AU2020104368A4

AU2020104368A4 - Cement Filling Material for Co-solidifying Antimony and Preparation Method Thereof

Info

Publication number: AU2020104368A4
Application number: AU2020104368A
Authority: AU
Inventors: Wei Gao; Yunyun Li; Wen NI; Ke Wang; Qihui YAN; Yuying Zhang
Original assignee: University of Science and Technology Beijing USTB
Current assignee: University of Science and Technology Beijing USTB
Priority date: 2020-12-29
Filing date: 2020-12-29
Publication date: 2021-03-18
Anticipated expiration: 2028-12-29

Abstract

The invention relates to a cement filling material for co-solidifying antimony and a preparation method thereof, and belongs to the field of environmental protection of mine cement filling, solid waste resource utilization and synergetic treatment for antimony containing solid wastes. The preparation method comprises the following steps: milling the required raw materials, i.e., steel slag, desulfurization gypsum and blast furnace slag, with 0.01%-1% of moisture content according to the dry basis weight percentage of 45%-80%, 5%-20% and 10%-40%, milling independently or milling by mixed powder until the specific surface area is 200-600 m<2>/Kg, and uniformly mixing to obtain a cementing agent; drying the antimony-containing solid wastes until the moisture content is 0.01%-1%, grinding to the specific surface area of 100-1000m<2>/Kg, according to the weight ratio of the cementing agent/aggregate of 1/8-1/2, the weight ratio of the antimony-containing solid wastes/(cementing agent + aggregate) of 1/100-1/2, adding 0%-1% of water reducing agent, until the mass fraction of slurry is 65%-82%, and uniformly stirring to obtain the qualified mine cement filling material. The preparation method provided by the invention has the advantages of simple and easy operation, low energy consumption, low cost, no new solid waste generation, less environmental pollution and environmental protection.

Description

Cement Filling Material for Co-solidifying Antimony and

Preparation Method Thereof

TECHNICAL FIELD

The invention relates to the technical field of environmental science of mine

cement filling, solid waste resource utilization and synergetic disposal of antimony

containing solid waste, in particular to a cement filling material for synergetic disposal

of antimony-containing solid waste, steel slag and desulfurization gypsum and a

preparation method thereof.

BACKGROUND

The current industrial system is actually a process of extracting resources and

discharging waste. Mining activities are the main source of waste discharged to the

environment, and their solid waste emissions account for 80%-85% of industrial

waste emissions. Mine mining leaves a large area of goaf, and the piled-up waste

rock, waste residue yard and the constructed tailings dam bring serious hidden

dangers in the safety area and environmental load.

Filling mining method belongs to artificial support mining method. In the mine

house or block, with the advancement of the mining face, filling materials are sent to

the goaf to carry out ground pressure management, control of surrounding rock

caving and surface movement, and mining is carried out on or under the protection of

the formed filling body. This method is applicable to mining high-grade, scarce and

precious ore bodies with unstable surrounding rock. The surface is not allowed to

collapse and the mining conditions are complicated, such as water bodies, railway

trunk lines, ore bodies under main buildings and ore bodies with spontaneous

combustion and fire risks. It is also an effective measure to control ground pressure

during deep mining. The advantages of filling method are strong adaptability, high

ore recovery rate, low dilution rate, safer operation, utilization of industrial waste, protection of surface, etc. The disadvantages are complex process, high cost, low labor productivity and ore block production capacity.

