CN103833249B - Chromium removal enhancer and preparation method thereof - Google Patents
Chromium removal enhancer and preparation method thereof Download PDFInfo
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- CN103833249B CN103833249B CN201410097962.3A CN201410097962A CN103833249B CN 103833249 B CN103833249 B CN 103833249B CN 201410097962 A CN201410097962 A CN 201410097962A CN 103833249 B CN103833249 B CN 103833249B
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Abstract
The invention provides a method for preparing a chromium removal enhancer. The method comprises the following steps: (a) calcining kaolin, mixing the calcined kaolin and an acid solution, performing suction filtration, and washing and drying the obtained solid; (b) mixing the kaolin obtained in the step (a) and an mixed solution, and reacting to obtain the chromium removal enhancer, wherein the mixed solution is a mixed solution of a reducing agent, an antioxidant, an enhancer and water. According to the chromium removal enhancer prepared by the invention, the kaolin is taken as a raw material, the reducing agent, the antioxidant and the enhancer are mixed with the modified kaolin, and the chromium removal enhancer is obtained after the reaction. According to the chromium removal enhancer prepared by the invention, due to dual effects of adsorption and reduction, hexavalent chromium in cement is effectively removed, and physical properties of the cement are improved. The invention also provides the chromium removal enhancer prepared according to the method.
Description
Technical field
The present invention relates to harmful substance in cement and remove technical field, particularly relate to a kind of except chromium increasing
Strong agent and preparation method thereof.
Background technology
Chromium is a kind of argenteous hard metal, mainly with crome metal, trivalent chromium and Cr VI three
The form of kind occurs.The compound of chromium is the most toxic, and wherein Cr VI toxicity is maximum.Sexavalence
Chromium is the property swallowed or imbedibility poisonous substance, and human body is mainly chronic murder by poisoning, and it can be by digestion
Road, respiratory tract, skin and mucosa invade human body；And Cr VI has strong oxidation, therefore
Chromic chronic poisoning often starts gradually to develop into incurable with local lesion.
All can produce Cr VI in the raw material of cement and production process, the Cr VI in cement is same
Sample also can produce serious harmful effect to human body, makes skin pain fester, and is formed and is difficult to cure
Cement dermatitis or cement eczema.In June, 2003, European Union promulgates instruction, forbids selling on market
With use the water soluble hexavalent chromium content cement more than 0.0002% and cement products；2006 7
Month, European standard ENl96.10-2006 is issued and implemented.In recent years, the hexavalent chromium polluted problem of cement
Also result in the great attention of relevant department.But in cement and concrete except chromium special assistant also
Rarely found.
The Chinese patent of Publication No. CN101282917A discloses a kind of liquid for cement
Chromium remover, it includes can hydratable cement particles and be incorporated into cement with the form of association complex
Metal Substrate chromium reducing agent in Li, association complex is by Metal Substrate chromium reducing agent and non-wood quality
The form of sulphonate-base complex is formed.This liquid chromium remover is not very notable except chromium effect, its
Secondary it is it reducing agent is the most oxidized during preserving and using to lose reduction.
Kaolin is a kind of natural non-metallic mineral, has abundant reserves in China, extensively applies
In the field such as chemical industry, building materials.Kaolin has cation exchange capacity (CEC), preferable fire resistance etc. to manage
Change character, of many uses.Thus, the application provides a kind of except chromium increasing with Kaolin for raw material
Strong agent.
Summary of the invention
Present invention solves the technical problem that and be to provide one except chromium effect preferably except chromium strengthens
Agent and preparation method thereof.
In view of this, this application provides a kind of except the preparation method of chromium reinforcing agent, including following
Step:
A) Kaolin is calcined, the Kaolin after calcining is mixed with acid solution, then
Carry out sucking filtration, be dried after the solid washing that will obtain；
B) Kaolin step a) obtained mixes with mixed liquor, obtains except chromium strengthens after reaction
Agent；Described mixed liquor is the mixed liquor of reducing agent, antioxidant, reinforcing agent and water.
Preferably, the temperature of described calcining is 800～900 DEG C, and the time of described calcining is 2h～4h.
