CN115924945A - Calcined hydrotalcite and preparation method thereof, composition for preparing high-durability marine concrete, concrete and preparation method thereof - Google Patents
Calcined hydrotalcite and preparation method thereof, composition for preparing high-durability marine concrete, concrete and preparation method thereof Download PDFInfo
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- CN115924945A CN115924945A CN202211449649.2A CN202211449649A CN115924945A CN 115924945 A CN115924945 A CN 115924945A CN 202211449649 A CN202211449649 A CN 202211449649A CN 115924945 A CN115924945 A CN 115924945A
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- concrete
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- hydrotalcite
- calcined hydrotalcite
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 55
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 55
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 55
- 239000004567 concrete Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 239000012190 activator Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 16
- 239000011707 mineral Substances 0.000 claims abstract description 16
- 239000004576 sand Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- -1 cation salt Chemical class 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 14
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 238000003763 carbonization Methods 0.000 abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 4
- 229910001294 Reinforcing steel Inorganic materials 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000004566 building material Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 229920000876 geopolymer Polymers 0.000 abstract description 2
- 235000010755 mineral Nutrition 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229920003041 geopolymer cement Polymers 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000010881 fly ash Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000011150 reinforced concrete Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
Classifications
-
- 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
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the technical field of building materials, and discloses calcined hydrotalcite, a preparation method thereof, a composition for preparing high-durability marine concrete, concrete and a preparation method thereofThe method is carried out. The calcined hydrotalcite has a chemical formula of MO & aA 2 O 3 ·bH 2 O, wherein M is at least one selected from Mg, ca, zn, cu, co and Mn; a is at least one selected from Al, ga, fe and Cr. The marine geopolymer and the concrete thereof prepared by matching the calcined hydrotalcite with specific amount of mineral powder, standard sand and alkali activator can improve the chloride ion adsorption capacity of the concrete and reduce the corrosion of chloride ions to reinforcing steel bars; simultaneously, the catalyst can also absorb carbonate ions in the solution and increase the CO 2 Thereby enhancing the carbonization resistance of the polymer and the concrete.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to calcined hydrotalcite and a preparation method thereof, a composition for preparing high-durability marine concrete, concrete and a preparation method thereof.
Background
Ocean economy is a new engine for global economic growth, industry upgrading and technological innovation in the 21 st century. China is a big ocean country, the ocean construction is accelerated, and the vigorous development of ocean resources has great strategic significance on the social and economic development of China. In recent years, the construction of marine infrastructures based on reinforced concrete has increased dramatically, including coastal docks, cross-sea bridges and tunnels, offshore drilling platforms, and the like.
Compared with the atmospheric environment, the marine environment containing high concentration of chloride ions can significantly reduce the durability and service life of the reinforced concrete structure. The high-concentration chloride ions penetrate through a concrete protective layer to damage a passive film on the surface of the steel bar, so that the steel bar is corroded, the concrete is peeled off, the service life of infrastructure is seriously damaged, and huge economic loss is caused.
Therefore, designing and preparing high-performance and high-durability marine concrete is an important scientific and engineering problem which needs to be solved urgently at present.
The geopolymer concrete is a new type of gelled material formed by using active silica-alumina material through chemical excitation under the alkaline condition. The carbon emission of the alkali-activated cementing material with a well-designed composition in the production process can be reduced by about 80 percent compared with that of common Portland cement, and the alkali-activated cementing material has remarkable environmental protection characteristics and great application potential. In geopolymer concrete prepared from different raw materials (slag, fly ash, calcined clay and the like), the geopolymer concrete has high alkalinity and good corrosion resistance, can protect reinforcing steel bars, and has great potential and application prospect in preparing high-performance and high-durability marine concrete.
However, the lower resistance to carbonation is one of the major problems with geopolymer concrete. CO in the air 2 As an acid gas, enters the concrete through the poresInside, reacts with the solution in the pores to generate carbonate ions, and when the carbonate ions in the solution in the pores are saturated, calcium carbonate begins to be generated, so that Ca 2+ The concentration plays an important role in carbonization of alkali-activated slag. Geopolymer concrete has a lower calcium to silicon ratio than cement concrete and is therefore more susceptible to carbonization.