Cement filling materials are generally slurry or paste formed by taking gravel,

river sand or gobi aggregate or tailings as aggregates and mixing and stirring with

cement and other cementing agents with water, and are transported to the filling area

by pipeline pumping or gravity flow. Cement filling material contains a certain

proportion of cementing agent, which has higher strength and integrity and higher

operation safety. It can meet various underground support requirements and improve

ore recovery rate and stope operation efficiency. With the popularization and

application of mine filling mining technology, filling cementing agents are also

continuously updated, providing an effective way for the resource utilization of bulk

industrial solid wastes. As the most common cementing agent in the construction

industry, cement's production process itself has the characteristics of high energy

consumption and serious pollution. In recent years, a large number of new cementing

materials have appeared, which are basically improved on the basis of ordinary

Portland cement or blast furnace slag cement, i.e., blast furnace slag, fly ash and the

like with a history of high heat are used to replace some cement clinker. In Canadian

Louvicourt Mine, 20% cement and 80% iron smelting slag are used as cementing

agent. The content of the cementing agent is 2%-4.5% of the paste solids. The

bonding effect between the composite cementing agent and tailings is good. Chang

Xiaona and others added a large amount of fly ash into Portland cement binder,

which increased the strength at 28-56d of the filling body by more than 70%.

Steel slag is a solid slag body composed of slag-making materials, smelting

reactants, eroded furnace body and fettling materials, impurities brought in by metal

burden and slag-making materials specially added to adjust the properties of steel

slag in the process of steel production. Steel slag is a by-product of the process of

producing steel. In production, 15%-20% of steel slag is produced for every 1t of steel produced. In our country, the total amount of steel slag accumulated in steel mills nationwide exceeds 200 million tons, covering an area of more than 6,666,667 square meters, and still increases by more than 30 million tons per year. If the steel slag is not comprehensively utilized, it will occupy more and more land, pollute the environment and cause waste of resources.

Desulfurization gypsum is a by-product of wet flue gas desulfurization

technology adopted in thermal power plants. In recent years, with the vigorous

implementation and promotion of wet flue gas desulfurization as the mainstream

technology in our country, the emission of flue gas desulfurization gypsum, a by

product, is increasing day by day. According to statistics, the emission of flue gas

desulfurization gypsum in China reached 52.3 million tons at the end of 2010, and it

was predicted that the emission of flue gas desulfurization gypsum in China would

reach 100 million tons by 2020. If such a large amount of flue gas desulfurization

gypsum is not efficiently utilized, it is bound to cause secondary pollution to China's

land resources and environment. On the other hand, the main mineral phase

composition of flue gas desulfurization gypsum is dihydrate gypsum, which has full

potential as gypsum resource. If it can be utilized as a resource, it will definitely solve

the problem of lack of natural gypsum resources in many provinces of our country.

Antimony is a widely distributed toxic element, which mainly exists in the

lithosphere in the form of sulfide, namely, stibnite, and coexists with arsenic sulfide

and oxide. At present, antimony is not only used in printing, lead-acid batteries,

electronic instruments, ammunition, pigments and ceramic glaze colors, but also is

the main component of antimony flame retardants and motor vehicle brake pads. In

addition, antimony also has important applications in medical and health fields, such

as antimony agents, which are widely used in the treatment of Asian cholera,

intermittent hysteria, tuberculosis, schistosomiasis, kala-azar and many other

diseases. At the same time, a large number of antimony and its compounds have entered various environmental media, causing environmental pollution and harm to human health, which has gradually emerged and attracted more and more attention.

Antimony has been proved to be toxic and carcinogenic to human beings and

organisms, and causes diseases of liver, skin, respiratory system and cardiovascular

system. Antimony poisoning has the characteristics of a long incubation period.

Excessive antimony may also cause acute heart diseases, which is suspected to be

one of the possible causes of "sudden infant death syndrome". Long-term inhalation

of antimony powder and antimony-containing smoke can cause "antimony

pneumoconiosis" or "antimony pneumoconiosis" and lung cancer. Many cases of

antimony poisoning have been reported in antimony mining areas in China. Antimony

and its compounds are listed as priority pollutants by the United States

Environmental Protection Agency and the European Union. Antimony is listed as

hazardous waste in the Basel Convention's restrictions on transboundary movement

of hazardous waste. Based on the production and reserves of antimony, China faces

the most serious risk of antimony pollution. According to the statistical report of the

United States Geological Survey (USGS, 2012) on the world non-ferrous metal trade,

the world antimony output in 2011 was 169,000 tons, of which 150,000 tons were

from China, contributing more than 88.8% of the total, while China's arsenic output

was only 52,000 tons during the same period. Arsenic pollution to the environment

has attracted extensive attention, while antimony pollution has always existed, but it

has not been paid enough attention and effectively controlled.

