CN115521099B - 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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- 241000251468 Actinopterygii Species 0.000 title claims abstract description 72
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 19
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 17
- 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
- 239000012190 activator Substances 0.000 claims abstract description 7
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 5
- 239000002893 slag Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 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
- 229910052602 gypsum Inorganic materials 0.000 claims description 10
- 239000010440 gypsum Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 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 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000010881 fly ash Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007873 sieving 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
- 239000004568 cement Substances 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 239000013535 sea water Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- 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
- 239000004567 concrete Substances 0.000 description 7
- 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
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 230000035699 permeability Effects 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- -1 compound aluminosilicate Chemical class 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
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 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
- 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 235000012211 aluminium silicate Nutrition 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
- 229920005601 base polymer Polymers 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010220 ion permeability Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000007885 magnetic separation 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
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 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
- 239000002699 waste material Substances 0.000 description 1
- 239000010920 waste tyre Substances 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 a geopolymer artificial fish reef, a method for preparing the geopolymer artificial fish reef and the geopolymer artificial fish reef. The composition comprises the following components: aluminosilicate material, calcium ore, activator 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, a step of; the excitant is a mixture with the modulus of 1.0-2.0, which is obtained by adjusting sodium silicate by sodium hydroxide. The mechanical properties of the artificial fish reef prepared by the composition provided by the invention in sea water are increased along with the time, and the artificial fish reef has better and better mechanical properties; and has more excellent resistance to penetration of chloride ions; meanwhile, the carbon emission of the artificial fish reef is only 18-34% of that of an ordinary Portland cement artificial fish reef, and the raw materials are all derived from industrial solid waste, so that the artificial fish reef is economical and environment-friendly, and the problem of resource shortage of traditional building materials such as cement and stone can be effectively relieved.
Description
Technical Field
The invention relates to the technical field of artificial fish reefs, in particular to a composition for preparing a geopolymer artificial fish reef, a method for preparing the geopolymer artificial fish reef and the geopolymer artificial fish reef.
Background
The fish reef is a reef, is a habitat for providing propagation, growth, rope baits and refuge enemies for fishes, 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 humans is increasing, and marine pollutants such as petroleum, pesticides, domestic sewage, garbage, chemical waste liquid and the like generated by various production activities severely damage the marine ecosystem. In addition, the high-intensity operations with killing performance such as over-fishing can lead to sharp reduction of fish habitat, reduce the population quantity of fish, gradually decline fishery resources and lead to serious challenges in maintaining the marine ecological balance.
The artificial fish reef is used as an artificial structure in the ocean, provides more and safer habitat for fish, and plays an important role in enriching and improving the ocean ecosystem.
At present, most of artificial fish reefs are prepared by using cement concrete as a raw material, but the cement concrete consumes a great amount of building materials such as cement, sand and the like, so that the burden of building material resources is increased, and the production cost is increased; 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 easy to carbonize, and the concrete is easy to deteriorate under salt corrosion and biological corrosion in the ocean, so that the durability of the cement concrete is insufficient and the service life of the cement concrete is reduced.
Other types of artificial reefs, such as steel artificial reefs, are transported to a wharf after components are prepared in a factory, and then assembled and put in the field, so that the cost is high, and the popularization are not easy; for example, bamboo or wooden fish reefs are poor in wind and wave resistance and easy to corrode, so that the fish reefs are rarely used; and the artificial fish reef is mainly formed by stacking waste tires, waste boat bodies and the like, has the characteristic of low cost, but contains a plurality of harmful substances, and is easy to cause environmental pollution.
The geopolymer is an inorganic low-carbon nonmetal cementing material obtained by taking aluminosilicate as a raw material and alkali excitation at normal temperature, has the advantages of quick hardening, early strength, acid and alkali resistance, low permeability, corrosion resistance, good durability and the like, and therefore, the geopolymer artificial fish reef not only has higher seawater corrosion resistance and permeability resistance, but also has the advantages of economy, low carbon and environmental protection, and has wide prospect in ocean engineering application.
