CN101560071B - Porous material of phosphate-based geopolymer and preparation method thereof - Google Patents

Porous material of phosphate-based geopolymer and preparation method thereof Download PDF

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Publication number
CN101560071B
CN101560071B CN2009101140997A CN200910114099A CN101560071B CN 101560071 B CN101560071 B CN 101560071B CN 2009101140997 A CN2009101140997 A CN 2009101140997A CN 200910114099 A CN200910114099 A CN 200910114099A CN 101560071 B CN101560071 B CN 101560071B
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China
Prior art keywords
porous material
phosphate
preparation
powder
based geopolymer
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CN2009101140997A
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CN101560071A (en
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崔学民
刘乐平
邱树恒
贺艳
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Guangxi University
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Guangxi University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding

Abstract

The present invention discloses a porous material of phosphate-based geopolymer and a preparation method thereof. The preparation method comprises the following steps of: adopting metakaolin, alumina (or aluminium hydroxide), phosphoric acid and water as raw materials, adopting aluminium powder as a foaming agent and under a lower temperature ( 50-90 DEG C) preparing the porous material which adopts geopolymer material as a skeleton and has good properties. By testing the properties of the porous material, the result shows that the porous material has compression strength of 2.0 to 15.0MPa, apparent porosity of 30 percent to 70 percent, volume density of 0.40cm<3> to 1.0g/cm<3> and high-temperature resistance of more than 1300 DEG C; and the porous material with different properties and porous structures can be obtained by controlling molar ratio of Al/Si and P/Al and reaction conditions. The porous material of phosphate-based geopolymer and a preparation method thereof provided by the present invention has simple technique and low cost and is expected to be applied in the fields of insulating materials, waste gas absorbing materials, sewage filtering materials, energy absorbing materials, insulating and encapsulating materials, military, aerospace and the like.

