CN113562996A - Superfine copper-based carbon-free cementing material and preparation method and application thereof - Google Patents
Superfine copper-based carbon-free cementing material and preparation method and application thereof Download PDFInfo
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- CN113562996A CN113562996A CN202110826182.8A CN202110826182A CN113562996A CN 113562996 A CN113562996 A CN 113562996A CN 202110826182 A CN202110826182 A CN 202110826182A CN 113562996 A CN113562996 A CN 113562996A
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 97
- 239000010949 copper Substances 0.000 title claims abstract description 97
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 75
- 239000000843 powder Substances 0.000 claims abstract description 70
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 30
- 239000011707 mineral Substances 0.000 claims abstract description 30
- 239000003349 gelling agent Substances 0.000 claims abstract description 23
- 239000013543 active substance Substances 0.000 claims abstract description 21
- 239000010881 fly ash Substances 0.000 claims abstract description 18
- 239000002893 slag Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000011593 sulfur Substances 0.000 claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000012190 activator Substances 0.000 claims abstract description 4
- 239000004568 cement Substances 0.000 claims description 46
- 239000004567 concrete Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- 239000002131 composite material Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 13
- 230000022676 rumination Effects 0.000 claims description 12
- 208000015212 rumination disease Diseases 0.000 claims description 12
- 239000007767 bonding agent Substances 0.000 claims description 10
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 229920000142 Sodium polycarboxylate Polymers 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 239000002956 ash Substances 0.000 claims description 7
- 229910052916 barium silicate Inorganic materials 0.000 claims description 7
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 7
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical group O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000011491 glass wool Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 239000010440 gypsum Substances 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 150000004760 silicates Chemical class 0.000 claims description 7
- 239000000344 soap Substances 0.000 claims description 7
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 7
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- 229940117013 triethanolamine oleate Drugs 0.000 claims description 7
- 229960004418 trolamine Drugs 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 19
- 229910052799 carbon Inorganic materials 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000009826 distribution Methods 0.000 description 8
- 239000004576 sand Substances 0.000 description 7
- 239000002910 solid waste Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Abstract
The invention relates to a superfine copper-based carbon-free cementing material, a preparation method and application thereof, wherein the superfine copper-based carbon-free cementing material comprises the following components in parts by weight: exciting agent: 60-120 parts by weight; the specific surface area is more than 700m2Per kg; ash-slag or fly ash of solid sulfur: 5-15 parts by weight; other auxiliary agents: 8 parts by weight; the activator comprises: 30-70 parts of copper tailings and 30-50 parts of S95 mineral powder by weight are ground to obtain the copper tailings with the specific surface area of more than 700m2/kg of superfine mineral powder; the other auxiliary agents comprise active agents, binding agents, grinding aids and gelling agents.
Description
Technical Field
The invention belongs to the technical field of novel environment-friendly materials, relates to industrial solid waste utilization, and particularly relates to a superfine copper-based carbon-free cementing material, and a preparation method and application thereof.
Background
Tailings are the main industrial solid wastes of resource-type cities, have significant environmental problems and potential safety hazards, and mainly comprise:
1. tailings are a source of pollution causing significant environmental problems
The outstanding features are land encroachment, vegetation destruction, land degradation, desertification, dust pollution, water pollution and the like. The tailings have fine granularity, are piled up for a long time, are seriously weathered, generate secondary dust raising, and fly around in peripheral areas, particularly in drought and high wind seasons, the fine-particle tailings are emptied, so that the yellow dragon in several miles can be formed, the pollution to the surrounding soil is caused, and the body health of residents is seriously influenced. Tailings are one of the key dust sources for the generation of sand storms.
2. Tailings ponds are also a significant source of danger
The tailing pond is a special structure for stockpiling flow plastic objects (tailings), is listed as a major hazard by the national security supervision department, accounts for 30 percent of the tailing pond with potential safety hazards in black mine tailing ponds running nationwide, and breaks the dam of the tailing pond every year in China, thereby causing major casualties and property loss.
Over the years, mine solid waste stockpiling induces secondary geological disasters, such as large engineering and geological disasters of a dump landslide, debris flow, dam break of a tailing pond and the like, and brings great loss to the society. Statistics of 2500 or more large-scale tailings ponds in China show that debris flow and dam break 200 are left over since the 80 s of the 20 th century.
