The preparation method of rubber filling, rubber filling and application thereof
Technical field
The invention belongs to the technical scopes that solid waste resource recovery utilizes, in particular to a kind of to utilize coal gasification fine slag system
The method of standby rubber filling, rubber filling obtained and application thereof, and the product of rubber and plastic being prepared using above-mentioned filler.
Background technique
Coal Gasification Technology is one of the core content of clean coal technology, and coal is carried out incomplete oxidation to obtain for downstream
Utilize can coal-fired gasification gas (such as raw gas), in recent years quickly become coal resources and using energy source important directions.Closely
Over 20 years, China mostly has built a collection of coal chemical industry enterprises in Yulin, Ordos, inner Mongolia, Shanxi Changzhi etc.,
It goes into operation successively, yield increases year by year, and the clean comprehensive utilization of coal resources takes on a certain scale in China.
In Coal Gasification Technology system, by while carbonaceous part is largely converted into gas in coal, association in raw coal
Inorganic mineral components, the catalyst of addition and gasification are not thorough remaining carbonaceous and can be arranged in the form of residue (coal gas slugging)
Out.Because the difference of mode is discharged, coal gas slugging is divided into thick slag and fine slag again, wherein the thick slag refers to via coal gasifier
The residue of furnace bottom discharge, and fine slag refers to and is carried secretly by coal gasification gas and in the purification process after coal gasification gas leaves coal gasifier
Separate the residue of discharge.The yield of coal gasification residue increases quickly with the development of Chemical Industry, land occupation when stacking,
Environment is polluted, new solid waste urgently to be resolved is had become.
In recent years, started the concern for causing some scholars around the utilization of coal chemical industry slag.201510148929.3 disclosure of CN
A kind of light ceramic and its methods and applications processed using the gentle slugging preparation of flyash, describes and utilizes flyash and gasification
Slag prepares light ceramic and its preparation method;CN 201510420421.4 disclose it is a kind of for produce the composition of ceramic for filtration with
And ceramic for filtration and its preparation method and application, describe the method for preparing ceramic for filtration using gasification slag for main component;CN
201310207509.9 disclose the method that activation coal gasification lime-ash realizes the separation of ferro-aluminum calcium, describe coal gas slugging is dry
Afterwards, chilling obtains activated material after being calcined at 700 to 1100 DEG C 75 minutes, then by activated material and hydrochloric acid solution or sulfuric acid solution
Reaction realizes aluminium, iron, Calcium compounds separation, and can use the calorific value of carbon residue in coal gasification lime-ash;CN
201210511610.9 disclose a kind of processing method of coal chemical industry gasification slag, describe the gentle slugging of coal slime after evenly mixing
Clay wash is added, using high-pressure pump pipe conveying technology, mixture is transported in the fluidized-bed combustion boiler furnace outside hundreds of meters, is led to
Cross the utilization of burning again that fluidized-bed combustion boiler combustion technology realizes gasification slag;Shenhua Ningxia Coal Industry Group Co., Ltd. Yang Shuai and
Shi Lijun publishes an article in August, 2013 " coal chemical industry " in, describes Shenhua Ningxia Coal Industry Group Co., Ltd .'s coal chemical industry
Various oxide component contents and loss on ignition in 3 kinds of coal gasification fine slags of output, in conjunction with total utilization of PCA national standard and
Professional standard has carried out feasibility analysis for cement, concrete, building materials and road foundation blend composition etc. to coal gasification fine slag,
It proposes coal gasification fine slag and mixes the suggestion for burning that utilization and sorting utilize;Liu Ziliang etc. is total using having carried out both at home and abroad to gasification slag
Knot is included in sewage treatment, builds the road, is non-burning brick, applying in cement and concrete etc..Data from recent years shows, Ren Menyi
It is recognized the harm of coal gas slugging, starts its composed structure of system research from different perspectives and characteristic, and start to pay attention at its
It sets and Utilizing question.
It is comprehensive about the research report of coal gasification slag it is found that existing utilize about coal gasification body refuse, mainly for
The wherein other components such as sa inorganic component other than the higher charcoal of content, only a few studies are reported coal gas slugging weight
New mixing is coal-fired to be used as fuel treatment, is seldom related to the development and utilization of wherein rich charcoal component.In fact, gasification slag in sa
The charcoal coexisted can also have an impact the performance of sial component.
