CN111807749B - Hexavalent chromium reducing agent and preparation method thereof - Google Patents
Hexavalent chromium reducing agent and preparation method thereof Download PDFInfo
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- CN111807749B CN111807749B CN202010529246.3A CN202010529246A CN111807749B CN 111807749 B CN111807749 B CN 111807749B CN 202010529246 A CN202010529246 A CN 202010529246A CN 111807749 B CN111807749 B CN 111807749B
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- hexavalent chromium
- reducing agent
- melamine resin
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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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/60—Methods for eliminating alkali metals or compounds thereof, e.g. from the raw materials or during the burning process; methods for eliminating other harmful components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
Abstract
The invention discloses a hexavalent chromium reducing agent, which comprises the following components: 11-23 parts of ferrous ions, 2-9 parts of stannous ions, 2-4 parts of heteroetherified melamine resin, 1-2 parts of sodium para-aminosalicylate, 0.2-0.4 part of nano-alumina, 40-60 parts of solvent, 4-6 parts of dispersant and 2-4 parts of stabilizer; the solvent is triethanolamine, ethylenediamine and water in a ratio of 2-4: 1-2: 6-8; the stabilizer is lignosulfonate.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of building materials, and particularly relates to a hexavalent chromium reducing agent and a preparation method thereof.
[ background of the invention ]
The cement is an indispensable building material in national economic development and is also one of the artificial building materials with the largest yield in the world at present. Meanwhile, the per-capita consumption of cement is an important index for measuring whether the country is developed or not, and the cement plays an important role in the development and progress of human civilization. In view of the development of the current state of the art in the world, no building material has been able to replace cement for a short time.
Because the content of hexavalent chromium in the cement exceeds the standard and the harm is caused to human and environment, the treatment of the hexavalent chromium in the cement is imperative. Hexavalent chromium is 100 times more toxic than trivalent chromium, so control of Cr6+ in cement generally uses a chemical reductant method, i.e. reduction of soluble Cr (vi) to Cr (iii) with low toxicity. Since the durability of the existing reducing agents such as ferrous sulfate to reduce hexavalent chromium is a serious problem, it is very sensitive to humidity and temperature, and its reducing power is gradually lost after grinding and during the storage of cement. This requires the use of larger doses of ferrous sulphate, which is more expensive than desired. Cement is generally alkaline, a plurality of reducing agents can play a reducing role under an acidic condition, and the reducing effect is easily lost under an alkaline condition, so that the development of an efficient, cheap and stable reducing agent capable of effectively reducing the high-toxicity hexavalent chromium in the cement into the low-toxicity trivalent chromium for a long time is needed.
Chinese patent (CN106365479B) discloses a cement hexavalent chromium compound reducing agent, wherein the mass percentages of sodium sulfite 15-20%, ferrous sulfate 60-70%, manganese sulfate 10-20%, stannous sulfate 1-10%, and total amount 100% are all mass percentages, the provided cement hexavalent chromium compound reducing agent has good chemical stability, can reduce water-soluble hexavalent chromium into trivalent chromium, and the content of hexavalent chromium can be maintained at 2ppm level for 3 months, the fineness of cement can be reduced by adding the reducing agent before grinding, the strength of cement in 3 days and 28 days can be remarkably increased, and the actual dosage is less than 1/10 of ferrous sulfate. The method has the characteristics of high reduction rate, good selectivity, simple and convenient experimental operation and the like, and has cheap and easily obtained raw materials and very high application prospect.
[ summary of the invention ]
The invention provides a hexavalent chromium reducing agent and a preparation method thereof, and the prepared hexavalent chromium reducing agent has excellent performance, is environment-friendly, simple and convenient and has low price.
In order to solve the technical problems, the invention adopts the following technical scheme:
a hexavalent chromium reducing agent comprising: 11-23 parts of ferrous ions, 2-9 parts of stannous ions, 2-4 parts of heteroetherified melamine resin, 1-2 parts of sodium para-aminosalicylate, 0.2-0.4 part of nano-alumina, 40-60 parts of solvent, 4-6 parts of dispersant and 2-4 parts of stabilizer; the solvent is triethanolamine, ethylenediamine and water in a ratio of 2-4: 1-2: 6-8; the stabilizer is lignosulfonate.