CN107663035a discloses an aluminum ash base polymer cementing material, which is characterized by comprising the following components: 100 parts of compound aluminosilicate powder, 80-150 parts of water glass, 10-30 parts of sodium hydroxide and 10-50 parts of water, wherein the compound aluminosilicate powder is prepared by mixing, grinding and sieving 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. Although the geopolymer gel material has higher mechanical strength, the high content of the exciting agent in the prior art leads to excessive economic cost.
CN108892464a discloses an environment-friendly cementing material, which is characterized by comprising the following raw materials in parts by weight: 3 to 4 parts of converter 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 polyaluminum, 0.05 to 0.06 part of calcium chloride, 3 to 5 parts of plaster of paris and 3 to 4kg of alkali activator. Although the environment-friendly cementing material has good compressive strength and setting time, the prior art needs 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 the geopolymer artificial fish reef with good erosion resistance, permeability resistance and durability.
In order to achieve the above object, a first aspect of the present invention provides a composition for preparing a geopolymer artificial fish reef, comprising the following components:
aluminosilicate material, calcium ore, activator 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, a step of;
the calcium ore is selected from at least one of carbide slag and gypsum;
the excitant is a mixture with the modulus of 1.0-2.0 and the solid content of 42.5-51.4wt% obtained by adjusting sodium silicate with sodium hydroxide;
in the exciting agent, na is used 2 O is calculated, and the alkalinity of the exciting agent is 4-8wt%;
the water-to-solid ratio in the composition is 26-34wt%.
In a second aspect, the invention provides a method of preparing a geopolymer artificial fish reef using a composition as described in the first aspect, comprising:
(1) Carrying out first mixing on an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Performing second mixing on the mixture I, the 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 described in the second aspect.
Compared with the prior art, the invention has at least the following advantages:
the invention uses aluminosilicate material and calcium ore as raw material, uses Si-O bond and Al-O bond contained in both them to make depolymerization and polycondensation to form a material mainly composed of ionic bond and covalent bond, and uses [ SiO ] 4 ]And [ AlO ] 4 ]The tetrahedral structural units are alternately bonded through shared oxygen to form a three-dimensional space net-shaped structure material so as to prepare the artificial fish reef.
The mechanical properties of the artificial fish reef prepared by the composition provided by the invention in sea water are not obviously reduced, but rather the artificial fish reef shows better mechanical properties with the increase of time; the diffusion coefficient of chloride ions in seawater is smaller, and the anti-chloride ion permeability is more excellent; meanwhile, the carbon emission of the artificial fish reef is only 18-34% of that of an ordinary Portland cement artificial fish reef, and the raw materials are all derived from industrial solid waste, so that the artificial fish reef is economical and environment-friendly, and the problem of resource shortage of traditional building materials such as cement and stone can be effectively relieved.
The geopolymer artificial fish 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 fish reef can be prolonged.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the 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, activator 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, a step of;
the calcium ore is selected from at least one of carbide slag and gypsum;
the excitant is a mixture with the modulus of 1.0-2.0 and the solid content of 42.5-51.4wt% obtained by adjusting sodium silicate with sodium hydroxide;
in the exciting agent, na is used 2 O is calculated, and the alkalinity of the exciting agent is 4-8wt%;
the water-to-solid ratio in the composition is 26-34wt%.
Preferably, the aluminosilicate material is selected from at least one of slag, fly ash, metakaolin and red mud.
Preferably, the gypsum is selected from at least one of 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 Specific surface area is more than or equal to 400m 2 The activity index per kg in 7 days is more than or equal to 95 percent. The inventor of the invention discovers that the geopolymer artificial fish reef prepared under the preferred condition has better impermeability and mechanical properties.
Preferably, the fly ash contains Al 2 O 3 And SiO 2 And the sieving allowance of a square hole sieve with 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 And has an average particle diameter of less than 20 μm and a specific surface area of 400-600m 2 Per 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 (Na) 2 O, and Na 2 The O content is 10-15wt%, the grain diameter is less than or equal to 70 mu m, and the formula is 0.3mmThe screen allowance of the hole screen is more than 80 percent, and the volume weight is 0.8-1.0g/cm 3 。
Preferably, ca (OH) in the carbide slag 2 The content of (C) is more than or equal to 90wt%, the particle diameter of more than 80% is 10-50 μm, and the specific surface area is 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 percent is 30-60 mu m.