Preferably, described acid solution is hydrochloric acid, sulphuric acid or phosphoric acid.
Preferably, described reducing agent is ferrous sulfate, ferrous chloride, stannous sulfate or protochloride
Stannum.
Preferably, described antioxidant is citric acid, ascorbic acid or oxalic acid.
Preferably, described reinforcing agent is sodium chloride, calcium chloride, sodium sulfate, triethanolamine or three
Isopropanolamine.
Preferably, the concentration of described acid solution is 0.1mol/L～0.5mol/L.
Present invention also provides prepared by the preparation method described in such scheme except chromium reinforcing agent.
Preferably, described include except chromium reinforcing agent:
Reducing agent 10wt%～20wt%；
Antioxidant 1wt%～5wt%；
Reinforcing agent 20wt%～30wt%；
Kaolin surplus.
Preferably, the content of described reducing agent is 12wt%～17wt%, containing of described antioxidant
Amount is 2wt%～3wt%, and the content of described reinforcing agent is 22wt%～27wt%.
This application provides a kind of except the preparation method of chromium reinforcing agent.In preparation except chromium reinforcing agent
During, first Kaolin is calcined, then by the Kaolin after calcining and acid solution
Mixing, is modified in an acidic solution, Kaolin and reducing agent after finally processing, anti-
Oxidant, reinforcing agent mix, and i.e. obtain except chromium reinforcing agent after reaction.
Kaolinic basic structure is silicon-oxy tetrahedron and alumina octahedral, kaolin calcined after meeting
Increase its surface area, pore volume, and silicon dioxide and alchlor content all increases, active site
Increasing, the kaolinic said structure after calcining makes it have preferable gelation activity, is conducive to
The hydration of cement and the increase each age strength of cement, and there is suction from surrounding medium
Attached various ion and the performance of impurity；Kaolin after calcining processes through acid solution, can widen height
The mesopore pore size of ridge soil, and form new surface microporous structure, pore-size distribution more disperse, flat
All apertures increase, and pore volume and specific surface area increase, and are greatly improved the absorbability of chromium ion；
Reducing agent can effective reduction of hexavalent chromium；Reducing agent load simultaneously can be filled with cement on the kaolin
Tap is touched, and is reduced by chromium to greatest extent；Antioxidant reduces reducing agent and in preparation and preserved
Oxidation in journey, it is ensured that the reduction effect of reducing agent；Reinforcing agent can be effectively improved the thing of cement
Rationality energy, promotes the hydration process of cement, makes each age strength of cement all improve.
In sum, the present invention prepare except chromium reinforcing agent by absorption and reduction dual function, have
The Cr VI removed in cement of effect, improves the physical property of cement simultaneously.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
With advantage rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of except the preparation method of chromium reinforcing agent, including following step
Rapid:
A) Kaolin is calcined, the Kaolin after calcining is mixed with acid solution, then
Carry out sucking filtration, be dried after the solid washing that will obtain；
B) Kaolin step a) obtained mixes with mixed liquor, obtains except chromium reinforcing agent；Institute
State the mixed liquor that mixed liquor is reducing agent, antioxidant, reinforcing agent and water.
This application provides a kind of except chromium reinforcing agent and preparation method thereof, described except chromium reinforcing agent be
With modified kaolin as carrier, it is used for removing chromic reinforcing agent in cement or concrete.This
The reinforcing agent that invention provides is under the dual function of absorption and reduction, it is possible to effectively remove in cement
Cr VI to reduce harm to human body Yu environment, this reinforcing agent can also be effectively improved simultaneously
The physical property of cement.
During preparation is except chromium reinforcing agent, first Kaolin has been carried out modification by the application.
Kaolin of the present invention is a kind of natural non-metallic mineral, and its basic structure is silicon-oxy tetrahedron
With aluminum-oxygen tetrahedron.First Kaolin calcined by the application, during kaolin calcined,
Various impurity in Kaolin aperture are removed, thus have widened kaolinic aperture, add
Kaolinic microcellular structure；On the other hand, calcining makes kaolinic structure there occurs change, Al
It is active four-coordination and pentacoordinate by inert hexa-coordinate structural transformation, creates simultaneously
Substantial amounts of active silica.
