CN112876788A - Foaming material and preparation method and application thereof - Google Patents
Foaming material and preparation method and application thereof Download PDFInfo
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- CN112876788A CN112876788A CN202110163442.8A CN202110163442A CN112876788A CN 112876788 A CN112876788 A CN 112876788A CN 202110163442 A CN202110163442 A CN 202110163442A CN 112876788 A CN112876788 A CN 112876788A
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
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- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08K3/20—Oxides; Hydroxides
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Abstract
The invention discloses a foaming material and a preparation method and application thereof, wherein the foaming material comprises the following raw materials in parts by weight: 30-50 parts of polyvinyl chloride, 1-2.5 parts of foaming agent, 3-5 parts of toughening agent, 3-5 parts of functional auxiliary agent, 3-5 parts of lubricant and 50-80 parts of modified slag powder; the modified slag powder is obtained by grafting a coupling agent on activated slag powder, the slag powder is at least one of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag, the content of heavy metal in the activated slag powder is not higher than 10 wt%, and the pH value is 7.0-7.5. According to the invention, most heavy metals in the slag are sorted out in advance, and trace heavy metals are fixed in the foaming material through the coupling agent, so that the problem of secondary pollution to the environment caused by massive seepage of heavy metals in the slag from products after long-term storage in the prior art is solved.
Description
Technical Field
The invention belongs to the field of solid waste treatment, and particularly relates to a foaming material and a preparation method and application thereof.
Background
At the present stage, the utilization rate of slag in China is low, a large amount of slag is stacked and treated, a large amount of land is occupied, the management cost is increased for enterprises, and insoluble solids contained in the slag easily cause environmental pollution.
At present, solid wastes such as copper smelting slag, steel slag, fly ash and the like are generally used for preparing building materials, red mud and phosphogypsum are reported to be used for filling foaming materials, and the problem that the solid wastes pollute the environment is partially solved. However, the slag is only filled as a common filler, the utilization rate of a large amount of heavy metals in the slag is low, and the heavy metals are easy to seep out of the product after long-term storage, so that secondary pollution is caused to the environment.
Disclosure of Invention
According to the invention, part of heavy metal in the slag is recycled firstly, and then the rest part is used for preparing the foaming material, and the slag which recycles part of heavy metal can be added into the foaming material after being activated in a large amount, so that the utilization rate of heavy metal in solid waste is improved, the utilization rate of the rest part of slag is improved, and the production cost of the foaming material is reduced.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a foaming material, which comprises the following raw materials in parts by weight: 30-50 parts of polyvinyl chloride, 1-2.5 parts of foaming agent, 3-5 parts of toughening agent, 3-5 parts of functional auxiliary agent, 3-5 parts of lubricant and 50-80 parts of modified slag powder; the modified slag powder is obtained by grafting a coupling agent on activated slag powder, the slag powder is at least one of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag, the content of heavy metal in the activated slag powder is not higher than 10 wt%, and the pH value is 7.0-7.5.
On the basis of the technical scheme, the modified slag powder is obtained by reacting slag powder with fineness of more than 500 meshes with a coupling agent at 110-115 ℃.
On the basis of the technical scheme, in the slag powder, the red mud and the titanium dioxide slag account for at least 80 wt% of the total weight, and the balance is at least one of phosphogypsum, copper smelting slag and steel slag.
On the basis of the technical scheme, the weight ratio of the red mud to the titanium white slag is 1: 0.8-1.2.
On the basis of the technical scheme, the slag powder consists of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag in a weight ratio of 35:35:10: 10.
On the basis of the technical scheme, the polyvinyl chloride is PVC8 type resin powder; the foaming agent is an AC foaming agent; the functional auxiliary agent is chlorinated polyethylene; the lubricant is at least one of paraffin, polyethylene wax and stearic acid; the toughening agent is at least one of powder nitrile butadiene rubber, MBS, impact resistant ACR and ABS high rubber powder.
In a second aspect, the present invention provides a method for preparing the above foaming material, comprising the following steps: mixing all the raw materials at the speed of 850-1100 rpm for 5-8 minutes to obtain a mixture; adding the mixture into an extrusion forming machine, sequentially setting the machine barrel temperature of 200 ℃, 190 ℃, 185 ℃ and 180 ℃ along the output direction of the mixture, setting the rotating speed of a main machine to be 10-20 r/min, setting the current to be 45-50A, setting the extrusion pressure to be 10-20 MPa, and cutting after extrusion.