The invention mainly solves the problem of a large amount of copper tailings generated in the process of refining copper in the locations of copper ore resources. So far, the copper tailings bring serious harm to local natural environment and living environment of people, and are one of the key points of national environmental governance. The invention is just the industrial solid waste utilization of the copper tailings.
Disclosure of Invention
The invention aims to provide an ultrafine copper-based carbon-free cementing material, a preparation method and application thereof, which greatly improve the activity and strength of industrial waste residues and mineral powder, complement the advantages of various micro powders, greatly improve the addition amount in cement and concrete, reduce the clinker consumption and realize carbon emission reduction.
In order to achieve the above purpose, the invention adopts the technical scheme that: the superfine copper-based carbon-free cementing material comprises the following components in parts by weight:
exciting agent: 60-120 parts by weight; the specific surface area reaches 700m2/kg；
Ash-slag or fly ash of solid sulfur: 5-15 parts by weight;
other auxiliary agents: 8 parts by weight;
the activator comprises: 30-70 parts of copper tailings and 30-50 parts of S95 mineral powder by weight are ground to obtain the copper tailings with the specific surface area of more than 700m2/kg of superfine mineral powder;
the other auxiliary agents comprise active agents, binding agents, grinding aids and gelling agents.
Furthermore, the specific surface area of the superfine copper-based carbon-free cementing material reaches 700m2/kg。
Still further, the exciting agent is prepared by grinding copper tailings and S95 mineral powder through a rumination type open circuit regrinding process, and the specific surface area reaches 720m2/kg。
Furthermore, the superfine copper-based carbon-free cementing material is prepared by grinding through a rumination type open-circuit regrinding process, and the specific surface area reaches 720m2/kg。
Still further, the other auxiliary agents include: 1-5 parts of gelling agent, 0.1-0.5 part of grinding aid, 1-2 parts of active agent and the balance of bonding agent; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: (4-5): (4-5.5): (3-4) a composite gelling agent; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: (3-5): (3-4): (1-1.5) the composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 2: (3-5): (2-4) the complex active agent; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: (3-3.5) the complex binder.
Still further, the copper tailings can be replaced by slag or steel slag.
A preparation method of an ultrafine copper-based carbon-free cementing material comprises the following steps:
a) pretreating component materials;
b) weighing the components;
c) grading compatibility;
d) assembling grinding equipment;
e) rumination type open circuit regrinding;
f) detecting the granularity and the activity;
the grading compatibility in the step b) comprises first-grade compatibility and multi-grade compatibility, wherein the first-grade compatibility is to carry out step e) grinding on the components in the step b) to the particle size in the same range by one-step preparation;
the multistage compatibility comprises the following steps: preparing the exciting agent component, grinding the component in the step e) to the particle size in the same range, grinding other components to the particle size in another range, and mixing or grinding the exciting agent with the other components; and the exciting agent component is firstly prepared and ground in the step e) to the particle size in the same range, then the solid sulfur ash or the fly ash is prepared and ground in the step e) to the particle size in the other range, the rest of the components are ground to the particle size in the other range, and the exciting agent, the solid sulfur ash or the fly ash are mixed or ground with the rest of the components.
Furthermore, the grinding equipment for each grade of grinding with multi-grade compatibility is matched with corresponding grinding body grading adjustment.
Still further, the step e) rumination type open circuit regrinding process sequentially comprises the following steps: drying the raw material components
Electronic scale batching
Rumination type superfine grinding
And (6) warehousing the finished product.
The application of the superfine copper-based carbon-free cementing material is characterized in that 15-20 wt% of the superfine copper-based carbon-free cementing material is added into cement; 15 to 35 percent of cement mixing amount is replaced in the concrete.
The invention has the technical effects that: the invention is characterized in that the difficult problem of mine tailings is solved, tailings discharged from copper ore dressing and copper tailings piled in a tailing pond are compounded by a plurality of effective additives, and then the superfine copper-based carbon-free cementing material is obtained by grinding through the process. The superfine copper-based carbon-free cementing material produced by the formula is added into cement as a mixed material, and an admixture in concrete replaces cement, so that the production of low-carbon cement and low-carbon concrete is realized.
Drawings
FIG. 1 is a particle size distribution diagram of ultra-fine (S95) ore powder in the test of the present invention;
FIG. 2 is a particle size distribution diagram of the ultra-fine copper tailings in the test of the present invention.