Further, the hexavalent chromium reducing agent comprises: 17 parts by weight of ferrous ions, 5.5 parts by weight of stannous ions, 3 parts by weight of heteroetherified melamine resin, 1.5 parts by weight of sodium para-aminosalicylate, 0.3 part by weight of nano-alumina, 50 parts by weight of solvent, 5 parts by weight of dispersant, and 3 parts by weight of stabilizer II, wherein the solvent is triethanolamine, ethylenediamine and water in a ratio of 3: 1.5: 7.
Further, the hexavalent chromium reducing agent, wherein the stannous ion is derived from any one of stannous sulfate and stannous chloride or a mixture of the two.
Further, the hexavalent chromium reducing agent, wherein the ferrous ion is derived from any one of ferrous sulfate, ferrous chloride or a mixture of the two.
Further, the hexavalent chromium reducing agent, wherein the lignosulfonate is calcium lignosulfonate.
Further, the hexavalent chromium reducing agent, wherein the dispersant is one or a mixture of two of polyethylene glycol and triisopropanolamine, wherein the molecular weight of the polyethylene glycol is 200-400.
Further, the hexavalent chromium reducing agent is prepared by the method that triethanolamine is used for adjusting the pH value of a formaldehyde aqueous solution to 10-11, then melamine and the formaldehyde aqueous solution are mixed according to a proportion, the mixture is heated to 70-80 ℃, after the color of the mixed solution is gradually changed from white to clear and transparent, methanol and butanol are added for continuous reaction for 2-4 hours, and the hetereetherified melamine resin is obtained respectively; the molar ratio of the raw materials of melamine, formaldehyde, methanol and butanol in the hetereetherified melamine resin is 1: 5: 3.
The preparation method of the hexavalent chromium reducing agent comprises the following steps:
(1) uniformly mixing a solvent, ferrous ions, stannous ions and a stabilizer at the temperature of 20-40 ℃, and filtering by using a 200-mesh screen to obtain a first mixture;
(2) adding a dispersing agent into the first mixture, and uniformly mixing;
(3) and (3) uniformly mixing the heteroetherification melamine resin, the sodium p-aminosalicylate and the nano aluminum oxide, adding the mixture into the solution obtained in the step (2), uniformly mixing, and filtering by using a 200-mesh screen.
Compared with the prior art, the hexavalent chromium reducing agent greatly reduces the using amounts of a dispersing agent and a stabilizing agent, and meanwhile, the stabilizing agent lignosulfonate has certain environmental protection problems.
[ detailed description ] embodiments
In order to facilitate a better understanding of the invention, the following examples are given to illustrate, but not to limit the scope of the invention.
A hexavalent chromium reducing agent comprising: 11-23 parts of ferrous ions, 2-9 parts of stannous ions, 2-4 parts of heteroetherified melamine resin, 1-2 parts of sodium para-aminosalicylate, 0.2-0.4 part of nano-alumina, 40-60 parts of solvent, 4-6 parts of dispersant and 2-4 parts of stabilizer; the solvent is triethanolamine, ethylenediamine and water in a ratio of 3: 1.5: 7; the stabilizer is lignosulfonate.
The stannous ion is derived from stannous chloride. The ferrous ion is derived from ferrous chloride. The lignosulfonate is calcium lignosulfonate. The dispersant is polyethylene glycol, and the molecular weight of the polyethylene glycol is 200-400.
The preparation method of the hetermanized melamine resin comprises the steps of adjusting the pH value of a formaldehyde aqueous solution to 10-11 by using triethanolamine, then mixing melamine and the formaldehyde aqueous solution in proportion, heating to 75 ℃, adding methanol and butanol to continue to react for 3 hours after the color of the mixed solution is gradually changed from white to clear and transparent, and respectively obtaining hetermanized melamine resin; the molar ratio of the raw materials of melamine, formaldehyde, methanol and butanol in the hetereetherified melamine resin is 1: 5: 3.
