CN102391694B - Method for preparing plastic filler from waste residue in crystal industry - Google Patents
Method for preparing plastic filler from waste residue in crystal industry Download PDFInfo
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- CN102391694B CN102391694B CN 201110266395 CN201110266395A CN102391694B CN 102391694 B CN102391694 B CN 102391694B CN 201110266395 CN201110266395 CN 201110266395 CN 201110266395 A CN201110266395 A CN 201110266395A CN 102391694 B CN102391694 B CN 102391694B
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Abstract
The invention discloses a method for preparing a plastic filler from waste residue in the crystal industry. The method comprises the following steps of: (1) primarily screening the waste residue by using screening equipment to remove impurities and large particles; (2) grinding the waste residue by using grinding equipment, and finely screening; (3) dehydrating and drying particles of the waste residue; and (4) performing surface coating treatment on the particles of the waste residue by using a surfactant to obtain a highly activated inorganic filler capable of being directly filled in plastics. The waste residue is properly treated to form the filler applied to the plastics; and by the method, a great amount of waste residue generated in the crystal industry can be recycled, the pollution of the waste residue on the environment is lightened, the exploitation of inorganic minerals is saved, and good social benefit is achieved.
Description
Technical field
The present invention relates to utilize quartzy industry waste residue to prepare the method for plastic filler, be specifically related to by carrying out surface treatment to the control of grain diameter and to waste particle, obtain directly to be filled in the weighting material in the plastics, purpose is to realize the recycling of solid wastes recycle, belongs to the environmental protection field.
Background technology
Quartzy industry is to be initial feed with crystal glass (normally high flint glass), is processed into the industry of the glasswork with quartzy characteristic of different shape by means such as cut mechanically, grinding, polishings.In the course of processing of crystal product, can bring a large amount of waste residues, according to statistics, one ton of crystal glass of every processing is with the waste residue that produces 30%, for the smallclothes goods, its waste residue amount can be bigger, and only in Pujiang area, Zhejiang, nearly will consume every day 2000 tons crystal glass, well imagine that its waste residue amount also is huge.All the time, the processing of the waste residue the like waste that produces in the quartzy processing is a difficult problem, owing to there are not recycle means well, quartzy waste residue is to be transported to refuse landfill to handle as a kind of solid waste always, but the development along with quartzy industry, the waste residue that produces is more and more, and so many waste residues are not born in the landfill place.The source mill that has a large amount of middle and small scales in the quartzy industry all is disorderly to fall everywhere for waste residue, perhaps directly is discharged in the river, causes waste residue in river bottom sediment, forms white hard material, and " white pollution " is very outstanding, severe contamination soil and river.And As time goes on, if waste residue can not be utilized effectively, waste residue is along with the river spreads, and its contaminated area enlarges fast.At present, the residue contamination problem of crystal glass industry has had a strong impact on the environment of locality and adjacent periphery, has caused the attention of environment hosts department, also is the key that is related to quartzy industry final and decisive juncture simultaneously.Therefore the waste residue that must study quartzy industry is handled problems.
Handle problems in the face of serious day by day quartzy industry waste residue, responsible departments of the government and crystal glass industry are all trying every possible means to solve always, and the relevant quartzy industry waste residue with subsidy of guiding is handled project.But according to literature survey, the processing achievement that does not also have the relevant waste residue of technical literature report, just have in some news report and mention, company limited proposes such as the tame environment-friendly building materials of Pujiang ten thousand, quartzy waste residue press process is become fragment of brick, this method can consume waste residue outwardly, solve the handling problem of waste residue to a certain extent, but this complex process in fact, the energy consumption height, and fragment of brick is low value-added product, faces problem from economy, brings restriction thereby the power that can lack Sustainable development is the long-term disposal of waste residue.And Pujiang constant force ornaments company limited has proposed a kind of method of quartzy refuse reclamation, and its operation comprises operations such as waste residue sub-sieve, mix, high temperature melt, shaping traction.After finishing the waste residue sub-sieve, mix batchings such as small portion tackiness agent by a certain percentage, the High Temperature Furnaces Heating Apparatus that puts it into 1650 degree is melted into bath of glass, form again the cooling and through tractor to finishing room, utilize the starting material of quartzy waste refabrication crystal, can carry out the utilization of waste residue, but the problem that this method faces is, because waste residue component complexity, be to obtain for glass ingredient by sub-sieve only, can only utilize some scrap stock, therefore to the processing of waste residue be have circumscribed, the reasonable plan that can not handle as the waste residue of maximum.