At present, some mineral admixtures such as fly ash, silica fume and ultra-fine fly ash are generally added to improve the durability of concrete, and the addition of these mineral admixtures can improve the pore structure and prevent the invasion of harmful substances to some extent. However, the addition amount is too much, the specific surface area is large, the fluidity is poor, and the durability of concrete is reduced; and the strength is reduced due to too little mixing amount. The rust inhibitor is a chemical substance commonly used in concrete for protecting steel bars, and a small amount of rust inhibitor can prevent or slow down the corrosion of the steel bars. However, some rust inhibitors, such as nitrite salts, which are the main component of the rust inhibitor, have disadvantages of local corrosion and accelerated corrosion when the chloride ion concentration reaches a certain level, and also cause alkali-aggregate reaction, which affects slump, etc.
Therefore, in view of the above problems and disadvantages, it is desirable to prepare an additive for marine concrete with high performance and high durability, which is resistant to both chloride ion corrosion and carbonation corrosion.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide an additive which can enable marine concrete to have good chloride ion corrosion resistance and carbonization corrosion resistance (good durability).
In order to achieve the above object, a first aspect of the present invention provides a calcined hydrotalcite having a chemical formula of MO · aA 2 O 3 ·bH 2 O，
Wherein M is selected from at least one of Mg, ca, zn, cu, co and Mn;
a is selected from at least one of Al, ga, fe and Cr;
a is selected from any number from 0.1 to 0.5, and b is selected from any integer.
A second aspect of the present invention provides a method for preparing the calcined hydrotalcite described in the first aspect, which comprises: calcining hydrotalcite;
wherein the conditions of the calcination treatment include: the initial temperature is 20-35 deg.C, the heating rate is 5-10 deg.C/min, the termination temperature T is 400-600 deg.C, and the temperature is maintained at T for 3-8h.
In a third aspect, the present invention provides a composition for preparing high durability marine concrete, comprising the following components:
mineral powder, standard sand, coarse aggregate, an alkali activator and calcined hydrotalcite;
the content of the mineral powder is 10-20wt% based on the total weight of the composition; the content of the standard sand is 20-35wt%; the content of the coarse aggregate is 35-50wt%; the content of the alkali activator is 5-10wt%; the content of the calcined hydrotalcite is 0.1-1.5wt%;
the calcined hydrotalcite is the calcined hydrotalcite described in the foregoing first aspect.
A fourth aspect of the present invention provides a method for preparing high durability marine concrete using the composition described in the aforementioned third aspect, comprising:
(i) Performing first mixing on mineral powder, standard sand and calcined hydrotalcite to obtain a mixture I;
(ii) And secondly, mixing the mixture I with an alkali activator to obtain the high-durability marine concrete.
A fifth aspect of the invention provides a highly durable marine concrete produced by the method described in the fourth aspect.
Compared with the prior art, the invention has at least the following advantages:
(1) The calcined hydrotalcite provided by the invention has a structure memory effect, and when the calcined hydrotalcite is added into a solution containing anions, water and the anions in the solution can be absorbed, and the original structure is recovered. The polymer is mixed with mineral powder, standard sand and alkali activator to prepare the polymer and concreteThe ability of the concrete to adsorb chloride ions can be improved, and the corrosion of the chloride ions to the reinforcing steel bars is reduced; simultaneously, the catalyst can also absorb carbonate ions in the solution and increase the CO 2 Thereby enhancing the carbonization resistance of the polymer and the concrete.
(2) The calcined hydrotalcite provided by the invention has smaller particle size and large specific surface area, can be used as a seed crystal to accelerate the hydration process at an early stage, so that more hydration products and a more compact structure are generated, and meanwhile, the calcined hydrotalcite can be filled in pores of a matrix, so that the pore structure, a slurry-aggregate interface and the like are improved, and chloride ions and CO are avoided 2 Enter the inside of the matrix to improve the durability of the marine geopolymer and the concrete thereof.
(3) According to the calcined hydrotalcite provided by the invention, on one hand, the adsorption of carbonate ions reduces the contact probability of the carbonate ions with calcium ions and other calcium-containing substances, and simultaneously releases OH - The pH value of the solution in the pores can be buffered; on the other hand, it has anion exchange adsorption capacity and can release corrosion-inhibiting ions (such as AO) during anion exchange 2 - ) And inhibiting the corrosion of the steel bars.
