CN115521099A - Composition for preparing geopolymer artificial fish reef, method for preparing geopolymer artificial fish reef, and geopolymer artificial fish reef - Google Patents
Composition for preparing geopolymer artificial fish reef, method for preparing geopolymer artificial fish reef, and geopolymer artificial fish reef Download PDFInfo
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- CN115521099A CN115521099A CN202211302767.0A CN202211302767A CN115521099A CN 115521099 A CN115521099 A CN 115521099A CN 202211302767 A CN202211302767 A CN 202211302767A CN 115521099 A CN115521099 A CN 115521099A
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- 241000251468 Actinopterygii Species 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000011575 calcium Substances 0.000 claims abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 19
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 4
- 239000002893 slag Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910052602 gypsum Inorganic materials 0.000 claims description 11
- 239000010440 gypsum Substances 0.000 claims description 11
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000004568 cement Substances 0.000 abstract description 8
- 239000013535 sea water Substances 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 7
- 239000011398 Portland cement Substances 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000004575 stone Substances 0.000 abstract description 2
- 230000035515 penetration Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000004567 concrete Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 238000004131 Bayer process Methods 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000011413 geopolymer cement Substances 0.000 description 1
- 229920003041 geopolymer cement Polymers 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010920 waste tyre Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K61/00—Culture of aquatic animals
- A01K61/70—Artificial fishing banks or reefs
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K61/00—Culture of aquatic animals
- A01K61/70—Artificial fishing banks or reefs
- A01K61/77—Artificial fishing banks or reefs of monolithic form, e.g. blocks
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00758—Uses not provided for elsewhere in C04B2111/00 for agri-, sylvi- or piscicultural or cattle-breeding applications
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/24—Sea water resistance
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Environmental Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Biodiversity & Conservation Biology (AREA)
- Animal Husbandry (AREA)
- Zoology (AREA)
- Marine Sciences & Fisheries (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Artificial Fish Reefs (AREA)
Abstract
The invention relates to the technical field of artificial fish reefs and discloses a composition for preparing geopolymer artificial fish reefs, a method for preparing the geopolymer artificial fish reefs and the geopolymer artificial fish reefs. The composition comprises the following components: aluminosilicate material, calcium ore, excitant and water; wherein the content weight ratio of the aluminosilicate material to the calcium ore is 1.5-9.0:1; the excitant is a mixture with the modulus of 1.0-2.0 obtained by adjusting sodium silicate with sodium hydroxide. The artificial fish reef prepared from the composition provided by the invention has better and better mechanical properties with the increase of time in seawater; and has more excellent chloride ion penetration resistance; meanwhile, the carbon emission is only 18-34% of that of the common portland cement artificial fish reef, and the raw materials are all derived from industrial solid wastes, so that the method is economic and environment-friendly, and can effectively solve the problem of resource shortage of traditional building materials such as cement and stone.
Description
Technical Field
The invention relates to the technical field of artificial fish reefs, in particular to a composition for preparing geopolymer artificial fish reefs, a method for preparing geopolymer artificial fish reefs and the geopolymer artificial fish reefs.
Background
The fish reef is a reef, is a habitat for fish to breed, grow, make a bait and shelter, can effectively improve the marine ecological environment, and is very important for maintaining the marine ecological balance. However, with the development of industrial civilization in the world, the influence of industrial production and social activities of human beings is increasing, and marine ecosystems are seriously damaged by marine pollutants such as petroleum, pesticides, domestic sewage, garbage, chemical waste liquid and the like generated by various production activities. In addition, high-intensity operations with killing property such as over-fishing and the like sharply reduce the habitat of the fishes, reduce the population quantity of the fishes, gradually decline fishery resources and make the maintenance of marine ecological balance seriously challenged.
The artificial fish reef is used as an artificial structure in the ocean, provides more and safer habitats for fishes, and has very important function on enriching and improving the ocean ecosystem.
At present, most of the artificial fish reefs are prepared by using cement concrete as a raw material, but the cement concrete consumes a large amount of building materials such as cement, gravel and the like, so that the burden of building material resources is increased, and the production cost is increased; moreover, the cement concrete is easy to cause environmental pollution due to the characteristics of high energy consumption and high carbon emission; on the other hand, cement concrete is easily carbonized, and deterioration of concrete is easily caused by salt erosion and biological corrosion in the sea, so that durability is insufficient and service life is reduced.