Effective joint and synergetic disposal of all kinds of industrial wastes is an

effective measure and general trend to realize environmental treatment and resource

utilization.

No matter what kind of technology is adopted in the hazardous waste disposal

process, residues that need final disposal will be generated. Safe landfill is the final

disposal technology and also a technology with relatively high environmental risks.

Domestic and foreign requirements on the site selection and seepage prevention of

safe landfill sites are very high. Since safe landfill is only a safe disposal method of

hazardous waste and does not have the effect of "harmlessness", leachate and

landfill gas will still cause potential environmental pollution. Therefore, hazardous

waste solidification/stabilization treatment is mostly required before safe landfill of

hazardous waste. Solidification/stabilization technology is to reduce the toxicity and

mobility of hazardous wastes by adding curing agents or stabilizers. Currently,

relatively mature solidification/stabilization technologies include: Cement curing

method, lime curing method, plastic curing method, melt curing method, self

cementing curing method and agent stabilization technology, etc. The

solidification/stabilization technology in the prior art faces the problems of high cost,

large capacity-increasing ratio and large area occupied by subsequent safe landfill.

SUMMARY

The invention relates to a cement filling material for co-solidifying antimony and

a preparation method thereof, which aims at solving the following problems in the

prior art:

1. Cement filling mining has high cost and large cement consumption;

2. Large stockpiling of industrial solid wastes, steel slag and desulfurization

gypsum causes waste of resources and environmental pollution.

3. Environmental pollution caused by antimony-containing solid waste and

potential environmental pollution and land waste caused by traditional safe landfill

method for disposal of antimony-containing solid waste.

The invention realizes the replacement of cement by a mine cementing agent

prepared by a full solid waste system; The antimony-containing solid waste is safely

disposed of, and the toxicity of the leaching solution obtained by the toxic leaching

method is greatly reduced; The solidified body after "harmless" solidification treatment is filled into the underground goaf, thus saving a large area of land required for solid waste landfill.

The technical solution adopted to realize the above-mentioned object of the

invention is as follows:

A cement filling material for co-solidifying antimony, comprising cementing agent,

aggregate, water reducing agent and antimony-containing solid waste, characterized

in that: the cementing agent comprises 45%-80% of steel slag, 5%-20% of

desulfurization gypsum and 10%-40% of blast furnace slag in weight percentage;

the aggregate comprises one or more of mountain sand, river sand, tailings or

waste rock.

the water reducing agent is one or more of lignosulfonate water reducing agent,

naphthalene series high-efficiency water reducing agent, melamine series high

efficiency water reducing agent, sulfamate series high-efficiency water reducing

agent, fatty acid series high-efficiency water reducing agent and polycarboxylate

series high-efficiency water reducing agent.

the antimony-containing solid waste refers to the solid waste whose antimony

concentration in the leaching solution exceeds 5pg/L specified in Standards for

Drinking Water Quality according to the leaching procedure specified in Solid Waste

Extraction Procedure for Leaching Toxicity-Horizontal Vibration Method (HJ557-2009)

and whose antimony content exceeds the background value of Chinese soil by 0.38

2.98mg/kg.

The steel slag powder is furnace slag produced in the process of steelmaking

process, containing 5%-30% of tricalcium silicate, 5%-30% of dicalcium silicate (2S),

%-38% of RO phase, 2%-8% of ferric oxide, 0.5%-5% of calcium hydroxide, 0.5%

% of ferric hydroxide, 0.01%-3% of free calcium oxide, 0.01%-10% of calcium carbonate, 0.01%-8% of magnesium carbonate, 0.01%-3% of ferric carbonate and

0.01%-3% of other impurities.

The desulfurization gypsum refers to a by-product of a wet flue gas

desulfurization technology adopted by a thermal power plant, and the main

component is calcium sulfate dihydrate.

