CN117510110A - Chromium-reducing additive and method for rotary kiln burned cement clinker - Google Patents
Chromium-reducing additive and method for rotary kiln burned cement clinker Download PDFInfo
- Publication number
- CN117510110A CN117510110A CN202311415678.1A CN202311415678A CN117510110A CN 117510110 A CN117510110 A CN 117510110A CN 202311415678 A CN202311415678 A CN 202311415678A CN 117510110 A CN117510110 A CN 117510110A
- Authority
- CN
- China
- Prior art keywords
- chromium
- rotary kiln
- cement
- reducing additive
- cement clinker
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000004568 cement Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000654 additive Substances 0.000 title claims abstract description 25
- 230000000996 additive effect Effects 0.000 title claims abstract description 23
- 239000011651 chromium Substances 0.000 claims abstract description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 19
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 16
- 238000006722 reduction reaction Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 6
- 229910052582 BN Inorganic materials 0.000 claims abstract description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 238000010304 firing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims 2
- 235000012054 meals Nutrition 0.000 claims 1
- 230000000171 quenching effect Effects 0.000 claims 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000001737 promoting effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 6
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical class [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
-
- 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
- C04B7/43—Heat treatment, e.g. precalcining, burning, melting; Cooling
- C04B7/44—Burning; Melting
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a chromium-reducing additive for rotary kiln burned cement clinker and a method thereof, wherein the effective components of the chromium-reducing additive comprise at least one of boron carbide and boron nitride. The chromium-reducing additive and the cement raw material are uniformly mixed and then are sent into a rotary kiln together for calcination, and the self-valence-changing reduction reaction of hexavalent chromium is promoted by the boron-containing component, so that the content of hexavalent chromium in the cement clinker is reduced. The invention utilizes the promoting effect of the chromium reducing additive on the self-valence-changing reduction reaction of the chromates to ensure that the chromates (CrO) 4 2‑ ) Decomposing to form Cr 2 O 3 And oxygen to achieve the technical effect of in-situ high-temperature reduction of hexavalent chromium in the rotary cement kiln.
Description
Technical Field
The invention belongs to the technical field of inorganic nonmetallic materials, and particularly relates to a chromium-reducing additive for rotary kiln sintered cement clinker and a method thereof.
Background
Compared with the traditional raw materials, the content of harmful ions in the industrial solid waste is higher. In particular to the oxidation of chromium ions in solid wastes such as steel slag and the like into Cr in the cement firing process 6+ Soluble chromates are formed. Cr (Cr) 6+ The biological toxicity and the environmental hazard are Cr due to the strong oxidizing property and the dissolubility 3+ Hundred times of equivalent low-valence heavy metal ions.
Water-soluble Cr in cement 6+ The skin of the human body is contacted with the skin to generate allergic hazard, the human body is accessed to generate cancerogenic risk, and meanwhile, the water, soil and ecological environment are polluted and destroyed. Cr (Cr) 6+ The regulation and control of environmental effects are important guarantees for safely using a large amount of solid waste to replace cement raw materials. Limiting and measuring method of water-soluble hexavalent chromium (VI) in cement (GB 31893-2015) of national standard of China limits soluble Cr in cement 6+ The amount is less than 10mg/kg.
The prior technical proposal uses additive with reducibility to regulate and control the soluble Cr in cement 6+ Is not limited. Common cement chromium reduction additives include ferrous salts (ferrous sulfate), stannous salts (stannous sulfate), and the like. Because of low cost and high reduction efficiency, ferrous sulfate is the most widely applied chromium reducing agent in the cement industry at present. Ferrous sulfate is easily oxidized by air, and can not maintain reducibility after long-term storage. And Fe (Fe) 2+ The critical temperature for maintaining reducibility is 90 ℃, if ferrite is added into a clinker mill, the high temperature (105 ℃) in the mill will lead to Fe 2+ First oxidized to Fe 3+ The reducibility is lost. The reduction efficiency and the storage property of stannous salt and trivalent antimony salt are better than those of ferrous sulfate, but the cost is higher, and harmful metal ions such as tin, antimony and the like can be additionally introduced into cement.
Disclosure of Invention
The invention aims to: due to the high temperature, oxidizing and alkaline environments of cement manufacturing processes, reducing atmospheres, such as CO and CH 4 And the like are difficult to apply to rotary cement kilns. Therefore, if the method for in-situ high-temperature reduction of hexavalent chromium in the rotary kiln of cement can be developed, chromium element is converted into trivalent chromium with low harm in the cement firing process, the method can be compatible with the process environment of cement production, the process is not required to be regulated, the cost of an externally added chromium reducing agent can be saved, and the method has remarkable economic and social values.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the chromium reducing additive for rotary kiln sintered cement clinker has at least one of boron carbide and boron nitride as effective component.
