CN110407490A - A kind of preparation method of the compound high additive cement of inorganic solid waste - Google Patents
A kind of preparation method of the compound high additive cement of inorganic solid waste Download PDFInfo
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- CN110407490A CN110407490A CN201910805480.1A CN201910805480A CN110407490A CN 110407490 A CN110407490 A CN 110407490A CN 201910805480 A CN201910805480 A CN 201910805480A CN 110407490 A CN110407490 A CN 110407490A
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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
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The present invention discloses a kind of preparation method of compound high additive cement of inorganic solid waste, includes the following steps: that four kinds or more industrial residues are prepared and mixed according to the chemical composition of cement by (1)；(2) it is acidic activated that the progress of acid solution exciting agent is added into mixed sludge；(3) product after will be acidic activated carries out superfine grinding, obtains ultra-fine solid waste spike powder；(4) ultra-fine solid waste spike powder is mixed with 50~80% quality volume with portland cement, the compound high additive cement of inorganic solid waste is made.Method of the invention coupled based on chemical composition, the synergy of the mechanical force activating of acidic activated and high fineness these three effects, improve the activity of solid waste spike, the composite mixed cement of inorganic solid waste of preparation is in the case where 50~80% high solid waste volume, it still is able to reach the minimum compressive strength standard requirement of ordinary portland cement, overcomes the low disadvantage of high solid waste volume cement early strength.
Description
Technical field
The present invention relates to a kind of preparation methods of inorganic compound high additive cement of solid waste, belong to solid waste and utilize field.
Background technique
Common inorganic solid waste includes slag, steel slag, flyash, red mud, iron tailings, lithium slag, nickel slag, carbide slag, waste and old
Concrete, desulfurized gypsum etc..Currently, generally by the levigate mixing material or concrete admixture as cement of above-mentioned waste residue, it is right
In the high slag of activity, quality volume of the fine powder in cement is usually no more than 40%, and the steel slag of other low activities, fine coal
The volumes such as ash, red mud, iron tailings, lithium slag are very low, are sometimes a few percent.This is because their a large amount of incorporations can make cement
Early stage mechanical strength greatly declines, and 28 days intensity also has decline to a certain extent；On the other hand, certain waste residue (such as steel
Slag) in containing free MgO, CaO, or the low activity containing MgO and CaO endanger mineral, this is serious to restrict the utilization of these waste residues,
So that these waste residues is become the significant problem of environmental improvement, is also the huge waste of non-renewable resources.
Summary of the invention
Goal of the invention: waste residue utilization in the prior art there are aiming at the problem that, the present invention provides a kind of inorganic solid waste is multiple
Close the preparation method of high additive cement.
Technical solution: a kind of preparation method of the inorganic compound high additive cement of solid waste of the present invention, including walk as follows
It is rapid:
(1) four kinds or more industrial residues are prepared and is mixed according to the chemical composition of cement；
(2) it is acidic activated that the progress of acid solution exciting agent is added into mixed sludge；
(3) product after will be acidic activated carries out superfine grinding, obtains ultra-fine solid waste spike powder；
(4) ultra-fine solid waste spike powder is mixed with 50~80% quality volume with portland cement, inorganic solid waste is made
Compound high additive cement.
In above-mentioned steps (1), industrial residue can be selected from slag, steel slag, flyash, red mud, iron tailings, lithium slag, nickel slag, electricity
Rock ballast, waste and old concrete, desulfurized gypsum etc..To level off to mass percent that chemistry of cement forms to greatest extent as target, meter
Calculation obtains the quality proportioning of four kinds or more industrial residues.
In above-mentioned steps (2), acid solution exciting agent is preferably the dilute sulfuric acid of 10% volumetric concentration, 30% volumetric concentration
Sulfurous acid (H2SO3), 20% volumetric concentration acetic acid (CH3COOH), 15% volumetric concentration oxalic acid (H2C2O4One or more of)
Mixed solution.Further, the additive amount of acid solution exciting agent is the 1~4% of industrial residue gross mass.