Since the 1990s, people just recognize that inorganic particle improves rubber and plastic system for that can become among rubber and plastic
Moral character can and reduce the effective way of cost, in addition to the carbon black and white carbon black powder dedicated for filler, such as aluminium oxide, carbonic acid
The oxides such as calcium, talcum, kaolinite, montmorillonite powder and silicate powder, which are also studied, to be utilized.Inorganic filler is dosed in rubber and plastic
Raw rubber or resin usage amount can be reduced, anti-flammability is improved, increases hardness and mechanical strength and reduce cost, obtained universal
Using.It is good to obtain filler compatibility but since the surface polarity of inorganic powder particle influences its dispersibility in the polymer
Effect, generally require to carry out surface organics coating modification, however, this can also correspondingly increase cost simultaneously.In recent years, with people
To solid waste comprehensive utilization attention, it is also more and more to its processing modified research on utilization as rubber filling, close
In mineral surface modification and its in rubber and plastic using having considerable report, as the Zhang Yun of University Of Chongqing cherishes doctor (2004)
It conducts a research specifically for fly ash micro-sphere surface organic modification as rubber filling;Liu Shan (2012) changes fly ash micro-sphere
Property PVC composite material has carried out experimental study etc..About carbon to inorganic powder surface polarity improvement result, in patent
200910218038.5, in 201110355054.6 and 201210288939.3, respectively in diatomite, oil shale waste and flyash
Carbon has been paid close attention in acid dissolution slag system and there is effect to powder just face performance, but related method does not account for its particle shape
The influence of convection current change craftsmanship.
So far, it yet there are no for coal gasification fine slag medium high carbon content microballon without modified directly as rubber or modeling
The relevant report of stream change supporting material.
Summary of the invention
The one side of the purpose of the present invention is to provide a kind of method using the preparation gum filler of coal gasification fine slag, is made
Gum filler and application thereof, filler prepared in accordance with the present invention can be without organically-modified and direct compared with conventional filler
Preparation for rubber product or plastic products, it is possible to reduce or without using traditional compatilizer.
The purpose of the present invention further aspect is that providing the rubber product being prepared using above-mentioned filler or plastics system
Product.Filler of the invention can play rheological agent effect well, improve its processing performance, in addition it can in products obtained therefrom
Play the role of reinforcing agent, improve the intensity of product, hardness, ageing resistance and improve its high-temperature stability, realizes coal gasification fine slag
High value added product development and utilization.
The method provided by the invention for preparing rubber filling using coal gasification fine slag, adopts the following technical scheme that
A method of rubber filling is prepared using coal gasification fine slag, which comprises
A, appropriate coal gasification fine slag is taken, water is added to prepare the coal gasification fine slag slurry for being contained in 10-30wt% admittedly;
B, the slurry of step a configuration is sufficiently stirred, later by gravity cyclonic separation, collects heavy separation product
The compound slurry of Silicon-rich is obtained, and the Silicon-rich composite mortar is separated by solid-liquid separation and is dried, wherein in the solid-liquid
It further include screening process before separation or after being dried, to separate big in the Silicon-rich composite mortar or desciccate
Grain makes the granularity of gained powder be not more than 200 mesh (i.e. granularity is less than or equal to partial size corresponding to 200 mesh Taylor standard sieves), with
As rubber filling.
In the present invention, the coal gasification fine slag is to be carried secretly by coal gasification gas and after coal gasification gas leaves coal gasifier
The residue of separation discharge in purification process (such as through cyclone dust removal, bag-type dust and/or washing), coal gasification course is this field
It is known, it will be appreciated by those skilled in the art that the inorganic mineral composition of pit ash is primarily formed as contained in feed coal, with
And be not gasified totally and remaining charcoal in gasification, inevitably carry solid phase group in coal gasification gas caused by coal gasification secretly
Point, wherein the lesser solid phase components of granularity leave gasification furnace and form coal gasification fine slag, and all components are amorphous state, and partial size is little
In 120 μm.
