag, while the product has simple production process, cheap, water-proof skid-proof, heat conduction are warming, sound absorption properties Well, the advantages that comfortable foot feeling degree is good, has preferable social benefit and market prospects.
Embodiment
Below in conjunction with preferred embodiment, to according to tea saponin modification sulfate slag proposed by the present invention and its with waste or used plastics system Into composite floor brick embodiment, feature and its effect, describe in detail as after.
A kind of tea saponin modification sulfate slag, it is characterised in that：By 5~8wt% Tea Saponins, 3~6wt%NaOH and 89% ~92wt% sulfate slags form, and make in the steps below：
28 DEG C are added to sulfate slag and NaOH in high-speed mixer, and Tea Saponin is added again when stirring 5~7 minutes, 70 DEG C Heating stirring 4~5 minutes, obtains tea saponin modification sulfate slag；
Described Tea Saponin is a kind of candy glucoside compound by being extracted in tea tree seed, is a kind of day of good performance Right surfactant, the structure of Tea Saponin are as follows：
Described sulfate slag is that pyrite manufactures the waste residue discharged during sulfuric acid or sulfurous acid through broken, grinding, screening Gained afterwards, sulfate slag particle diameter≤350 μm.
Described tea saponin modification sulfate slag and composite floor brick made of waste or used plastics, by the raw material of following parts by weight It is made：
Waste and old 15~22 parts of polydiphenyl ether plastics,
78~85 parts of tea saponin modification sulfate slag；
Make in the steps below：
A, after waste and old polydiphenyl ether plastics is cleaned, 1.7h is dried at a temperature of 115 DEG C, then after being crushed to below 4mm, obtains A Product；
B, after A product and tea saponin modification sulfate slag being stirred with homogenizer, B product are obtained；
C, B product are placed on three-roller open mill and plasticated in flakes, 200~210 DEG C of temperature, piece 0.5~0.8mm of thickness, then sent Enter and be molded on hot press, 170 DEG C~180 DEG C of molding temperature, pressure 4.5MPa, 5~7 minutes time, obtain C product；
D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
The polyphenylene oxide product that the waste and old polydiphenyl ether plastics is industrial production and human lives are abandoned, selected from electronic apparatus Part, auto parts, household electrical appliance, office equipment, industrial machinery part, medical treatment and health leisure utensil, tubing, section bar, Sheet material.
Embodiment 1：
Tea saponin modification sulfate slag is made in the steps below：
28 DEG C are added to 92Kg sulfate slags and 3KgNaOH in high-speed mixer, are added when stirring 5~7 minutes, 70 DEG C 5Kg Tea Saponins are stirred under heating 4~5 minutes, obtain tea saponin modification sulfate slag.
Composite floor brick is made in the steps below：
A, by after the waste and old polydiphenyl ether plastics cleanings of 150Kg, 1.7h is dried at a temperature of 115 DEG C, then be crushed to below 4mm Afterwards, A product are obtained；
B, after A product and 850Kg tea saponin modification sulfate slags being stirred with homogenizer, B product are obtained；
C, B product are placed on three-roller open mill and plasticated in flakes, 200~210 DEG C of temperature, piece 0.5~0.8mm of thickness, then sent Enter and be molded on hot press, 170 DEG C~180 DEG C of molding temperature, pressure 4.5MPa, 5~7 minutes time, obtain C product；
D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
With the identical material prescription of embodiment 1, technological process, technological parameter under the conditions of, it is even using conventional silane The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to sulfate slag, and reproduction is compound Floor tile, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry Proposed standard (HG/T 3747.1-2004) performs, and the effect of modified sulfate slag is contrasted, its testing result such as table 1~7 It is shown.
The composite floor brick Hardness results of table 1
The composite floor brick tensile strength testing result of table 2
The composite floor brick tearing strength testing result of table 3
The composite floor brick wearability testing result of table 4
The composite floor brick heated dimensions of table 5 change performance test results
The composite floor brick fire resistance testing result of table 6
The composite floor brick brittleness temperature testing result of table 7
From table 1~7 as can be seen that the present embodiment finished product correlated performance detection result reaches state's public places in Nan Chong and family lives The floor tile standard of the local ground laying such as residence, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry proposed standard (HG/T3747.1-2004) conventional silane coupler, titanate coupling agent, Aluminate, and under the conditions of same recipe are superior to The coupling agents such as coupling agent, stearic acid make its comixing compatibility with waste and old polydiphenyl ether plastics, combination to the modified effect of sulfate slag Property is greatly improved, the larger performance for improving composite floor brick, while adds the filling of inorganic filler sulfate slag Number, effectively reduce the cost of product.The target of the present invention is realized.
