JPH03205331A - Cement admixture - Google Patents
Cement admixtureInfo
- Publication number
- JPH03205331A JPH03205331A JP14848589A JP14848589A JPH03205331A JP H03205331 A JPH03205331 A JP H03205331A JP 14848589 A JP14848589 A JP 14848589A JP 14848589 A JP14848589 A JP 14848589A JP H03205331 A JPH03205331 A JP H03205331A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- water
- hexavalent chromium
- reducing agent
- chromium
- 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.)
- Pending
Links
- 239000004568 cement Substances 0.000 title claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 33
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 31
- 239000000126 substance Substances 0.000 abstract description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- 239000011651 chromium Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- -1 No. 1g4 Chemical class 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- LXMQZGGLHVSEBA-UHFFFAOYSA-N chromium;trihydrate Chemical compound O.O.O.[Cr] LXMQZGGLHVSEBA-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【発明の詳細な説明】 本発明は、セメント添加剤に関する。[Detailed description of the invention] The present invention relates to cement additives.
セメントは、製造時に使用する焼成窯のクロム−マグネ
シャ系の耐火材と原料間の種々の高温熱化学反応を経て
微量ではあるが、不可壁的に六価クロムを含有している
。その六価クロムはセメントと水が混練されると、その
水中に溶解し、その水が流出することなくコンクリ−１
・として固化する場合は六価クロムはコンクリート中に
固定され問題となることはないが、ブリージング水とし
て放出される場合、および未固化の状態で洗浄水と混合
されて放出される場合は環境に放流されて環境汚染の点
から問題となっていた。このように六価クロムが流出す
ると、六価クロムは酸化力が強く、そのため自然界へ流
出した場合はｆｌ１康上有害な物質として各種法令で厳
しく規制されている。Cement irrevocably contains hexavalent chromium, albeit in a trace amount, through various high-temperature thermochemical reactions between raw materials and the chromium-magnesia-based refractory material in the firing kiln used during manufacturing. When cement and water are mixed, the hexavalent chromium dissolves in the water, and the water does not flow out and is added to the concrete layer.
・If it solidifies as a solid, hexavalent chromium is fixed in the concrete and does not pose a problem, but if it is released as breathing water or mixed with cleaning water in an unsolidified state, it may be harmful to the environment. The water was released into the river and became a problem in terms of environmental pollution. When hexavalent chromium leaks out in this way, hexavalent chromium has a strong oxidizing power, and therefore, if it leaks into the natural world, it is strictly regulated by various laws and regulations as a substance harmful to FL1 health.
従来このような問題点を解決するために種々の方法が提
案されている。すなわち（１）六価クロムを含有しない
セメントを製造する方法。（２）セメントと水とを混合
して出る余剰水あるいは未固化コンクリートから放出さ
れる水を処理して六価クロムを除去する方法が考えられ
ろ。Various methods have been proposed to solve these problems. Namely, (1) a method for producing cement that does not contain hexavalent chromium. (2) Consider a method to remove hexavalent chromium by treating surplus water from mixing cement and water or water released from unsolidified concrete.
しかしながら前記（１）の方法は製造工程を大幅に変更
する必要があり、耐火材としてクロムーマグネシャ系に
代る材質のものが現在明らかになっていないｔコめに該
方法による解決は実質的に不可能である。また前記（２
）の方法は従来からコンクリ〜１・二次製品の工場等で
実施されているが、複雑な処理工程を必要とし経済的な
負担が大きい欠点があった。However, method (1) requires a significant change in the manufacturing process, and since there is currently no known material that can replace the chrome-magnesia system as a refractory material, this method is practically impossible to solve. It is technically impossible. Also, the above (2
The method (2) has been practiced in concrete, primary and secondary product factories, etc., but it has the disadvantage of requiring complicated processing steps and imposing a large economic burden.
本発明者は前記方法とはまったく別異の方法で環境汚染
のない六価クロムの除去法につき種々研究を重ねた結果
本発明を完或するに至った。The present inventor has completed the present invention as a result of repeated research into a method for removing hexavalent chromium that does not pollute the environment, using a method completely different from the method described above.
すなわち、本発明はセメント中に還元剤を含有するセメ
ント添加剤を混入させてセメントと水との混練時にセメ
ント中に含まれる六価クロムと反応させて六価クロムを
不溶性物質となし、コンクリート内に固定または水中か
ら除去するものである。That is, the present invention mixes a cement additive containing a reducing agent into cement and reacts with hexavalent chromium contained in the cement when cement and water are mixed to make hexavalent chromium an insoluble substance. or removed from the water.
