CN108373298B - Nickel iron slag oxalate chemical bonding cementing material - Google Patents

Nickel iron slag oxalate chemical bonding cementing material Download PDF

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CN108373298B
CN108373298B CN201810156911.1A CN201810156911A CN108373298B CN 108373298 B CN108373298 B CN 108373298B CN 201810156911 A CN201810156911 A CN 201810156911A CN 108373298 B CN108373298 B CN 108373298B
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oxalate
nickel
chemical bonding
slag
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CN108373298A (en
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罗中秋
周新涛
王敬冬
王昊
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Kunming University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/005—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 gelatineous or gel forming binders, e.g. gelatineous Al(OH)3, sol-gel binders
    • 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

Abstract

The invention discloses a nickel iron slag oxalate chemical bonding cementing material, belonging to the technical field of building materials; the chemical bonding cementing material composition comprises 100 parts of nickel-iron slag and 25-45 parts of acid component by weight; the cementing material is stirred and mixed with water, and has the excellent performances of controllable condensation speed, quick hardening, high early strength, quick low-temperature condensation speed, good wear resistance and frost resistance, dry shrinkage and the like; the oxalate chemical bonding cementing material is prepared by utilizing the composite metal oxide in the nickel-iron slag, the material preparation cost is reduced, a new way is improved for the efficient resource utilization of the nickel-iron slag, and the method has certain environmental protection and economic benefits.