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 previously mentioned, the first aspect of the present invention provides a calcined hydrotalcite having the formula MO aA 2 O 3 ·bH 2 O，
Wherein M is selected from at least one of Mg, ca, zn, cu, co and Mn;
a is selected from at least one of Al, ga, fe and Cr;
a is selected from any number from 0.1 to 0.5, and b is selected from any integer.
Preferably, M is selected from at least one of Mg, ca, zn and Cu.
Preferably, a is selected from at least one of Al and Fe.
Preferably, the hydrotalcite has an average particle size of 1 to 3 μm.
As previously mentioned, a second aspect of the present invention provides a process for preparing the calcined hydrotalcite of the first aspect, comprising: calcining hydrotalcite;
wherein the conditions of the calcination treatment include: the initial temperature is 20-35 deg.C, the heating rate is 5-10 deg.C/min, the termination temperature T is 400-600 deg.C, and the temperature is maintained at T for 3-8h.
The hydrotalcite of the present invention may be natural hydrotalcite or synthetic hydrotalcite.
Preferably, the method further comprises: the hydrotalcite is synthesized by one of a coprecipitation method, a hydrothermal synthesis method and an ion exchange method.
According to a preferred embodiment, the method further comprises: synthesizing the hydrotalcite by adopting a coprecipitation method comprising the following steps of:
(1) In the presence of water I, carrying out contact reaction I on a soluble divalent cation salt and an alkaline substance I to obtain a product I;
(2) In the presence of water II, carrying out contact reaction II on the mixture I and an alkaline substance II in a dropwise manner, and then drying to obtain the hydrotalcite;
wherein the mixture I contains soluble trivalent cation salt and the product I.
It should be noted that the present invention does not require any particular kind of the water I and the water II, and is only to show that they are added in different steps. In addition, the water I and the water II in the present invention only serve as solvents, the present invention has no particular limitation on the amount thereof, and those skilled in the art can select them according to technical means known in the art, and hereinafter, the present invention exemplarily provides a preferred embodiment, and those skilled in the art should not be construed as limiting the present invention.
Preferably, the alkaline substance I and the alkaline substance II are respectively and independently selected from at least one of potassium hydroxide, sodium hydroxide, ammonia water, sodium carbonate, potassium carbonate and urea.
Preferably, in step (1), the soluble divalent cation salt and the alkaline substance I are used in a molar ratio of 1:1-3.
Preferably, in step (1), the conditions of the contact reaction I include: the temperature is 120-170 ℃ and the time is 2-4h. More preferably, in step (1), the conditions of the contact reaction I include: the temperature is 140-160 ℃ and the time is 2-3h.
Preferably, in step (2), the soluble trivalent cation salt, the product I and the alkaline substance II are used in a molar ratio of 1: 1/(2 a): 2/a-10/a; wherein a is selected from any number of 0.1-0.5.
Preferably, in step (2), the conditions of the contact reaction II include: the pH value is 9-10, the temperature is 50-170 ℃, and the time is 12-15h.
According to a particularly preferred embodiment, step (2) comprises: in the presence of water II, simultaneously dropwise adding the mixture I and the alkaline substance II to perform a contact reaction II-1, after dropwise adding, performing a contact reaction II-2, and then drying to obtain the hydrotalcite; and controlling the dropping speed of the mixture I and the alkaline substance II so that the pH value in the contact reaction II-1 system is 9-10.
Preferably, the conditions of the contact reaction II-1 include: the pH value is 9-10, the temperature is 50-60 ℃, and the time is 2-3h.
Preferably, the conditions of the contact reaction II-2 include: the temperature is 60-170 ℃ and the time is 10-12h. Further preferably, the conditions of the contact reaction II-2 include: the temperature is 120-150 ℃ and the time is 10-12h.
Preferably, the drying conditions include: the temperature is 60-70 ℃ and the time is 20-26h.
It is noted that the process of the present invention may also include various post-treatment means known in the art, such as washing, filtration, and the like. The following description of the invention is provided by way of example for a preferred embodiment and should not be construed as limiting the invention by those skilled in the art.
As previously mentioned, a third aspect of the present invention provides a composition for preparing high durability marine concrete, the composition comprising the following components:
mineral powder, standard sand, coarse aggregate, an alkali activator and calcined hydrotalcite;
the content of the mineral powder is 10-20wt% based on the total weight of the composition; the content of the standard sand is 20-35wt%; the content of the coarse aggregate is 35-50wt%; the content of the alkali activator is 5-10wt%; the content of the calcined hydrotalcite is 0.1-1.5wt%;
the calcined hydrotalcite is the calcined hydrotalcite described in the foregoing first aspect.