Preferably, caSO in the phosphogypsum 4 ·2H 2 The O content is more than or equal to 90wt%, the average grain diameter is 10-110 μm, and the density is 2050-2045kg/m 3 Specific surface area > 100m 2 /kg. The inventor of the invention discovers that the geopolymer artificial fish reef prepared under the preferred condition has better impermeability and mechanical properties.
As previously mentioned, a second aspect of the present invention provides a method of preparing a geopolymer artificial fish reef using a composition as described in the first aspect, comprising:
(1) Carrying out first mixing on an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Performing second mixing on the mixture I, the 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 comprise: is carried out under the stirring condition, 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: the stirring is carried out under the stirring condition, the stirring is carried out for 1-3min at the revolution speed of 57-67rpm and the rotation speed of 135-145rpm, and then the stirring is carried out for 1-3min at the revolution speed of 115-135rpm and the rotation speed of 275-295rpm, and the temperature is 20-30 ℃.
In the present invention, the revolution speed and the rotation speed refer to the rotation speed of the stirring blade.
According to a particularly preferred embodiment, the sodium water glass is subjected to modulus adjustment by the sodium hydroxide, is sealed at 20-30 ℃ for more than 24 hours and then is used as an exciting agent.
The amounts and types of the respective components according to the second aspect of the present invention are the same as those of the corresponding components according to the first aspect of the present invention, and are not described herein in detail, and those skilled in the art should not be construed as limiting the present invention.
As previously described, a third aspect of the present invention provides a geopolymer artificial fish reef prepared by the method described in the second aspect.
The invention will be described in detail below by way of examples.
In the examples below, all the raw materials used are commercially available, unless otherwise specified.
Unless otherwise specified, the room temperature or normal temperature means 25.+ -. 5 ℃.
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 A specific surface area of 425m 2 The 7-day activity index was 95% per kg, purchased from the wuhan iron and steel company, 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 days activity index 75%, available from Wuhan Steel Co.
Fly ash: the national grade I low-calcium fly ash contains Al 2 O 3 、SiO 2 CaO and MgO, the residual amount of the 45 mu m square-hole sieve is 10.7%, and the specific surface area is 256m 2 Kg, purchased from Guangdong Zhongshan.
Metakaolin: contains Al 2 O 3 And SiO 2 An average particle diameter of 4.02 μm and a specific surface area of 495m 2 Per kg, density 2590kg/m 3 The activity index was 110%, purchased from inner MongoliaSuper kaolin limited.
Red mud: bayer process red mud containing SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 And Na (Na) 2 O，Na 2 The O content is 10wt%, the average grain diameter is 10 mu m, the square-hole sieve allowance of 0.3mm is 10%, and the volume weight is 1.0g/cm 3 Purchased from Chongqing.
Silicate material:
p.o42.5 portland cement.
Calcium ore:
carbide slag: ca (OH) 2 The content of (C) was 90% by weight, the average particle diameter was 35. Mu.m, and the specific surface area was 947m 2 Kg, purchased from Henan;
gypsum: phosphogypsum I, caSO 4 ·2H 2 The O content was 90wt%, the average particle diameter was 45 μm, and the density was 2100kg/m 3 Specific surface area 105m 2 Kg, available from Yichang in Hubei.
Phosphogypsum II, caSO 4 ·2H 2 The O content was 80wt%, the average particle diameter was 30 μm, and the density was 2000kg/m 3 Specific surface area 105m 2 Kg, available from Yichang in Hubei.
Exciting agent:
sodium hydroxide: analytical purity > 96%, and is purchased from Tianjin North Union construction engineering Co.
Sodium water glass: modulus 3.24, baume 39.5, na 2 The O content is 9.25 percent, siO 2 The content was 29%.