Other types of artificial reefs, such as steel artificial reefs, are transported to a wharf after parts are prepared in a factory, and then are assembled and put in place, so that the cost is high, and the artificial reefs are not easy to popularize; the artificial reef is like a bamboo or wooden reef, has poor wind wave resistance and is easy to corrode, so the artificial reef is rarely used; and the artificial fish reef made of the wastes is mainly formed by stacking waste tires, waste ship bodies and the like, and has the characteristic of low cost, but the wastes contain a plurality of harmful substances and easily cause environmental pollution.
The geopolymer is an inorganic low-carbon nonmetal cementing material which is obtained by taking aluminosilicate as a raw material and performing alkali excitation at normal temperature, and has the advantages of high hardening speed, high early strength, acid and alkali resistance, low permeability, corrosion resistance, good durability and the like, so that the geopolymer artificial fish reef not only has high seawater corrosion resistance and high permeability resistance, but also is economic in cost, low-carbon and environment-friendly, and has a wide prospect in ocean engineering application.
CN107663035A discloses an aluminum ash based geopolymer cementing material, which is characterized by comprising the following components: 100 parts of compound silica-alumina powder, 80-150 parts of water glass, 10-30 parts of sodium hydroxide and 10-50 parts of water, wherein the compound silica-alumina powder is prepared by mixing 100 parts of activated aluminum ash raw materials, 1-5 parts of phosphogypsum, 1-5 parts of rice hull ash, 5-10 parts of silica fume, 10-20 parts of metakaolin and 10-20 parts of slag, grinding and sieving. Although the geopolymer cement has high mechanical strength, the prior art has high content of the activator, resulting in high economic cost.
CN108892464A discloses an environment-friendly cementitious material, which is characterized in that the cementitious material comprises the following raw materials in parts by weight: 3 to 4 parts of converter steel slag, 2.5 to 3.0 parts of blast furnace slag, 0.5 to 1.0 part of ordinary portland cement, 0.1 to 0.2 part of polyaluminium chloride, 0.05 to 0.06 part of calcium chloride, 3 to 5 parts of calcined gypsum and 3 to 4kg of alkali activator. Although the environment-friendly cementing material has good compressive strength and setting time, the prior art needs to carry out the steps of crushing, magnetic separation, sieving, continuous ball milling and the like, and the preparation process is complex.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a geopolymer artificial fish reef with good erosion resistance, impermeability and durability.
In order to achieve the above objects, a first aspect of the present invention provides a composition for preparing a geopolymer artificial fish reef, the composition comprising the following components:
aluminosilicate material, calcium ore, excitant and water;
wherein the weight ratio of the content of the aluminosilicate material to the content of the calcium ore is 1.5-9.0:1;
the calcium ore is selected from at least one of carbide slag and gypsum;
the excitant is a mixture of sodium silicate adjusted by sodium hydroxide, the modulus of the mixture is 1.0-2.0, and the solid content of the mixture is 42.5-51.4 wt%;
in the activator, na is added 2 The alkalinity of the exciting agent is 4-8wt% calculated by O;
the water-solid ratio in the composition is 26-34wt%.
A second aspect of the present invention provides a method for preparing a geopolymer artificial fish reef using the composition described in the first aspect, comprising:
(1) Firstly mixing an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Secondly, mixing the mixture I, an exciting agent and water to obtain a mixture II;
(3) And pouring and molding the mixture II to obtain the geopolymer artificial fish reef.
A third aspect of the present invention provides a geopolymer artificial fish reef prepared by the method of the second aspect.
Compared with the prior art, the invention has at least the following advantages:
the invention adopts aluminosilicate material and calcium ore as raw materials, utilizes Si-O bond and Al-O bond contained in the aluminosilicate material and the calcium ore to carry out depolymerization firstly and then polycondensation to form a composite material which mainly comprises ionic bond and covalent bond and is prepared from [ SiO ] 4 ]And [ AlO 4 ]The tetrahedral structure unit is formed by sharing the materials of the three-dimensional space net structure formed by alternate bonding of oxygen to prepare the artificial fish reef.