On the basis of the technical scheme, the preparation method of the modified slag powder comprises the following steps: and stirring the slag powder at the speed of 850-1000 rpm, adding a coupling agent when the temperature of the slag powder reaches 110-115 ℃, and continuously mixing for 3-5 minutes to obtain the modified slag powder.
On the basis of the technical scheme, the coupling agent is a silane coupling agent, and the weight ratio of the coupling agent to the slag powder is 1: 20 to 60.
In a third aspect, the invention provides an application of the foamed material or the foamed material prepared by the preparation method in preparation of foamed profiles, such as integrated wallboards, ceilings, keels, leg wires, door strips, door pockets, trays and the like.
The invention principle of the invention is as follows:
the method comprises the steps of firstly recovering part of heavy metals in the slag in a separation mode, and then using the rest part of the slag to prepare the foaming material; the slag with part of heavy metal recovered still contains trace heavy metal, can promote the foaming of the AC foaming agent, improves the foaming efficiency, and simultaneously, the part of heavy metal is combined with the by-product of the AC foaming agent in the later period to stabilize the foaming speed, thereby avoiding the unformed section bar caused by violent foaming. And the weakly acidic slag can be combined with ammonia gas generated by the AC foaming agent, so that the AC foaming agent is prevented from generating side reaction.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) according to the invention, part of heavy metals in the slag are sorted out, so that the problem of low utilization rate of the heavy metals in the slag in the prior art is solved.
(2) According to the invention, most heavy metals in the slag are sorted out firstly, and then trace heavy metals are fixed in the foaming material through the coupling agent, so that the problem of secondary pollution to the environment caused by massive seepage of heavy metals in the slag from products after long-term storage in the prior art is solved.
(3) The invention does not add a foaming regulator, thereby saving the production cost.
(4) According to the invention, the slag is stirred at a high speed before foaming, so that on one hand, the slag can be activated into layered silicate, and the binding force with PVC is improved; on the other hand, the heavy metal can be activated to promote the foaming of the AC foaming agent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The foaming material provided by the invention comprises the following raw materials in parts by weight: 30-50 parts of polyvinyl chloride, 1-2.5 parts of foaming agent, 3-5 parts of toughening agent, 3-5 parts of functional auxiliary agent, 3-5 parts of lubricant and 50-80 parts of modified slag powder; the modified slag powder is obtained by grafting a coupling agent on activated slag powder, the slag powder is powder of at least one of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag, the content of heavy metal in the activated slag powder is not higher than 10 wt%, and the pH value is 7.0-7.5.
Before the slag powder is used, most heavy metals are sorted out by utilizing the difference between heavy metal components and nonmetal components, wherein the difference between the heavy metal components and the nonmetal components comprises one or more of the combination of the difference of specific magnetization coefficients, the difference of specific gravities, the difference of hydrophilicity and the difference of electrical conductivity; the comprehensive separation method for the slag comprises one or more of magnetic separation, gravity separation, flotation and electric separation.
The specific magnetization coefficients of the ilmenite, the trace nickel, the cobalt, the copper, the excessive reduced iron powder and other heavy metals in the titanium white slag which are not subjected to acidolysis reaction and the silicon oxide, the aluminum oxide and other non-metals in the titanium white slag have larger difference, and the reduced iron powder, the nickel-cobalt metal and the ilmenite are removed step by preferentially adopting a graded magnetic separation mode, so that the separation and the separation of the heavy metals are realized.
The specific magnetization coefficients of heavy metals such as iron oxide and titanium oxide in the red mud and non-metals such as silicon oxide and aluminum oxide in the red mud are greatly different, and the separation of titanium and iron elements or oxides thereof is preferably realized by adopting a multi-stage magnetic separation mode.
The specific magnetization coefficients of iron, lead, zinc and other metal oxides in copper smelting slag and steel slag and silicon oxide, calcium oxide, aluminum oxide and other non-metals are greatly different, and the separation of iron, lead and zinc elements or oxides thereof is preferably realized by adopting a multi-stage magnetic separation mode.