In above-mentioned steps (3), the specific surface area of the ultra-fine solid waste spike powder obtained after superfine grinding is preferably 500~
800m2/kg。
Inventive principle: the present invention is by four kinds and the above waste residue, to level off to the quality hundred that chemistry of cement forms to greatest extent
Point than being target, quality proportioning is calculated, acid solution exciting agent is then added and destroys free MgO, CaO, or containing MgO and
The structure of the low activity mineral of CaO, and then levigate to high fineness, obtain 4 kinds or more of ultra-fine solid waste spike powder, then with
Portland cement mixing, is made cement；Pass through chemical composition coupling, acidic activated and high fineness mechanical force activating three
The synergy of kind effect, substantially increases the activity of solid waste spike, the quality of the cement of the waste residue containing high additive enable expires
Sufficient portland-type cement performance standard.
The utility model has the advantages that compared with prior art, there are following advantages by the present invention: method of the invention is based on chemical composition coupling
It closes, the synergy of the mechanical force activating of acidic activated and high fineness these three effects, the work of solid waste spike greatly improved
Property, the composite mixed cement of inorganic solid waste of preparation still is able to reach common in the case where 50~80% high solid waste volume
The minimum compressive strength standard requirement of portland cement, overcomes the low disadvantage of high solid waste volume cement early strength and part is useless
The damaging effect of free MgO, CaO or the low activity mineral containing MgO and CaO in slag；Simultaneously as this method can be great
The activity of low activity waste residue (steel slag, iron tailings, lithium slag, carbide slag, waste and old concrete etc.) is improved, is low activity waste residue in cement
In it is a large amount of using providing a kind of new method.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of the compound high additive cement of inorganic solid waste of the invention.
Specific embodiment
Technical solution of the present invention is described further with reference to the accompanying drawing.
Such as Fig. 1, a kind of preparation method of inorganic compound high additive cement of solid waste of the invention includes the following steps:
(1) four kinds or more waste residues are prepared and is mixed according to the chemical composition of cement；Specifically, with to greatest extent
The mass percent of the chemistry of cement that levels off to composition is target, and the quality proportioning of four kinds or more industrial residues is calculated；
(2) it is acidic activated that the progress of acid solution exciting agent is added into mixed sludge；
(3) product after will be acidic activated carries out superfine grinding, obtains ultra-fine solid waste spike powder；
(4) ultra-fine solid waste spike powder is mixed with 50~80% quality volume with portland cement, inorganic solid waste is made
Compound high additive cement.
Industrial residue in step (1) can be selected from slag, steel slag, flyash, red mud, iron tailings, lithium slag, nickel slag, calcium carbide
Slag, waste and old concrete, desulfurized gypsum etc..The following table 1 lists the main component of several industrial residues.
1 industrial residue main component of table
| Compound | SiO2 | CaO | Al2O3 | Fe2O3 | MgO |
| Iron-tion slag | 28~32 | 46~50 | 8~10 | 2~5 | 3~7 |
| Blast-furnace cinder | 31~44 | 31~50 | 6~18 | 0.2~1.5 | 0.05~2.6 |
| Steel slag | 10~15 | 40~60 | 2~5 | 5~10 | 2~10 |
| Flyash | 48~52 | 3~5 | 27~30 | 6~8 | 0.5~2 |
| Red mud from sintering process | 15~25 | 20~40 | 10~20 | 5~12 | 1~2 |
| Iron tailings | 30~50 | 10~30 | 2~10 | 10~20 | 5~15 |
| Nickel slag | 30~50 | 5~15 | 2~10 | 5~12 | 20~30 |
| Lithium slag | 40~50 | 10~15 | 10~20 | 0.2~1.5 | 0.2~1.5 |
| Carbide slag | 2~10 | 60~80 | 2~5 | 0.5~2 | 1~2 |
| Waste and old concrete | 40~60 | 20~30 | 10~20 | 1~2 | 1~2 |
Embodiment 1
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, additional amount
It is the 1% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2Ultra-fine solid waste spike powder is made in/kg；
It is incorporated into PII42.5 portland cement with 65% volume, high additive cement material is made.Water mixing, water-cement ratio is added
It is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, after standard curing 3 days, 28 days, is pressed
GB175-2017 surveys its compression strength.As a result 2 be see the table below.