The mechanical property of the artificial fish reef prepared by the composition provided by the invention in seawater is not obviously reduced, but better and better mechanical property is shown along with the increase of time; the diffusion coefficient of chloride ions in seawater is small, and the water-soluble polymer has more excellent chloride ion permeation resistance; meanwhile, the carbon emission is only 18-34% of that of the common portland cement artificial fish reef, and the raw materials are all derived from industrial solid wastes, so that the method is economic and environment-friendly, and can effectively solve the problem of resource shortage of traditional building materials such as cement and stone.
The geopolymer artificial reef prepared by the composition provided by the invention has excellent erosion resistance, impermeability and durability in seawater, so that the service life of the geopolymer artificial reef can be prolonged.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
As described above, in a first aspect, the present invention provides a composition for preparing a geopolymer artificial fish reef, comprising the following components:
aluminosilicate material, calcium ore, excitant and water;
wherein the weight ratio of the content of the aluminosilicate material to the content of the calcium ore is 1.5-9.0:1;
the calcium ore is selected from at least one of carbide slag and gypsum;
the excitant is a mixture which is obtained by adjusting sodium silicate by sodium hydroxide, has the modulus of 1.0-2.0 and the solid content of 42.5-51.4 wt%;
in the activator, na is added 2 The alkalinity of the excitant is 4-8wt% calculated by O;
the water-solid ratio in the composition is 26-34wt%.
Preferably, the aluminosilicate material is selected from at least one of slag, fly ash, metakaolin, red mud.
Preferably, the gypsum is at least one selected from desulfurized gypsum and phosphogypsum.
Preferably, the slag contains CaO and Al 2 O 3 And SiO 2 And the density is more than or equal to 2800kg/m 3 The specific surface area is more than or equal to 400m 2 The activity index is more than or equal to 95 percent in 7 days per kg. The inventor of the invention finds that the geopolymer artificial fish reef prepared under the preferable condition has better impermeability and mechanical property.
Preferably, the fly ash contains Al 2 O 3 And SiO 2 The screen allowance of the square hole screen with the size of 45 mu m is less than or equal to 20 percent, and the specific surface area is more than or equal to 250m 2 /kg。
Preferably, the metakaolin contains Al 2 O 3 And SiO 2 The average grain diameter is less than 20 mu m, and the specific surface area is 400-600m 2 Kg, density 2500-2700kg/m 3 The activity index is more than or equal to 110 percent.
Preferably, the red mud contains SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 And Na 2 O, and Na 2 The content of O is 10-15wt%, the grain diameter is less than or equal to 70 mu m, the screen allowance of a 0.3mm square-hole screen is more than 80%, and the volume weight is 0.8-1.0g/cm 3 。
Preferably, ca (OH) in the carbide slag 2 The content of (B) is more than or equal to 90wt%, and more than 80% of the particles have a particle size of 10-50 μm and a specific surface area of 800-1000m 2 /kg。
Preferably, caSO in the desulfurized gypsum 4 ·2H 2 The content of O is more than or equal to 90wt%, the grain diameter is less than or equal to 90 mu m, and the grain diameter of more than 85% is 30-60 mu m.
Preferably, the CaSO in the phosphogypsum 4 ·2H 2 The content of O is more than or equal to 90wt%, the average grain diameter is 10-110 mu m, and the density is 2050-2045kg/m 3 Specific surface area > 100m 2 (iv) kg. The inventor of the invention finds that the geopolymer artificial fish reef prepared under the preferable condition has better impermeability and mechanical property.
As previously mentioned, a second aspect of the present invention provides a method for preparing a geopolymer artificial fish reef using the composition as described in the first aspect, comprising:
(1) Firstly mixing an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Secondly, mixing the mixture I, an exciting agent and water to obtain a mixture II;
(3) And pouring and molding the mixture II to obtain the geopolymer artificial fish reef.
According to a preferred embodiment, in step (1), the conditions of the first mixing include: under the condition of stirring, the revolution speed is 57-67rpm, the rotation speed is 135-145rpm, the temperature is 20-30 ℃, and the time is 1-3min.