The preparation method of the hexavalent chromium reducing agent comprises the following steps:
(1) uniformly mixing a solvent, ferrous ions, stannous ions and a stabilizer at 30 ℃, and filtering by using a 200-mesh screen to obtain a first mixture;
(2) adding a dispersing agent into the first mixture, and uniformly mixing;
(3) and (3) uniformly mixing the heteroetherification melamine resin, the sodium p-aminosalicylate and the nano aluminum oxide, adding the mixture into the solution obtained in the step (2), uniformly mixing, and filtering by using a 200-mesh screen.
Example 1
A hexavalent chromium reducing agent comprising: 17 parts by weight of ferrous ions, 5.5 parts by weight of stannous ions, 3 parts by weight of heteroetherified melamine resin, 1.5 parts by weight of sodium para-aminosalicylate, 0.3 part by weight of nano-alumina, 50 parts by weight of solvent, 5 parts by weight of dispersant and 3 parts by weight of stabilizer.
Example 2
A hexavalent chromium reducing agent comprising: 11 parts by weight of ferrous ions, 9 parts by weight of stannous ions, 2 parts by weight of heteroetherified melamine resin, 2 parts by weight of sodium para-aminosalicylate, 0.2 part by weight of nano-alumina, 60 parts by weight of solvent, 4 parts by weight of dispersant and 4 parts by weight of stabilizer.
The rest is the same as in example 1.
Example 3
A hexavalent chromium reducing agent comprising: 23 parts by weight of ferrous ions, 2 parts by weight of stannous ions, 4 parts by weight of heteroetherified melamine resin, 1 part by weight of sodium para-aminosalicylate, 0.4 part by weight of nano-alumina, 40 parts by weight of solvent, 6 parts by weight of dispersant and 2 parts by weight of stabilizer.
The rest is the same as in example 1.
Comparative example 1
The preparation process is basically the same as that of the example 1, except that the raw materials for preparing the hexavalent chromium reducing agent lack the hetereetherified melamine resin, sodium p-aminosalicylate and nano-alumina.
Comparative example 2
Essentially the same procedure as in example 1, except that the starting material for the hexavalent chromium reducing agent lacks the heteroetherified melamine resin.
Comparative example 3
Essentially the same procedure as in example 1 except that the starting material for the hexavalent chromium reducing agent lacks sodium para-aminosalicylate.
Comparative example 4
The process was essentially the same as that of example 1, except that no nano-alumina was added to the starting material for the hexavalent chromium reducing agent.
Comparative example 5
Substantially the same procedure as in example 1 was conducted except that 12 parts by weight of a dispersant and 10 parts by weight of a stabilizer were added to the starting materials for preparing the hexavalent chromium reducing agent.
Comparative example 6
The hexavalent chromium reducing agent was prepared according to the procedure of CN104496251B example 1.
Mixing the following materials in proportion: 63% of clinker, 8% of gypsum, 18% of slag and 11% of fly ash by mass, and then 0.005% of chromium trioxide is doped in the fly ash by mass to obtain a mixed material.
Adding the hexavalent chromium reducing agent product obtained in the embodiment with the mass fraction of 0.1% of the total mass of the mixture into the obtained mixture, and mixing and grinding for 25min to obtain the treated cement. According to the solid waste leaching toxicity leaching method-sulfuric acid nitric method of HJ/T299 and the solid waste leaching toxicity leaching method-horizontal oscillation method of HJ 557, leaching tests are carried out on clinker hydration samples of different ages, and according to the determination of GB 7467 water quality-hexavalent chromium, the concentration of hexavalent chromium in leachate is determined by the dibenzoyl dihydrazide spectrophotometry, and according to the GB/T17671 cement mortar strength test method (ISO method), the compressive strength of a cement hardening test body is tested, and the determination results are shown in the following table.
