CN110981265B - Polycarboxylic acid dispersant, phosphogypsum slurry, and preparation methods and applications of polycarboxylic acid dispersant and phosphogypsum slurry - Google Patents

Polycarboxylic acid dispersant, phosphogypsum slurry, and preparation methods and applications of polycarboxylic acid dispersant and phosphogypsum slurry Download PDF

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CN110981265B
CN110981265B CN201911041487.7A CN201911041487A CN110981265B CN 110981265 B CN110981265 B CN 110981265B CN 201911041487 A CN201911041487 A CN 201911041487A CN 110981265 B CN110981265 B CN 110981265B
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polycarboxylic acid
phosphogypsum
acid dispersant
aqueous solution
vopeg
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CN110981265A (en
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刘东亚
何新耀
李玉博
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Jiahua Chemical Shanghai Co ltd
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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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/142—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements
    • C04B28/143—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21F—SAFETY DEVICES, TRANSPORT, FILLING-UP, RESCUE, VENTILATION, OR DRAINING IN OR OF MINES OR TUNNELS
    • E21F15/00—Methods or devices for placing filling-up materials in underground workings
    • E21F15/005—Methods or devices for placing filling-up materials in underground workings characterised by the kind or composition of the backfilling material
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/408—Dispersants
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00034—Physico-chemical characteristics of the mixtures
    • C04B2111/00146—Sprayable or pumpable mixtures
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries

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Abstract

The polycarboxylic acid dispersant and the phosphogypsum slurry as well as the preparation method and the application of the polycarboxylic acid dispersant and the phosphogypsum slurry are provided by the invention, wherein the polycarboxylic acid dispersant comprises VOPEG (volatile organic polyethylene glycol), and the VOPEG is a mixture of 4-hydroxybutyl vinyl polyoxyethylene ether and 4-hydroxybutyl vinyl polyoxyethylene butylene ether; by adding VOPEG, the copolymerization activity of a high-activity double bond connected with an oxygen atom in the VOPEG is utilized, so that the activity matching degree of the VOPEG and a small molecular monomer acrylic acid is better, and meanwhile, the position of the double bond is not isomeric, so that the synthesized polycarboxylic acid dispersant has a more extended side chain comb structure and better degree of freedom; the polycarboxylic acid dispersant has the functions of dispersing, reducing viscosity, better collapse protection performance and bleeding resistance, reduces the risk of pipe blockage of the phosphogypsum slurry in a long-distance pumping process when being applied to the phosphogypsum slurry, and can adapt to different types of phosphogypsum backfill materials.

Description

Polycarboxylic acid dispersant, phosphogypsum slurry, and preparation methods and applications of polycarboxylic acid dispersant and phosphogypsum slurry
Technical Field
The invention relates to the technical field of tailing filling, in particular to a polycarboxylic acid dispersant, phosphogypsum slurry, and preparation methods and applications of the polycarboxylic acid dispersant and the phosphogypsum slurry.
Background
China is a big agricultural country, the demand of phosphorus fertilizers is huge every year, with the rapid development of the phosphorus fertilizer industry, the discharge amount of a byproduct-phosphogypsum is in a blowout type growth trend, the yield is up to 5000 ten thousand tons every year, and the phosphogypsum has great environmental pollution and needs to spend a large amount of manpower and material resources to treat the phosphogypsum every year, so in recent years, the comprehensive utilization of the phosphogypsum is a problem which needs to be solved urgently.
The comprehensive application fields of the existing phosphogypsum mainly comprise: the method comprises the following steps of adopting phosphogypsum as a main filling material, performing underground goaf filling, performing phosphogypsum roadbed material, replacing natural gypsum with phosphogypsum to produce a soil conditioner and the like, wherein the application of the phosphogypsum to the backfill of a mine site is an important method for treating the phosphogypsum at present.