The kaolinic structure obtained through calcining makes it have preferable gelation activity, is conducive to
The hydration of cement also increases the intensity of cement each age；Kaolin also has from surrounding simultaneously
Medium adsorbs the performance of various ion and impurity, and there is ion exchangeable matter in the solution.
The temperature of herein described calcining is preferably 800 DEG C～900 DEG C, more preferably 850 DEG C～880 DEG C；
The time of described calcining is preferably 2h～4h, more preferably 3h～3.5h.
According to the present invention, Kaolin is after high-temperature calcination, and the application is by the Kaolin after calcining
Carrying out acid treatment, the Kaolin after will calcining mixes with acid solution, by the kaolinite after calcining
Soil is modified in an acidic solution, then carries out sucking filtration, makes solid-liquid separation, by solid-liquid separation
After solid washing after be dried, obtained modified Kaolin.Described acid solution is preferably
Hydrochloric acid, sulphuric acid or phosphoric acid.The concentration of described acid solution is preferably 0.1mol/L～0.5mol/L,
More preferably 0.1mol/L～0.3mol/L.The tool that Kaolin after calcining processes in an acidic solution
Body process is:
Kaolin after calcining is added to acid solution, at 80 DEG C～100 DEG C, stirs 4h～5h,
Then carry out sucking filtration, be dried after the solid washing that will obtain.
Kaolin after calcining can widen kaolinic mesopore hole through the process of acid solution
Footpath, increases big, the volume of mesopore, and forms some new surface microporous structures, pore-size distribution
More disperse, average pore size increases, and pore volume and specific surface area increase, the absorption to chromium ion
Ability is greatly improved.In summary, Kaolin makes kaolinic structure there occurs through modification
State change, thus substantially increase the modified Kaolin absorbability to chromium.
The present invention is then by modified Kaolin and reducing agent, antioxidant, reinforcing agent, water
Mixing, i.e. obtains except chromium reinforcing agent after reaction.Herein described reducing agent be preferably ferrous sulfate,
Ferrous chloride, stannous sulfate or stannous chloride；Described antioxidant is preferably Water-soluble antioxidant
Agent, more preferably citric acid, ascorbic acid or oxalic acid；Described reinforcing agent be preferably inorganic salt or
Organic reinforcing agent, described inorganic salt is preferably sodium chloride, calcium chloride or sodium sulfate, described organic
Reinforcing agent is preferably triethanolamine or triisopropanolamine.Herein described Kaolin, reducing agent,
After antioxidant, reinforcing agent mix with water, there is ion exchange and complex reaction, thus obtain
Except chromium reinforcing agent.
Above-mentioned reducing agent can effective reduction of hexavalent chromium, make chromic content meet standard and want
Ask, and reducing agent can load abundant on the kaolin and cements, to greatest extent will
Chromium reduces.Antioxidant can reduce reducing agent oxidation during preparation and preservation, enters one
Step ensures the reduction effect of reducing agent.And reinforcing agent can improve the physical property of cement, promote
The hydration process of cement, makes cement all improve at each age strength.Therefore, this Shen
After please modified Kaolin being mixed with reducing agent, antioxidant, reinforcing agent so as to get
Except chromium can be reduced by chromium reinforcing agent to greatest extent, and reducing agent can be reduced in preparation and preservation
During oxidation, make except chromium reinforcing agent has higher stability, and cement can be improved
Physical property.
According to the present invention, in order to enable modified Kaolin and antioxidant, reducing agent,
Reinforcing agent mix homogeneously, as method for optimizing, the described preparation process except chromium reinforcing agent particularly as follows:
Reducing agent, antioxidant, reinforcing agent are configured to mixed liquor with water；
Kaolin through modification is mixed with described mixed liquor, stirring 2h～3h, sucking filtration,
Pulverize after Feng Ganing, obtain except chromium reinforcing agent.