Detailed Description
In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. The following is a preferred embodiment of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
The invention is characterized in that the difficult problem of mine tailings is solved, tailings discharged from copper ore dressing and copper tailings piled in a tailing pond are compounded by a plurality of effective additives, and the superfine copper-based carbon-free cementing material is obtained by grinding through the process. The superfine copper-based carbon-free cementing material produced by the formula is added into cement as a mixed material, and an admixture in concrete replaces cement, so that the production of low-carbon cement and low-carbon concrete is realized.
The scheme of the invention can also be directly applied to cement production. I.e. slag (S95 mineral powder) and fly ash (or solid sulfur slag) which are added in the cement production process, usually only powderGrinding to a specific surface area of 400m2About/kg; similarly, the scheme of the invention can also be directly applied to concrete production, and the specific surface area of the S95 mineral powder and the first-grade fly ash doped in the concrete is also 400-420 m2About/kg. That is, usually, neither slag nor fly ash is ground sufficiently, and the performance is not fully exerted, so that the addition amount of both in cement and concrete is limited. Thus, the ultrafine test mills of the applicant of application No. 2021213943042 were used to obtain ultrafine composites having specific surface areas of greater than 700m2In terms of/kg. Thus, the scheme of the invention can also be directly applied to cement production and concrete production.
The scheme of the invention optimizes and mixes the copper tailings, the furnace slag or the steel slag and the like with the S95 mineral powder, and then mixes and grinds the mixture to the specific surface area of 700m2More than kg (30 mu m sieve residue)<0.5%) of the superfine copper-based carbon-free cementing material, so that the activity and the strength of the industrial waste residue and the mineral powder are greatly improved, the advantages of various micro powders are complemented, the addition amount of the micro powders in cement and concrete is greatly increased, the clinker consumption is reduced, and carbon emission reduction is realized.
More specifically, the present invention comprises: the components are designed into (30-70 parts by weight of copper tailings, 30-50 parts by weight of S95 mineral powder, 5-15 parts by weight of solid sulfur ash slag or fly ash, and 8 parts by weight of other auxiliary agents (active agent, bonding agent, grinding aid and gelling agent)) and the grinding process (rumination type open circuit re-grinding process). Wherein: the component design solves the proportion and grinding gradation of the formula; the grinding process solves the problem of the formation of the form of the substances in the formula, and the realization of a physical shelf structure model for improving the strength of the superfine copper-based carbon-free cementing material formed by the formula in main materials (cement and concrete) is solved.
The principle of the invention is a technical scheme for changing waste into valuable, which is provided for the copper tailings serving as a pollution source. The copper tailings are used as main raw materials to obtain a specific excitant (superfine mineral powder), and a proper amount of sulfur-fixing ash (or fly ash) and adjusting materials (including an activator and the like) are added to obtain the superfine copper-based carbon-free cementing material. It can be added to cement at 15 wt% (i.e. 15: 85) or to concrete instead of 15-35% cement (i.e. 15 wt: the weight of the concrete is (15% -35%): (65-85%) ], not only reduces the production cost of concrete, but also can improve the performance of premixed concrete, improve the strength index after hardening and greatly reduce the hydration heat index of concrete. Is an energy-saving and environment-friendly material which utilizes waste and reduces emission.