The preparation method of the foaming material provided by the invention comprises the following steps: mixing all the raw materials at the speed of 850-1100 rpm for 5-8 minutes to obtain a mixture; and adding the mixture into an extrusion forming machine, setting the temperature of a machine barrel to be 200 ℃, 190 ℃, 185 ℃ and 180 ℃ in sequence, setting the rotating speed of a main machine to be 10-20 r/min, setting the current to be 45-50A and the extrusion pressure to be 10-20 MPa, and cutting after extrusion.
The preparation method of the modified slag powder comprises the following steps: and stirring the slag powder at the speed of 850-1000 rpm, adding a coupling agent when the temperature of the slag powder reaches 110-115 ℃, and continuously mixing for 3-5 minutes to obtain the modified slag powder.
The polyvinyl chloride adopted in the following examples is PVC8 type resin powder, the adopted foaming agent is AC foaming agent with molecular weight of 116 gas forming amount and Ml/g more than or equal to 215-235, the adopted foaming regulator is acrylate processing aid, the adopted functional aid is chlorinated polyethylene CPE135A, the adopted lubricant is stearic acid, paraffin or polyethylene wax can also be adopted, and the adopted toughening agent is powder nitrile butadiene rubber, MBS, impact resistant ACR or ABS high rubber powder can also be adopted.
Example 1: recovery of heavy metals
Before the slag is utilized, the slag such as red mud, titanium white slag, phosphogypsum, copper smelting slag, steel slag and the like is comprehensively sorted by utilizing the difference between heavy metal components and nonmetal components, and after most of heavy metals in the red mud, the titanium white slag, the phosphogypsum, the copper smelting slag and the steel slag are recycled and sorted, the residual part of the slag is slag powder with the fineness of more than or equal to 500 meshes. Tables 1 to 5 show the content comparison of the components before and after the separation of different slags:
TABLE 1 titanium dioxide acidolysis tailings content before and after separation
TABLE 2 Red mud tailings content before and after separation
TABLE 3 content of components before and after separation of phosphogypsum tailings
TABLE 4 copper smelting slag tailings content before and after separation
TABLE 5 Steel slag tailings content before and after separation
Example 2: preparation of different kinds of modified slag powder
The titanium white slag powder which is not sorted and is sorted in the embodiment 1 is respectively subjected to activation grafting: adding 50 parts by weight of titanium white slag powder with the water content of less than or equal to 3 wt% and the fineness of more than or equal to 500 meshes into a high-speed mixer, starting the high-speed mixer to 900 revolutions per minute, stirring for about 5 minutes until the temperature of the titanium white slag powder reaches 110-115 ℃, adding 1 part by weight of silane coupling agent (KH560), continuously mixing for 5 minutes to activate the titanium white slag powder, then placing the titanium white slag powder into a cold mixing cylinder of the high-speed mixer, reducing the rotating speed to 60 revolutions per minute, and discharging for later use when the temperature is reduced to about 45 ℃ to obtain the modified titanium white slag powder.
The red mud, the phosphogypsum, the copper smelting slag and the steel slag which are not sorted and are sorted in the embodiment 1 are respectively subjected to activated grafting according to the activated grafting method to obtain different types of modified slag powder.
Examples 3 to 19: preparation of foamed material by chemical foaming method
(1) Adding 55 parts by weight of modified slag powder, 45 parts by weight of polyvinyl chloride, 1.5 parts by weight of AC foaming agent, 3.2 parts by weight of chlorinated polyethylene, 3.0 parts by weight of lubricant and 3.5 parts by weight of toughening agent into a mixer, stirring for 5 minutes at the rotating speed of 850 revolutions per minute to obtain a mixture;
(2) adding the mixture into 65/132 taper special-shaped twin-screw, setting the cylinder temperature at 200 ℃, 190 ℃, 185 ℃ and 180 ℃, the confluence core at 190 ℃, the die temperature at 190 ℃, the main machine rotation speed at 12 r/min, the current at 45A, the extrusion pressure at 15MPa and 18MPa, extruding into the required plate shape through the die, cooling through a setting table, drawing through a tractor, completing cutting through a cutting machine and blanking through a turning frame according to the product requirements, and preparing the foamed product with the properties as shown in tables 6-9.