For example, chinese patent document CN103755182A discloses a preparation method of a phosphogypsum cementing material, which is prepared by grinding dihydrate phosphogypsum, fly ash, an alkaline excitation material and a water reducing agent by using a grinding aid; according to the method, an alkaline exciting material is added to adjust the acidity and alkalinity of the phosphogypsum, a water reducing agent is added into the mixed slurry of the phosphogypsum to improve the fluidity of the slurry and reduce the using amount of water, and then cementing materials such as cement, fly ash and the like are added to be mixed and then to fill holes in a mine field. The common polycarboxylic acid water reducing agent has poor applicability when being applied to phosphogypsum slurry due to poor extension and freedom of a side chain comb-shaped structure, and the problems are difficult to improve.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the phosphogypsum slurry in the prior art is poor in collapse performance, easy to bleed, high in viscosity, easy to block pipes in the long-distance slurry pumping process and the like, and provides a polycarboxylic acid dispersant, the phosphogypsum slurry, and preparation methods and applications of the polycarboxylic acid dispersant and the phosphogypsum slurry.
Therefore, the invention provides the following technical scheme:
a polycarboxylic acid dispersant comprises the following raw materials: VOPEG, wherein the VOPEG is a mixture of 4-hydroxybutyl vinyl polyoxyethylene ether and 4-hydroxybutyl vinyl polyoxyethylene polyoxybutylene ether.
The number average molecular weight of the VOPEG is 1000-5000.
The proportion of the VOPEG is 30-35% of the total weight of the raw materials of the polycarboxylic acid dispersing agent.
The polycarboxylic acid dispersant also comprises the following raw materials: an oxidizing agent, acrylic acid, a chain transfer agent, water, and a reducing agent;
based on the total weight of the raw materials of the polycarboxylic acid dispersant, the proportion of the oxidant is 0.3-0.5%, the proportion of the acrylic acid is 5-8%, the proportion of the chain transfer agent is 0.2-0.3%, the proportion of the water is 58-62%, and the proportion of the reducing agent is 0.1-0.2%.
The reducing agent is one or two of modified sodium formaldehyde sulfoxylate and vitamin C;
the oxidant is hydrogen peroxide and/or ammonium persulfate;
the chain transfer agent is at least one of mercaptoethanol, mercaptopropionic acid, sodium methallylsulfonate, sodium bisulfite and isopropanol.
The invention also provides a preparation method of the polycarboxylic acid dispersant, which comprises the following steps:
and (2) sequentially dropwise adding a mixed aqueous solution of acrylic acid and a chain transfer agent and an aqueous solution of a reducing agent into a mixed aqueous solution of VOPEG and an oxidizing agent at the temperature of 10-15 ℃, and adding alkali for neutralization after the reaction is finished to prepare the polycarboxylic acid dispersant, wherein the reaction temperature and the neutralization temperature are controlled to be 10-30 ℃.
In the mixed aqueous solution of VOPEG and oxidant, the concentration of VOPEG is 1.1-1.2kg/L, and the concentration of oxidant is 0.01-0.02 kg/L;
in the mixed water solution of the acrylic acid and the chain transfer agent, the concentration of the acrylic acid is 0.15-0.3kg/L, and the concentration of the chain transfer agent is 0.005-0.01 kg/L;
the concentration of the reducing agent in the reducing agent aqueous solution is 0.01-0.1 kg/L.
The concentration of each substance in each solution mentioned above means the mass of each substance contained in each liter of water.
The dropping time of the mixed aqueous solution of the acrylic acid and the chain transfer agent is 30-50 min;
the dropping time of the reducing agent aqueous solution is 40-60 min.
The invention also provides phosphogypsum slurry which is characterized in that the raw material of the phosphogypsum slurry comprises the polycarboxylic acid dispersant; wherein the mass of the polycarboxylic acid dispersant accounts for 0.1-0.3% of the total mass of the raw materials.
The raw materials of the phosphogypsum slurry also comprise: ardealite, a cementing material, an alkaline regulator, an early strength auxiliary agent and a rheological auxiliary agent;
based on the total weight of the raw materials of the phosphogypsum slurry,
the proportion of the phosphogypsum is 40-47%; the proportion of the cementing material is 7-10%; the proportion of the alkaline regulator is 0.05-0.1%; the proportion of the early strength auxiliary agent is 0.05-0.1%; the proportion of the rheological additive is 0.05-0.1%; the proportion of the water is 45-50%.
The rheological additive is cellulose ether;
the alkaline regulator is one or more of calcium hydroxide, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and triethylamine;
the early strength additive is any one of ethanolamine, diethanolamine and triethanolamine.