Example 1: a superfine copper-based carbon-free cementing material comprises 30 parts by weight of copper tailings, 30 parts by weight of S95 mineral powder and 720m of specific surface area2Per kg; fly ash: 5 parts by weight; specific surface area of 720m2Per kg; 1 part by weight of gelling agent, 0.5 part by weight of grinding aid, 1 part by weight of active agent and the balance of binder; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: 4: 4: 3; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: 3: 3: 1, a composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 2: 3: 2; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: 3, the specific surface area of the composite binder reaches 700m2/kg。
Example 2: a superfine copper-based carbon-free cementing material comprises 70 parts by weight of copper tailings, 50 parts by weight of S95 mineral powder and 720m of specific surface area2Per kg; fly ash: 15 parts by weight; specific surface area of 720m2Per kg; 5 parts of gelling agent, 0.5 part of grinding aid, 2 parts of active agent and the balance of binder; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: 5: 5.5: 4; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: 5: 4: 1.5 of a composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 2: 5: 4; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: 3.5 composite binder with specific surface area up to 700m2/kg。
Example 3: an ultrafine copper-based carbon-free cementing material, 50 weight of copper tailings45 parts of S95 mineral powder and 720m of specific surface area2Per kg; ash-slag or fly ash of solid sulfur: 9 parts by weight; specific surface area of 720m2Per kg; 3 parts of gelling agent, 0.25 part of grinding aid, 1.5 parts of active agent and the balance of binder; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: 4.5: 5: 3.5 of a composite gelling agent; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: 4: 3.5: 1.2 of a composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 1: 2: 2; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: 3.2 composite binder with specific surface area up to 700m2/kg。
Example 4: a superfine copper-based carbon-free cementing material comprises 50 parts by weight of copper tailings, 42 parts by weight of S95 mineral powder and 720m of specific surface area2Per kg; ash-slag or fly ash of solid sulfur: 12 parts by weight; specific surface area 710m2Per kg; 3 parts of gelling agent, 0.3 part of grinding aid, 1.7 parts of active agent and the balance of binder; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: 4.5: 4.5: 3.5 of a composite gelling agent; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: 3.5: 3.5: 1, a composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 1: 2: 2; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: 3.5 composite binder with specific surface area up to 700m2/kg。
Example 5: an ultrafine copper-based carbon-free cementing material comprises 65 parts by weight of copper tailings, 45 parts by weight of S95 mineral powder and 700m of specific surface area2Per kg; ash-slag or fly ash of solid sulfur: 5 parts by weight; specific surface area 700m2Per kg; 4 parts of gelling agent, 0.5 part of grinding aid, 2 parts of active agent and the balance of binder; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5:4: 4.5: 4; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: 3.5: 4: 1, a composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 2: 3: 3, a complex active agent; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: 3.5 composite binder with specific surface area up to 700m2/kg。
The scheme of the invention is that S95 mineral powder and fly ash (or solid sulfur ash) are used as base materials to be ground to obtain the superfine copper-based carbon-free cementing material. The obtained material of the invention can be used as a cement admixture and a concrete admixture. On one hand, the material is applied to cement as a mixed material, so that the use amount of clinker in the cement is reduced, and low-carbon cement is produced; on the other hand, the additive is added into concrete to be used as an admixture to replace cement, so that the dosage of the cement is reduced, and the low-carbon concrete is formed. The key point is that the service performance of the cement and the concrete is greatly improved while the strength of the cement and the concrete is not reduced.
The following are the test report specific data:
firstly, raw materials:
P.O 42.5 cement (Changfeng conch)
S95 mineral powder (Ma gang Jiahua)
Copper tailings (Tianma mountain mining tailings pond of copper tomb non-ferrous metal group company)
Example materials of the invention
ISO standard sand.
II, testing the instrument:
SM500 model test mill, Euromex LS-POP (9) laser particle size analyzer, sand mixer, cement sand fluidity tester, sand test block, vibrating table, standard curing box, and sand fracture and compression resistance tester.
Third, test content
3.1 ultrafine grinding
And carrying out superfine grinding on the S95 mineral powder and the copper tailings in a test mill of a graded grinding body.
3.2 particle size distribution test
The particle size distribution of the ultra-fine (S95) ore powder and the ultra-fine copper tailings is tested by using a laser particle size analyzer. In addition, the specific gravities of the two materials were measured, and the corresponding specific surface areas were calculated.
3.3 Activity index and fluidity ratio of carbon-free cementitious Material
The ultrafine (S95) mineral powder and the ultrafine copper tailings are compounded with other components to form the copper-based carbon-free cementing material, and the activity index and the fluidity ratio of the copper-based carbon-free cementing material are measured according to GB/T18046-2017 'granulated blast furnace slag powder for cement, mortar and concrete'.
Fourth, test results and discussion
1. Particle size distribution
The results of the particle size distribution test of the ultra-fine (S95) ore powder and the ultra-fine copper tailings are shown in Table 1.
Table 1 particle size test results
2. Activity index, fluidity ratio
The test mixture ratio is shown in Table 2, the standard sand dosage is 1350g, the water consumption is 225g, and the test result is shown in Table 3.
Table 2 activity index, fluidity ratio test mix units: g
TABLE 3 fluidity ratio and Activity index test results
As shown in Table 3, the fluidity ratio and the activity index of the copper-based carbon-free cementing material prepared by compounding the superfine (S95) mineral powder and the superfine copper tailings with other components are both superior to the indexes of S95 mineral powder.
