CN113480229A - Composite liquid chromium removal agent and preparation method and application thereof - Google Patents
Composite liquid chromium removal agent and preparation method and application thereof Download PDFInfo
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- CN113480229A CN113480229A CN202110891421.8A CN202110891421A CN113480229A CN 113480229 A CN113480229 A CN 113480229A CN 202110891421 A CN202110891421 A CN 202110891421A CN 113480229 A CN113480229 A CN 113480229A
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- ferrous sulfate
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- Ceramic Engineering (AREA)
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- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a composite liquid chromium removing agent and a preparation method and application thereof, wherein the composite liquid chromium removing agent comprises the following raw materials: 20-30% of ferrous sulfate heptahydrate, 10-30% of antimony oxychloride, 43-60% of water, 5-10% of organic solvent, 2-10% of methyl cellulose, or 20-30% of ferrous sulfate heptahydrate, 10-30% of antimony trichloride, 43-60% of water, 5-10% of organic solvent and 2-10% of methyl cellulose. The composite liquid chromium removing agent provided by the invention is a mixed phase of an organic phase and a water phase, and ferrous sulfate heptahydrate and antimony oxychloride are combined through an organic solvent and methyl cellulose to jointly play a reducing role, so that the chromium removing effect is better; the addition of the ferrous sulfate can prevent the agglomeration of antimony oxychloride and methylcellulose, and the ferrous sulfate can prevent the oxidation of oxygen in the air in the system.
Description
Technical Field
The invention belongs to the technical field of chromium removal agents, and particularly relates to a composite liquid chromium removal agent as well as a preparation method and application thereof.
Background
The cement chromium reducing agent is mainly used in cement production to reduce hexavalent chromium in cement into trivalent chromium, so that the content of hexavalent chromium in cement is reduced. The mandatory national standard GB 31893-2015 in 2016 clearly limits the content of hexavalent chromium in cement to not exceed 10 mg/kg.
In the prior art, a single reducing agent, such as ferrous sulfate, is often adopted as the reducing agent, so that the treatment effect is poor. And the ferrous sulfate is easily oxidized by oxygen in the air and loses efficacy, so that more water-soluble hexavalent chromium still remains in the cement, and the chromium removal requirement cannot be met.
Disclosure of Invention
The invention aims to provide a composite liquid chromium removing agent and a preparation method thereof, which have the advantages of stable product and good chromium removing effect.
The invention also aims to provide the application of the composite liquid chromium remover, which is used for removing chromium from cement, and has the advantages of low consumption and good chromium removal effect.
The specific technical scheme of the invention is as follows:
a composite liquid chromium removing agent comprises the following raw materials in percentage by mass:
20-30% of ferrous sulfate heptahydrate, 10-30% of antimony oxychloride, 43-60% of water, 5-10% of organic solvent and 2-10% of methyl cellulose;
the total amount of the raw materials is 100 percent.
Or, the compound liquid chromium removing agent comprises the following raw materials in percentage by mass:
20-30% of ferrous sulfate heptahydrate, 10-30% of antimony trichloride, 43-60% of water, 5-10% of organic solvent and 2-10% of methyl cellulose;
the total amount of the raw materials is 100 percent.
The viscosity of the methyl cellulose is 40000-100000 mPa.s, and the higher the viscosity is, the higher the molecular weight of the corresponding methyl fiber degree is.
The organic solvent is selected from ethanol or N, N-dimethylformamide.
The invention provides a preparation method of a composite liquid chromium remover, which comprises the following steps:
A. dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring to obtain a mixed solution;
B. and D, directly adding the antimony oxychloride with the formula amount into the solution prepared in the step A, uniformly stirring, adding the organic solvent with the formula amount, and uniformly mixing to obtain the compound liquid chromium remover.
In the step A, the stirring refers to stirring for 10-30 min at room temperature;
in the step B, the stirring time is 30-60 min at room temperature;
or, the preparation method of the composite liquid chromium removing agent provided by the invention comprises the following steps:
1) dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring to obtain a mixed solution;
2) dissolving the antimony trichloride in the formula amount in the organic solvent in the formula amount, pouring the obtained solution into the mixed solution, and uniformly stirring to obtain the composite liquid chromium remover.