The invention also provides a preparation method of the phosphogypsum slurry, which comprises the following steps:
firstly, adjusting the pH value of an ardealite aqueous solution to 10-13 by using an alkaline regulator;
and then adding a cementing material, uniformly stirring, adding a polycarboxylic acid dispersant, a rheological aid and an early strength aid, and uniformly mixing to obtain the phosphogypsum slurry.
The invention also provides the application of the polycarboxylic acid dispersant or the polycarboxylic acid dispersant prepared by the preparation method of the polycarboxylic acid dispersant or the phosphogypsum slurry prepared by the preparation method of the phosphogypsum slurry in the long-distance pumping process from backfilling to tailing.
The technical scheme of the invention has the following advantages:
1. according to the polycarboxylic acid dispersant provided by the invention, by adding VOPEG, the copolymerization activity of a high-activity double bond connected with an oxygen atom in VOPEG is utilized, so that the activity matching degree of the polycarboxylic acid dispersant and micromolecular monomer acrylic acid is better, and meanwhile, as the position of the double bond is not isomeric, the synthesized polycarboxylic acid dispersant has a side chain comb structure which is more extended and has better freedom degree; the polycarboxylic acid dispersant has the functions of dispersing, reducing viscosity, better collapse protection performance and bleeding resistance, reduces the risk of pipe blockage of the phosphogypsum slurry in a long-distance pumping process when being applied to the phosphogypsum slurry, and can adapt to different types of phosphogypsum backfill materials.
2. According to the polycarboxylic acid dispersant provided by the invention, the molecular weight of VOPEG is limited, the length of the side chain of the polycarboxylic acid dispersant is limited, and the dispersing performance of the polycarboxylic acid dispersant is further improved.
3. According to the polycarboxylic acid dispersant provided by the invention, the content ratio of VOPEG is limited, the side chain density degree of the polycarboxylic acid dispersant is effectively adjusted, the wrapping property and the winding property of the side chain of the polycarboxylic acid dispersant are improved, the intercalation adsorption of other materials to dispersant molecules is reduced, the polycarboxylic acid dispersant has the functions of dispersing, reducing viscosity, better collapse protection performance and bleeding resistance, the risk of pipe blockage of phosphogypsum slurry in a long-distance pumping process is reduced when the polycarboxylic acid dispersant is applied to the phosphogypsum slurry, and the polycarboxylic acid dispersant can adapt to different types of phosphogypsum backfill materials.
4. According to the preparation method of the polycarboxylic acid dispersant, the reaction temperature is controlled, so that the degree of extension, the degree of freedom and the degree of density of molecular side chains of the polycarboxylic acid dispersant can be effectively adjusted, the polycarboxylic acid dispersant prepared by the method has a dispersing function, has the functions of reducing viscosity, better collapse protection performance and bleeding resistance, reduces the risk of pipe blockage of phosphogypsum slurry in a long-distance pumping process when the polycarboxylic acid dispersant is applied to the phosphogypsum slurry, and can adapt to different types of phosphogypsum backfill materials.
5. According to the preparation method of the polycarboxylic acid dispersant, the dropping sequence and the dropping time of the materials are limited, the density degree of the molecular side chain of the polycarboxylic acid dispersant is further adjusted, and the viscosity reduction effect of the polycarboxylic acid dispersant is further improved.
6. According to the phosphogypsum slurry, the polycarboxylic acid dispersant is added, and the mass ratio of the polycarboxylic acid dispersant is limited, so that the viscosity of the phosphogypsum slurry is effectively reduced, the collapse resistance and the bleeding resistance of the phosphogypsum slurry are improved, and the risk of pipe blockage of the phosphogypsum slurry in the process of pumping over a long distance is further reduced; more slurry can be conveyed in the same time period, so that the efficiency is improved, and the use amount of water is reduced, so that the subsequent generated wastewater is less and is more environment-friendly; and the adaptability is good, the possibility of bleeding of the slurry is reduced, and the environment-friendly effect is realized.
7. The fluidity of the phosphogypsum slurry is further adjusted by adding the rheological additive, so that the bleeding of the phosphogypsum slurry is avoided; the content of soluble phosphorus in the phosphogypsum and the pH value of the slurry are adjusted by adding an alkaline regulator, so that the content of phosphorus in the slurry can be reduced, and the fluidity of the slurry can be increased; the inventor finds that the rheological additive and the polycarboxylic acid dispersant can play a synergistic role, reduce the viscosity of the phosphogypsum slurry, further improve the fluidity and the dispersibility of the phosphogypsum slurry and effectively reduce the bleeding property of the phosphogypsum slurry.