TABLE 6 comparison of density experiments for different modified slag powders and foamed products thereof
TABLE 7 foaming products without added modified red mud powder
TABLE 8 foaming product without added modified titanium white slag powder
TABLE 9 foaming products with different proportions of modified slag powder
The experimental results show that the combined addition of the five modified slag powders is superior to the foaming products without adding red mud powder and titanium dioxide slag powder. The inventor analyzes that the red mud is alkaline, the conventional pH value is 8-10, the titanium white slag is acidic, the pH value after water treatment is about 6, the pH value of the modified slag powder prepared according to the proportion in the table 9 is about 7.5, and the foaming effect is improved.
Examples 20 to 24
Modified slag powder, which is composed of 35%, 10% and 10% of modified titanium white slag powder, modified red mud powder, modified phosphogypsum powder, modified copper smelting slag powder and modified steel slag powder in sequence, is selected, and a test sample, namely a 150 cm-20 cm foamed profile, is prepared according to the same method and parameters as in examples 3-19. Table 10 shows the raw material ratios of examples 20 to 24.
TABLE 10 raw material ratios of examples 20 to 24
The foamed sections prepared in examples 20 to 24 were tested according to GB/T24137-.
TABLE 11 foamed profiles Performance parameters prepared in examples 20-24
As shown in Table 11, the foamed materials prepared in examples 20 to 24 have low density, low water absorption and excellent other performance test results.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The foaming material is characterized by comprising the following raw materials in parts by weight: 30-50 parts of polyvinyl chloride, 1-2.5 parts of foaming agent, 3-5 parts of toughening agent, 3-5 parts of functional auxiliary agent, 3-5 parts of lubricant and 50-80 parts of modified slag powder; the modified slag powder is obtained by grafting a coupling agent on activated slag powder, the slag powder is at least one of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag, the content of heavy metal in the modified slag powder is not higher than 10 wt%, and the pH value is 7.0-7.5.
2. The foamed material according to claim 1, characterized in that: the modified slag powder is obtained by reacting slag powder with the granularity of more than 500 meshes with a coupling agent at 110-115 ℃.
3. The foamed material according to claim 1, characterized in that: in the slag powder, the red mud and the titanium white slag account for at least 80 wt% of the total weight, and the balance is at least one of phosphogypsum, copper smelting slag and steel slag.
4. The foamed material according to claim 3, characterized in that: the weight ratio of the red mud to the titanium white slag is 1: 0.8-1.2.
5. The foamed material according to claim 4, wherein: the slag powder consists of red mud, titanium white slag, phosphogypsum, copper smelting slag and steel slag according to the weight ratio of 35:35:10: 10.
6. The foamed material according to claim 1, characterized in that: the polyvinyl chloride is PVC8 type resin powder; the foaming agent is an AC foaming agent; the functional auxiliary agent is chlorinated polyethylene; the lubricant is at least one of paraffin, polyethylene wax and stearic acid; the toughening agent is at least one of powder nitrile butadiene rubber, MBS, impact resistant ACR and ABS high rubber powder.
7. The process for producing the foamed material according to any one of claims 1 to 6, comprising the steps of: mixing all the raw materials at the speed of 850-1100 rpm for 5-8 minutes to obtain a mixture; adding the mixture into an extrusion forming machine, sequentially setting the machine barrel temperature of 200 ℃, 190 ℃, 185 ℃ and 180 ℃ along the output direction of the mixture, setting the rotating speed of a main machine to be 10-20 r/min, setting the current to be 45-50A, setting the extrusion pressure to be 10-20 MPa, and cutting after extrusion.
8. The method for producing a foamed material according to claim 7, wherein: the preparation method of the modified slag powder comprises the following steps: and stirring the slag powder at the speed of 850-1000 rpm, adding a coupling agent when the temperature of the slag powder reaches 110-115 ℃, and continuously mixing for 3-5 minutes to obtain the modified slag powder.
9. The method for producing a foamed material according to claim 8, wherein: the coupling agent is a silane coupling agent, and the weight ratio of the coupling agent to the slag powder is 1: 20 to 80 parts.
10. Use of the foamed material according to any one of claims 1 to 6 or the foamed material prepared by the preparation method according to any one of claims 7 to 9 in the preparation of foamed profiles.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110163442.8A CN112876788B (en) | 2021-02-05 | 2021-02-05 | Foaming material and preparation method and application thereof |
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| CN115141440A (en) * | 2022-08-04 | 2022-10-04 | 中塑新材料技术(吉林)有限公司 | Preparation method of modified slag composite material |
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