The blast furnace slag is granular blast furnace slag formed after the slag

generated in the ironmaking process of the metallurgical blast furnace is rapidly

cooled with water, also known as water slag or water-quenched slag, and the main

chemical composition ranges from: 38%-49% of CaO, 26%-42% of Si0 2 , 6%-17% of

A12 03 ,1%-13% of MgO, 0.1%-2% of MnO, 0.07%-2.5% of FeO, and 0.2%-1.5% of S.

The action mechanism of the cementing agent is as follows:

The core problem is that the filling material can obtain good strength so that the

cementing material in the filling material can be hydrated to produce sufficient C-S-H

gel. However, the molar ratio of (SiO2+Al203)/(CaO+MgO) in C-S-H gel, which

contributes the most to the strength of the filling material, is within the range of 0.6

0.8. Sufficient research results show that the higher the ratio in C-S-H gel within this

range, the greater its contribution to the strength of the filling material. C-S-H gel is a

chain-like silicate formed by silicon-oxygen tetrahedron, and the molar ratio of

(Si02+Al203)/(CaO+MgO) in water quenched granulated blast furnace slag is above

0.9.

The ratio of (Si02+Al203)/(CaO+MgO+FeO) in steel slag is very low, generally

lower than 0.15. Therefore, if the steel slag is ground into fine powder, the ability of

the steel slag fine powder to provide silicon (aluminum) oxygen tetrahedron for

cementation hardening and strength growth of the filling material is extremely weak.

In C-S-H gel, not only a large number of silicon-oxygen tetrahedrons can be replaced

by aluminum-oxygen tetrahedrons and a certain amount of iron-oxygen tetrahedrons, but also calcium ions can be replaced by a large number of divalent ions such as magnesium ions and ferrous ions. Therefore, if the steel slag powder can be ground into micron-sized fine powder so that the hydration reaction can occur quickly, a large amount of divalent metal cations can be provided for the cementing system.

The content of alumina in granulated blast furnace slag is generally high and is

linked with silicon oxide tetrahedron in the form of aluminum oxide tetrahedron in the

glass body of blast furnace slag. When the blast furnace slag comes into contact with

the higher pH solution formed by the steel slag, the aluminum oxide tetrahedron

tends to depolymerize from the link of the silicon oxide tetrahedron into the solution.

When there is more gypsum in the system, ettringite crystallization reaction can

occur rapidly.

4H3AI042-+6Ca2++6CaSO4-2H20+40H

+44H20-*2(3CaO-Al2O3-3CaSO4-32H20)

Ettringite is a double salt with very low solubility. The solubility product constants

of ettringite reported by C. B. Satish et al. in Pages 1-19, Chemical Geology, (148)

1998 are 10-111.6. Its continuous crystallization leads to the decrease of A13+ ion

concentration in the solution, which moves the balance of the above reaction formula

to the right and makes reaction continue. The dissolution of a large amount of A13+

ions breaks the link between the aluminum-oxygen tetrahedron and the silicon

oxygen tetrahedron in the granulated blast furnace slag micropowder, and greatly

improves the activity of the remaining silicon-oxygen tetrahedron, thus continuously

producing the depolymerization of the silicon (aluminum)-oxygen tetrahedron,

creating conditions for the formation of a large amount of C-S-H gel.

The formation of a large amount of C-S-H gel requires not only a large amount of

active silicon (aluminum) oxygen tetrahedrons, but also a large number of divalent

cations such as calcium, magnesium and iron. The hydration of steel slag can effectively provide these divalent metal cations. Therefore, ultra-fine steel slag powder ground into micron scale, blast furnace water quenched slag powder and industrial by-product gypsum powder can be combined to make mine filling cementing material instead of cement.