Embodiment 2
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, mixed acid
Gross mass is the 3% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2Ultra-fine solid waste is made in/kg
Spike powder；It is incorporated into PII42.5 portland cement with 65% volume, high additive cement material is made.Water mixing is added,
Water-cement ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, standard curing 3 days, 28 days
Afterwards, its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Embodiment 3
Blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum are matched with 30%, 40%, 15%, 12%, 3% quality
Than mixing, the sulfurous acid (H of 10% volumetric concentration is then added2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20% body
Product concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, and mixed acid is total
Quality is the 4% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2/ kg is made ultra-fine solid waste and mixes
Feed powder；It is incorporated into PII42.5 portland cement with 65% volume, high additive cement material is made.Water mixing, water is added
Glue ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, after standard curing 3 days, 28 days,
Its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Embodiment 4
Steel slag, red mud, lithium slag, desulfurized gypsum are mixed with 50%, 30%, 15%, 5% quality proportioning, are then added
Sulfurous acid (the H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20% volumetric concentration acetic acid
(CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, and mixed acid gross mass is waste residue
The 3% of gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2Ultra-fine solid waste spike powder is made in/kg；With 65%
Volume be incorporated into PII42.5 portland cement, high additive cement material is made.Water mixing, water-cement ratio 0.44 is added.
Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, after standard curing 3 days, 28 days, by GB175-2017
Survey its compression strength.As a result 2 be see the table below.
Embodiment 5
Iron-tion slag, red mud, lithium slag, desulfurized gypsum are mixed with 30%, 50%, 15%, 5% quality proportioning, then
Sulfurous acid (the H of 10% volumetric concentration is added2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20% volumetric concentration acetic acid
(CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, and mixed acid gross mass is waste residue
The 3% of gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2Ultra-fine solid waste spike powder is made in/kg；With 65%
Volume be incorporated into PII42.5 portland cement, high additive cement material is made.Water mixing, water-cement ratio 0.44 is added.
Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, after standard curing 3 days, 28 days, by GB175-2017
Survey its compression strength.As a result 2 be see the table below.
Embodiment 6
Waste and old concrete, red mud, lithium slag, desulfurized gypsum are mixed with 40%, 40%, 15%, 5% quality proportioning, after
And sulfurous acid (the H of 10% volumetric concentration is added2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20% volumetric concentration acetic acid
(CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, and mixed acid gross mass is waste residue
The 3% of gross mass；It is handled again through superfine grinding, surface area reaches 700 ± 10m2Ultra-fine solid waste spike powder is made in/kg；With 65%
Volume be incorporated into PII42.5 portland cement, high additive cement material is made.Water mixing, water-cement ratio 0.44 is added.
Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, after standard curing 3 days, 28 days, by GB175-2017
Survey its compression strength.As a result 2 be see the table below.
Embodiment 7
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, mixed acid
Gross mass is the 3% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 500 ± 10m2Ultra-fine solid waste is made in/kg
Spike powder；It is incorporated into PII42.5 portland cement with 65% volume, high additive cement material is made.Water mixing is added,
Water-cement ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, standard curing 3 days, 28 days
Afterwards, its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Embodiment 8
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, mixed acid
Gross mass is the 3% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 800 ± 10m2Ultra-fine solid waste is made in/kg
Spike powder；It is incorporated into PII42.5 portland cement with 65% volume, high additive cement material is made.Water mixing is added,
Water-cement ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, standard curing 3 days, 28 days
Afterwards, its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Embodiment 9
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, mixed acid
Gross mass is the 3% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 800 ± 10m2Ultra-fine solid waste is made in/kg
Spike powder；It is incorporated into PII42.5 portland cement with 50% volume, high additive cement material is made.Water mixing is added,
Water-cement ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, standard curing 3 days, 28 days
Afterwards, its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Embodiment 10
By blast-furnace cinder, steel slag, flyash, iron tailings, desulfurized gypsum with 30%, 40%, 15%, 12%, 3% quality
Proportion mixing, is then added the sulfurous acid (H of 10% volumetric concentration2SO4), the sulfurous acid (H of 30% volumetric concentration2SO3), 20%
Volumetric concentration acetic acid (CH3) and 15% volumetric concentration oxalic acid (H COOH2C2O4), four kinds of sour mass ratioes are 1:1:1:1, mixed acid
Gross mass is the 3% of waste residue gross mass；It is handled again through superfine grinding, surface area reaches 800 ± 10m2Ultra-fine solid waste is made in/kg
Spike powder；It is incorporated into PII42.5 portland cement with 80% volume, high additive cement material is made.Water mixing is added,
Water-cement ratio is 0.44.Cement slurry is poured in 4cm × 4cm × 16cm mold, vibration moulding, standard curing 3 days, 28 days
Afterwards, its compression strength is surveyed by GB175-2017.As a result 2 be see the table below.