Preferably, the ore powder is selected from at least one ore powder of grade S95 or above.
Preferably, the average particle size of the standard sand is 0.05-8mm, the content of silicon dioxide is more than 96wt%, and the loss on ignition is not more than 0.4wt%.
Preferably, the coarse aggregate is selected from at least one of crushed stone, gravel and pebble, and the average particle diameter of the coarse aggregate is 5-25mm.
Preferably, the alkali activator is at least one selected from sodium hydroxide and sodium water glass. More preferably, the alkali activator is a combination of sodium hydroxide and sodium silicate, and the modulus is 0.1-2.
Particularly preferably, the alkali activator is a combination of sodium hydroxide and sodium silicate, and the modulus is 0.1 to 1. The inventor of the invention finds that the marine concrete obtained under the preferable condition has better carbonization corrosion resistance.
As previously mentioned, a fourth aspect of the invention provides a method of preparing high durability marine concrete using a composition as described in the previous third aspect, comprising:
(i) Performing first mixing on mineral powder, standard sand and calcined hydrotalcite to obtain a mixture I;
(ii) And secondly, mixing the mixture I with an alkali activator to obtain the high-durability marine concrete.
The amount and kind of each component related to the fourth aspect of the present invention are the same as the amount and kind of the corresponding component described in the third aspect of the present invention, and are not described herein again, and those skilled in the art should not be construed as limiting the present invention.
Preferably, in step (i), the conditions of the first mixing include: under the condition of stirring, the rotating speed of the stirring is 150-300rpm, the time is 1-4min, and the temperature is 20-40 ℃. More preferably, in step (i), the conditions of the first mixing include: under the condition of stirring, the rotating speed of the stirring is 200-300rpm, the time is 2-4min, and the temperature is 20-30 ℃.
Preferably, in step (ii), the conditions of the second mixing comprise: under the condition of stirring, the rotating speed of the stirring is 200-400rpm, the time is 2-8min, and the temperature is 20-40 ℃. More preferably, in step (ii), the conditions of the second mixing include: under the condition of stirring, the rotating speed of the stirring is 240-350rpm, the time is 4-6min, and the temperature is 20-30 ℃.
As previously mentioned, a fifth aspect of the invention provides a highly durable marine concrete produced by the method of the fourth 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.
In the following examples, the room temperature means 25 ± 2 ℃ unless otherwise specified.
Raw materials:
magnesium chloride: from Shanghai McLin Biochemical technology, inc.
Zinc chloride: purchased from the national pharmaceutical group chemical agents limited.
Copper chloride: from Shanghai McLin Biochemical technology, inc.
Sodium hydroxide: purchased from the national pharmaceutical group chemical agents limited.
Sodium carbonate: from Shanghai McLin Biochemical technology, inc.
Ammonia water: from Shanghai McLin Biochemical technology, inc.
Aluminum sulfate: from Shanghai McLin Biochemical technology, inc.
Iron chloride: purchased from the national pharmaceutical group chemical agents limited.
Mineral powder: s95-grade mineral powder purchased from Hunan Sanhong building materials Co., ltd.
Fly ash: purchased from Changan Yiyang power generation Co.
Silica fume: purchased from solid strength limited of Hunan.
Standard sand I: china ISO standard sand, purchased from Xiamen Aisiou Standard Sand Co.
Coarse aggregate: gravel with an average particle size of 20mm, purchased from Changsha, hunan.
Alkali activator I: the modulus was 1 and the solids content was 22.44wt% for the combination of sodium hydroxide and sodium water glass.
Alkali activator II:10wt% aqueous sodium hydroxide solution.