8. According to the preparation method of the phosphogypsum slurry, the pH value of a phosphogypsum aqueous solution is adjusted by using an alkaline regulator, and the feeding sequence is limited, so that the prepared phosphogypsum slurry has low viscosity, high collapse-protecting performance and bleeding resistance, and the risk of pipe blockage of the phosphogypsum slurry in the process of pumping over long distance is reduced; more slurry can be conveyed in the same time period, so that the efficiency is improved, and the use amount of water is reduced, so that the subsequent generated wastewater is less and is more environment-friendly; the method has good adaptability, reduces the possibility of bleeding of the slurry, and is green and pollution-free.
9. The polycarboxylic acid dispersant and the application of the phosphogypsum slurry in the ultra-long distance pumping process when backfilling tailings, the low viscosity, the high collapse-protection performance and the bleeding resistance of the polycarboxylic acid dispersant and the phosphogypsum slurry are utilized, so that the risk of pipe blockage of the phosphogypsum slurry in the ultra-long distance pumping process is effectively reduced; more slurry can be conveyed in the same time period, so that the efficiency is improved, and the use amount of water is reduced, so that the subsequent generated wastewater is less and is more environment-friendly; the method has good adaptability, reduces the possibility of bleeding of the slurry, and is green and pollution-free.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Cellulose ethers were purchased from Gomes chemical Co., Ltd, Shandong;
VOPEG (hydroxybutyl vinyl polyoxyethylene ether) was purchased from optimization chemical (Michelson) Inc. and has a number average molecular weight of 1000-.
Example 1
The embodiment provides a polycarboxylic acid dispersant and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: 5kg of acrylic acid and 0.25kg of chain transfer agent mercaptoethanol are dissolved in 32kg of water and uniformly mixed for later use;
preparation of reducing agent aqueous solution: dissolving 0.1kg of reducing agent modified rongalite in 1kg of water, and uniformly mixing for later use;
dissolving 30kg of VOPEG (the number average molecular weight is 1200) in 25kg of water, then adding 0.5kg of hydrogen peroxide serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and the chain transfer agent within 30min at 15 ℃; then dripping the reducing agent aqueous solution within 40 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 15 and 30 ℃).
Example 2
The embodiment provides a polycarboxylic acid dispersant and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: dissolving 8kg of acrylic acid and 0.2kg of chain transfer agent sodium methyl propane sulfonate in 30kg of water, and uniformly mixing for later use;
preparation of reducing agent aqueous solution: dissolving 0.2kg of reducing agent vitamin C in 3kg of water, and uniformly mixing for later use;
dissolving 35kg of VOPEG (number average molecular weight of 1000) in 30kg of water, adding 0.3kg of ammonium persulfate serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and the chain transfer agent within 35min at 10 ℃; then dropwise adding the reducing agent aqueous solution within 50 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 10 and 30 ℃).
Example 3
The embodiment provides a polycarboxylic acid dispersant and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: dissolving 6kg of acrylic acid and 0.3kg of chain transfer agent mercaptopropionic acid in 30kg of water, and uniformly mixing for later use;
preparation of reducing agent aqueous solution: dissolving 0.15kg of reducing agent modified rongalite in 2kg of water, and uniformly mixing for later use;
dissolving 34kg of VOPEG (with the number average molecular weight of 5000) in 25kg of water, adding 0.3kg of hydrogen peroxide serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and the chain transfer agent at the temperature of 12 ℃ within 45 min; then dripping the reducing agent aqueous solution within 60 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 12 and 30 ℃).
Example 4
The embodiment provides a polycarboxylic acid dispersant and a preparation method thereof, and the preparation method specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: dissolving 8kg of acrylic acid and 0.1kg of mercaptoethanol as chain transfer agents and 0.15kg of isopropanol in 35kg of water, and uniformly mixing for later use;
preparation of reducing agent aqueous solution: dissolving 0.05kg of modified rongalite and 0.05kg of vitamin C in 1kg of water, and uniformly mixing for later use;
dissolving 33kg of VOPEG (number average molecular weight of 3000) in 29kg of water, adding 0.4kg of hydrogen peroxide serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and the chain transfer agent at 13 ℃ within 25 min; then dripping the reducing agent aqueous solution within 40 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 13 and 30 ℃).