Comparative example 1
Water is added in PII42.5 portland cement to mix, water-cement ratio 0.44.By cement slurry pour into 4cm × 4cm ×
In the mold of 16cm, vibration moulding surveys its compression strength by GB175-2017 after standard curing 3 days, 28 days.As a result it see the table below
2。
Strength of cement table is made in 2 Examples 1 to 6 of table and comparative example 1
As shown in Table 2, compared with the portland cement in comparative example 1 undoped with inorganic solid waste, embodiment is prepared inorganic
It is minimum can to reach ordinary portland cement substantially in the case where 50~80% high solid waste volume for the composite mixed cement of solid waste
Compressive strength standard requirement, overcomes the low disadvantage of high solid waste volume cement early strength.
Claims (5)
1. a kind of preparation method of the compound high additive cement of inorganic solid waste, which comprises the steps of:
(1) four kinds or more industrial residues are prepared and is mixed according to the chemical composition of cement；
(2) it is acidic activated that the progress of acid solution exciting agent is added into mixed sludge；
(3) product after will be acidic activated carries out superfine grinding, obtains ultra-fine solid waste spike powder；
(4) the ultra-fine solid waste spike powder is mixed with 50~80% quality volume with portland cement, inorganic solid waste is made
Compound high additive cement.
2. the preparation method of the compound high additive cement of inorganic solid waste according to claim 1, which is characterized in that step (1)
In, the industrial residue be selected from slag, steel slag, flyash, red mud, iron tailings, lithium slag, nickel slag, carbide slag, waste and old concrete and
Desulfurized gypsum.
3. the preparation method of the compound high additive cement of inorganic solid waste according to claim 1, which is characterized in that step (2)
In, the acid solution exciting agent is the dilute sulfuric acid of 10% volumetric concentration, the sulfurous acid of 30% volumetric concentration, 20% volumetric concentration
The mixed solution of one or more of acetic acid, 15% volumetric concentration oxalic acid.
4. the preparation method of the compound high additive cement of inorganic solid waste according to claim 1, which is characterized in that step (2)
In, the additive amount of the acid solution exciting agent is the 1~4% of industrial residue gross mass.
5. the preparation method of the compound high additive cement of inorganic solid waste according to claim 1, which is characterized in that step (3)
In, the specific surface area of the ultra-fine solid waste spike powder obtained through superfine grinding is 500~800m2/kg。
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| CN113149569A (en) * | 2021-05-11 | 2021-07-23 | 山东大学 | High-pressure jet grouting waterproof curtain support anti-seepage curing material and preparation method and application thereof |
| CN114315184A (en) * | 2022-01-18 | 2022-04-12 | 淮南众诺环境科技有限公司 | Ultra-fine admixture for solid waste based composite lithium slag and preparation method and application thereof |
| CN115231892A (en) * | 2022-06-17 | 2022-10-25 | 中铁投资集团有限公司 | Cement-free muck curing agent and preparation method and application thereof |
| CN115259759A (en) * | 2022-07-28 | 2022-11-01 | 中建八局第三建设有限公司 | Solid waste base composite soil curing agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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