Embodiment 2：
Tea saponin modification sulfate slag is made in the steps below：
28 DEG C are added to 90Kg sulfate slags and 4KgNaOH in high-speed mixer, are added when stirring 5~7 minutes, 70 DEG C 6Kg Tea Saponins are stirred under heating 4~5 minutes, obtain tea saponin modification sulfate slag.
Composite floor brick is made in the steps below：
A, by after the waste and old polydiphenyl ether plastics cleanings of 180Kg, 1.7h is dried at a temperature of 115 DEG C, then be crushed to below 4mm Afterwards, A product are obtained；
B, after A product and 820Kg tea saponin modification sulfate slags being stirred with homogenizer, B product are obtained；
C, B product are placed on three-roller open mill and plasticated in flakes, 200~210 DEG C of temperature, piece 0.5~0.8mm of thickness, then sent Enter and be molded on hot press, 170 DEG C~180 DEG C of molding temperature, pressure 4.5MPa, 5~7 minutes time, obtain C product；
D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
With the identical material prescription of embodiment 2, technological process, technological parameter under the conditions of, it is even using conventional silane The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to sulfate slag, and reproduction is compound Floor tile, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry Proposed standard (HG/T 3747.1-2004) performs, and the effect of modified sulfate slag is contrasted, its testing result such as table 8~14 It is shown.
The composite floor brick Hardness results of table 8
The composite floor brick tensile strength testing result of table 9
The composite floor brick tearing strength testing result of table 10
The composite floor brick wearability testing result of table 11
The composite floor brick heated dimensions of table 12 change performance test results
The composite floor brick fire resistance testing result of table 13
The composite floor brick brittleness temperature testing result of table 14
From table 8~14 as can be seen that the present embodiment finished product correlated performance detection result reaches state's public places in Nan Chong and family The floor tile standard of the local ground laying such as house, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry recommends mark Accurate (HG/T3747.1-2004), and conventional silane coupler, titanate coupling agent, aluminic acid are superior under the conditions of same recipe The coupling agents such as ester coupling agent, stearic acid make its comixing compatibility with waste and old polydiphenyl ether plastics, knot to the modified effect of sulfate slag Conjunction property is greatly improved, the larger performance for improving composite floor brick, while adds filling out for inorganic filler sulfate slag Number is filled, effectively reduces the cost of product.The target of the present invention is realized.
Embodiment 3：
Tea saponin modification sulfate slag is made in the steps below：
28 DEG C are added to 89Kg sulfate slags and 6KgNaOH in high-speed mixer, and Kg is added when stirring 5~7 minutes, 70 DEG C Tea Saponin is stirred under heating 4~5 minutes, obtains tea saponin modification sulfate slag.
Composite floor brick is made in the steps below：
A, by after the waste and old polydiphenyl ether plastics cleanings of 220Kg, 1.7h is dried at a temperature of 115 DEG C, then be crushed to below 4mm Afterwards, A product are obtained；
B, after A product and 780Kg tea saponin modification sulfate slags being stirred with homogenizer, B product are obtained；
C, B product are placed on three-roller open mill and plasticated in flakes, 200~210 DEG C of temperature, piece 0.5~0.8mm of thickness, then sent Enter and be molded on hot press, 170 DEG C~180 DEG C of molding temperature, pressure 4.5MPa, 5~7 minutes time, obtain C product；
D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
With the identical material prescription of embodiment 3, technological process, technological parameter under the conditions of, it is even using conventional silane The coupling agents such as connection agent, titanate coupling agent, aluminate coupling agent, stearic acid are modified processing to sulfate slag, and reproduction is compound Floor tile, by carrying out physico-chemical analysis to finished product, technical requirements are pressed《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry Proposed standard (HG/T 3747.1-2004) is performed, and the effect of modified sulfate slag is contrasted, and its testing result such as table 15~ Shown in 21.