Description

A kind of porous material of phosphate-based geopolymer and preparation method thereof
Technical field
The present invention relates to geology polymer material and foam porous material field, particularly relate to a kind of phosphoric acid or phosphate base geopolymer porous material and preparation method thereof.
Background technology
The geology polymeric material is divided into base geology polymeric material and phosphate geology polymeric material.The research of base geology polymeric material is morning relatively, and the application of this class material can be traced back to ancient times, promptly with kaolin, dolomite or limestone and salt lake composition Na 2CO 3, plant ash composition K 2CO 3And the mixture of silica, add water and mix and stir the back and produce highly basic NaOH and KOH, react with other component, generate the mineral association binding agent and make rostone.
Human meso-position radius D such as the Zhou Xintao of South China Science ﹠ Engineering University, Su Dagen 50For metakaolin and the phosphate solution prepared in reaction of 1.8um goes out phosphoric acid (phosphoric acid salt) the base geological polymer material that 7d ultimate compression strength reaches 92.5MPa, have good middle temperature stability, refractoriness is up to 1550 ℃.People such as the new great waves of this periphery are aluminium source and silicon source with the metakaolin, and phosphoric acid is phosphorus source hydrothermal method synthesized silicon-aluminum phosphate molecular sieve, and specific surface area is 205.9m 2/ g, mean pore size is 9.72nm, belongs to mesoporous material.The Cao Deguang of Guangxi University studies synthetic, the structure of phosphate-based geopolymer material, prepares the geology polymer material that 28d ultimate compression strength is 59.5MPa.Mineral bonding theory has been proposed, for the research of phosphate-based geopolymer material provides the important theory foundation.And applied for the patent of the method for phosphoric acid and alumina-silica material preparation mineral polymer and matrix material thereof.
The patent situation relevant with foam porous material preparation technology is as follows:
The patent No. has been 200310114507.1 Chinese disclosure of the Invention a kind of polymorph A l 2O 3Fiber preform legal system is equipped with the method for porous ceramics.This method comprises feedstock production, blank forming and step such as burns till: (1) with alumina powder jointed, clay, high temperature adhesives, mud additive by mass percentage 70-80,10-15,4-19,1-2 mix the back ball milling with water and be prepared into mud, again mud, dispergator are mixed with into filling mud with pore-forming material; (2) with polymorph A l 2O 3The ceramic fiber weak point is cut, dispersed with stirring in water, and the adding binding agent is made fibre stuff; (3) fibre stuff is injected mould and make preform and dry; (4) drying is good preform is put into plaster mould, and the filling mud that reinjects also vacuumizes together; (5) preform drying, the high temperature that will fill mud burns till.The product strength height that this invention makes, thermal shock resistance is strong, and production technique is simple, yield rate height, suitable especially high temperature coal (cigarette) the air filter suitability for industrialized production of ceramic filter element.Its weak point is that the acquisition of this porous ceramic bodies all will be through the roasting of 1000 ℃ even higher temperature, complex process, preparation cost height.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of cost is low, technology is simple, the porous material of phosphate-based geopolymer of nontoxic pollution-free, starting material wide material sources and preparation method thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
1. porous material of phosphate-based geopolymer, in parts by weight, the porous material composition of raw materials is made up of by weight 1: 1 solid phase and liquid phase;
Solid phase is formed by 100 parts of weight parts: metakaolin 65-95 part, aluminum oxide or aluminium hydroxide 0.5-35 part and Al powder 0.08-0.2 part;
The liquid phase component is formed by 100 parts of weight parts: phosphoric acid 52-85 part, water 15-48 part.
The above-mentioned aluminum oxide or the consumption of aluminium hydroxide are 1.0-2.0 for the mol ratio of Al and Si in the adjusting solid phase; And the mol ratio of P and Al is 1.4-3.4 in the control composition of raw materials.
Above-mentioned metakaolin is that the kaolin after above kaolin raw ore powder of 200 orders or the process washing is calcined gained powder more than 2 hours in 600-900 ℃ of air.
Above-mentioned aluminum oxide or aluminium hydroxide are that fineness is greater than 200 purpose technical grade powders; Above-mentioned aluminium powder is that granularity is greater than 400 purpose technical grade aluminium powders; It is 85% PHOSPHORIC ACID TECH.GRADE that above-mentioned phosphoric acid adopts mass concentration.
Above-mentioned porous material of phosphate-based geopolymer, the ultimate compression strength of this porous material between the 2.0-15.0Mpa, apparent porosity between 30%-70%, volume density is at 0.40g/cm 3-1.0g/cm 3Between, can anti-high temperature more than 1300 ℃.
2. the preparation method of a porous material of phosphate-based geopolymer comprises the steps:
(1) solid phase preparation of raw material:
Metakaolin, aluminum oxide or aluminium hydroxide and aluminium powder in the solid phase prescription are mixed, and it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
(2) liquid phase feed preparation:
Phosphoric acid and water in the liquid phase prescription are mixed in proportion back stand-by;
(3) liquid phase that solid phase powder and phosphoric acid and water are formed is that 1: 1 mixed is even by mass ratio, again water regulate slurry viscosity to 0.1-5Pa.S, through stir, stand-by after the homogenize;
(3) slurry with step (2) injects acidproof mould, at room temperature place 0-24h after, maintenance 2-8h in 50 ℃ of-90 ℃ of thermostat containers, obtaining void content is hole, polymers Quito, the phosphoric acid ground material of 30-70%;
(4) porous material after the demoulding obtains material requested through cutting processing.
Compared with prior art, the present invention has the following advantages:
1. it is simple to the invention provides a kind of technology, nontoxic pollution-free, cost is low, and starting material spread all over all over the world, and has a preparation temperature low (50-90 ℃ of scope), the porous material void content of preparation is controlled, and the perforate void content can reach 50vol% even higher, and ultimate compression strength is greater than 2MPa, indeformable under 1300 ℃ of high temperature, high air penetrability is arranged, can obtain the advantages such as porous material of different performance and pore structure by different proportionings of control and reaction conditions., this material directly prepares the goods of complicated shape because by slurry foaming preparation, can making it foam in different moulds, and simple.