Example 5
The embodiment provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 40kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; then adding 0.05kg of alkaline regulator sodium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 10, then adding 8kg of cementing material, uniformly stirring, adding 0.12kg of polycarboxylic acid dispersant prepared in the embodiment 1, 0.1kg of rheological aid cellulose ether and 0.08kg of early strength aid ethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Example 6
The embodiment provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 47kg of phosphogypsum in 50kg of water to obtain a phosphogypsum water solution; and then adding 0.1kg of alkaline regulator triethylamine, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 11, then adding 10kg of cementing material, uniformly stirring, adding 0.15kg of polycarboxylic acid dispersant prepared in the example 2, 0.05kg of rheological aid cellulose ether and 0.05kg of early strength aid diethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Example 7
The embodiment provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 43kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; then adding 0.04kg of alkaline regulator sodium hydroxide and 0.04kg of potassium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 13, then adding 7kg of cementing material, uniformly stirring, adding 0.1kg of polycarboxylic acid dispersant prepared in the embodiment 3, 0.08kg of rheological aid cellulose ether and 0.1kg of early strength aid diethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Example 8
The embodiment provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 47kg of phosphogypsum in 47kg of water to obtain a phosphogypsum water solution; then adding 0.04kg of alkaline regulator sodium hydroxide and 0.04kg of ammonium bicarbonate, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 13, then adding 9kg of cementing material, uniformly stirring, adding 0.3kg of polycarboxylic acid dispersant prepared in the embodiment 4, 0.08kg of rheological aid cellulose ether and 0.1kg of early strength aid diethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Example 9
The embodiment provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 40kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; then adding 0.05kg of alkaline regulator sodium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 10, then adding 8kg of cementing material, uniformly stirring, adding 0.12kg of polycarboxylic acid dispersant prepared in the example 1 and 0.08kg of early strength assistant ethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Comparative example 1
The comparative example provides a polycarboxylic acid dispersant and a preparation method thereof, and specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: 5kg of acrylic acid and 0.25kg of chain transfer agent mercaptoethanol are dissolved in 32kg of water and uniformly mixed for later use;
preparation of aqueous solution of reducing agent: dissolving 0.1kg of reducing agent modified rongalite in 1kg of water, and uniformly mixing for later use;
dissolving 30kg of TPEG (isoamylene alcohol polyoxyethylene ether, the molecular weight is 1200) in 25kg of water, then adding 0.5kg of hydrogen peroxide serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and a chain transfer agent within 30min at 15 ℃; then dripping the reducing agent aqueous solution within 40 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 15 and 30 ℃).
Comparative example 2
The comparative example provides a polycarboxylic acid dispersant and a preparation method thereof, and specifically comprises the following steps:
preparation of mixed aqueous solution of acrylic acid and chain transfer agent: 5kg of acrylic acid and 0.25kg of chain transfer agent mercaptoethanol are dissolved in 32kg of water and uniformly mixed for later use;
preparation of reducing agent aqueous solution: dissolving 0.1kg of reducing agent modified sodium formaldehyde sulfoxylate in 1kg of water, and uniformly mixing for later use;
dissolving 30kg of VOPEG (the number average molecular weight is 1200) in 25kg of water, then adding 0.5kg of hydrogen peroxide serving as an oxidant, uniformly stirring, and dropwise adding the mixed aqueous solution of acrylic acid and the chain transfer agent within 30min at 25 ℃; then dripping the reducing agent aqueous solution within 40 min; after reacting for 1h, adding sodium hydroxide for neutralization to obtain the polycarboxylic acid dispersant (the reaction temperature and the neutralization temperature are controlled between 25 and 30 ℃).