セメント中における六価クロムはクロム酸塩（ＭＣｒＯ
４１ （Ｍは陽イオンを示す）の固体として存在する
が、この塩の水に対する溶解度が比較的大きいために水
と混合するとクロム酸イオン（Ｃ ｒ ０４！−）の形
で水中に溶解する。このクロム酸イオンは十六価の電子
価をもつが、これを三価に還元するとｐＨ約６以上のア
ルカリ側で水酸化クロム（Ｃｒ （ＯＨ）３）を形成し
、不溶性物質に変化する。Hexavalent chromium in cement is chromate (MCrO
41 (M represents a cation), but since the solubility of this salt in water is relatively high, when mixed with water, it dissolves in water in the form of chromate ions (C r 04!-). This chromate ion has an electron valence of 16, but when it is reduced to trivalent, it forms chromium hydroxide (Cr (OH) 3) on the alkaline side with a pH of about 6 or more, and turns into an insoluble substance.
本発明者は六価クロムのこれらの性質を利用して本発明
を完成させたものである。すなわちセメント水と水とを
混練するとセメントの強い塩基性のために水のｐＨは１
３以上の強アルカリ性となり、セメント中の六価クロム
を三価クロムに還元することにより自ずから水酸化クロ
ムの不溶物質として折出させる乙とができ、コンクリー
ト中に固定または水中から除去することができる。The present inventor has completed the present invention by utilizing these properties of hexavalent chromium. In other words, when cement water and water are kneaded, the pH of the water becomes 1 due to the strong basicity of cement.
It has a strong alkalinity of 3 or more, and by reducing hexavalent chromium in cement to trivalent chromium, it can be precipitated as an insoluble chromium hydroxide substance, which can be fixed in concrete or removed from water. .
次に還元剤として第１鉄イオンを用いた場合の例につい
て以下に化学式で示すと次のとおりである。Next, an example of a case where ferrous ions are used as a reducing agent is shown below in the form of a chemical formula.
Ｃｒ０４’−＋３Ｆｅ”＋４８２０＝Ｃｒ”＋３Ｆｅ”
＋８ （ＯＨ）−・・・・・・・・ （１）
Ｃｒ３◆＋３（ＯＨ）一＝Ｃｒ （ＯＨ）３ ・・・・
・・・・ （２）本発明のセメント添加剤として使用さ
れる還元剤としては第１鉄、第１錫、第１バナジウム、
第１ｇ４等のイオンから構成される塩類が挙げられ、こ
れらの塩類としては硫酸塩、硝酸塩、塩化物、種々の複
塩が挙げられるが、特に硫酸塩が好ましい。Cr04'-+3Fe"+4820=Cr"+3Fe"
+8 (OH)−・・・・・・・・・ (1) Cr3◆+3(OH)−=Cr(OH)3 ・・・・
(2) Reducing agents used as cement additives of the present invention include ferrous iron, ferrous tin, ferrous vanadium,
Examples include salts composed of ions such as No. 1g4, and examples of these salts include sulfates, nitrates, chlorides, and various double salts, with sulfates being particularly preferred.
本発明のセメント添加剤は、セメント製造時に添加する
か、あるいは工事等の使用の際にセメントと水とを混練
するときに添加して使用することもできる。The cement additive of the present invention can be added during the production of cement, or when kneading cement and water during use in construction work.
本発明は、セメント添加剤をセメントと水との混練時に
加えておくことによって六価クロムを不溶性物質として
コンクリート中に固定することができるので、接触後放
出される水に六価クロムを除去するための水処理を実施
する必要がなくなる。さらに地層中に、その地層中の水
の移動を止めるために行なうセメントミルクによるグラ
ウチングにおいては六価クロムはグラウトを実施した部
分にのみとどまり、水と共に不特定部分に移動すること
を防止する効果がある。In the present invention, hexavalent chromium can be fixed in concrete as an insoluble substance by adding a cement additive at the time of mixing cement and water, so that hexavalent chromium can be removed from the water released after contact. This eliminates the need for water treatment. Furthermore, when grouting with cement milk is carried out to stop the movement of water within a geological formation, hexavalent chromium remains only in the grouted area and has the effect of preventing it from migrating with water to unspecified areas. be.
実施例１
ボルトランドセメント（六価クロム８．２ＰＰｍ含有）
にｍａｉｌ第１鉄（Ｆａ８０４、Ｈ２ｏ１粉末を添加し
て、これにボルトランドセメント１００重量部に対して
水５０重量部を加えて混練した後遠心分離器で水を回収
し、その中の六価クロムの濃度を測定した。Example 1 Boltland cement (containing hexavalent chromium 8.2PPm)
After adding ferrous iron (Fa804, H2O1 powder) and kneading it with 50 parts by weight of water per 100 parts by weight of Bortland cement, the water was collected in a centrifuge, and the hexavalent The concentration of chromium was measured.