At the handling problem of crystal glass waste residue, not only to realize and can handle, but also economy must be arranged, should realize social benefit, also must have an economic benefit, could realize Sustainable development like this, the processing scheme of waste residue is only optimum scheme.
As a whole, the method that does not also have the good quartzy waste residue of recycle now.Therefore, in order to effectively utilize quartzy waste residue, and do not produce new pollution, be necessary to study new recycle method, can efficiently utilize waste residue, can not bring new pollutent again simultaneously, and cyclic utilization method also should have economy, main purpose of the present invention that Here it is.
Summary of the invention
Technical problem to be solved by this invention just provides a kind ofly utilizes quartzy industry waste residue to prepare the method for plastic filler, can efficiently utilize waste residue, can not bring new pollutent again simultaneously, and cyclic utilization method also has economy.
For solving the problems of the technologies described above, the present invention adopts following technical scheme: a kind ofly utilize quartzy industry waste residue to prepare the method for plastic filler, it is characterized in that having following technological process:
(1) utilizes screening plant that waste residue is carried out primary dcreening operation and remove foreign material and macrobead;
(2) by levigate equipment waste residue is carried out levigate and dusting cover;
(3) waste particle is dehydrated;
(4) utilize tensio-active agent that waste particle is carried out the surface and coat to handle, what obtain activating can directly be filled in mineral filler in the plastics.
Preferably, waste particle is carried out surface coating processing and has following steps:
(1) stirs in machine or the kneader at height, quantitative quartzy waste residue is heated to 100 ℃～120 ℃;
(2) in waste residue, add the coupling agent of 0.5%～2% weight, combination treatment 20～30 minutes;
(3) in waste residue, add the organic silicon surfactant of 0.5～1% weight, combination treatment 20～30 minutes.Above ratio is the waste residue weight percent.
Preferably, described coupling agent is stearic acid, aluminic acid ester or titanic acid ester, and described organic silicon surfactant is epoxy radicals silicone hydride, aminosilane or vinyl silanes.
Preferably, the specification of selecting sieve during the waste residue primary dcreening operation grinds the particle median size and is not less than 300 orders for being not more than 2mm when waste residue is levigate.
Preferably, the screening plant of primary dcreening operation and dusting cover use comprises stationary screen, vibratory screening apparatus or dusting cover.
Preferably, described levigate equipment is selected ball mill, rod mill, autogenous mill, pebble mill or superfine grinding equipment.
The temperature of oven dry is 40 ℃～60 ℃ when preferably, dry.
Preferably, dehydrate water content＜0.05% of the quartzy waste residue in back.
Preferably, link-suspended basket centrifuge or horizontal helical type whizzer are selected in dehydration, and dryer or pneumatic conveying dryer are selected in oven dry.
Preferably, with the quartzy waste residue Inorganic Fillers Filled of the activation that makes in polypropylene, loading level is 10% of polypropylene weight, in the high-speed stirring machine, mix the quartzy waste residue of load weighted activation and polypropylene, in twin screw extruder, melt extrude then, water-cooled tie rod and pelletizing obtain being filled with the PP matrix material of quartzy waste residue.
The present invention has utilized quartzy waste residue to characteristics such as the unreactiveness of plastics and grain graininess are little, through suitable processing, can be prepared into the weighting material that is applied to plastics to waste residue, replaces widely used inorganic mineral filler.By this method, a large amount of waste residues that can recycle quartzy industry produces, reduced the pollution of waste residue to environment, the exploitation of also having saved inorganic mineral simultaneously, have good social benefit, and the particle fineness of these waste residues is little, has reduced the work that grinds in a large number, save tooling cost, can bring good economic benefit.