Description

Nickel iron slag oxalate chemical bonding cementing material
Technical Field
The invention relates to a nickel iron slag oxalate chemical bonding cementing material, and belongs to the technical field of building materials.
Background
The ferronickel slag is granulated slag formed by water quenching of waste discharged from laterite-nickel ore in the smelting process of extracting metallic nickel or ferronickel alloy. Although the iron-nickel slag has similar aluminum and silicon active components with blast furnace slag and fly ash, the chemical components of the produced iron-nickel slag are different from the blast furnace slag and the fly ash due to different smelting raw materials and processes, so that the comprehensive utilization rate is low and is only 10%. According to statistics, the amount of ferronickel slag discharged in China every year reaches more than 1500 million tons, and the accumulated stock over the years is nearly 1 hundred million tons, which approximately accounts for 1/5 of the total amount of metallurgical slag. The nickel-iron slag contains a large amount of SiO2(40% -50%), MgO (25% -35%), FeO (5% -10%) and small amount of Cr, Co, Mn, Ti, etc., and the main phases are olivine. At present, the research on the resource utilization of the nickel-iron slag mainly comprises the aspects of recovering valuable metals, portland cement admixtures, building materials and the like. The valuable metals are recovered, and the content of the valuable metals remaining in the slag is limited, so that even if all the valuable metals are recovered, the influence on the reduction of the slag amount is very little, and even the valuable metals are possibly greatly increased. In the aspects of portland cement admixtures and building materials, the material has a swelling problem due to the high MgO content in the nickel-iron slag. Therefore, a new technical approach for resource utilization of the ferronickel slag is urgently needed.
The method can be used for preparing a chemical bonding cementing material based on the high content characteristic of the ferronickel slag metal oxide (MgO (25% -35%) and FeO (5% -10%)). Chemical Bonded Ceramics (CBC) is a novel inorganic gelled material produced by acid-base chemical reaction of alkaline earth metal oxides (MgO, ZnO, FeO) with acid or soluble acid salt, additives, mineral admixtures, etc. in a certain proportion. Currently, magnesium phosphate chemically bonded cementitious materials are being studied more. The magnesium phosphate chemically bonded cementing material is prepared from magnesium oxide and phosphate (NH)4H2PO4、KH2PO4、(NH4)2HPO4、K2HPO4And several kinds of double salt), retarder (borax), admixture (fly ash) and the like. The magnesium phosphate chemically bonded cementitious material has better performance than the traditional cement in many aspects, such as the advantages of quick setting, quick hardening, high early strength, high low-temperature setting speed, high bonding strength with old concrete, good wear resistance and frost resistance, small drying and the like. The unique performance of the magnesium phosphate cement makes the magnesium phosphate cement have wide application prospect in the aspects of rapid repair of expressways, airport runways and main roads, solid waste treatment and solidification and the like. However, the magnesium phosphate chemical bonding gelled material has too high solidification speed at high temperature, is not beneficial to construction operation, and is not rapid enough at extremely low temperature. In addition, the raw material adopted in the preparation process of the magnesium phosphate chemical bonding material is magnesium oxide which is used as a chemical reagent and is expensive. Therefore, the development direction of preparation and application research of the phosphate chemical bonding material is to improve the construction operability of the material and search for a proper reaction raw material to replace MgO so as to reduce the preparation cost of the material.
Disclosure of Invention
The invention aims to provide a chemical bonding cementing material of oxalate of nickel-iron slag, which takes the nickel-iron slag as a raw material and salt rich in oxalate or oxalic acid as an acidic component to prepare the chemical bonding cementing material of oxalate of nickel-iron slag; the ferronickel slag oxalate chemical bonding cementing material prepared by the method still has the excellent performances of quick setting and hardening, high early strength, high low-temperature setting speed, good wear resistance and frost resistance, dry shrinkage and the like. The method has the advantages that the ferronickel slag is used for replacing magnesium oxide in the traditional method, the material preparation cost is reduced, a new way is provided for efficient resource utilization of the ferronickel slag, and the method has certain environmental protection and economic benefits.
The invention relates to a composition of a ferronickel slag oxalate chemical bonding cementing material, which comprises 100 parts of ferronickel slag and 25-45 parts of acid components by weight.
The chemical bonding cementing material of the ferronickel slag oxalate can also be added with 1 to 10 weight portions of retarder.
And grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5%.
The acidic component is one or more of oxalic acid, sodium hydrogen oxalate and sodium oxalate.
The retarder is one or more of boric acid, borax, sodium tripolyphosphate and triethanolamine.
The invention has the advantages and beneficial effects that:
(1) the application method of the nickel iron slag oxalate chemical bonding cementing material is similar to that of common silicate, only water needs to be added, and the operation is simple;
(2) the nickel-iron slag and the acidic component are subjected to acid-base chemical reaction to form an inorganic gelled material taking oxalate as a binder phase, so that the material has excellent performances of quick setting and hardening, high early strength, high low-temperature setting speed, good wear resistance and frost resistance, shrinkage and the like;
(3) the nickel-iron slag, the oxalic acid and the oxalate acid components are compounded, and the retarder is added, so that the reaction speed of the material can be adjusted, the solidification speed of the material is improved, the operability of the material is improved, the construction difficulty is reduced, and the application prospect of the nickel-iron slag oxalate chemical bonding cementing material is expanded;
(4) the oxalate chemical bonding cementing material is prepared by utilizing the composite metal oxide in the nickel-iron slag, the material preparation cost is reduced, a new way is improved for the efficient resource utilization of the nickel-iron slag, and the method has certain environmental protection and economic benefits.
Drawings
FIG. 1 is an SEM image of ferronickel slag;
fig. 2 is an SEM photograph of the nickel iron slag oxalate chemical bonding material of example 2.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1
(1) The chemical bonding binding material of the oxalate of the ferronickel slag consists of 1000g of the ferronickel slag and 350g of acidic components (oxalic acid); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5%;
(2) the preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the materials on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time for 30min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is.
Example 2
(1) The chemical bonding binding material of the oxalate of the ferronickel slag consists of 1000g of the ferronickel slag, 350g of an acidic component (oxalic acid) and 60g of a retarder (boric acid); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 310g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm × 20mm, and carrying out vibration forming on a vibration table to obtain a ferronickel slag oxalate chemical bonding material sample, testing the setting time of the ferronickel slag oxalate chemical bonding material sample to be 55min, demoulding the sample after forming for 3h, curing the sample to a certain age by adopting a natural curing mode to test the compressive strength of the sample, and testing the compressive strength of the sample 3d to be 33.45MPa, wherein the SEM of the material of the embodiment is shown in figure 2, and as can be seen from the figure, after the reaction of the loose angular irregular particles (figure 1) of the ferronickel slag, the acid components and the retarder are connected into a whole, and a hardened.
Example 3
(1) The chemical bonding binding material of the oxalate of the ferronickel slag comprises 1000g of the ferronickel slag, 400g of an acidic component (oxalic acid) and 100g of a retarder (boric acid); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 300g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the materials on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time for 70min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is.
Example 4
(1) The chemical bonding binding material of the ferronickel slag oxalate consists of 1000g of ferronickel slag, 300g of acidic component (oxalic acid) and 100g of retarder (50% of boric acid and 50% of sodium tripolyphosphate); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5%;
(2) the preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the mixture into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the mixture on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time of the sample to be 40min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing the sample to a certain age in a natural curing mode, wherein the compressive strength.
Example 5
(1) The chemical bonding binding material of the oxalate of the ferronickel slag comprises 1000g of the ferronickel slag, 250g of an acidic component (oxalic acid) and 60g of a retarder (80 percent of boric acid and 20 percent of borax); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the materials into a 20mm × 20mm × 20mm six-link die, forming the materials in a vibration table in a vibration mode to obtain a nickel-iron slag oxalate chemical bonding material sample, testing the setting time of the nickel-iron slag oxalate chemical bonding material sample to be 50min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is 34.96 MPa.
Example 6
(1) The chemical bonding binding material of the nickeliferous iron slag oxalate consists of 1000g of nickeliferous iron slag, 350g of acidic component (oxalic acid) and 60g of retarder (40% of boric acid, 20% of borax, 20% of sodium tripolyphosphate and 20% of triethanolamine); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the mixture into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the mixture on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time of the sample to be 45min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing the sample to a certain age in a natural curing mode, wherein the compressive strength.
Example 7
(1) The chemical bonding binding material of the nickel iron slag oxalate consists of 1000g of nickel iron slag, 450g of acidic component (oxalic acid) and 70g of retarder (40% of boric acid, 20% of borax, 20% of sodium tripolyphosphate and 20% of triethanolamine); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 350g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the materials on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time of the sample to be 65min, forming the sample for 3h, then demoulding, and testing the compressive strength of the sample by adopting a natural curing mode to a certain age, wherein the compressive strength of.
Example 8
(1) The chemical bonding binding material of the ferronickel slag oxalate consists of 1000g of ferronickel slag, 250g of acidic components (oxalic acid 80 percent and sodium hydrogen oxalate 20 percent) and 50g of retarder (boric acid 40 percent, borax 20 percent, sodium tripolyphosphate 20 percent and triethanolamine 20 percent); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the materials into a 20mm × 20mm × 20mm six-link die, forming the materials in a vibration table in a vibration mode to obtain a nickel-iron slag oxalate chemical bonding material sample, testing the setting time of the nickel-iron slag oxalate chemical bonding material sample to be 60min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is 28.98 MPa.
Example 9
(1) The chemical bonding binding material of the oxalate of the ferronickel slag comprises 1000g of the ferronickel slag, 300g of acidic components (60 percent of oxalic acid and 40 percent of sodium oxalate) and 40g of retarder (80 percent of boric acid and 20 percent of borax); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the materials on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time of the sample to be 85min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the.
Example 10
(1) The chemical bonding binding material of the ferronickel slag oxalate consists of 1000g of ferronickel slag, 450g of acidic components (75% of oxalic acid and 25% of sodium hydrogen oxalate) and 30g of retarder (80% of boric acid and 20% of borax); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 350g of water, mixing and stirring for 3min, quickly pouring the materials into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming the materials on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time of the sample to be 75min, demoulding the sample after forming for 3h, and testing the compressive strength of the sample by curing the sample to a certain age in a natural curing mode, wherein the compressive strength.
Example 11
(1) The chemical bonding binding material of the ferronickel slag oxalate consists of 1000g of ferronickel slag and 250g of acidic components (60% of oxalic acid, 20% of sodium hydrogen oxalate and 20% of sodium oxalate); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 330g of water, mixing and stirring for 4min, quickly pouring into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time for 90min, demoulding after the sample is formed for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is 26.56.
Example 12
(1) The chemical bonding binding material of the nickeliferous iron slag oxalate consists of 1000g of nickeliferous iron slag, 280g of acidic components (60% of oxalic acid, 20% of sodium hydrogen oxalate and 20% of sodium oxalate) and 20g of retarder (50% of borax, 25% of boric acid and 25% of sodium tripolyphosphate); grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
(2) The preparation of the sample comprises the steps of weighing the corresponding materials in the step (1), adding 400g of water, mixing and stirring for 4min, quickly pouring into a six-link die with the thickness of 20mm × 20mm, the thickness of × 20mm and the thickness of 20mm, the thickness of × mm and the thickness of 20mm, vibrating and forming on a vibrating table to obtain a sample of the ferronickel slag oxalate chemical bonding material, testing the setting time to be 85min, demoulding after the sample is formed for 3h, and testing the compressive strength of the sample by curing in a natural curing mode to a certain age, wherein the compressive strength of the sample 3d is 27..
The above-described embodiments are only some of the preferred embodiments of the present invention, and variations and substitutions which are within the scope of the present invention and which are made by those skilled in the art are also intended to be included in the scope of the present invention.