A preparation method of the cement filling material for co-solidifying antimony as

above, characterized in that: the milled steel slag, blast furnace slag and

desulfurization gypsum are mixed evenly to prepare a cementing material, antimony

containing solid waste, aggregate and water reducing agent, water is added for

uniform mixing, with the specific steps as follows:

(1)milling the required raw materials, i.e., steel slag, desulfurization gypsum and

blast furnace slag, with 0.01%-1% of moisture content according to the dry basis

weight percentage of 45%-80%, 5%-20% and 10%-40%, milling independently or

milling by mixed powder until the specific surface area is 200-600 m<2>/Kg, and

uniformly mixing to obtain a cementing agent;

(2)drying the antimony-containing solid wastes until the moisture content is

0.01%-1%, grinding to the specific surface area of 100-1000m<2>/Kg, according to

the weight ratio of the cementing agent/aggregate of 1/8-1/2, the weight ratio of the

antimony-containing solid wastes/(cementing agent + aggregate) of 1/100-1/2,

adding 0%-1% of water reducing agent, until the mass fraction of slurry is 65%-82%,

and uniformly stirring to obtain the qualified mine cement filling material.

After the filling material is solidified, the leaching concentration of antimony is

lower than the drinking water standard, i.e. 55pg/L.

Compared with the prior art, the invention has the advantages of:

1. More than 90% of the raw materials of mine cement filling material are from

industrial solid wastes.

2. Mine cement filling material is used to synergistically dispose of antimony

containing solid waste, steel slag and desulfurization gypsum to realize waste

treatment.

3. The strength of the cement filling material for the synergetic disposal of

antimony-containing solid waste, steel slag and desulfurization gypsum meets the

requirements of the filling mining method. At the same time, the leaching

concentration of antimony is greatly reduced, the leaching toxicity is reduced, the

drinking water standard can be reached, and a large area of land required for safe

landfill is saved.

4. The preparation method of cement filling material for synergetic disposal of

antimony-containing solid waste, steel slag and desulfurization gypsum is very simple

and easy to operate, with low energy consumption, and the equipment used is very

common, so the cost is low, no new solid waste is generated, it has low

environmental pollution and is very environmentally friendly.

DESCRIPTION OF THE INVENTION

The invention will be described in detail with reference to embodiments.

Embodiment 1

The invention relates to a mine cementing agent, which is prepared from the

following raw materials by weight percentage:

60% of steel slag

30% of Blast furnace slag

10% of desulfurization gypsum

The invention relates to a preparation method of cement filling material for

synergetic disposal of antimony-containing solid waste, steel slag and desulfurization gypsum, which is characterized in that: Mixing the ground steel slag, blast furnace slag and desulfurization gypsum evenly to prepare cementing material, antimony containing solid waste, aggregate and water reducing agent, adding water and mixing them evenly, with the following specific steps:

weight percentage of 60%, 30% and 10%, milling by mixed powder until the specific

surface area is 480 m<2>/Kg, and uniformly mixing to obtain a cementing agent;

(2)The antimony-containing solid waste disposed of is lead-zinc mine tailings.

According to the weight ratio of cementing agent/aggregate of 1/3 and the mass

fraction of slurry of 80%, qualified mine cement filling material can be obtained by

evenly stirring.

Lead-zinc mine tailings are selected as aggregates and are also antimony

containing solid waste. The concentration of antimony in the leaching solution is

540pg/L.

Experiment 1. The cement filling material prepared in Embodiment 1 for

synergetic disposal of antimony-containing solid waste, steel slag and desulfurization

gypsum is subjected to uniaxial infinite compressive strength test and antimony

toxicity leaching test.

1. Experimental method

1) Experimental group: The filling material described in Embodiment 1 is injected

into a 70.7x70.7x70.7mm standard test mold and shaken with a shaking table for 30s;

2) Control group: Grade 42.5 cement is used as the cementing agent, the weight

ratio of cementing agent/aggregate is 1/4, and other steps are exactly the same as

those of the test group.

3) After 24 hours of static curing, the films of the experimental group and the

control group were removed, and were put into standard curing boxes for curing

respectively. At the age nodes, uniaxial unconfined compressive strength test and

antimony toxicity leaching test were carried out respectively.