Preparation example 1
(1) In the presence of 80L of water I, carrying out contact reaction I on 240mol of magnesium chloride and 480mol of sodium hydroxide, filtering, and washing with deionized water until the pH value of the solution is 7 to obtain a product I;
wherein the dosage molar ratio of the soluble divalent cation salt to the alkaline substance I is 1:2;
the conditions of the contact reaction I are as follows: the temperature is 120 ℃, and the time is 3 hours;
(2) Simultaneously dropwise adding a mixture I consisting of a product I with the concentration of 3mol/L and aluminum sulfate with the concentration of 1mol/L and a mixed solution of sodium carbonate with the concentration of 1mol/L and sodium hydroxide with the concentration of 16mol/L into a three-neck flask for carrying out contact reaction II-1, and controlling the dropwise adding speed to ensure that the pH value of a contact reaction II-1 system is 9.5;
the dosage molar ratio of the soluble trivalent cation salt to the product I to the alkaline substance II is 1:3:17;
the conditions of the contact reaction II-1 are as follows: the temperature is 60 ℃, and the time is 2h;
after the dropwise addition, quickly transferring the reaction solution into a reaction kettle for contact reaction II-2, naturally cooling to room temperature, filtering, and washing with deionized water until the pH value is 7; then drying the hydrotalcite in an oven at 65 ℃ for 24 hours to obtain hydrotalcite S1;
the conditions of the contact reaction II-2 are as follows: the temperature is 150 ℃, and the time is 12h;
(3) Calcining the hydrotalcite S1 to obtain MgO & 1/6Al 2 O 3 ·4H 2 Calcined hydrotalcite of O H1 having an average particle size of 2.5 μm;
the conditions of the calcination treatment were: the initial temperature was 25 deg.C, the rate of temperature rise was 5 deg.C/min, the end temperature T was 500 deg.C, and held at T for 4h.
Preparation example 2
This preparation was carried out analogously to preparation 1, with the exception that: equimolar replacement of magnesium chloride by zinc chloride, and
replacement of aluminum sulfate equimolar to ferric chloride, and
the conditions of the calcination treatment were adjusted to: the initial temperature is 30 ℃, the heating rate is 10 ℃/min, the termination temperature T is 600 ℃, and the temperature is kept for 6h at the T temperature;
the other conditions were the same as in preparation example 1, and ZnO 1/6Fe was obtained 2 O 3 ·6H 2 O, and an average particle diameter of 1.5 μm.
Preparation example 3
This preparation was carried out in a similar manner to preparation 1, except that: equimolar replacement of magnesium chloride with copper chloride, and
replacing the mixed solution of sodium carbonate and sodium hydroxide with an ammonia water solution with the concentration of 8 mol/L;
the dosage molar ratio of the soluble trivalent cation salt to the product I to the alkaline substance II is 1:3:13;
the other conditions were the same as in preparation example 1, and CuO.1/6 Al was prepared 2 O 3 ·4H 2 Calcined hydrotalcite of O H3 having an average particle diameter of2μm。
Comparative preparation example 1
This comparative preparation was carried out analogously to preparation 1, with the exception that:
adjusting the concentration of the product I to 0.5mol/L;
the dosage molar ratio of the soluble trivalent cation salt to the product I to the alkaline substance II is 1:1/2:3; the other conditions were the same as in preparation example 1, and MgO. Al was obtained 2 O 3 ·4H 2 O calcined hydrotalcite DH1 having an average particle size of 3 μm.
Comparative preparation example 2
This comparative preparation was carried out in a similar manner to preparation 1, except that:
adjusting the termination temperature T in the calcination treatment to 800 ℃; the other conditions were the same as in preparation example 1, and MgO.1/6 Al was prepared 2 O 3 ·6H 2 O calcined hydrotalcite DH2 having an average particle size of 2.7 μm.
Example 1
This example illustrates the composition of the present invention for preparing high durability marine concrete according to the formulation and process parameters of table 1, and the method of preparing the high durability marine concrete as described below.
(i) Performing first mixing on mineral powder, standard sand and calcined hydrotalcite to obtain a mixture I;
(ii) Secondly, mixing the mixture I with an alkali activator to obtain the high-durability marine concrete T1;
wherein the first mixing conditions are as follows: stirring at 150rpm for 4min at room temperature;
the conditions for the second mixing are: the stirring was carried out at 240rpm for 4min at room temperature.
The remaining examples and comparative examples of the present invention were prepared using similar formulations and methods as in example 1 to produce high durability marine concrete, with specific composition formulations and process parameters as shown in table 1.
TABLE 1
TABLE 1
Test example
The high durability marine concrete prepared in the examples and comparative examples was tested according to the following method, and the test results are shown in table 2:
(1) The chloride migration coefficient was obtained by driving chloride ions into the sample by an external voltage and measuring the depth of chloride penetration, with reference to northern european standard NT Build 492.