This application provides a kind of except the preparation method of chromium reinforcing agent.In preparation except chromium reinforcing agent
During, first Kaolin is calcined, then by the Kaolin after calcining at acid solution
In process, finally will process after Kaolin mix with reducing agent, antioxidant, reinforcing agent
Close, i.e. obtain except chromium reinforcing agent.Kaolinic basic structure is silicon-oxy tetrahedron and alumina octahedral
Body, kaolin calcined after can increase its surface area, pore volume, there is stronger ionic adsorption and make
With；Kaolin after calcining processes through acid solution, further increases the energy of adsorption to chromium ion
Power；And reducing agent can effective reduction of hexavalent chromium；Reducing agent load simultaneously on the kaolin can be with
Cement is fully contacted, and is reduced by chromium to greatest extent；Antioxidant reduce reducing agent preparation and
Oxidation during preservation, it is ensured that the stability of reducing agent；Reinforcing agent can be effectively improved cement
Physical property, promote cement hydration process, make each age strength of cement all have certain proposing
High.In sum, the present invention except chromium reinforcing agent by absorption and reduction dual function, have
The Cr VI removed in cement of effect, and make except chromium reinforcing agent has higher stability.
Present invention also provides by prepared by said method except chromium reinforcing agent, as preferably side
Case, described includes except chromium reinforcing agent:
Reducing agent 10wt%～20wt%；
Antioxidant 1wt%～5wt%；
Reinforcing agent 20wt%～30wt%；
Kaolin surplus.
According to the present invention, except reducing agent described in chromium reinforcing agent is preferably ferrous sulfate, protochloride
Ferrum, stannous sulfate or stannous chloride；Described antioxidant is preferably water soluble antioxidant, more
It is preferably citric acid, ascorbic acid or oxalic acid；Described reinforcing agent is preferably inorganic salt or organic increasing
Strong agent, described inorganic salt is preferably sodium chloride, calcium chloride or sodium sulfate, described organic reinforcing agent
It is preferably triethanolamine or triisopropanolamine.Described herein except the reducing agent in chromium reinforcing agent,
Kaolin, antioxidant and the content of reinforcing agent, can be according to chromic in cement or concrete
Content carries out suitable adjustment.Preferably, the content of described reducing agent is preferably
12wt%～17wt%, more preferably 14wt%～16wt%.The content of described antioxidant is preferred
For 1.8wt%～4wt%, more preferably 2wt%～3wt%.The content of described reinforcing agent is
22wt%～27wt%, more preferably 24wt%～26wt%.
In order to be further appreciated by the present invention, below in conjunction with embodiment the present invention is provided except chromium increase
Strong agent and preparation method thereof is described in detail, and protection scope of the present invention is not by following example
Restriction.
Raw material in following example is commercially available prod.
Embodiment 1
(1) Kaolin is calcined 3h at 850 DEG C；
(2) under agitation the Kaolin after calcining is joined the sulfuric acid solution of 0.1mol/L
In, stir 4h, sucking filtration, washing at 80 DEG C, dry stand-by；
(3) sodium chloride of the ferrous sulfate of 15wt%, the citric acid of 3wt%, 25wt% is added
The mixed liquor of 500mL it is configured in deionized water；
(4) step 2 is taken) the kaolinic 57wt% that obtains joins the mixing of step 3) preparation
In liquid, continuous stirring 2h, sucking filtration, natural air drying, pulverize, i.e. prepare except chromium reinforcing agent.
In cement, the mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.Detection is originally
Embodiment prepare except chromium reinforcing agent, without increasing except chromium except the preparation of chromium reinforcing agent and comparative example 1
The removal efficiency of chrome of strong agent, as shown in table 1, table 1 is that embodiment removes chromium reinforcing agent except chromium with comparative example
The tables of data of effect.
Embodiment 2
(1) Kaolin is calcined 4h at 900 DEG C；
(2) under agitation the Kaolin after calcining is joined in the hydrochloric acid solution of 0.15mol/L,
Stir 4h, sucking filtration, washing at 80 DEG C, dry stand-by；
(3) ferrous chloride of 10wt%, the ascorbic acid of 1wt%, the calcium chloride of 20wt% are added
Enter to be configured to the mixed liquor of 500mL in deionized water；
(4) step 2 is taken) the kaolinic 69wt% that obtains joins the mixing of step 3) preparation
In liquid, continuous stirring 2h, sucking filtration, natural air drying, pulverize, i.e. prepare except chromium reinforcing agent.