Embodiment
On chemical constitution, the crystal glass waste residue mainly contains: silicate glass composition, quartz sand, cerium oxide rare earth and calcium carbonate etc., these compositions have determined waste residue directly not utilize and have been prepared into the used raw material of quartzy industry, but clearly these components do not have chemically reactive as plastic filler.In addition, from the particle characteristics of waste residue, its size distribution is as shown in table 1.
Table 1: typical quartzy waste residue size distribution
From size distribution, its most of particle size distribution between 20 microns and 100 microns, i.e. 200 orders-600 purpose scope, the inorganic particle in this particle size range only needs simple levigate processing just to can be used as plastic filler to use.Therefore, from the angle of plastic filler, quartzy waste residue has characteristics such as unreactiveness, particle be tiny, can be used as plastic filler and uses.
The inventor herein has carried out deep research, found that quartzy waste residue has unreactiveness and the little characteristics of grain graininess, through suitable processing, can become the weighting material of plastics to waste residue, can substitute the inorganic mineral filler that is widely used in the plastics fully, thereby finish the present invention.
Want the quartzy waste residue of recycle, need to understand the characteristics of quartzy waste residue.
The patent inventor at first from the processing analysis of crystal glass the composition of quartzy waste residue, by can analyze the composition source of waste residue to the understanding of quartzy complete processing.The raw material of crystal product is crystal glass, the waste residue that produces in cutting, grinding process mainly is crystal glass, simultaneously in cutting and grinding process, cutting and grinding tool (as quartzy emery wheel etc.) also have wearing and tearing partly and enter in the glass waste residue, therefore the composition that contains crystal glass and quartzy emery wheel in the waste residue of this part, crystal glass wherein is with silicate (SiO
2) glass is base material; And in polishing process, goods are through further grinding and buffing, crystal glass still has small part to be worn away and enters in the waste residue, simultaneously, in polishing process, use polishing wheel to carry out grinding and buffing, polishing wheel also has the wearing and tearing of part and becomes waste residue, polishing wheel mainly is to be made by polishing powder, calcium carbonate, quartz sand and portion of hot solidity binder resin, and polishing powder mainly is high-content cerium oxide rare earth, therefore, the waste residue that forms in polishing process has comprised crystal glass, cerium oxide, calcium carbonate, quartz sand and portion of hot thermosetting resin.Usually, the waste residue that the waste residue of cutting and grinding and polishing back produce all mixes, therefore, generally speaking, the crystal glass waste residue mainly contains: silicate glass composition, quartz sand, cerium oxide and calcium carbonate, these compositions have determined waste residue directly not utilize and have been prepared into the used raw material of quartzy industry.Main composition in the waste residue is inorganic oxide or salt substantially, the chemical property of these components is relatively stable, high temperature resistant difficult decomposition, certain rigidity and hardness are arranged, this has possessed the characteristic that can be used as plastic filler, can replace conventional plastics inorganic mineral filler, such as calcium carbonate, kaolin, talcum powder etc., quartzy waste residue and these inorganic mineral fillers have similar character.On the other hand, will be as plastic filler, also require weighting material to have thinner grain diameter, the mechanical property of plastics so can not deteriorate significantly after being filled into plastics, and on grain diameter, because waste residue is that crystal glass produces in physical refining process, mainly is some fine particles, the particle size range of typical waste residue is as shown in table 1.From the data of table 1 as can be seen, the particle of waste residue is thinner, though the particle size range that requires than common plastic filler is bigger, very approaching, can do the particle diameter requirement that simple process just can reach plastic filler.
The inventor herein just is being based on the front to the understanding of quartzy waste residue characteristics, therefore the novel method of recycle waste residue has been proposed, the creative proposition is used as plastic filler to the crystal glass waste residue, and both the quartzy waste residue of reusable edible can reduce plastic industry again to the consumption of inorganic mineral.And quartzy waste residue itself has thinner grain graininess, just satisfies plastic filler to the requirement of grain graininess, and its processing cost is lower, so its filling cost in plastics is significantly less than traditional inorganic mineral, has better economic.