(2) And (3) determining the carbonization depth by referring to GB/T50082-2009 Standard test method for long-term performance and durability of common concrete.
TABLE 2
The results in table 2 show that the concrete prepared from the composition containing the calcined hydrotalcite provided by the present invention has both good resistance to chloride ion attack and resistance to carbonization attack, and thus has high durability.
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 combinations of various technical features 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 calcined hydrotalcite having a chemical formula MO & aA 2 O 3 ·bH 2 O，
Wherein M is selected from at least one of Mg, ca, zn, cu, co and Mn;
a is selected from at least one of Al, ga, fe and Cr;
a is selected from any number from 0.1 to 0.5, and b is selected from any integer.
2. A process for preparing the calcined hydrotalcite of claim 1, characterized in that the process comprises: calcining hydrotalcite;
wherein the conditions of the calcination treatment include: the initial temperature is 20-35 ℃, the heating rate is 5-10 ℃/min, the termination temperature T is 400-600 ℃, and the temperature is kept for 3-8h at the T temperature;
preferably, the method further comprises: the hydrotalcite is synthesized by one of a coprecipitation method, a hydrothermal synthesis method and an ion exchange method.
3. The method of claim 2, wherein the method further comprises: synthesizing the hydrotalcite by adopting a coprecipitation method comprising the following steps:
(1) In the presence of water I, carrying out contact reaction I on a soluble divalent cation salt and an alkaline substance I to obtain a product I;
(2) In the presence of water II, carrying out contact reaction II on the mixture I and an alkaline substance II in a dropwise manner, and then drying to obtain the hydrotalcite;
wherein the mixture I contains soluble trivalent cation salt and the product I.
4. The process according to claim 3, wherein in step (1), the soluble divalent cation salt and the alkaline substance I are used in a molar ratio of 1:1-3; and/or the presence of a gas in the gas,
in step (1), the conditions of the contact reaction I include: the temperature is 120-170 ℃ and the time is 2-4h.
5. The process according to claim 3 or 4, wherein in step (2), the soluble trivalent cation salt, the product I and the basic substance II are used in a molar ratio of 1: 1/(2 a): 2/a-10/a; wherein a is selected from any number of 0.1-0.5; and/or the presence of a gas in the gas,
in step (2), the conditions of the contact reaction II comprise: the pH value is 9-10, the temperature is 50-170 ℃, and the time is 12-15h.
6. The composition for preparing the high-durability marine concrete is characterized by comprising the following components in parts by weight:
mineral powder, standard sand, coarse aggregate, an alkali activator and calcined hydrotalcite;
the content of the mineral powder is 10-20wt% based on the total weight of the composition; the content of the standard sand is 20-35wt%; the content of the coarse aggregate is 35-50wt%; the content of the alkali activator is 5-10wt%; the content of the calcined hydrotalcite is 0.1-1.5wt%;
the calcined hydrotalcite is the calcined hydrotalcite described in claim 1.
7. The composition as claimed in claim 6, wherein the ore powder is at least one selected from ore powder of grade S95 or above; and/or the presence of a gas in the gas,
the average grain diameter of the standard sand is 0.05-8mm, the content of silicon dioxide is more than 96wt%, and the loss on ignition is not more than 0.4wt%; and/or the presence of a gas in the gas,
the coarse aggregate is selected from at least one of crushed stone, gravel and pebble, and the average particle size of the coarse aggregate is 5-25mm; and/or the presence of a gas in the gas,
the alkali activator is at least one selected from sodium hydroxide and sodium water glass.
8. A method for preparing high durability marine concrete using the composition of claim 6 or 7, comprising:
(i) Performing first mixing on mineral powder, standard sand and calcined hydrotalcite to obtain a mixture I;
(ii) And secondly, mixing the mixture I with an alkali activator to obtain the high-durability marine concrete.
9. The method of claim 8, wherein in step (i), the conditions of the first mixing comprise: stirring at 150-300rpm for 1-4min at 20-40 deg.C; and/or the presence of a gas in the gas,
in step (ii), the conditions of the second mixing include: under the condition of stirring, the rotating speed of the stirring is 200-400rpm, the time is 2-8min, and the temperature is 20-40 ℃.
10. High durability marine concrete prepared by the method of claim 8 or 9.
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