Comparative example 3
The comparative example provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 40kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; and then adding 0.05kg of alkaline regulator sodium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 10, then adding 8kg of cementing material, uniformly stirring, adding 0.12kg of polycarboxylic acid dispersant prepared in the comparative example 1, 0.1kg of rheological aid cellulose ether and 0.08kg of early strength aid ethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Comparative example 4
The comparative example provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 40kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; and then adding 0.05kg of alkaline regulator sodium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 10, then adding 8kg of cementing material, uniformly stirring, adding 0.12kg of polycarboxylic acid dispersant prepared in the comparative example 2, 0.1kg of rheological aid cellulose ether and 0.08kg of early strength aid ethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Comparative example 5
The comparative example provides phosphogypsum slurry and a preparation method thereof, and the preparation method specifically comprises the following steps:
dissolving 40kg of phosphogypsum in 50kg of water to obtain a phosphogypsum aqueous solution; and then adding 0.05kg of alkaline regulator sodium hydroxide, uniformly mixing, measuring the pH value of the phosphogypsum aqueous solution to be 10, then adding 8kg of cementing material, uniformly stirring, adding 0.1kg of rheological aid cellulose ether and 0.08kg of early strength aid ethanolamine, and uniformly mixing to obtain the phosphogypsum slurry.
Examples of the experiments
The phosphogypsum slurry prepared in the above examples 5-7 and comparative examples 3-5 was subjected to performance tests and respectively applied to long-distance pumping in tailing backfilling, and specific test results and phenomena applied to the long-distance pumping process in tailing backfilling are shown in table 1. The specific test method is as follows:
measuring the viscosity; and (3) under normal temperature and normal pressure, using an NDJ-8S digital rotational viscometer, adopting a No. 2 rotor, taking a measurement position of a 200g prepared phosphogypsum slurry immersed rotor, starting measurement, reading a value after the reading of the viscometer is stable, and taking an average value after three times of measurement.
The bleeding property is characterized by 1h of bleeding amount, and the specific detection method comprises the following steps: 500g of each of the phosphogypsum slurries prepared in the examples 5 to 7 and the comparative examples 3 to 5 are kept stand for 1 hour at normal temperature and pressure, and the supernatant of the phosphogypsum slurry is taken and weighed to obtain the bleeding amount.
The slump retention is characterized by 1h diffusivity loss, and the specific test method is to test the 1h diffusivity loss of the phosphogypsum slurry by referring to GB/T8077-2000 'concrete admixture homogeneity test method';
the fluidity is characterized by initial diffusivity, and the specific detection method is to test the initial diffusivity of the phosphogypsum slurry by referring to GB/T8077-2000 'concrete admixture homogeneity test method';
the strength detection method is to test the 14d compressive strength of the phosphogypsum slurry by referring to GB/T50080-2002 Standard of Performance test methods of common concrete mixtures.
Table 1 performance test results of phosphogypsum slurries prepared in examples 5-7 and comparative examples 3-5 and phenomena of long distance pumping process for tailings backfilling
Figure BDA0002250375070000121
Figure BDA0002250375070000131
As can be seen from the data in the table above, the comparative examples 5 to 8 show that the above properties of the phosphogypsum slurry are only slightly changed within the range of the mixture ratio of each material in the phosphogypsum slurry provided by the invention, and the application of the phosphogypsum slurry is not influenced; by comparing example 5 with example 9, it can be seen that the phosphogypsum slurry has slight bleeding when no rheological additive is added, which indicates that the bleeding resistance of the phosphogypsum slurry can be improved by adding the rheological additive; comparing example 5 with comparative example 3, it can be seen that the dispersant prepared by using the VOPEG monomer can reduce the viscosity and improve the bleeding resistance and collapse prevention performance when being applied to the phosphogypsum slurry compared with the polycarboxylic acid dispersant prepared by using the TPEG monomer; as can be seen from the comparison between example 5 and comparative example 4, the polycarboxylic acid dispersant prepared in the initial reaction temperature range provided by the present invention can reduce the viscosity and improve the bleeding resistance when applied to phosphogypsum slurry under the same other conditions; by comparing the example 5 with the comparative example 5, the polycarboxylic acid dispersant provided by the invention can obviously improve the dispersibility of the phosphogypsum slurry, reduce the viscosity and bleeding property thereof, and is suitable for long-distance pumping, so that the polycarboxylic acid dispersant provided by the invention has excellent performance in the application of the phosphogypsum slurry: the high-dispersity, bleeding resistance and collapse resistance are achieved, meanwhile, the viscosity can be reduced, the pipe blockage phenomenon of phosphogypsum slurry in a long-distance pumping process is effectively avoided, and the high-dispersity, bleeding resistance and collapse resistance can be adapted to different types of phosphogypsum backfill materials.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.