Filling inorganic mineral in plastics is a kind of widely used method of plastic working industry, and its purpose has two: the one, reduce cost, and reduce the consumption of plastics, because the cost of inorganic mineral wants cheap a lot of for plastic raw materials; Next is to improve performance, behind the interpolation inorganic mineral, can improve rigidity and hardness and the resistance toheat of plastics in plastics.As the inorganic mineral of plastic filler, two requirements are satisfied in its basic demand: the one, not with plastic body generation chemical reaction; The 2nd, thin grain graininess be arranged, grain graininess is the deteriorate significantly performance of plastics of senior general too, and this will cause plastic material to lose efficacy and can't use, and require to be not less than 400 orders usually.In the plastic working industry, using maximum inorganic mineral fillers is exactly calcium carbonate (or Wingdale), and this material extensively exists at nature, and stable in properties, not with matrix plastic generation chemical reaction.But calcium carbonate is that form with ore exists at nature, needs mining, as mineral filler the time, also needs to utilize mechanical means levigate, reach the particle size range of filled plastics, so its prime cost is in the levigate stage.And that quartzy waste residue has just obtained in the quartzy course of processing is levigate, so its particle diameter is less, approaches and uses, and only needs simple process, greatly reduces and grinds cost.
From the situation of literature survey, though the technology of inorganic mineral filled plastics is ripe relatively, also not about utilizing the bibliographical information of quartzy waste residue filled plastics.This patent has proposed quartzy waste residue filled plastics first, reaches the purpose of the quartzy waste residue of recycle, realizes that the resource utilization of quartzy waste residue is recycled.Can solve the pollution problem of quartzy industry waste residue, can produce economic worth again, have obvious social and economic benefit.
Propose to utilize quartzy waste residue to prepare the processing method of plastic filler at the present invention, comprised following steps:
(1) utilizes screening plant that waste residue is carried out primary dcreening operation and remove foreign material and macrobead;
(2) carry out levigate by levigate equipment such as ball mills to waste residue and sieve, obtain the waste particle of certain particle size range;
(3) particle is dehydrated;
(4) utilize tensio-active agent that particle is carried out the surface and coat to handle, what obtain activating can directly be filled in mineral filler in the plastics.
Quartzy industry waste residue is the waste that produces in the process that crystal glass is processed, be characterized in that particle is tiny, particle diameter has certain distribution, can there be some macrobead things, waste residue is in banking process simultaneously, have some foreign material and sneak into, these macrobeads and foreign material can worsen the performance of plastics, need dispose.Can utilize screening plant that waste residue is carried out primary dcreening operation removes.Method for sieving of the present invention can be selected various screening plants, comprises stationary screen, vibratory screening apparatus, dusting cover, preferably selects vibratory screening apparatus.Vibratory screening apparatus is done judder with short arc, high vibration number, has eliminated the latch up phenomenon of material, makes sieve that higher screening efficiency and throughput be arranged, power consumption is little, simple structure, and operation, Maintenance and Repair are more convenient, floor space is little, is widely used, preferred vibratory screening apparatus.Select the specification of sieve for being not more than 2mm, preferably be not more than 1mm, more preferably no more than 0.5mm.Can remove particle diameter like this greater than macrobead thing and the foreign material of 0.5mm.
After removing foreign material and macrobead thing, the median size of waste residue requires biggerly greatly about about 200 orders than plastic filler particle diameter, also need to carry out levigate to waste residue and sieve by levigate equipment, obtains meeting the waste particle of plastic filler particle diameter requirement.In the grinding process to quartzy waste residue of the present invention, can select various pulverising apparatus, comprise ball mill, rod mill, autogenous mill, pebble mill and superfine grinding equipment, preferred spheres grinding machine and rod mill, more preferably ball mill.In grinding process, according to the requirement to grain diameter, can adopt the separate unit ball mill, also can use many table grinders, carry out plural serial stage technology.Grind grain graininess and be not less than 300 orders, preferably be not less than 400 orders.