According to another preferred embodiment, in step (2), the conditions of the second mixing include: stirring the mixture for 1 to 3 minutes at a revolution speed of 57 to 67rpm and a rotation speed of 135 to 145rpm under the stirring condition, and then stirring the mixture for 1 to 3 minutes at a revolution speed of 115 to 135rpm and a rotation speed of 275 to 295rpm at a temperature of between 20 and 30 ℃.
In the present invention, the revolution speed and the rotation speed are both the rotation speed of the stirring blades.
According to a particularly preferred embodiment, the sodium water glass is used as an activator after the modulus has been adjusted with the sodium hydroxide and sealed at 20 to 30 ℃ for more than 24 hours.
The amount and kind of each component involved in the second aspect of the present invention are the same as those of the corresponding component in the first aspect of the present invention, and are not described herein again, and those skilled in the art should not understand that the present invention is limited.
As described above, the third aspect of the present invention provides a geopolymer artificial fish reef prepared by the method described in the second aspect.
The present invention will be described in detail below by way of examples.
In the following examples, the raw materials used are all commercially available unless otherwise specified.
The room temperature or the ordinary temperature means 25. + -. 5 ℃ unless otherwise specified.
Raw materials:
aluminosilicate material:
slag I: s95-grade granulated blast furnace slag powder containing CaO and Al 2 O 3 And SiO 2 Density of 2800kg/m 3 Specific surface area of 425m 2 Perkg, 7 day activity index 95%, purchased from Wuhan Steel Co., ltd.
Slag II: s75-grade granulated blast furnace slag powder containing CaO and Al 2 O 3 And SiO 2 Density of 2800kg/m 3 Specific surface area of 420m 2 Per kg,7 day activity index of 75%, purchased from Wuhan Steel Co., ltd.
Fly ash: national grade I low calcium fly ash containing Al 2 O 3 、SiO 2 CaO and MgO, the sieve residue of a 45-micron square-hole sieve is 10.7 percent, and the specific surface area is 256m 2 Per kg, purchased from Zhongshan, guangdong.
Metakaolin: containing Al 2 O 3 And SiO 2 Average particle diameter of 4.02 μm and specific surface area of 495m 2 A density of 2590kg/m 3 The activity index was 110% and was purchased from inner Mongolia super-kaolin Co.
Red mud: bayer process red mud containing SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 And Na 2 O，Na 2 O content of 10wt%, average particle diameter of 10 μm, and 0.3mm square mesh sieve residue of 10%, volume weight of 1.0g/cm 3 Purchased from Chongqing.
Silicate material:
p.o42.5 portland cement.
Calcium ore:
carbide slag: ca (OH) 2 Has an average particle diameter of 35 μm and a specific surface area of 947m in an amount of 90wt% 2 Per kg, purchased from Henan;
gypsum: phosphogypsum I, caSO 4 ·2H 2 O content of 90wt%, average particle diameter of 45 μm, and density of 2100kg/m 3 Specific surface area 105m 2 Perkg, purchased from Yichang, hubei.
Phosphogypsum II, caSO 4 ·2H 2 The content of O was 80% by weight, the average particle diameter was 30 μm, and the density was 2000kg/m 3 Specific surface area of 105m 2 Perkg, purchased from Yichang, hubei.
Exciting agent:
sodium hydroxide: the purity is more than 96 percent, and the product is purchased from Tianjin North Union construction engineering Co., ltd.
Sodium water glass: modulus of 3.24, baume degree of 39.5, na 2 O content of 9.25% and SiO 2 The content is 29%.
Example 1
This example illustrates the composition for preparing geopolymer artificial fish reef according to the present invention, the formulation and process parameters of table 1, and the preparation of the geopolymer artificial fish reef as described below.