The composite floor brick Hardness results of table 15
The composite floor brick tensile strength testing result of table 16
The composite floor brick tearing strength testing result of table 17
The composite floor brick wearability testing result of table 18
The composite floor brick heated dimensions of table 19 change performance test results
The composite floor brick fire resistance testing result of table 20
The composite floor brick brittleness temperature testing result of table 21
From table 15~21 as can be seen that the present embodiment finished product correlated performance detection result reaches state's public places in Nan Chong and family The floor tile standard of the local ground laying such as house, i.e.,《Rubber and plastic pavement part 1 rubber floor covering》Chemical industry recommends mark Accurate (HG/T3747.1-2004), and conventional silane coupler, titanate coupling agent, aluminic acid are superior under the conditions of same recipe The coupling agents such as ester coupling agent, stearic acid make its comixing compatibility with waste and old polydiphenyl ether plastics, knot to the modified effect of sulfate slag Conjunction property is greatly improved, the larger performance for improving composite floor brick, while adds filling out for inorganic filler sulfate slag Number is filled, effectively reduces the cost of product.The target of the present invention is realized.
The above described is only a preferred embodiment of the present invention, not making any formal limitation to the present invention, appoint Without departing from technical solution of the present invention content, what the technical spirit according to the present invention was made to above example any simply repaiies for what Change, equivalent variations and modification, in the range of still falling within technical solution of the present invention.

Claims (4)

  1. A kind of 1. tea saponin modification desulfurization ash, it is characterised in that：By 6~10wt% Tea Saponins, with 90%~94wt% desulfurization ash Composition, makes in the steps below：
    60 DEG C are added to desulfurization ash and Tea Saponin in high-speed mixer, stir 6~8 minutes, obtain tea saponin modification desulfurization Lime-ash；
    Described Tea Saponin is a kind of candy glucoside compound by being extracted in tea tree seed, is a kind of natural table of good performance Face activating agent, the structure of Tea Saponin are as follows：
    。
  2. 2. tea saponin modification desulfurization ash as claimed in claim 1, it is characterised in that：Described desulfurization ash is that steel plant burn Caused lime-ash after freezing of a furnace flue gas dry desulfurizing is obtained by after broken, grinding, screening, desulfurization ash particle diameter≤700 μm.
  3. 3. tea saponin modification desulfurization ash as claimed in claim 1 or 2 and composite floor brick, its feature made of waste or used plastics It is：It is prepared from the following raw materials in parts by weight：
    Waste and old 16~27 parts of Polyethylene terephthalate plastic,
    73~84 parts of tea saponin modification desulfurization ash；
    Make in the steps below：
    A, after waste and old Polyethylene terephthalate plastic is cleaned, 1.5h is dried at a temperature of 130 DEG C, then be crushed to 3mm After below, A product are obtained；
    B, after A product and tea saponin modification desulfurization ash being stirred with homogenizer, B product are obtained；
    C, B product are placed on three-roller open mill and plasticated in flakes, 270~280 DEG C of temperature, the 8mm of piece thickness 0.5~0., be then fed into heat It is molded on press, 170 DEG C~180 DEG C of molding temperature, pressure 4.0MPa, 3~4 minutes time, obtains C product；
    D, C product are pressed into long 300mm, got product after wide 300mm, thick 1.5mm standard size cutting cut-parts.
  4. 4. tea saponin modification desulfurization ash as claimed in claim 3 exists with composite floor brick, its feature made of waste or used plastics In：The poly terephthalic acid that the waste and old Polyethylene terephthalate plastic is industrial production and human lives are abandoned is Glycol ester articles, selected from electrical outlets, electric power connector, electric cooker handle, circuit breaker shell, motor fan shell, instrument machine Tool part, counting machine part, electric iron, the accessory of electromagnetic stove oven；Flow control valve, carburetor cover, car in auto industry Window controller, foot operated speed changer, distribution board cover；Mechanical industry gear, blade, belt pulley, pump component, in addition also have wheelchair car body And wheel, lampshade shell, illuminator enclosure, drain connection, slide fastener, clock and watch part, atomiser units；Various poly- terephthaldehydes Plastic bottle, film, sheet material, the section bar of sour hexylene glycol ester articles material.
CN201710387387.4A 2017-05-27 2017-05-27 Tea saponin modification desulfurization ash and its with waste or used plastics made of composite floor brick Pending CN107459806A (en)

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Application Number Priority Date Filing Date Title
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Publication Number Publication Date
CN107459806A true CN107459806A (en) 2017-12-12

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