In step a of the invention, when being mixed and made into slurry using coal gasification fine slag and water, those skilled in the art's reason
Solution, the gasification fine slag can be dry slag and be also possible to wet slag, make the solid content of slurry in 10wt%~30wt%, preferably
15wt%~25wt%, such as 20wt%.In a preferred embodiment, after the coal gasification fine slag slurry at least 1h of configuration
Subsequent stir process, such as 1.5h, 2h or 5h are carried out again, are come into full contact with, are soaked with water so that coal gasification is refined, thus favorably
In subsequent cyclonic separation.
In step b in the present invention, slurry is stirred, then cyclonic separation obtains the compound slurry of Silicon-rich;Wherein,
The stirring is processing means commonly used in the art, such as can be stirred using mixing plant, it is preferred to use reinforcement
Blender is stirred.In a preferred embodiment, in the preparation process of Silicon-rich composite mortar, stirring condition is that stirring turns
Speed is not less than 1500r/min, and mixing time is no less than 30min;Preferably, speed of agitator is 1800~3000r/min, when stirring
Between be 60min~180min;In order to subsequent cyclonic separation.The study found that by above-mentioned strong stirring, especially for leaching
Bubble treated pulp separation better effect.Cyclonic separation is processing means commonly used in the art, such as can be using eddy flow point
Cyclonic separation is carried out from device, in cyclonic separation, due to gravity, the lesser charcoal component of density is mainly from eddy flow point in fine slag
It is overflowed from the top of device, and the biggish sa component of density (heavy separation product) is then mainly discharged from bottom, divides to realize
From.
In step b of the invention, resulting Silicon-rich composite mortar is subsequent will also to carry out being separated by solid-liquid separation and to separating obtained
Solid phase is dried, and above-mentioned treatment process is known in the art, such as slurry is carried out plate compression or centrifuge separation,
Then obtained solid product is obtained into desciccate in 60-110 DEG C of dry 4-8h;Wherein, before the separation of solid and liquid or dry
Further include screening process after dry processing, such as the Silicon-rich composite mortar is sieved using vibrating screen before separation of solid and liquid
Divide processing, to separate the bulky grain in the Silicon-rich composite mortar, or after drying treatment using vibrating screen directly to dry
Dry product carries out screening process, to separate the bulky grain in desciccate.In the present invention, by above-mentioned screening process, make most
The granularity of gained powder is not more than 200 mesh, preferably no greater than 300 mesh, such as 250 or 350 mesh eventually, for use as rubber product or modeling
Filler in material products.
In the present invention, although handling by eddy flow, charcoal component in part can be still contained in the Silicon-rich composite mortar.By
In coal gasification reaction belong to coal incomplete oxidation reaction, remain charcoal in gasification with reducing atmosphere (coal gasification gas,
Also referred to as synthesis gas or raw gas) continuous contact at high operating temperatures, so that form, activity of charcoal etc. be not in coal gasification fine slag
The residual carbon being same as in conventional coal-fired ashes, research find that after processing part charcoal is coated on gasification slag bead surface, favorably
In reducing the glass microballoon surface polarity in powder, improve the compatibility with rubber and plastic macromolecule material, give full play to rheology and
Supplement effect.
In one embodiment of the present invention, in filler powder carbon content be not less than 5wt%, such as 8-20wt%,
10wt%, 15wt% or 18wt%.For carbon content in the solid phase of powder or the compound slurry of Silicon-rich, those skilled in the art's reason
Solution can be controlled by modes such as the charging angle of adjusting cyclone or feed rates, to increase or decrease carbon therein
Component.
Filler provided by the invention is the filler being prepared by the above method.
The present invention also provides above-mentioned fillers to prepare the application in rubber product or plastic products.
The present invention also provides a kind of rubber products, are prepared by the raw material for including raw rubber, filler and additive, described
Filler is 0.65~1:1, such as 0.8:1 with the dosage mass ratio of the raw rubber, and the filler include the first filler and
Second filler, first filler are carbon black, and second filler is rubber filling of the invention;Preferably, it described second fills out
The mass ratio of material and the first filler is not more than 1:1, preferably 1:2~1:9, such as 1:3 or 1:4;Wherein the additive can be with
It is rubber additive commonly used in the art, such as vulcanizing agent and antioxidant etc., is known in the art;The rubber product preparation
Mixing and moulding process be it is known in the art, which is not described herein again.