In the step 1), the stirring refers to stirring for 10-30 min at room temperature;
in the step 2), the stirring time is 30-60 min at room temperature;
the composite liquid chromium removing agent obtained by the two methods is blue-white pasty liquid containing ferrous sulfate and antimony oxychloride.
In the design, a plurality of reducing agents such as sodium thiosulfate, sodium sulfite and sodium bisulfite are selected, cannot coexist with antimony oxychloride and can generate chemical reaction, and through a large amount of exploration, the ferrous sulfate and the antimony oxychloride designed by the invention do not generate chemical reaction and can coexist under the system of the invention.
The invention provides an application of a compound liquid chromium remover, which is used for removing chromium from cement.
When the composite liquid chromium remover is used for removing chromium from cement, the chromium remover with the mass of two ten-thousandth of the cement is added.
The chromium removing agent generally adopts reducing agents, the reducing agents are various in types, each reducing agent has unique chemical and physical properties, some reducing agents are easily dissolved in an aqueous phase medium, and some reducing agents are easily dissolved in an organic phase medium and are insoluble in an aqueous phase. Ferrous sulfate is cheap in chromium, has good reducing performance, is easy to dissolve in water, and is almost insoluble in ethanol. Antimony trichloride is easily soluble in organic phases such as ethanol, diethyl ether and the like, and is dissolved in water to generate antimony oxychloride. The invention utilizes the ferrous sulfate heptahydrate and the antimony oxychloride as main chromium removal components, and the ferrous sulfate heptahydrate is added to effectively reduce the hexavalent chromium content in the cement. Antimony oxychloride is the product of the hydrolysis of antimony trichloride. Methyl cellulose is nonionic cellulose ether, has the functions of thickening, surface activity, film forming property and forming thermal gel, has excellent wettability, dispersibility, adhesiveness, thickening property, emulsifying property, water-retaining property and film forming property, and the aqueous solution of the methyl cellulose is quite stable at normal temperature. Therefore, the novel liquid chromium removing agent provided by the invention consists of ferrous sulfate heptahydrate, antimony oxychloride, water (aqueous phase medium), N-dimethylformamide or ethanol (organic phase medium) and methyl cellulose. The composite liquid chromium removing agent provided by the invention is a mixed phase of an organic phase and a water phase, and ferrous sulfate heptahydrate and antimony oxychloride are combined through an organic solvent and methylcellulose. The methyl cellulose has different molecular weights, the methyl cellulose with high molecular weight is selected, the adhesive force of the methyl cellulose is high, ferrous sulfate and antimony oxychloride can coexist in the system and play a role of reduction together, the composite liquid chromium remover provided by the invention can effectively prevent ferrous sulfate from being oxidized by oxygen in the air, and because the methyl cellulose with high molecular weight has emulsifying property and film-forming property, the contact between the ferrous sulfate and the oxygen can be effectively reduced, the ferrous sulfate is prevented from being oxidized, and secondly, the consistency of the ferrous sulfate and antimony oxychloride system can be increased by adding an organic solvent into a water phase, the dissolution of the oxygen in the air is reduced, and the ferrous sulfate is protected from being oxidized. Comparing a ferrous sulfate system, an antimony oxide system and a mixed system of the ferrous sulfate system and the antimony oxide system, the finding that the chromium removal effect of the mixed system of the ferrous sulfate system and the antimony oxide system is better than the sum of the chromium removal effects of the ferrous sulfate system and the antimony oxide system, which are independent, shows that the ferrous sulfate system and the antimony oxide system have a synergistic effect. Meanwhile, in the experimental process, the fact that antimony oxychloride and methyl cellulose in a single antimony oxychloride system are easy to agglomerate is found. The addition of ferrous sulfate and ferrous sulfate in antimony oxychloride system forms a uniformly distributed pasty suspension compared with the single antimony oxychloride system.
Detailed Description
Example 1
A composite liquid chromium removing agent comprises the following raw materials in percentage by mass:
22% of ferrous sulfate heptahydrate, 15% of antimony oxychloride, 48% of water, 7% of absolute ethyl alcohol, 8% of methyl cellulose and 40000mPa.s of methyl cellulose viscosity.