In cement, the mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.Detection is originally
Embodiment prepare except chromium reinforcing agent, without increasing except chromium except the preparation of chromium reinforcing agent and comparative example 1
The removal efficiency of chrome of strong agent, as shown in table 1, table 1 is that embodiment removes chromium reinforcing agent except chromium with comparative example
The tables of data of effect.
Embodiment 3
(1) Kaolin is calcined 3.5h at 860 DEG C；
(2) under agitation the Kaolin after calcining is joined in the hydrochloric acid solution of 0.25mol/L,
Stir 4h, sucking filtration, washing at 80 DEG C, dry stand-by；
(3) stannous chloride of 20wt%, the oxalic acid of 5wt%, the sodium sulfate of 30wt% are joined
Deionized water is configured to the mixed liquor of 500mL；
(4) step 2 is taken) the kaolinic 45wt% that obtains joins the mixing of step 3) preparation
In liquid, continuous stirring 2h, sucking filtration, natural air drying, pulverize, i.e. prepare except chromium reinforcing agent.
In cement, the mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.Detection is originally
Embodiment prepare except chromium reinforcing agent, without increasing except chromium except the preparation of chromium reinforcing agent and comparative example 1
The removal efficiency of chrome of strong agent, as shown in table 1, table 1 is that embodiment removes chromium reinforcing agent except chromium with comparative example
The tables of data of effect.
Embodiment 4
(1) Kaolin is calcined 3.8h at 880 DEG C；
(2) under agitation the Kaolin after calcining is joined in the phosphoric acid solution of 0.5mol/L,
Stir 4h, sucking filtration, washing at 80 DEG C, dry stand-by；
(3) calcium chloride of the stannous sulfate of 18wt%, the citric acid of 4wt%, 22wt% is added
The mixed liquor of 500mL it is configured in deionized water；
(4) step 2 is taken) the kaolinic 56wt% that obtains joins the mixing of step 3) preparation
In liquid, continuous stirring 2h, sucking filtration, natural air drying, pulverize, i.e. prepare except chromium reinforcing agent.
In cement, the mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.Detection is originally
Embodiment prepare except chromium reinforcing agent, without increasing except chromium except the preparation of chromium reinforcing agent and comparative example 1
The removal efficiency of chrome of strong agent, as shown in table 1, table 1 is that embodiment removes chromium reinforcing agent except chromium with comparative example
The tables of data of effect.
Comparative example 1
(1) by the ferrous sulfate of mass fraction 15%, the citric acid of 3wt%, the chlorination of 25wt%
Sodium joins the mixed liquor liquid being configured to 500mL in deionized water.
(2) Kaolin taking 57wt% joins in mixed liquor, continuous stirring 2h, sucking filtration, from
So air-dry, pulverize, i.e. prepare except chromium reinforcing agent.
In cement, the mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.In cement
The mensuration of chromium content uses diphenyl carbazide spectrophotometry to measure.The detection embodiment of the present invention
Preparation except chromium reinforcing agent, without except the preparation of chromium reinforcing agent and comparative example 1 except chromium reinforcing agent
Removal efficiency of chrome, as shown in table 1, table 1 is that embodiment removes chromium reinforcing agent except chromium effect with comparative example
Tables of data.
Table 1 embodiment of the present invention and comparative example are except the tables of data of the removal efficiency of chrome of chromium reinforcing agent
| Group | Except chromium reinforcing agent consumption/% | Chromium clearance/% |
| Embodiment 1 | 0.03 | 99.4 |
| Embodiment 2 | 0.03 | 99.5 |
| Embodiment 3 | 0.03 | 99.6 |
| Embodiment 4 | 0.03 | 99.3 |
| Blank example | 0 | 0 |
| Comparative example 1 | 0.03 | 82 |
In cement, add that the embodiment of the present invention 1, comparative example 1 obtain except chromium reinforcing agent and
Without except chromium reinforcing agent, the performance of test cement, the application is at φ 500mm × 500mm mark
Testing in the little mill of quasi experiment, the material proportion of cement is: the grog of 46.0wt%, 4.0wt%
Gypsum Fibrosum and the slag of 50.0%, experimental result is as shown in table 2.