The present invention also provides a kind of plastic products, are prepared by the raw material for including resin, filler and additive, described
Filler is filler as claimed in claim 7;Preferably, in terms of the total amount of raw material, the dosage of the filler is 5~50wt%, than
Such as 10wt%, 20wt%, 30wt% or 40wt%;Wherein the additive can be plastic products addition commonly used in the art
Agent, such as antioxidant etc. are known in the art;The mixing of the plastic products preparation and moulding process are ripe for this field
Know, which is not described herein again.
Compared with prior art, the invention has the following advantages that
1, in the present invention, coal gasification fine slag used be coal after high-temperature gasification by the nothing of wherein main siliceous, aluminium etc.
Machine minerals conversion at amorphous silicon aluminum substance (while also containing calcium, iron etc.) and residual charcoal mixture, with conventional fire coal
Ashes are different, since coal gasification reaction belongs to the incomplete oxidation reaction of coal, remain charcoal in gasification with reproducibility gas
Continuous contact, the process are similar to the activation of coal to atmosphere (coal gasification gas, also referred to as synthesis gas or raw gas) at high operating temperatures
Processing, so that form, activity of charcoal etc. are different from the remaining char in conventional coal-fired ashes in coal gasification fine slag.And this hair
Microballon significant difference in bright coal gasification fine slag in microballon and flyash is that its component all exists with amorphous state state, and portion
Unformed charcoal is divided to be distributed in glass microballoon surface, so that the polar character of sial glass microballoon is alleviated, with rubber and resin
Compatibility it is good, it is not necessary that rubber and plastic supporting material can be become in organically-modified situation, prepare plastic products and rubber
It can lack in product with even without compatilizer or modifying agent;
2, the present invention is acted synergistically in fine slag by many kinds of measures, realizes the separation of bulky grain charcoal and sial metallic substance,
Good separation;And coal gasification solid impurity particle is fine, and the fine slag after separation helps to reduce polarity, improves phase without being crushed
Capacitive;
3, using method of the invention, the carbon containing glass microballoon in coal gasification fine slag can be made without organically-modified item
The preparation of product of rubber and plastic is directly used under part, the spherical state of sa microballon in fine slag is distributed in linear high molecular material
Moving resistance is small, can play rheological agent effect, improve its processing performance, reduces abrasion of the material to equipment container material;It is spherical
The good dispersion of particle, plays the role of reinforcing agent in products obtained therefrom, can improve the intensity, hardness, ageing resistance of product simultaneously
Its high-temperature stability is improved, realizes the high value added product exploitation of coal gasification fine slag.
Specific embodiment
Below with reference to embodiment, the present invention is described in detail, but the present invention is not limited to this.
In following embodiment/comparative example, coal gasification fine slag used is from the industry of Ordos, inner Mongolia Jungar Banner main road
Garden, property/combination are as follows: carbon content is about 38wt%, and silica is about 25wt%, and all components are amorphous state, grain
Diameter is less than 120 μm.
Embodiment 1
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1800r/min, mixing time is
30min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 14wt% in the powder, and grain diameter is not more than 300 mesh;
Natural rubber raw rubber 15g is weighed, takes filler powder 2.5g, semi-reinforcing hydrocarbon black 7.5g, additive: zinc oxide 0.61g,
Stearic acid 0.2g, sulphur 0.2g and vulcanization accelerator TMTD 0.2g;By above-mentioned material under the conditions of 80 DEG C of kneading machine, revolving speed
It for 32r/min, is kneaded after 25min, in 130 DEG C of vulcanization 25min, obtained sample placement tests its tensile strength afterwards for 24 hours and is
27.0MPa(GB/T528-2009)。
Comparative example 1
The difference from embodiment 1 is that the filler powder in embodiment 1 is replaced with etc. to the semi-reinforcing hydrocarbon black of quality,
His process is identical with condition, and obtained sample tensile strength is 23.6MPa.