The preparation method of the compound liquid chromium removing agent comprises the following steps:
A. dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring for 30min to obtain a mixed solution;
B. and D, directly adding the antimony oxychloride with the formula amount into the solution prepared in the step A, uniformly stirring for 60min, and then adding the organic solvent with the formula amount to obtain the compound liquid chromium remover.
Mixing 5kg of chromium-containing clinker and 211g of dihydrate gypsum to obtain a sample, adding two parts by mass of the prepared composite liquid chromium remover to the sample, mixing, polishing, and taking the sample after polishing as a sample added with the chromium remover; mixing the same 5kg of chromium-containing clinker and 211g of dihydrate gypsum according to the same method, and grinding the mixture to obtain a sample without the chromium removal agent;
the hexavalent chromium content was measured according to GB 31893-2015 limit and determination method for water-soluble hexavalent chromium (VI) in cement, and the results are shown in Table 1.
Table 1 shows the hexavalent chromium content without and after adding the chromium removing agent
| Sample (without chromium remover) | 2.4mg/kg |
| Sample (two-ten-thousandth chromium remover) | 0.5mg/kg |
Carrying out chemical component analysis on the cement sample doped with the chromium removing agent:
the chemical analysis experiment is carried out on the sample which is not added with the chromium removing agent and is doped with the two-ten-thousandth chromium removing agent after small grinding according to GB/T176-.
TABLE 2 chemical property test of cement samples undoped and doped with chromium removing agent
| Chemistry | No chromium removing agent is added | Two parts per million% |
| Sodium oxide | 0.03 | 0.03 |
| Magnesium oxide | 0.52 | 0.51 |
| Aluminum oxide | 4.12 | 4.05 |
| Silicon dioxide | 16.81 | 16.77 |
| Sulfur trioxide | 3.06 | 2.99 |
| Potassium oxide | 0.64 | 0.63 |
| Calcium oxide | 65.00 | 65.14 |
| Titanium dioxide | 0.26 | 0.27 |
| Ferric oxide | 4.15 | 4.25 |
| Chloride ion | 0.01 | 0.02 |
The experimental results are as follows: compared with the chemical composition data of the cement after the small grinding without adding the chromium removing agent and doping two ten-thousandth of the chromium removing agent, the results of the chemical compositions (the chemical compositions of calcium, magnesium, iron, aluminum and silicon) all meet the requirements of GB 175 general Portland cement on calcium, magnesium, iron, aluminum and silicon, and the addition of the chromium removing agent does not influence the chemical compositions in the cement.
The sample after the small mill without the addition of the chromium removing agent and the doped chromium removing agent was subjected to standard consistency, setting time and stability tests according to GB/T1346-2011 inspection method for standard consistency water consumption, setting time and stability of cement, and 3-day strength tests, and the results are shown in Table 3.
Table 3 shows the physical property tests of cement samples not doped with chromium remover and doped with chromium remover in different amounts
The experimental results are as follows: compared with the cement which is not added with the chromium removing agent and is doped with two ten-thousandth of the chromium removing agent and subjected to small grinding, the cement which is not added with the chromium removing agent and subjected to the standard consistency, setting time, stability and 3-day bending and compression resistance test has no great change compared with the sample which is not added with the chromium removing agent, and the cement meets the national standard requirements.
The synergistic effect of the ferrous sulfate and the antimony oxychloride in the mixed system is as follows:
scheme 1 formula: 48% of water, 7% of absolute ethyl alcohol, 8% of methyl cellulose, 22% of ferrous sulfate and 15% of sodium chloride; the viscosity of the methyl cellulose is 40000 mPa.s.
The preparation method of scheme 1 comprises the following steps: dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring for 30min to obtain a mixed solution; and adding the sodium chloride with the formula amount, stirring for 60min uniformly, and adding the absolute ethyl alcohol with the formula amount to obtain the compound liquid chromium remover.