Claims (4)

1. The chemical bonding cementing material for the ferronickel slag oxalate is characterized in that: the composition and the weight portion are 100 portions of nickel-iron slag and 25 to 45 portions of acid component;
the acidic component is one or more of oxalic acid, sodium hydrogen oxalate and sodium oxalate.
2. The ferronickel slag oxalate chemically bonded cementitious material of claim 1, characterized in that: the composition also comprises 1-10 parts by weight of retarder.
3. The ferronickel slag oxalate chemically bonded cementitious material according to claim 1 or 2, characterized in that: grinding the nickel-iron slag powder and sieving the powder with a 80-mesh sieve, wherein the sieve residue is less than 5 percent.
4. The ferronickel slag oxalate chemically bonded cementitious material of claim 2, characterized in that: the retarder is one or more of boric acid, borax, sodium tripolyphosphate and triethanolamine.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218016A (en) * 1997-11-25 1999-06-02 徐文靖 Magnesium mineral board
CN1343641A (en) * 2000-09-21 2002-04-10 王恕昌 Ordinary-temp solidifying agent for preparing building material
CN106007430A (en) * 2016-05-12 2016-10-12 昆明理工大学 Copper-slag-based ferritic oxalate chemical bonded material and application thereof
CN106045351A (en) * 2016-05-30 2016-10-26 昆明理工大学 Water-granulated-slag-based oxalate chemical bonding material and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1218016A (en) * 1997-11-25 1999-06-02 徐文靖 Magnesium mineral board
CN1343641A (en) * 2000-09-21 2002-04-10 王恕昌 Ordinary-temp solidifying agent for preparing building material
CN106007430A (en) * 2016-05-12 2016-10-12 昆明理工大学 Copper-slag-based ferritic oxalate chemical bonded material and application thereof
CN106045351A (en) * 2016-05-30 2016-10-26 昆明理工大学 Water-granulated-slag-based oxalate chemical bonding material and application thereof

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