The preparation method of the geopolymer artificial fish reef comprises the following steps:
(1) First mixing an aluminosilicate material with calcium ore to obtain a mixture I;
(2) Secondly, mixing the mixture I, an exciting agent and water to obtain a mixture II;
(3) Pouring and molding the mixture II to obtain the geopolymer artificial fish reef J1;
wherein the first mixing conditions are as follows: stirring at revolution speed of 62rpm and rotation speed of 140rpm at room temperature for 2min;
the conditions for the second mixing are: stirring is carried out under the stirring condition, stirring is carried out for 2min at a revolution speed of 62rpm and a rotation speed of 140rpm, and then stirring is carried out for 2min at a revolution speed of 125rpm and a rotation speed of 285rpm, wherein the temperature is room temperature.
Examples 2 to 4
Examples 2-4 were carried out using the same procedure as in example 1, except that in examples 2-4:
the formulations of the compositions and process parameters used for preparing geopolymer artificial fish reefs were varied, as shown in table 1.
And preparing the geopolymer artificial fish reef J2-J4.
Example 5
This example was carried out using the same procedure as example 4, except that: the geopolymer artificial fish reef J5 was prepared by replacing the slag I with the slag II by the same weight under the same conditions as in example 4.
Example 6
This example was carried out using the same procedure as example 2, except that: replacing the equal weight of the phosphogypsum I with the phosphogypsum II, and preparing the geopolymer artificial fish reef J6 under the same conditions as the example 2.
Comparative example 1
This comparative example was carried out using the same procedure as example 4, except that: and replacing the equal weight of the slag I with silicate materials, replacing the equal weight of the carbide slag with phosphogypsum I, and preparing the geopolymer artificial fish reef DJ1 by using the same conditions as the example 4, wherein the specific reference is given in Table 1.
Comparative example 2
This comparative example was carried out using the same procedure as example 4, except that: the amount of slag I was 50kg, the amount of carbide slag was 50kg, and the other conditions were the same as in example 4, and geopolymer artificial fish reef DJ2 was prepared, as specifically shown in table 1.
Comparative example 3
This comparative example was carried out using the same procedure as example 4, except that: the excitant is sodium water glass with the modulus of 3.24, the rest conditions are the same as those of the example 4, and the geopolymer artificial fish reef DJ3 is prepared, and the specific reference is shown in the table 1.
Comparative example 4
This comparative example was carried out using the same procedure as example 4, except that: the modulus of the excitant is 1.8, the alkalinity is 2wt%, the rest conditions are the same as those of the example 4, and the geopolymer artificial fish reef DJ4 is prepared, and the specific reference is shown in the table 1.
Comparative example 5
This comparative example was carried out using the same procedure as example 4, except that: the water-solid ratio in the composition was 24%, and the rest conditions were the same as in example 4, and geopolymer artificial fish reef DJ5 was prepared, specifically referring to table 1.
Comparative example 6
This comparative example was carried out using the same procedure as example 4, except that: the excitant is 20wt% of Na 2 CO 3 The solution was dissolved under the same conditions as in example 4,a geopolymer artificial fish reef DJ6 was prepared, see table 1 for details.
TABLE 1
TABLE 1
Note: in the table in the first column of rotation speed: 62/140 represents revolution speed 62rpm and rotation speed 140rpm;62/140+125/285 represents the revolution speed of 62rpm and the rotation speed of 140rpm; the revolution speed was 125rpm and the rotation speed was 285rpm.
Test example
The geopolymer artificial fish reefs prepared in the examples and comparative examples were tested according to the following method, and the specific test results are shown in table 2.
(1) Compressive strength: refer to GB/T17671-2021, cement mortar Strength test method (ISO method).
(2) Diffusion coefficient of chloride ion: the determination is carried out by referring to JCT 1086-2008 & ltmethod for inspecting diffusion coefficient of cement chloride ion & gt.
(3) Carbon emission:
which indicates the amount of carbon emissions,
represents the carbon emission, w, per 1 ton of i-th raw material produced i The mass percentage of the ith raw material in the geopolymer artificial reef is shown.
TABLE 2
As can be seen from the results in table 2, the geopolymer artificial fish reef prepared by using the composition provided by the present invention has mechanical properties that do not decrease with time but increase with time; the diffusion coefficients of the chloride ions are smaller than those of the artificial fish reef prepared from the silicate material, which shows that the seawater erosion resistance of the geopolymer artificial fish reef is superior to that of the silicate material artificial fish reef, and the raw materials of the geopolymer artificial fish reef are all derived from industrial solid wastes; the carbon emission is low and is only 18-34% of that of the silicate artificial fish reef.