2. porous material of the present invention is expected at lagging material, waste gas sorbing material, the sewage water filtration material, and fields such as energy absorbing material, insulation-encapsulated material, military and space are applied.
3. exempted high-sintering process after the technology of the present invention's proposition belongs to geopolymer system foam process and adds pore-forming material technology compounding technology, particularly low-temp foaming, and the restriction of not restricted appearance shape, by retrieval, there is not similar techniques to declare patent.
Embodiment
The invention will be further described below in conjunction with embodiment, but need to prove, embodiment does not constitute the restriction to the claimed scope of the present invention.
Embodiment 1:
The preparation method is as follows:
1. solid phase preparation of raw material:
1) preparation of metakaolin: with fineness is that kaolin powder that the North Sea, Guangxi Yanzhou Mining Group more than 200 orders produces, through washing after preferred obtained metakaolin, Al in the metakaolin in 2 hours through calcining in 900 ℃ of air 2O 3: SiO 42.35%, 2: Fe 56.91%, 2O 3: 0.74%, use Al 2O 3Regulate its Al/Si (mol ratio)=1.0, P/Al (mol ratio)=1.4;
2) solid ingredient is as follows by 100 parts of weight proportionings: 95 parts of metakaolins, 4.9 parts in＞200 purpose aluminum oxide, 0.5 part of＞400 purpose aluminium powder;
3) solid ingredient is mixed, it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
2. liquid phase feed preparation:
By 100 parts of weight, proportioning is as follows: the technical grade weight concentration is 52 parts of 85% phosphoric acid, 48 parts in water; It is stand-by to mix in proportion the back;
3. solid phase and liquid phase are mixed with 1: 1 weight ratio, regulate viscosity, stir after the homogenize in 10 minutes stand-by to 0.1Pa.S;
4. 3. slurries that obtain are injected the acid resistance mould, place 50 ℃ of left and right sides thermostat containers, the constant temperature foaming got final product the demoulding after 8 hours.
5. test its mechanical property and pore structure after the gained porous material being cut into regular shape, its basic index is as follows: ultimate compression strength is 2Mpa, and void content is about 70%, and volume density is at 0.50g/cm 3About, can anti-high temperature more than 1300 ℃.
Embodiment 2:
The preparation method is as follows:
1. solid phase preparation of raw material:
1) preparation of metakaolin: identical with embodiment 1, just use Al 2O 3Regulate its Al/Si (mol ratio)=1.5, P/Al (mol ratio)=2.5;
2) solid ingredient is as follows by 100 parts of weight proportionings: 77 parts of metakaolins, 22.92 parts in＞200 purpose aluminum oxide, 0.08 part of＞400 purpose aluminium powder;
3) solid ingredient is mixed, it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
2. liquid phase feed preparation:
By 100 parts of weight, proportioning is as follows: the technical grade weight concentration is 76 parts of 85% phosphoric acid, 24 parts in water; It is stand-by to mix in proportion the back;
3. solid phase and liquid phase are mixed with 1: 1 weight ratio, regulate viscosity, stir after the homogenize in 10 minutes stand-by to 2.5Pa.S;
4. 3. slurries that obtain are injected the acid resistance mould, at room temperature react 12h, place 60 ℃ of left and right sides thermostat containers, the constant temperature foaming got final product the demoulding after 6 hours.
5. test its mechanical property and pore structure after the gained porous material being cut into regular shape, its basic index is as follows: ultimate compression strength is 10Mpa, and void content is about 60%, and volume density is at 0.65g/cm 3About, can anti-high temperature more than 1300 ℃.
Embodiment 3:
The preparation method is as follows:
2. solid phase preparation of raw material:
1) preparation of metakaolin: identical with embodiment 1, just use Al 2O 3Regulate its Al/Si (mol ratio)=2.0, P/Al (mol ratio)=3.4;
2) solid ingredient is as follows by 100 parts of weight proportionings: 65 parts of metakaolins, 34.92 parts in＞200 purpose aluminum oxide, 0.05 part of＞400 purpose aluminium powder;
3) solid ingredient is mixed, it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
2. liquid phase feed preparation:
By 100 parts of weight, proportioning is as follows: the technical grade weight concentration is 85 parts of 85% phosphoric acid, 15 parts in water; It is stand-by to mix in proportion the back;
3. solid phase and liquid phase are mixed with 1: 1 weight ratio, regulate viscosity, stir after the homogenize in 10 minutes stand-by to 5Pa.S;
4. 3. slurries that obtain are injected the acid resistance mould, at room temperature react 24h, place 90 ℃ of left and right sides thermostat containers, the constant temperature foaming got final product the demoulding after 4 hours.
5. test its mechanical property and pore structure after the gained porous material being cut into regular shape, its basic index is as follows: ultimate compression strength is 12Mpa, and void content is about 50%, and volume density is at 0.80g/cm 3About, can anti-high temperature more than 1300 ℃.
Embodiment 4:
The preparation method is as follows:
3. solid phase preparation of raw material:
1) preparation of metakaolin: identical with embodiment 1, just use Al 2O 3Regulate its Al/Si (mol ratio)=1.5, P/Al (mol ratio)=2.5;
2) solid ingredient is as follows by 100 parts of weight proportionings: 80 parts of metakaolins, 19.80 parts in＞200 purpose aluminum oxide, 0.2 part of＞400 purpose aluminium powder;
3) solid ingredient is mixed, it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
2. liquid phase feed preparation:
By 100 parts of weight, proportioning is as follows: the technical grade weight concentration is 80 parts of 85% phosphoric acid, 20 parts in water; It is stand-by to mix in proportion the back;
3. solid phase and liquid phase are mixed with 1: 1 weight ratio, regulate viscosity, stir after the homogenize in 10 minutes stand-by to 0.5Pa.S;
4. 3. slurries that obtain are injected the acid resistance mould, at room temperature react 12h, place 90 ℃ of left and right sides thermostat containers, the constant temperature foaming got final product the demoulding after 6 hours.
5. test its mechanical property and pore structure after the gained porous material being cut into regular shape, its basic index is as follows: ultimate compression strength is 2Mpa, and void content is about 80%, and volume density is at 0.40g/cm 3About, can anti-high temperature more than 1300 ℃.