次にその試験結果を示せば第１図のとおりである。Next, the test results are shown in Figure 1.
第１図から明らかなようにボル１・ランドセメントには
六価クロム８．２ＰＰｍを含有していることから、その
量から考察するとＦｅ８０４、Ｈ２ｏは４４ｍｇ／Ｋｇ
（セメント）が理論当量である。従って第１図からセ
メント中に含有される六価クロムの理論量の約１．５〜
１．６倍量の還元剤を添加すれば充分であることがわか
る。As is clear from Figure 1, Bol 1 Land Cement contains 8.2PPm of hexavalent chromium, and considering the amount, Fe804 and H2o are 44mg/Kg.
(cement) is the theoretical equivalent. Therefore, from Figure 1, the theoretical amount of hexavalent chromium contained in cement is about 1.5~
It can be seen that it is sufficient to add 1.6 times the amount of reducing agent.
実施例２
ボルトランドセメント（六価クロム１０，５ＰＰｍ含有
）１００重量部に対して水５０重量部を加え、さらに硫
酸第１鉄（ＦｌＩＳＯ４、Ｈ２ｏ ｌを添加して混練し
た後遠心分離器で水を分離回収し、その中に含まれる六
価クロムの濃度を測定した。その試験結果を示せば第２
図のとおりである。第２図から明らかなように六価クロ
ムのセメント中の濃度から計算される理論量の約１．５
〜１．６倍以上を添加すれば六価クロムを除去すること
ができろ。Example 2 50 parts by weight of water was added to 100 parts by weight of Bortland cement (containing 10.5 PPm of hexavalent chromium), and ferrous sulfate (FlISO4, H2Ol) was added and kneaded. was separated and recovered, and the concentration of hexavalent chromium contained therein was measured.
As shown in the figure. As is clear from Figure 2, approximately 1.5 of the theoretical amount calculated from the concentration of hexavalent chromium in cement.
Hexavalent chromium can be removed by adding ~1.6 times more.
【図面の簡単な説明】
第１図および第２図はボルトランドセメントに還元剤を
添加したときの分離水中の六価クロムの量を示した図で
ある。[Brief Description of the Drawings] Figures 1 and 2 are diagrams showing the amount of hexavalent chromium in separated water when a reducing agent is added to Boltland cement.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14848589A JPH03205331A (en) | 1989-06-13 | 1989-06-13 | Cement admixture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14848589A JPH03205331A (en) | 1989-06-13 | 1989-06-13 | Cement admixture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03205331A true JPH03205331A (en) | 1991-09-06 |
Family
ID=15453812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14848589A Pending JPH03205331A (en) | 1989-06-13 | 1989-06-13 | Cement admixture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03205331A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0934914A1 (en) * | 1998-01-27 | 1999-08-11 | Chemische Werke Zell-Wildshausen GMBH | Agent for the reduction do chromium(VI) ions in cement |
| JP2003093538A (en) * | 2001-09-26 | 2003-04-02 | Taiheiyo Cement Corp | Reduction method of hexavalent chrome by particle-size control of silicon |
| JP2003165758A (en) * | 2001-11-29 | 2003-06-10 | Denki Kagaku Kogyo Kk | Back-filling grout |
| JP2007014881A (en) * | 2005-07-07 | 2007-01-25 | Kajima Corp | Recycling method of concrete mass |
| JP2007522061A (en) * | 2003-11-21 | 2007-08-09 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Sulfate-dispersed chromate reducing agent |
| JP2008155101A (en) * | 2006-12-22 | 2008-07-10 | Taiheiyo Cement Corp | Elution restraining material of hexavalent chromium |
| JP4750029B2 (en) * | 2003-08-08 | 2011-08-17 | クリソ | Aqueous colloidal suspensions of hydroxides of at least one transition element for reducing chromium in cement |
| WO2011148512A1 (en) * | 2010-05-28 | 2011-12-01 | 株式会社 メニコン | Method for reducing hexavalent chromium, method for producing molded body, and method for improving soil |
| CN112456831A (en) * | 2020-10-13 | 2021-03-09 | 唐山冀东水泥外加剂有限责任公司 | High-temperature-resistant cement hexavalent chromium reducing agent |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5030927A (en) * | 1973-07-18 | 1975-03-27 | ||
| JPS5043123A (en) * | 1973-08-21 | 1975-04-18 | ||
| JPS5050288A (en) * | 1973-09-04 | 1975-05-06 | ||