The performance data table of the cement that table 2 embodiment of the present invention and comparative example obtain
From experimental result, add prepared by the present invention except chromium reinforcing agent after, in cement
Solubility content of 6-valence Cr ions is substantially reduced, and the physical properties of cement meets standard-required simultaneously,
Each age comprcssive strength and rupture strength all increase and improve.
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, it is also possible to the present invention is carried out some improvement and modification, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple amendment to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and is to fit to and principles disclosed herein and new
The widest scope that grain husk feature is consistent.
Claims (8)
1., except a preparation method for chromium reinforcing agent, comprise the following steps:
A) Kaolin is calcined, the Kaolin after calcining is mixed with acid solution, then takes out
Filter, is dried after the solid washing that will obtain；
B) Kaolin obtained by step a) mixes with mixed liquor, obtains except chromium reinforcing agent after reaction；Institute
State the mixed liquor that mixed liquor is reducing agent, antioxidant, reinforcing agent and water；
Described reinforcing agent is sodium chloride, calcium chloride, sodium sulfate, triethanolamine or triisopropanolamine；
Described include except chromium reinforcing agent:
Reducing agent 10wt%～20wt%；
Antioxidant 1wt%～5wt%；
Reinforcing agent 20wt%～30wt%；
The Kaolin of surplus.
Preparation method the most according to claim 1, it is characterised in that the temperature of described calcining is
800～900 DEG C, the time of described calcining is 2h～4h.
Preparation method the most according to claim 1, it is characterised in that described acid solution be hydrochloric acid,
Sulphuric acid or phosphoric acid.
Preparation method the most according to claim 1, it is characterised in that described reducing agent is that sulphuric acid is sub-
Ferrum, ferrous chloride, stannous sulfate or stannous chloride.
Preparation method the most according to claim 1, it is characterised in that described antioxidant is Fructus Citri Limoniae
Acid, ascorbic acid or oxalic acid.
Preparation method the most according to claim 1, it is characterised in that the concentration of described acid solution
For 0.1mol/L～0.5mol/L.
7. the preparation method described in any one of claim 1～6 prepare except chromium reinforcing agent.
The most according to claim 7 except chromium reinforcing agent, it is characterised in that the content of described reducing agent
For 12wt%～17wt%, the content of described antioxidant is 2wt%～3wt%, the content of described reinforcing agent
For 22wt%～27wt%.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104496243B (en) * | 2014-11-06 | 2017-03-22 | 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 |
| CN104496251B (en) * | 2014-11-25 | 2017-03-22 | 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 |
| CN105198260A (en) * | 2015-10-13 | 2015-12-30 | 云南锡业股份有限公司 | Special tin-containing additive for removing hexavalent chromium from cement and preparation method of additive |
| CN108585597B (en) * | 2018-07-24 | 2020-10-27 | 青神鑫统领建材有限公司 | Reduced hexavalent chromium type grinding aid and preparation method thereof |
| CN110316992B (en) * | 2019-04-04 | 2020-09-01 | 清华大学 | Steel slag-based cement hexavalent chromium solid reducing agent |
| CN112374789B (en) * | 2020-10-13 | 2022-05-24 | 唐山冀东水泥外加剂有限责任公司 | Cement hexavalent chromium reducing agent and preparation method thereof |
| CN112500013A (en) * | 2020-11-20 | 2021-03-16 | 华润水泥技术研发有限公司 | Preparation method of nano-loaded hexavalent chromium reducing agent for cement |
| CN112500014A (en) * | 2020-11-20 | 2021-03-16 | 华润水泥技术研发有限公司 | Preparation method of hexavalent chromium reducing agent for high-temperature-resistant cement |
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