Claims (6)

1. porous material of phosphate-based geopolymer, it is characterized in that: in parts by weight, described porous material composition of raw materials is made up of by mass ratio solid phase and liquid phase at 1: 1;
Solid phase is formed by 100 parts of weight parts: metakaolin 65-95 part, aluminum oxide or aluminium hydroxide 0.5-35 part and Al powder 0.08-0.2 part;
The liquid phase component is formed by 100 parts of weight parts: phosphoric acid 52-85 part, water 15-48 part.
2. porous material of phosphate-based geopolymer according to claim 1 is characterized in that: the consumption of described aluminum oxide or aluminium hydroxide is 1.0-2.0 for the mol ratio of Al and Si in the adjusting solid phase; And the mol ratio of P and Al is 1.4-3.4 in the control composition of raw materials.
3. porous material of phosphate-based geopolymer according to claim 1 is characterized in that: described metakaolin is that the kaolin after above kaolin raw ore powder of 200 orders or the process washing is calcined gained powder more than 2 hours in 600-900 ℃ of air.
4. porous material of phosphate-based geopolymer according to claim 1 is characterized in that: described aluminum oxide or aluminium hydroxide are that fineness is greater than 200 purpose technical grade powders; Described aluminium powder is that granularity is greater than 400 purpose technical grade aluminium powders; It is 85% PHOSPHORIC ACID TECH.GRADE that described phosphoric acid adopts mass concentration.
5. porous material of phosphate-based geopolymer according to claim 1 is characterized in that: the ultimate compression strength of this porous material between the 2.0-15.0MPa, apparent porosity between 30%-70%, volume density is at 0.40g/cm 3-1.0g/cm 3Between, can anti-high temperature more than 1300 ℃.
6. the preparation method of a porous material of phosphate-based geopolymer is characterized in that comprising the steps:
(1) solid phase preparation of raw material:
Metakaolin, aluminum oxide or aluminium hydroxide and aluminium powder in the solid phase prescription are mixed, and it is stand-by after 30 minutes to stir homogenizing in powder stirrer;
(2) liquid phase feed preparation:
Phosphoric acid and water in the liquid phase prescription are mixed in proportion back stand-by;
(3) liquid phase that solid phase powder and phosphoric acid and water are formed is that 1: 1 mixed is even by weight, again water regulate slurry viscosity to 0.1-5Pa ﹒ s, through stir, stand-by after the homogenize;
(4) slurry with step (3) injects acidproof mould, at room temperature place 0-24h after, maintenance 2-8h in 50 ℃ of-90 ℃ of thermostat containers, obtaining void content is the porous material of phosphate-based geopolymer of 30-70%;
(5) porous material after the demoulding obtains material requested through cutting processing.
CN2009101140997A 2009-05-26 2009-05-26 Porous material of phosphate-based geopolymer and preparation method thereof Expired - Fee Related CN101560071B (en)

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