The invention further provides a method for reducing the hexavalent chromium content in the cement clinker burned in the rotary kiln by adopting the chromium reducing additive, the chromium reducing additive and the cement raw material are uniformly mixed and then are sent into the rotary kiln to be calcined together, and the self-valence-changing reduction reaction of the hexavalent chromium is promoted by the boron-containing component, so that the hexavalent chromium content in the cement clinker is reduced.
Preferably, the chromium-reducing additive is mixed and ground until the particle size of the powder is less than 100 microns.
Further, the chromium-reducing additive and the cement raw material are 0.2-2% by mass percent: and (3) uniformly mixing 98-98.8%, and then feeding the mixture into a preheater arranged in a rotary kiln.
Further, the temperature of the firing zone of the rotary kiln is controlled to 1250-1450 ℃.
Further, the residence time of the mixture of the chromium-reducing additive and the cement raw material in the firing zone of the rotary kiln is 20-60 min.
Further, the cement clinker balls generated by calcination are cooled in a grate cooler after being discharged from a rotary kiln.
Preferably, the rapid cooling rate is 500-800 ℃/min.
Preferably, the particle size of the cement clinker balls produced by calcination is in the range of 0.5 to 2cm.
Preferably, the rotary kiln has a rotating speed of 0.8-1.5 r/min and an inclination of 3-5%.
The beneficial effects are that:
(1) The invention adopts substances such as externally doped boron carbide, boron nitride and the like as chromium reducing additives, and forms a high-temperature liquid phase in a rotary kiln sintering zone (1250-1450 ℃). The boron-containing component increases the surface tension of the liquid phase, and the liquid phase wraps the cement raw material to be burned to promote the agglomeration and sintering of the clinker balls.
(2) After the clinker is formed into balls in the method of the invention, the liquid phase of the boron-containing component isolates the materials in the balls from the outside airContact, so as to form an anoxic environment in the ball. In particular, boron carbide and boron nitride in the ball decompose to form CO 2 And NO 2 Further reducing the oxygen concentration in the ball, and forming an anoxic or even anaerobic environment.
(3) When the oxygen concentration in the clinker balls is less than 5% in the method of the invention, the chromates (CrO) 4 2- ) Decomposing to form Cr 2 O 3 And oxygen, and generating self-valence reduction reaction of chromate, thereby achieving the technical effect of in-situ high-temperature reduction of hexavalent chromium in the cement rotary kiln. The method does not need to adjust the cement sintering process and equipment transformation, has wide application range and has remarkable technical application value.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is an XPS diagram of clinker in example 1.
Fig. 2 is an XPS diagram of the clinker in comparative example 1.
FIG. 3 is a graph showing the effect of measuring the content of the water-soluble hexavalent chromium in example 1, comparative example 1 and example 4
FIG. 4 shows Cr at various stages in the firing process of the cement of the invention 6+ Content variation.
FIG. 5 is Cr in clinker 6+ Results were tested at 1380℃from the valence change.
Detailed Description
The invention will be better understood from the following examples.
The excellent effect of the scheme of the invention is explained by taking cement from a cement plant in Sichuan province as a specific example.
Table 1 shows the chemical composition of the cement clinker of the cement plant, wherein the total chromium content is 620mg/kg.
TABLE 1 (Unit: wt%)
| CaO | SiO 2 | Al 2 O 3 | Fe 2 O 3 | MgO | Na 2 O | K 2 O | Cr 2 O 3 | Loss on ignition | Other components | |
| Clinker material | 67.924 | 18.504 | 4.745 | 3.830 | 1.488 | 0.159 | 0.866 | 0.062 | 0.371 | 2.051 |
Table 2 shows the raw material ratios of examples 1 to 4 and comparative example 1. Feeding the mixed raw materials into a 3500t/d cement production line, wherein the inclination of a cement rotary kiln is 4%, the rotating speed is 1.1r/min, the temperature of a firing zone of the rotary kiln is 1250-1450 ℃, and the retention time of the firing zone is about 25min.
TABLE 2 (Unit: wt%)
| Cement raw material | Boron carbide | Boron nitride | |
| Example 1 | 98 | 2 | 0 |
| Example 2 | 98 | 0 | 2 |
| Example 3 | 98.8 | 0.2 | 0 |
| Example 4 | 99 | 0.5 | 0.5 |
| Comparative example 1 | 100 | 0 | 0 |
The water-soluble hexavalent chromium content of examples 1 to 4 and comparative example 1 was measured with reference to the national standard "limit amount of water-soluble hexavalent chromium (VI) in cement and measurement method" (GB 31893-2015), and the results are shown in Table 3. When the chromium-reducing additive is not used, the soluble hexavalent chromium of the cement reaches 44.3mg/kg, which is more than 4 times of the limit value of the national standard. After the chromium-reducing additive is used, the content of soluble hexavalent chromium in cement is obviously reduced. Fig. 1 and 2 are X-ray photoelectron spectra (XPS) of example 1 and comparative example 1, respectively, and the result shows that the chromium element in example 1 is almost entirely +3 valent. In contrast, the chromium element in comparative example 1 was almost entirely +6 valent. FIG. 3 is a graph showing the effect of measuring the content of the water-soluble hexavalent chromium in example 1, comparative example 1 and example 4, respectively.