2. Experimental results

1) The test results of uniaxial unconfined compressive strength are shown in the

following table:

Uniaxial unconfined compressive strength/MPa Age Experimental group Control group

3d 1.55 5.68

7d 9.35 10.56

28d 17.92 19.75

2) The concentration results of antimony leaching solution of all solid waste

cements in the test group are as follows:

Antimony leaching concentration/pg/L

Age Experime Control Drinking Detection

ntal group group water standard limit

3d ND 15

7d ND 31 5 0.2

28d ND 39

Embodiment 2

The invention relates to a mine cementing agent, which is prepared from the

following raw materials by weight percentage:

70% of steel slag

20% of blast furnace slag

10% of desulfurization gypsum

The invention relates to a preparation method of cement filling material for

gypsum, which is characterized in that: Mixing the ground steel slag, blast furnace

slag and desulfurization gypsum evenly to prepare cementing material, antimony

containing solid waste, aggregate and water reducing agent, adding water and

mixing them evenly, with the following specific steps:

weight percentage of 70%, 20% and 10%, milling by mixed powder until the specific

surface area is 450 m<2>/Kg, and uniformly mixing to obtain a cementing agent;

(2)The antimony-containing solid waste disposed of is lead-zinc mine tailings.

According to the weight ratio of cementing agent/aggregate of 1/3 and the mass

fraction of slurry of 75%, qualified mine cement filling material can be obtained by

evenly stirring.

Tin mine tailings are selected as aggregates and are also antimony-containing

solid waste. The concentration of antimony in the leaching solution is 1,410pg/L.

Experiment II. The cement filling material prepared in Embodiment 2 for

synergetic disposal of antimony-containing solid waste, steel slag and desulfurization gypsum is subjected to uniaxial infinite compressive strength test and antimony toxicity leaching test.

1. Experimental method

2) Control group: Grade 42.5 cement is used as the cementing agent, the weight

those of the test group.

3) After 24 hours of static curing, the films of the experimental group and the

control group were removed, and were put into standard curing boxes for curing

antimony toxicity leaching test were carried out respectively.

2. Experimental results

following table:

3d 1.21 3.76

7d 5.33 7.47

28d 9.47 11.53

2) The concentration results of antimony leaching solution of all solid waste

cements in the test group are as follows:

Antimony leaching concentration/pg/L

Age Experime Control Drinking Detection

ntal group group water standard limit

3d ND 26 5 0.2

7d ND 139

28d ND 402

Embodiment 3

The invention relates to a mine cementing agent, which is prepared from the

following raw materials by weight percentage:

65% of steel slag

25% of blast furnace slag

10% of desulfurization gypsum

The invention relates to a preparation method of cement filling material for

slag and desulfurization gypsum evenly to prepare cementing material, antimony

containing solid waste, aggregate and water reducing agent, adding water and

mixing them evenly, with the following specific steps:

weight percentage of 65%, 25% and 10%, milling by mixed powder until the specific

surface area is 460 m<2>/Kg, and uniformly mixing to obtain a cementing agent;

(2)The antimony-containing solid waste disposed of is lead-zinc mine tailings.

According to the weight ratio of cementing agent/aggregate, the weight ratio of

antimony-containing waste material/(cementing agent + aggregate) is 1/4, and the

mass fraction of slurry is 79%, qualified mine cement filling material can be obtained

by evenly stirring.

Tin mine tailings are selected as aggregates and are also antimony-containing

The additional antimony-containing waste is waste incineration fly ash, and the

concentration of antimony in the leaching solution is 795pg/L.

Experiment Ill. The cement filling material prepared in Embodiment 3 for

gypsum is subjected to uniaxial infinite compressive strength test and antimony

toxicity leaching test.

1. Experimental method

2) Control group: Grade 42.5 cement is used as cementing agent, and other

steps are exactly the same as those of the test group;

3) After 24 hours of static curing, the films of the experimental group and the

control group were removed, and were put into standard curing boxes for curing

antimony toxicity leaching test were carried out respectively.