Owing to can use water cooling and washing etc. in the quartzy course of processing, so waste residue has certain water-content usually, can remove surface water by whizzer earlier, by drying plant the water content of waste residue further reduced then.The present invention can select whizzer to quartzy waste residue dehydration, has comprised link-suspended basket centrifuge and horizontal helical type whizzer, and oven dry can be selected various drying plants, has comprised dryer, pneumatic conveying dryer.Through dehydrating water content＜0.05% of the quartzy waste residue in back, more preferably＜0.03%
Behind the quartzy waste residue that obtains certain particle size range and drying, before being packed into plastics, needing that also quartzy waste residue is carried out the surface and coat processing, improve the surface property of quartzy waste residue.Common quartzy waste residue is inorganics, and the surface has water-wet behavior, and plastics belong to organic polymer, have oil-wet behavior.Want quartzy waste residue to be packed in the plastics, hydrophilic and oil-wet behavior has repulsive interaction, and it is inhomogeneous to cause quartzy waste residue to disperse in plastic substrate, and a little less than interacting, causes mechanical property to worsen.Therefore need utilize coupling agent that quartzy waste residue is coated processing, change the surface property of quartzy waste particle.
So just obtained the good quartzy waste residue of activation, can directly use as plastic filler.The plastic filler that activation is good can directly mix back straight forming use with the plastics powder, also can be prepared into the high density master batch earlier, then master batch and plastic grain material is mixed the aftershaping use.
Quartzy waste residue weighting material can be applied to comprise thermoplastic resin in the various plastics, in PE, PP, ABS, PVC, HIPS etc., also can be applied in the thermosetting resin.Both can be fresh resin, also can be to reclaim in the plastics.
Specify embodiments of the invention below,
Embodiment 1
Get the quartzy waste residue of 50Kg, by vibratory screening apparatus (sieve diameter 0.5mm) waste residue is carried out primary dcreening operation and remove foreign material and macrobead.It is levigate in the ball mill the more quartzy waste residue after the screening to be packed into, and ball mill outlet sieve diameter is 400 orders (about 33 microns).Again the quartzy waste residue after levigate is dewatered by link-suspended basket centrifuge, and in baking oven, dry to water-content and be lower than 0.03%.Again quartzy waste residue is carried out the surface and coat processing: (1) is heated to 110 ℃ to quantitative quartzy waste residue in the kneader machine; (2) the aluminic acid ester of interpolation 2% weight (in quantitative quartzy waste residue weight), combination treatment 20 minutes; (3) add the organosilicon of 1% weight (in quantitative quartzy waste residue weight) again, combination treatment 20 minutes, the quartzy waste particle that obtains activating.Quartzy waste residue be filled into polypropylene (in), loading level is 10% (in polypropylene weight): stir at height and mix the quartzy waste residue of load weighted activation and polypropylene in the machine, in twin screw extruder, melt extrude then, water-cooled tie rod and pelletizing, obtain being filled with the PP matrix material of quartzy waste residue, be injection molded into standard model in injection moulding machine, test its mechanical property, it the results are shown in Table 2.
Embodiment 2
Quartzy waste residue treating processes is identical with embodiment 1, except ball mill outlet sieve diameter is 300 orders.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Embodiment 3
Quartzy waste residue treating processes is identical with embodiment 1, except ball mill outlet sieve diameter is 600 orders.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Embodiment 4
Quartzy waste residue treating processes is identical with embodiment 1, except water-content in the process of dehydrating is controlled 0.05%.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Embodiment 5
Quartzy waste residue treating processes is identical with embodiment 1, except the addition of surface treatment process aluminic acid ester is 1.0%.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
100 ℃～120 ℃ of waste residue temperature; In waste residue, add the aluminic acid ester of 0.5%～2% weight, combination treatment 20～30 minutes; In waste residue, add the organosilicon of 0.5～1% weight, combination treatment 20～30 minutes; The temperature of oven dry is 40 ℃～60 ℃ when dry.In experiment, change these processing parameters, little to result's influence, therefore do not list concrete parameter value.