Experiments show that the hexavalence chromium reducing agent can effectively enhance the long-term hexavalence chromium reducing effect by adding the hetereetherified melamine resin to the amino sodium salicylate and the nano aluminum oxide, the increase is not obvious in a short period, but the long-term effect is obvious, and the long-term effect and the obvious synergistic enhancement effect are achieved.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (2)
1. A hexavalent chromium reducing agent, comprising: 17 parts by weight of ferrous ions, 5.5 parts by weight of stannous ions, 3 parts by weight of heteroetherified melamine resin, 1.5 parts by weight of sodium para-aminosalicylate, 0.3 part by weight of nano-alumina, 50 parts by weight of solvent, 5 parts by weight of dispersant and 3 parts by weight of stabilizer; the solvent is triethanolamine, ethylenediamine and water in a ratio of 3: 1.5: 7; wherein the dispersant is one or a mixture of two of polyethylene glycol and triisopropanolamine; wherein the molecular weight of the polyethylene glycol is 200-400; the preparation method of the hetereetherified melamine resin comprises the following steps: regulating the pH value of a formaldehyde aqueous solution to 10-11 by using triethanolamine, then mixing melamine and the formaldehyde aqueous solution in proportion, heating to 70-80 ℃, adding methanol and butanol to continue reacting for 2-4 hours after the color of the mixed solution is gradually changed from white to clear and transparent, and respectively obtaining heteratherized melamine resin; the molar ratio of the raw materials of melamine, formaldehyde, methanol and butanol in the hetereetherified melamine resin is 1: 5: 3.
2. A process for the preparation of the hexavalent chromium reducing agent of claim 1, comprising:
(1) uniformly mixing a solvent, ferrous ions, stannous ions and a stabilizer at the temperature of 20-40 ℃, and filtering by using a 200-mesh screen to obtain a first mixture;
(2) adding a dispersing agent into the first mixture, and uniformly mixing;
(3) and (3) uniformly mixing the heteroetherification melamine resin, the sodium p-aminosalicylate and the nano aluminum oxide, adding the mixture into the solution obtained in the step (2), uniformly mixing, and filtering by using a 200-mesh screen.
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| CN202010529246.3A CN111807749B (en) | 2020-06-11 | 2020-06-11 | Hexavalent chromium reducing agent and preparation method thereof |
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| CN202010529246.3A CN111807749B (en) | 2020-06-11 | 2020-06-11 | Hexavalent chromium reducing agent and preparation method thereof |
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| CN111807749A CN111807749A (en) | 2020-10-23 |
| CN111807749B true CN111807749B (en) | 2022-04-12 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133434A1 (en) * | 1983-01-20 | 1985-02-27 | Cementa Ab | A method of reducing eczema-inducing chromium in cement by adding ferrous sulfate, an additive comprising ferrous sulfate and the use of the additive |
| CN104496243A (en) * | 2014-11-06 | 2015-04-08 | 中国建筑材料科学研究总院 | Hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN104496251A (en) * | 2014-11-25 | 2015-04-08 | 中国建筑材料科学研究总院 | Liquid hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN108314089A (en) * | 2018-02-01 | 2018-07-24 | 济南大学 | A kind of porous flower-shaped α-Fe2O3The synthetic method of self-assembled nanometer material |
| CN108755138A (en) * | 2018-04-04 | 2018-11-06 | 史国民 | A kind of textile fabric waterproofing agent and preparation method thereof that environment-friendly watertight is washed |
-
2020
- 2020-06-11 CN CN202010529246.3A patent/CN111807749B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0133434A1 (en) * | 1983-01-20 | 1985-02-27 | Cementa Ab | A method of reducing eczema-inducing chromium in cement by adding ferrous sulfate, an additive comprising ferrous sulfate and the use of the additive |
| CN104496243A (en) * | 2014-11-06 | 2015-04-08 | 中国建筑材料科学研究总院 | Hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN104496251A (en) * | 2014-11-25 | 2015-04-08 | 中国建筑材料科学研究总院 | Liquid hexavalent chromium reducing agent and preparation method thereof, cement and preparation method thereof |
| CN108314089A (en) * | 2018-02-01 | 2018-07-24 | 济南大学 | A kind of porous flower-shaped α-Fe2O3The synthetic method of self-assembled nanometer material |
| CN108755138A (en) * | 2018-04-04 | 2018-11-06 | 史国民 | A kind of textile fabric waterproofing agent and preparation method thereof that environment-friendly watertight is washed |
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