Claims (13)

1. The polycarboxylic acid dispersant is characterized by comprising the following raw materials in percentage by weight based on the total weight of the raw materials of the polycarboxylic acid dispersant: 30-35% of VOPEG, 0.3-0.5% of oxidant, 5-8% of acrylic acid, 0.2-0.3% of chain transfer agent, 58-62% of water and 0.1-0.2% of reducing agent;
the VOPEG is a mixture of 4-hydroxybutyl vinyl polyoxyethylene ether and 4-hydroxybutyl vinyl polyoxyethylene polyoxybutylene ether;
the preparation method of the polycarboxylic acid dispersant comprises the following steps:
and (2) sequentially dripping a mixed aqueous solution of acrylic acid and a chain transfer agent and an aqueous solution of a reducing agent into the mixed aqueous solution of VOPEG and an oxidizing agent at the temperature of 10-15 ℃, wherein the dripping time of the aqueous solution of the reducing agent is 40-60min, and after the reaction is finished, adding alkali for neutralization to prepare the polycarboxylic acid dispersing agent, wherein the reaction temperature and the temperature during neutralization are controlled to be 10-30 ℃.
2. The polycarboxylic acid dispersant of claim 1, wherein the number average molecular weight of said VOPEG is 1000-5000.
3. The polycarboxylic acid dispersant according to claim 1 or 2, characterized in that said reducing agent is one or both of modified sodium formaldehyde sulfoxylate and vitamin C.
4. The polycarboxylic acid dispersant according to claim 1 or 2, characterized in that said oxidizing agent is hydrogen peroxide and/or ammonium persulfate.
5. The polycarboxylic acid dispersant according to claim 1 or 2, characterized in that said chain transfer agent is at least one of mercaptoethanol, mercaptopropionic acid, sodium methallylsulfonate, sodium bisulfite, isopropanol.
6. The polycarboxylic acid dispersant according to claim 1, wherein the concentration of VOPEG is 1.1 to 1.2kg/L and the concentration of the oxidizing agent is 0.01 to 0.02kg/L in the aqueous solution of VOPEG and the oxidizing agent.
7. The polycarboxylic acid dispersant according to claim 1, wherein in said mixed aqueous solution of acrylic acid and chain transfer agent, the concentration of acrylic acid is 0.15 to 0.3kg/L and the concentration of chain transfer agent is 0.005 to 0.01 kg/L;
the concentration of the reducing agent in the reducing agent aqueous solution is 0.01-0.1 kg/L.
8. The polycarboxylic acid dispersant according to claim 6 or 7, characterized in that the dropping time of said mixed aqueous solution of acrylic acid and chain transfer agent is 30-50 min.
9. An phosphogypsum slurry, characterised in that the raw material of the phosphogypsum slurry comprises a polycarboxylic acid dispersant according to any one of the preceding claims 1-8; wherein the mass of the polycarboxylic acid dispersant accounts for 0.1-0.3% of the total mass of the raw materials.
10. The phosphogypsum slurry according to claim 9, wherein the raw materials of the phosphogypsum slurry further include: ardealite, a cementing material, an alkaline regulator, an early strength auxiliary agent and a rheological auxiliary agent;
based on the total weight of the raw materials of the phosphogypsum slurry,
the proportion of the phosphogypsum is 40-47%; the proportion of the cementing material is 7-10%; the proportion of the alkaline regulator is 0.05-0.1%; the proportion of the early strength auxiliary agent is 0.05-0.1%; the proportion of the rheological additive is 0.05-0.1%; the proportion of water is 45-50%.
11. The phosphogypsum slurry according to claim 10, characterised in that the rheological aid is a cellulose ether;
the alkaline regulator is one or more of calcium hydroxide, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate and triethylamine;
the early strength additive is any one of ethanolamine, diethanolamine and triethanolamine.
12. A method of preparing phosphogypsum slurry according to any one of claims 9 to 11, characterised by the steps of:
firstly, adjusting the pH value of an ardealite aqueous solution to 10-13 by using an alkaline regulator;
and then adding a cementing material, uniformly stirring, adding a polycarboxylic acid dispersant, a rheological aid and an early strength aid, and uniformly mixing to obtain the phosphogypsum slurry.
13. Use of a polycarboxylic acid dispersant according to any one of claims 1 to 8 or a phosphogypsum slurry according to any one of claims 9 to 11 or a method of making a phosphogypsum slurry according to claim 12 in a long distance pumping process during backfilling to tailings.
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