Comparing embodiment 1
Quartzy waste residue treating processes is identical with embodiment 1, except not adopting the levigate quartzy waste residue of ball mill.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Comparing embodiment 2
Quartzy waste residue treating processes is identical with embodiment 1, except water-content in the process of dehydrating is controlled 1.0%.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Comparing embodiment 3
Quartzy waste residue treating processes is identical with embodiment 1, coats processing except quartzy waste residue not being carried out the surface.Quartzy waste residue is filled in the polypropylene, tests its mechanical property, the results are shown in Table 2.
Comparing embodiment 4
Identical with embodiment 1, except quartzy waste residue is changed into calcium carbonate.And test is filled into the material mechanical performance behind the polypropylene, the results are shown in Table 2.
Table 2: the quartzy waste residue filling polypropylene composite material of each embodiment gained mechanical property
From the data of table 2 as can be seen, through the quartzy waste residue of method preparation of the present invention, bending can substitute inorganic mineral filler (as calcium carbonate) and be filled in the plastics, and its performance is very approaching.
Claims (9)
1. one kind is utilized quartzy industry waste residue to prepare the method for plastic filler, it is characterized in that having following technological process:
(1) utilizes screening plant that waste residue is carried out primary dcreening operation and remove foreign material and macrobead;
(2) by levigate equipment waste residue is carried out levigate and dusting cover;
(3) waste particle is dehydrated;
(4) utilize tensio-active agent that waste particle is carried out the surface and coat to handle, what obtain activating directly is filled in mineral filler in the plastics;
Waste particle is carried out surface coating processing has following steps:
(1) stirs in machine or the kneader at height, quantitative quartzy waste residue is heated to 100 ℃～120 ℃;
(2) in waste residue, add the coupling agent of 0.5%～2% weight, combination treatment 20～30 minutes;
(3) in waste residue, add the organic silicon surfactant of 0.5～1% weight, combination treatment 20～30 minutes.
2. the quartzy industry waste residue of utilization according to claim 1 prepares the method for plastic filler, it is characterized in that: described coupling agent is stearic acid, aluminic acid ester or titanic acid ester, and described organic silicon surfactant is epoxy radicals silicone hydride, aminosilane or vinyl silanes.
3. the quartzy industry waste residue of utilization according to claim 2 prepares the method for plastic filler, it is characterized in that: the specification of selecting sieve during the waste residue primary dcreening operation grinds the particle median size and is not less than 300 orders for being not more than 2mm when waste residue is levigate.
4. the quartzy industry waste residue of utilization according to claim 3 prepares the method for plastic filler, it is characterized in that: the screening plant that primary dcreening operation and dusting cover use comprises stationary screen, vibratory screening apparatus or dusting cover.
5. the quartzy industry waste residue of utilization according to claim 4 prepares the method for plastic filler, it is characterized in that: described levigate equipment is selected ball mill, rod mill, autogenous mill, pebble mill or superfine grinding equipment.
6. prepare the method for plastic filler according to the quartzy industry waste residue of each described utilization of claim 1 to 5, it is characterized in that: the temperature of oven dry is 40 ℃～60 ℃ when dry.
7. the quartzy industry waste residue of utilization according to claim 6 prepares the method for plastic filler, it is characterized in that: water content＜0.05% that dehydrates the quartzy waste residue in back.
8. the quartzy industry waste residue of utilization according to claim 7 prepares the method for plastic filler, it is characterized in that: link-suspended basket centrifuge or horizontal helical type whizzer are selected in dehydration, and dryer or pneumatic conveying dryer are selected in oven dry.
9. the quartzy industry waste residue of utilization according to claim 1 prepares the method for plastic filler, it is characterized in that: the quartzy waste residue Inorganic Fillers Filled of the activation that claim 1 method is made is in polypropylene, loading level is 10% of polypropylene weight, in homogenizer, mix the quartzy waste residue of load weighted activation and polypropylene, in twin screw extruder, melt extrude then, water-cooled tie rod and pelletizing obtain being filled with the PP matrix material of quartzy waste residue.
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| CN101020792B (en) * | 2006-11-24 | 2012-01-11 | 中国石油化工股份有限公司中原油田分公司采油工程技术研究院 | Process of preparing rubber filler with oil-bearing sludge |
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