2. Experimental results

following table:

3d 0.92 4.55

7d 4.65 8.69

28d 8.12 15.18

2) The concentration results of antimony leaching solution of all solid waste

cements in the test group are as follows:

Antimony leaching concentration/pg/L

Age Experime Control Drinking Detection

ntal group group water standard limit

3d ND 52

7d ND 113 5 0.2

28d 4 520

From the compressive strength test results and antimony leaching concentration

results of tests 1 to 3, it can be seen that the cement filling material provided by the

invention for synergetic disposal of antimony-containing solid waste, steel slag and

desulfurization gypsum meets the requirement that the strength of cement filling on

ore for 28 d is > 5MPa; The leaching concentration of antimony in different ages of

the solidified body is below the drinking water standard, even 5 0.2pg/L, which has

better solidification effect of antimony than the mine filling material with cement as

cementing agent. In a word, the cement filling material for synergetic disposal of antimony-containing hazardous wastes has simple preparation process, up-to standard strength, excellent antimony curing effect, high application value and good environmental benefits.

Claims

1. A cement filling material for co-solidifying antimony, comprising cementing

material, aggregate, water reducing agent and antimony-containing solid waste,

characterized in that: the cementing material comprises 45%-80% of steel slag, 5%

% of desulfurization gypsum and 10%-40% of blast furnace slag in weight

percentage;

the aggregate comprises one or more of mountain sand, river sand, tailings or

waste rock;

the water reducing agent is one or more of lignosulfonate water reducing agent,

naphthalene series high-efficiency water reducing agent, melamine series high

series high-efficiency water reducing agent;

the antimony-containing solid waste refers to the solid waste whose antimony

concentration in the leaching solution exceeds 5pg/L specified in Standards for

and whose antimony content exceeds the background value of Chinese soil by 0.38

2.98mg/kg.

2. The cement filling material for co-solidifying antimony according to claim 1,

characterized in that the steel slag is furnace slag produced in the process of

steelmaking process, containing 5%-30% of tricalcium silicate, 5%-30% of dicalcium

silicate (2S), 10%-38% of RO phase, 2%-8% of ferric oxide, 0.5%-5% of calcium

hydroxide, 0.5%-5% of ferric hydroxide, 0.01%-3% of free calcium oxide, 0.01%-10%

of calcium carbonate, 0.01%-8% of magnesium carbonate, 0.01%-3% of ferric

carbonate and 0.01%-3% of other impurities.

3. The cement filling material for co-solidifying antimony according to claim 1,

characterized in that the desulfurization gypsum refers to a by-product of a wet flue

gas desulfurization technology adopted by a thermal power plant, and the main

component is calcium sulfate dihydrate.

4. The cement filling material for co-solidifying antimony according to claim 1,

characterized in that the blast furnace slag is granular blast furnace slag formed after

the slag generated in the ironmaking process of the metallurgical blast furnace is

rapidly cooled with water, and the main chemical composition ranges from: 38%-49%

of CaO, 26%-42% of SiO2, 6%-17% of A1203, 1%-13% of MgO, 0.1%-2% of MnO,

0.07%-2.5% of FeO, 0.2%-1.5% of S.

5. A preparation method of the cement filling material for co-solidifying antimony

according to claim 1, characterized in that: the milled steel slag, blast furnace slag

and desulfurization gypsum are mixed evenly to prepare a cementing material,

antimony-containing solid waste, aggregate and water reducing agent, water is

added for uniform mixing, with the specific steps as follows:

weight percentage of 45%-80%, 5%-20% and 10%-40%, milling independently or

milling by mixed powder until the specific surface area is 200-600 m<2>/Kg, and

uniformly mixing to obtain a cementing agent;

(2)drying the antimony-containing solid wastes until the moisture content is

antimony-containing solid wastes/(cementing agent + aggregate) of 1/100-1/2,

adding 0%-i% of water reducing agent, until the mass fraction of slurry is 65%-82%,

and uniformly stirring to obtain the qualified mine cement filling material.