Fifth, conclusion
1. The experimental grinding results of the grinding body with the grading distribution show that the easy grindability of the powder of Jiahua S95 marfan and the copper tailings of Tianma mountain tailings pond of the company of nonferrous metal group of bronze tomb is better, and the superfine powder meeting the requirements of particle size distribution and fineness can be obtained by superfine grinding.
2. The fluidity ratio and the activity index of the copper-based carbon-free cementing material prepared by compounding the superfine (S95) mineral powder, the superfine copper tailings and other components are superior to the indexes of S95 mineral powder.
1. Super fine (S95) ore powder granularity detection report
2. Ultra-fine copper tailing granularity test report
The technology of the invention realizes the following elements: 1. utilization of copper tailings: firstly, the resource utilization of copper tailings is carried out, and the availability (radioactivity, S content and Cl content) is determined by chemical analysis—Detecting the ion, the ignition loss and the like to meet the standard), and drying for later use. 2. Designing components: activating agent is needed to excite the strength of the tailings, and proper grinding aid, additive and the like are selected according to the grindability. 3. Ultra-fine grinding: the rumination type grinding mechanism is applied, a pipe mill with large length-diameter ratio is adopted, the components are subjected to superfine grinding according to grading and superfine grinding by adopting an open circuit grinding process to form grain grading, the grain grading is physically mixed into a required shelf structure, and the shelf structure is added into an application object to form high strength and high performance characteristics. The invention is particularly suitable for industrial production: through reasonable process design, grinding body grading adjustment and rumination type grinding, the energy consumption level is higherLow production capacity.
The invention discloses a superfine copper-based carbon-free cementing material taking copper tailings as a main raw material, and a preparation method and application thereof. The superfine copper-based carbon-free cementing material is prepared from the following raw materials in parts by weight: 30-70 parts of copper tailings, 30-50 parts of active exciting agent (superfine mineral powder), 1-5 parts of gelling agent, 0.1-0.5 part of grinding aid and the like. The high-activity superfine copper-based carbon-free cementing material is prepared by mixing copper tailings, an active exciting agent, a grinding aid and other raw materials, and grinding and mixing grading through rumination grinding. Simple industrial production process, low energy consumption level, high industrial productivity, and specific surface area more than 700m2The performance of the material is more than the standard of S95 mineral powder per kg (30 micron screen residue is less than or equal to 0.5 percent). 15 percent of cement can be added, namely the clinker consumption is reduced by 15 percent, and low-carbon cement is formed; 60-80 kg of cement can be used in each cubic concrete, 40-60 kg of clinker is consumed less, and the low-carbon concrete is formed.
The production requirements of the low-carbon cement and the low-carbon concrete are met:
1. by adding the superfine copper-based carbon-free cementing material into the cement, 15 to 20 percent of the cement can be replaced, the dosage of clinker is reduced by 0.12 to 0.16 ton per ton of cement, and the produced cement emits less CO per ton than the conventional cement20.11-0.12 ton, so that the production of low-carbon cement becomes possible.
2. By adding the superfine copper-based carbon-free cementing material into concrete, 60-80 kg of cement can be used per cubic concrete, and the produced concrete emits less CO per cubic body than the conventional concrete26.6-9.6 kg, which is one of effective paths for producing low-carbon concrete.
The invention develops the superfine copper-based carbon-free cementing material as an additive of cement and concrete, and provides an innovative path for low-carbon development of cement enterprises and the concrete industry.
In addition, the applicant shows that various grinding devices such as a roller press, a vertical mill, a Raymond mill, a vibration mill, a ball mill and the like in China at present and various types of powder selectors matched with the grinding devices cannot produce powder with the specific surface area of more than or equal to 650m2High fineness product/kg (or production)Very low efficiency). The superfine test mill of the applicant of application No. 2021213943042 is matched with a large-length-diameter-ratio overlong tube mill, and is designed for a tube mill lining plate, a bin partition plate, a discharge grate plate and a grinding body, so that the fineness of the admixture of the formula is 30 mu m of screen residue under the condition of open circuit process<0.5% (specific surface area greater than 700 m)2Kg), the yield is 55-60 t/h, the system power consumption is 32-35 kWh/t, and the superfine copper-based carbon-free cementing material is successfully produced to be matched with the base material of the scheme of the invention.