In conclusion, the geopolymer artificial fish reef provided by the invention has excellent seawater corrosion resistance, is economic and environment-friendly, and has better durability in seawater, thereby prolonging the service life.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A composition for preparing geopolymer artificial fish reef, which is characterized by comprising the following components:
aluminosilicate material, calcium ore, excitant and water;
wherein the content weight ratio of the aluminosilicate material to the calcium ore is 1.5-9.0:1;
the calcium ore is selected from at least one of carbide slag and gypsum;
the excitant is a mixture which is obtained by adjusting sodium silicate by sodium hydroxide, has the modulus of 1.0-2.0 and the solid content of 42.5-51.4 wt%;
in the activator, na is added 2 The alkalinity of the exciting agent is 4-8wt% calculated by O;
the water-solid ratio in the composition is 26-34wt%.
2. The composition as claimed in claim 1, wherein the aluminosilicate material is selected from at least one of slag, fly ash, metakaolin, red mud; and/or the presence of a gas in the gas,
the gypsum is at least one selected from desulfurized gypsum and phosphogypsum.
3. The composition as set forth in claim 2, wherein the slag contains CaO, al 2 O 3 And SiO 2 And the density is more than or equal to 2800kg/m 3 The specific surface area is more than or equal to 400m 2 Per kg,7 days activity index is more than or equal to 95 percent; and/or the presence of a gas in the gas,
the fly ash contains Al 2 O 3 And SiO 2 The sieve allowance of the 45 mu m square-hole sieve is less than or equal to 20 percent, and the specific surface area is more than or equal to 250m 2 /kg。
4. The composition according to claim 2 or 3, wherein the metakaolin contains Al 2 O 3 And SiO 2 The average grain diameter is less than 20 mu m, and the specific surface area is 400-600m 2 Per kg, density 2500-2700kg/m 3 The activity index is more than or equal to 110 percent; and/or the presence of a gas in the gas,
the red mud contains SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 And Na 2 O, and Na 2 The content of O is 10-15wt%, the grain diameter is less than or equal to 70 mu m, the screen allowance of a 0.3mm square-hole screen is less than or equal to 20%, and the volume weight is 0.8-1.0g/cm 3 。
5. The composition according to any one of claims 2 to 4, wherein Ca (OH) in the carbide slag 2 The content of (A) is more than or equal to 90wt%, andmore than 80% of the particles have a particle size of 10-50 μm and a specific surface area of 800-1000m 2 /kg。
6. The composition of any one of claims 2-5, wherein CaSO is present in the desulfurized gypsum 4 ·2H 2 The content of O is more than or equal to 90wt%, the grain diameter is less than or equal to 90 mu m, and more than 85% of the grain diameter is 30-60 mu m; and/or the presence of a gas in the gas,
CaSO in the phosphogypsum 4 ·2H 2 The content of O is more than or equal to 90wt%, the average grain diameter is 10-110 mu m, and the density is 2050-2045kg/m 3 Specific surface area > 100m 2 /kg。
7. A method of preparing a geopolymer artificial fish reef, the method being performed using the composition of any one of claims 1 to 6 and comprising:
(1) First mixing an aluminosilicate material with calcium ore to obtain a mixture I;
(2) Secondly, mixing the mixture I, an exciting agent and water to obtain a mixture II;
(3) And pouring and molding the mixture II to obtain the geopolymer artificial fish reef.
8. The method of claim 7, wherein, in step (1), the conditions of the first mixing comprise: under the condition of stirring, the revolution speed is 57-67rpm, the rotation speed is 135-145rpm, the temperature is 20-30 ℃, and the time is 1-3min.
9. The method of claim 7 or 8, wherein in step (2), the conditions of the second mixing comprise: stirring at revolution speed of 57-67rpm and rotation speed of 135-145rpm for 1-3min, and stirring at revolution speed of 115-135rpm and rotation speed of 275-295rpm for 1-3min at 20-30 deg.C.
10. The geopolymer artificial fish reef prepared by the method of any one of claims 7-9.
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