Embodiment 2
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1600r/min, mixing time is
40min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 13wt% in the powder, and grain diameter is not more than 300 mesh;
Ethylene propylene diene rubber raw material 13.3g is weighed, takes filler powder 3.76g, semi-reinforcing hydrocarbon black 8.79g, additive: oxidation
Zinc 0.67g, stearic acid 0.2g, atoleine 6g, sulphur 0.2g, DCP 0.8g and vulcanization accelerator TMTD 0.2g;It will be above-mentioned
Material is under the conditions of 85 DEG C of kneading machine, revolving speed 30r/min, is kneaded after 25min, and sample suppresses 5 times in open mill, then
Hot-forming under 10MPa at 130 DEG C, it is 9.12MPa that its tensile strength is tested in obtained sample placement afterwards for 24 hours;
Comparative example 2
The difference from example 2 is that the filler powder in embodiment 2 is replaced with etc. to the semi-reinforcing hydrocarbon black of quality,
His process is identical with condition, and obtained sample tensile strength is 8.54MPa.
Embodiment 3
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1500r/min, mixing time is
40min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 16wt% in the powder, and grain diameter is not more than 300 mesh;
30g PE particulate material is weighed, filler powder is added, so that its content is reached the 10wt% of total amount, in kneading machine
170 DEG C of mixing 30min, revolving speed 50r/min, obtained sample is placed at room temperature to be tested its tensile strength afterwards for 24 hours and is
19.02MPa。
Comparative example 3
Identical as the condition of embodiment 3, difference is, doses commercially available 6000 mesh calcium carbonate powder, makes the total inventory of its Zhan
10wt%, be added antioxidant (propionic acid n-octadecyl alcohol ester) 0.3g, compatilizer (maleic anhydride grafting low density polyethylene (LDPE))
1.5g, other processes are identical with condition, and obtained sample tensile strength is 17.35MPa.
Embodiment 4
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1500r/min, mixing time is
40min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 16wt% in the powder, and grain diameter is not more than 300 mesh;
30g LDPE particulate material is weighed, filler powder is added, so that its content is reached the 40wt% of total amount, in kneading machine
170 DEG C of mixing 30min, revolving speed 50r/min, obtained sample is placed at room temperature to be tested its tensile strength afterwards for 24 hours and is
13.19MPa。
Comparative example 4
Difference with embodiment 4 is, doses commercially available 6000 mesh calcite in powder filler 40wt%, other processes and condition phase
Together, the sample tensile strength obtained is 9.89MPa.
Embodiment 5
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1500r/min, mixing time is
40min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 16wt% in the powder, and grain diameter is not more than 300 mesh;
ABS resin 30g, zinc stearate 1.5g, stearic acid 0.18g, EBS1.2g are uniformly mixed, and kneading machine heating is added, melts
After melting, filler 3.5g is added;In 240 DEG C of mixings 15min, revolving speed 30r/min;By mixed material, through hot press molding after,
Test tensile strength is 31.727MPa.
Comparative example 5
30g ABS particulate material is weighed, the commercially available calcium carbonate powder 3.5g of 6000 mesh is dosed, its amount of filling is made to reach total amount
10wt%, other additives are identical with condition, its tensile strength of obtained sample test is 26.842MPa.
Embodiment 6
100g coal gasification fine slag (wherein aqueous 55wt%) is weighed, being diluted with water to solid content is 20wt%, is adopted under room temperature
It is stirred with high velocity dispersators (Foshan Yi Fu Machinery Co., Ltd.), speed of agitator 1500r/min, mixing time is
40min;Slurry is imported in cyclone separator and is separated, obtained lower part slurry is Silicon-rich composite mortar, is set using vibrating screen
It is standby that screening process is carried out to Silicon-rich composite mortar, then slurry is separated by solid-liquid separation, filter cake is moved into dry in 110 DEG C of baking ovens
6h obtains filler powder, and carbon content is 16wt% in the powder, and grain diameter is not more than 300 mesh;
ABS resin 30g, zinc stearate 1.5g, stearic acid 0.18g, EBS1.2g are uniformly mixed, and kneading machine heating is added, melts
After melting, filler 15g is added;In 240 DEG C of mixings 15min, revolving speed 30r/min;By mixed material, through hot press molding after,
Test tensile strength is 22.2MPa.
Comparative example 6
30g ABS particulate material is weighed, the commercially available calcium carbonate powder 15g of 6000 mesh is dosed, its amount of filling is made to reach total amount
31wt%, other additives are identical with condition, its tensile strength of obtained sample test is 20.447MPa.