Example 1
This example illustrates the composition for preparing a geopolymer artificial fish reef according to the present invention according to the formulation and process parameters of table 1 and the geopolymer artificial fish reef is prepared as follows.
The preparation method of the geopolymer artificial fish reef comprises the following steps:
(1) Carrying out first mixing on an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Performing second mixing on the mixture I, the 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 condition is: the stirring is carried out under the condition of stirring, the revolution speed is 62rpm, the rotation speed is 140rpm, the temperature is room temperature, and the time is 2min;
the conditions for the second mixing are: the stirring was carried out under stirring conditions, and the temperature was room temperature, in which stirring was carried out at a revolution speed of 62rpm and a rotation speed of 140rpm for 2 minutes, and at a revolution speed of 125rpm and a rotation speed of 285rpm for 2 minutes.
Examples 2 to 4
Examples 2 to 4 were carried out using the same procedure as in example 1, except that in examples 2 to 4:
the composition formulations and process parameters used for preparing the geopolymer artificial fish reef were varied, see in particular table 1.
The geopolymer artificial fish reefs J2-J4 are prepared.
Example 5
This example was performed using the same procedure as in example 4, except that: the geopolymer artificial fish reef J5 was prepared by replacing the slag I with the slag II in the same weight and under the same conditions as in example 4.
Example 6
This example was performed using the same procedure as in example 2, except that: the weight of phosphogypsum I was replaced with phosphogypsum II, and the other conditions were the same as in example 2, to prepare the geopolymer artificial fish reef J6.
Comparative example 1
This comparative example was conducted using the same procedure as in example 4, except that: the geopolymer artificial fish reef DJ1 was prepared by replacing the same weight of slag I with a silicate material, replacing the same weight of carbide slag with phosphogypsum I, and the same conditions as those of example 4.
Comparative example 2
This comparative example was conducted using the same procedure as in 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, to prepare a geopolymer artificial fish reef DJ2, see Table 1 for details.
Comparative example 3
This comparative example was conducted using the same procedure as in example 4, except that: the excitant is sodium silicate with a modulus of 3.24, and the rest conditions are the same as those of the example 4, so that 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 conducted using the same procedure as in example 4, except that: the modulus of the activator was 1.8, the alkalinity was 2wt%, and the other conditions were the same as in example 4, to prepare a geopolymer artificial fish reef DJ4, see Table 1 for details.
Comparative example 5
This comparative example was conducted using the same procedure as in example 4, except that: the water-to-solid ratio in the composition was 24%, and the other conditions were the same as in example 4, to prepare a geopolymer artificial fish reef DJ5, see specifically Table 1.
Comparative example 6
This comparative example was conducted using the same procedure as in example 4, except that: 20wt% of Na as an activator 2 CO 3 The solution and the other conditions were the same as in example 4, and a geopolymer artificial fish reef DJ6 was prepared, see Table 1 for details.
TABLE 1
Table 1, below
Note that: in the table speed column: 62/140 represents revolution speed 62rpm and rotation speed 140rpm;62/140+125/285 indicates a revolution-first speed of 62rpm and a rotation speed of 140rpm; the revolution speed was 125rpm and the rotation speed was 285rpm.
Test case
The geopolymer artificial fish reefs prepared in the examples and comparative examples were tested according to the following methods, and specific test results are shown in table 2.
(1) Compressive strength: the measurement was performed with reference to GB/T17671-2021, method for testing Cement mortar strength (ISO method).
(2) Diffusion coefficient of chloride ion: the measurement was performed by referring to JCT 1086-2008, cement chloride ion diffusion coefficient test method.
(3) Carbon emission: represents carbon emission amount, +.>Represents the carbon emission amount, w, per 1 ton of i-th raw material produced i The weight percentage of the ith raw material in the geopolymer artificial fish reef is shown.
TABLE 2
As can be seen from the results in Table 2, the mechanical properties of the geopolymer artificial fish reef prepared by the composition provided by the invention in sea water are not reduced with time, but are increased with time; the diffusion coefficient of chloride ions is smaller than that of the artificial reef prepared from silicate materials, so that the seawater erosion resistance of the geopolymer artificial reef is better than that of the artificial reef prepared from silicate materials, and the raw materials of the geopolymer artificial reef are all derived from industrial solid wastes; the carbon emission is low and is only 18-34% of that of the artificial fish reef made of silicate materials.