Scheme 2 formula: 48% of water, 7% of absolute ethyl alcohol, 8% of methyl cellulose, 22% of sodium chloride and 15% of antimony oxychloride; the viscosity of the methyl cellulose is 40000 mPa.s.
The preparation method of scheme 2 is: dissolving the formula amount of sodium chloride in the formula amount of water to form a sodium chloride solution, adding the formula amount of methyl cellulose, and stirring for 30min to obtain a mixed solution; then adding antimony oxychloride with the formula amount, stirring for 60min uniformly, and then adding absolute ethyl alcohol with the formula amount to obtain the compound liquid chromium remover.
Scheme 3 formula: namely example 1.
Under the condition of keeping other components and quality unchanged, a mixed system of separately adding 22% of ferrous sulfate (formula of scheme 1), separately adding 15% of antimony oxychloride (formula of scheme 2), separately adding 22% of ferrous sulfate and 15% of antimony oxychloride (formula of scheme 3, namely example 1) is considered, gypsum with the same quality is added, two ten-thousandths of the amount of the formula of the scheme 1, the scheme 2 and the scheme 3 is respectively added for small grinding experiments, and the hexavalent chromium content is measured according to GB 31893-.
Table 4 shows the hexavalent chromium content without and after addition of the chromium removing agent
| Samples without added decolourizing agent | 2.4mg/kg |
| Scheme one formula with addition of two ten-thousandths | 2.0mg/kg |
| Scheme two formula with addition of two ten-thousandths | 1.3mg/kg |
| Scheme III formula with addition of two ten-thousandths | 0.5mg/kg |
The experimental results are as follows: the synergistic effect of ferrous sulfate and ferrous sulfate in antimony oxychloride system and antimony oxychloride can properly increase the chromium removal effect. In addition, in the experimental process, antimony oxychloride and methylcellulose in the formula II are easy to agglomerate, the addition of ferrous sulfate can reduce the agglomeration field, and simultaneously, the ferrous sulfate and the antimony oxychloride are uniformly dispersed to cooperatively play a role in chromium removal.
Claims (8)
1. The composite liquid chromium removing agent is characterized by comprising the following raw materials in percentage by mass:
20-30% of ferrous sulfate heptahydrate, 10-30% of antimony oxychloride, 43-60% of water, 5-10% of organic solvent and 2-10% of methyl cellulose.
2. The composite liquid chromium removing agent is characterized by comprising the following raw materials in percentage by mass:
20-30% of ferrous sulfate heptahydrate, 10-30% of antimony trichloride, 43-60% of water, 5-10% of organic solvent and 2-10% of methyl cellulose.
3. The composite liquid chromium remover according to claim 1 or 2, wherein the organic solvent is selected from ethanol or N, N-dimethylformamide.
4. The composite liquid chromium remover according to claim 1 or 2, wherein the viscosity of the methyl cellulose is 40000-100000 mPa.s.
5. The preparation method of the compound liquid chromium remover as claimed in claim 1, which is characterized by comprising the following steps:
A. dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring to obtain a mixed solution;
B. and D, directly adding the antimony oxychloride with the formula amount into the solution prepared in the step A, uniformly stirring, adding the organic solvent with the formula amount, and uniformly mixing to obtain the compound liquid chromium remover.
6. The preparation method of the compound liquid chromium remover as claimed in claim 2, characterized by comprising the following steps:
1) dissolving a formula amount of ferrous sulfate heptahydrate in a formula amount of water to form a ferrous sulfate aqueous solution, adding a formula amount of methylcellulose, and stirring to obtain a mixed solution;
2) dissolving the antimony trichloride in the formula amount in the organic solvent in the formula amount, pouring the obtained solution into the mixed solution, and uniformly stirring to obtain the composite liquid chromium remover.
7. The application of the compound liquid chromium remover as claimed in claim 1 or 2, which is used for removing chromium from cement.
8. Use according to claim 7, characterized in that a chromium removing agent of two parts per million by mass of cement is added for chromium removal of cement.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114213056A (en) * | 2022-01-17 | 2022-03-22 | 安徽精公检测检验中心有限公司 | Ferrous sulfate-antimony trisulfide composite liquid chromium remover and preparation method and application thereof |
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