Table 3 (Unit: mg/kg)
In order to further investigate the mechanism of chromium reduction, the applicant investigated the effect of firing temperature on Cr element in clinker, and the results are shown in fig. 4. Cr at 950-1450 DEG C 6+ The content is increased and then decreased. The maximum is reached at about 1250℃in the solid phase reaction zone. At 1250-1450 ℃, cr 6+ The content gradually decreases.
Cr in rotary kiln clinker 6+ The mechanism of the content reduction is shown in FIG. 5. At 1250-1450 ℃, cr 6+ The content gradually decreases. The reason is that at a temperature higher than 1350 ℃, cr 6+ Self-valence reaction occurs, decreasing to other valence states (+3, +4, +5):
the chromium-reducing additive of the invention can obviously promote the self-valence-changing reduction reaction of the chromates and decompose and generate Cr 2 O 3 And oxygen to achieve the technical effect of in-situ high-temperature reduction of hexavalent chromium in the rotary cement kiln.
The invention provides a chromium-reducing additive for rotary kiln burned cement clinker, a method and a method thereof, and the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made to those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. The chromium reducing additive for rotary kiln sintered cement clinker is characterized in that the effective components of the chromium reducing additive comprise at least one of boron carbide and boron nitride.
2. The method for reducing the hexavalent chromium content in the cement clinker burned in the rotary kiln by adopting the chromium-reducing additive as claimed in claim 1, which is characterized in that the chromium-reducing additive and the cement raw material are uniformly mixed and then are sent into the rotary kiln together for calcination, and the self-valence-changing reduction reaction of hexavalent chromium is promoted by the boron-containing component, so that the hexavalent chromium content in the cement clinker is reduced.
3. The method of claim 2, wherein the chromium reduction admixture has a powder particle size of less than 100 microns.
4. The method according to claim 2, wherein the chromium reducing additive and the cement raw material are 0.2-2% by mass percent: and mixing evenly 98-98.8%.
5. The method according to claim 2, wherein the firing zone temperature of the rotary kiln is controlled to 1250-1450 ℃.
6. The method according to claim 2 or 5, characterized in that the mixture of both the chromium reducing admixture and the cement raw meal is left in the firing zone of the rotary kiln for a time of 20-60 min.
7. The method according to claim 2 or 5, wherein the cement clinker produced by calcination is cooled by quenching in a grate cooler after exiting the rotary kiln.
8. The method of claim 7, wherein the quench cooling rate is 500-800 ℃/min.
9. The method of claim 7, wherein the particle size of the cement clinker balls produced by calcination is in the range of 0.5 to 2cm.
10. The method according to claim 2, wherein the rotary kiln has a rotation speed of 0.8-1.5 r/min and an inclination of 3-5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311415678.1A CN117510110B (en) | 2023-10-30 | 2023-10-30 | Chromium-reducing additive and method for rotary kiln burned cement clinker |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311415678.1A CN117510110B (en) | 2023-10-30 | 2023-10-30 | Chromium-reducing additive and method for rotary kiln burned cement clinker |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117510110A true CN117510110A (en) | 2024-02-06 |
| CN117510110B CN117510110B (en) | 2024-05-14 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819717A (en) * | 2016-03-12 | 2016-08-03 | 乔光明 | Production method of cement clinker |
| CN107915420A (en) * | 2017-11-16 | 2018-04-17 | 广东弘朝科技有限公司 | A kind of hexavalent chrome reduction agent and preparation method thereof |
| CN109879616A (en) * | 2019-03-25 | 2019-06-14 | 浙江红狮环保股份有限公司 | A kind of method of cement kiln synergic processing waste containing chromium |
| CN109942213A (en) * | 2019-05-05 | 2019-06-28 | 河北鼎星水泥有限公司 | A kind of low chromium clinker and preparation method thereof |
-
2023
- 2023-10-30 CN CN202311415678.1A patent/CN117510110B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105819717A (en) * | 2016-03-12 | 2016-08-03 | 乔光明 | Production method of cement clinker |
| CN107915420A (en) * | 2017-11-16 | 2018-04-17 | 广东弘朝科技有限公司 | A kind of hexavalent chrome reduction agent and preparation method thereof |
| CN109879616A (en) * | 2019-03-25 | 2019-06-14 | 浙江红狮环保股份有限公司 | A kind of method of cement kiln synergic processing waste containing chromium |
| CN109942213A (en) * | 2019-05-05 | 2019-06-28 | 河北鼎星水泥有限公司 | A kind of low chromium clinker and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李红霞: "《耐火材料手册》", 31 January 2021, 冶金工业出版社, pages: 479 * |
| 赵宏波: ""水泥生产中六价铬的来源与控制研究"", 《中国水泥》, 28 February 2021 (2021-02-28), pages 96 - 99 * |
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