In conclusion, the technology of the invention is characterized in that the difficult problem of mine tailings is solved, tailings discharged by copper ore dressing and copper tailings piled in a tailing pond are compounded by a plurality of effective additives, and then the superfine copper-based carbon-free cementing material is obtained by grinding through the process of the invention. The superfine copper-based carbon-free cementing material produced by the formula is added into cement as a mixed material, and an admixture in concrete replaces cement, so that the production of low-carbon cement and low-carbon concrete is realized.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. But all changes which come within the scope of the invention are intended to be embraced therein.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Claims (10)
1. The superfine copper-based carbon-free cementing material is characterized by comprising the following components in parts by weight:
exciting agent: 60-120 parts by weight; the specific surface area reaches 700m2/kg；
Ash-slag or fly ash of solid sulfur: 5-15 parts by weight;
other auxiliary agents: 8 parts by weight;
the activator comprises: 30-70 parts of copper tailings and 30-50 parts of S95 mineral powder by weight are ground to obtain the copper tailings with the specific surface area of more than 700m2/kg of superfine mineral powder;
the other auxiliary agents comprise active agents, binding agents, grinding aids and gelling agents.
2. The ultra-fine copper-based carbon-free cementing material according to claim 1, characterized in that the specific surface area of the ultra-fine copper-based carbon-free cementing material reaches 700m2/kg。
3. The superfine copper-based carbon-free cementing material according to claim 1 or 2, characterized in that the exciting agent is prepared by grinding copper tailings and S95 mineral powder through a rumination type open circuit regrinding process, and the specific surface area reaches 720m2/kg。
4. The superfine copper-based carbon-free cementing material of claim 2, wherein the superfine copper-based carbon-free cementing material is prepared by grinding through a rumination type open-circuit regrinding process, and the specific surface area reaches 720m2/kg。
5. The ultra-fine copper-based carbon-free cementitious material as claimed in claim 1, 2 or 4, wherein said other additives comprise: 1-5 parts of gelling agent, 0.1-0.5 part of grinding aid, 1-2 parts of active agent and the balance of bonding agent; the gelling agent is phosphogypsum powder in a weight ratio of: silicate salt: the lime powder comprises the following components: borax-5: (4-5): (4-5.5): (3-4) the complex gelling agent; the grinding aid is prepared from sodium polycarboxylate in a weight ratio: triethanolamine: glass wool: triethanolamine oleate soap ═ 3: (3-5): (3-4): (1-1.5) the composite grinding aid; the active agent is sodium silicate: barium silicate: sodium chromate 2: (3-5): (2-4) the complex active agent; the bonding agent is ground ceramic powder in weight ratio: 2, gypsum powder: (3-3.5) the complex binder.
6. The ultrafine copper-based carbon-free cementing material according to claim 5, characterized in that the copper tailings can be replaced by slag or steel slag.
7. The preparation method of the superfine copper-based carbon-free cementing material is characterized by comprising the following steps of:
a) pretreating component materials;
b) weighing the components;
c) grading compatibility;
d) assembling grinding equipment;
e) rumination type open circuit regrinding;
f) detecting the granularity and the activity;
the grading compatibility in the step b) comprises first-grade compatibility and multi-grade compatibility, wherein the first-grade compatibility is to carry out step e) grinding on the components in the step b) to the particle size in the same range by one-step preparation;
the multistage compatibility comprises the following steps: preparing the exciting agent component, grinding the component in the step e) to the particle size in the same range, grinding other components to the particle size in another range, and mixing or grinding the exciting agent with the other components; and the exciting agent component is firstly prepared and ground in the step e) to the particle size in the same range, then the solid sulfur ash or the fly ash is prepared and ground in the step e) to the particle size in the other range, the rest of the components are ground to the particle size in the other range, and the exciting agent, the solid sulfur ash or the fly ash are mixed or ground with the rest of the components.
8. The method for preparing the ultrafine copper-based carbon-free cementing material according to the claim 7, characterized in that the grinding equipment of each grinding stage with multi-stage compatibility is matched with the corresponding grinding body grading adjustment.
9. The preparation method of the ultrafine copper-based carbon-free cementing material according to claim 7, wherein the step e) of the ruminal open-circuit regrinding process sequentially comprises the following steps: raw material component drying → electronic scale batching → rumination type superfine grinding → finished product warehousing.
10. The application of the superfine copper-based carbon-free cementing material is characterized in that 15-20 wt% of the superfine copper-based carbon-free cementing material is added into cement; 15 to 35 percent of cement mixing amount is replaced in the concrete.
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