In conclusion, the geopolymer artificial fish reef provided by the invention has excellent seawater erosion resistance, is economical and environment-friendly, and has better durability in seawater, so that the service life is prolonged.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (9)
1. A composition for preparing a geopolymer artificial fish reef, which is characterized by comprising the following components:
aluminosilicate material, calcium ore, activator 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, a step of;
the aluminosilicate material is at least one selected from slag, fly ash, metakaolin and red mud;
the calcium ore is selected from at least one of carbide slag and gypsum; the gypsum is at least one selected from desulfurized gypsum and phosphogypsum;
the excitant is a mixture with the modulus of 1.0-2.0 and the solid content of 42.5-51.4wt% obtained by adjusting sodium silicate with sodium hydroxide;
in the exciting agent, na is used 2 O is calculated, and the alkalinity of the exciting agent is 4-8wt%;
the water-to-solid ratio in the composition is 26-34wt%.
2. The composition according to claim 1, wherein the slag contains CaO, al 2 O 3 And SiO 2 And the density is more than or equal to 2800kg/m 3 Specific surface area is more than or equal to 400m 2 The activity index per kg in 7 days is more than or equal to 95%; and/or the number of the groups of groups,
the fly ash contains Al 2 O 3 And SiO 2 And the sieving allowance of a square hole sieve with 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。
3. The composition according to claim 1 or 2, wherein the metakaolin comprises Al 2 O 3 And SiO 2 And has an average particle diameter of less than 20 μm and a specific surface area of 400-600m 2 Per kg, density 2500-2700kg/m 3 The activity index is more than or equal to 110%; and/or the number of the groups of groups,
the red mud contains SiO 2 、Al 2 O 3 、CaO、Fe 2 O 3 And Na (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 square hole sieve allowance of 0.3mm is less than or equal to 20%, and the volume weight is 0.8-1.0g/cm 3 。
4. Composition according to claim 1 or 2, wherein Ca (OH) in the carbide slag 2 The content of (C) is more than or equal to 90wt%, the particle diameter of more than 80% is 10-50 μm, and the specific surface area is 800-1000m 2 /kg。
5. The composition of claim 1 or 2, wherein CaSO in the desulfurized gypsum 4 ·2H 2 The content of O is more than or equal to 90wt percent, the grain diameter is less than or equal to 90 mu m, and the grain diameter of more than 85 percent is 30-60 mu m; and/or the number of the groups of groups,
CaSO in phosphogypsum 4 ·2H 2 The O content is more than or equal to 90wt%, the average grain diameter is 10-110 μm, and the density is 2050-2045kg/m 3 Specific surface area > 100m 2 /kg。
6. A method of preparing a geopolymer artificial fish reef, wherein the method is carried out using a composition according to any one of claims 1 to 5, comprising:
(1) Carrying out first mixing on an aluminosilicate material and calcium ore to obtain a mixture I;
(2) Performing second mixing on the mixture I, the exciting agent and water to obtain a mixture II;
(3) And pouring and molding the mixture II to obtain the geopolymer artificial fish reef.
7. The method of claim 6, wherein in step (1), the first mixing conditions comprise: is carried out under the stirring condition, the revolution speed is 57-67rpm, the rotation speed is 135-145rpm, the temperature is 20-30 ℃ and the time is 1-3min.
8. The method of claim 6 or 7, wherein in step (2), the conditions of the second mixing include: the stirring is carried out under the stirring condition, the stirring is carried out for 1-3min at the revolution speed of 57-67rpm and the rotation speed of 135-145rpm, and then the stirring is carried out for 1-3min at the revolution speed of 115-135rpm and the rotation speed of 275-295rpm, and the temperature is 20-30 ℃.
9. A geopolymer artificial fish reef prepared by the method of any one of claims 6 to 8.
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