| JPS5315264A (en) * | 1976-07-29 | 1978-02-10 | Taisei Corp | Method of stabilizing and depolluting sludges containing lead chromate |
| JPS5322867A (en) * | 1976-08-16 | 1978-03-02 | Matsumuragumi Kk | Method of depolluting industrial waste containing hexahydric chromium |
| JPS5328563A (en) * | 1976-08-31 | 1978-03-16 | Sumitomo Cement Co | Method of depolluting hexahydric chromium compounds in industrial wastes |
| JPS5344480A (en) * | 1976-10-06 | 1978-04-21 | Onoda Cement Co Ltd | Hydraulic composition for removing harmful substances |
| JPS53133578A (en) * | 1977-04-27 | 1978-11-21 | Sumitomo Cement Co | Method of solidifying waste containing trihydric chromium compounds by cement |
| JPS55109260A (en) * | 1979-02-15 | 1980-08-22 | Mitsubishi Heavy Ind Ltd | Concrete solidifying aid |
-
1989
- 1989-06-13 JP JP14848589A patent/JPH03205331A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5030927A (en) * | 1973-07-18 | 1975-03-27 | ||
| JPS5043123A (en) * | 1973-08-21 | 1975-04-18 | ||
| JPS5050288A (en) * | 1973-09-04 | 1975-05-06 | ||
| JPS5315264A (en) * | 1976-07-29 | 1978-02-10 | Taisei Corp | Method of stabilizing and depolluting sludges containing lead chromate |
| JPS5322867A (en) * | 1976-08-16 | 1978-03-02 | Matsumuragumi Kk | Method of depolluting industrial waste containing hexahydric chromium |
| JPS5328563A (en) * | 1976-08-31 | 1978-03-16 | Sumitomo Cement Co | Method of depolluting hexahydric chromium compounds in industrial wastes |
| JPS5344480A (en) * | 1976-10-06 | 1978-04-21 | Onoda Cement Co Ltd | Hydraulic composition for removing harmful substances |
| JPS53133578A (en) * | 1977-04-27 | 1978-11-21 | Sumitomo Cement Co | Method of solidifying waste containing trihydric chromium compounds by cement |
| JPS55109260A (en) * | 1979-02-15 | 1980-08-22 | Mitsubishi Heavy Ind Ltd | Concrete solidifying aid |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0934914A1 (en) * | 1998-01-27 | 1999-08-11 | Chemische Werke Zell-Wildshausen GMBH | Agent for the reduction do chromium(VI) ions in cement |
| JP2003093538A (en) * | 2001-09-26 | 2003-04-02 | Taiheiyo Cement Corp | Reduction method of hexavalent chrome by particle-size control of silicon |
| JP2003165758A (en) * | 2001-11-29 | 2003-06-10 | Denki Kagaku Kogyo Kk | Back-filling grout |
| JP4750029B2 (en) * | 2003-08-08 | 2011-08-17 | クリソ | Aqueous colloidal suspensions of hydroxides of at least one transition element for reducing chromium in cement |
| JP4712719B2 (en) * | 2003-11-21 | 2011-06-29 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Sulfate-dispersed chromate reducing agent |
| JP2007522061A (en) * | 2003-11-21 | 2007-08-09 | ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット | Sulfate-dispersed chromate reducing agent |
| JP2007014881A (en) * | 2005-07-07 | 2007-01-25 | Kajima Corp | Recycling method of concrete mass |
| JP4745955B2 (en) * | 2006-12-22 | 2011-08-10 | 太平洋セメント株式会社 | Hexavalent chromium elution inhibitor |
| JP2008155101A (en) * | 2006-12-22 | 2008-07-10 | Taiheiyo Cement Corp | Elution restraining material of hexavalent chromium |
| WO2011148512A1 (en) * | 2010-05-28 | 2011-12-01 | 株式会社 メニコン | Method for reducing hexavalent chromium, method for producing molded body, and method for improving soil |
| JP5602848B2 (en) * | 2010-05-28 | 2014-10-08 | 株式会社メニコン | Hexavalent chromium reduction method, molded body manufacturing method and ground improvement method |
| CN112456831A (en) * | 2020-10-13 | 2021-03-09 | 唐山冀东水泥外加剂有限责任公司 | High-temperature-resistant cement hexavalent chromium reducing agent |
| CN112456831B (en) * | 2020-10-13 | 2023-10-03 | 唐山冀东水泥外加剂有限责任公司 | High-temperature-resistant cement hexavalent chromium reducing agent |
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