重金属元素在水泥混凝土中的浸出性及固化机理研究
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摘要
摘 要
本文根据我国水泥厂利用回转窑焚烧危险废弃物的现状及今后废弃物处理
的发展目标确定了三种不同的水泥配料方案。首先从废弃物焚烧量、侵蚀性溶
液、混凝土孔结构三个方面对重金属元素在水泥混凝土中的浸出性进行了对比
分析。然后运用 X 射线衍射、电子探针、扫描电镜、核磁共振等方法对重金属
元素在水泥中的固化机理做了进一步的研究。结合以上两方面研究客观地评价
了利用水泥回转窑焚烧危险废弃物同时制备水泥的可行性，不仅实现了水泥的
生态化制备，而且为危险废弃物的处理开辟了新的途径。
本文研究结果表明，利用水泥回转窑焚烧危险废弃物后制备的水泥应用于
混凝土后 99%以上的重金属元素均可以固化在混凝土基体内部。这些微量重金
属元素既可以通过水泥水化产物的物理包容、吸附和化学结合的形式固化于硬
化浆体内，也可以通过混凝土结构的密实性降低其渗出，达到稳定化、无害化
的目的。不同的重金属离子在水泥中的存在形式和分布不同，铅、镍元素以化
合物的形式吸附在水泥颗粒表面。铬元素参与水泥水化反应生成类似于单硫型
水化硫铝酸盐结构的含铬结晶相。钴、镉元素取代水泥水化产物中的钙离子，
不会使原水化产物的结构发生晶格畸变，形成了相应的含钴、镉硅酸盐结晶相
和凝胶相。
Based on the analysis of the actuality and the target in future of the waste
disposal, this paper adopted three kinds of cement clinker system .And analyzed the
impact of the quantity of waste ,the causticity solution and the pore structure on the
lixiviation of heavey metals.Using XRD,EPMA,SEM and NMR to determine the
composition of hydrated production, the distribution of heavy metals, through which
solidified mechanism is discussed in detail.Accoring to two studies above, the
feasibility of using cement kiln to deal with hazardous waste and produce cement
was evaluated externally.Which not only realized entironment but also exploited an
new way to deal with hazardous waste.
In this paper , the conclusion showed that more 99%heavy metals could be
solidified in concrete by means of denseness,physical pack, adsorption and chemical
combination.The heavy meatal of Pb,Zn and Ni were adsorbed on surface of the
cement grains by means of compounds in the course of hydrating.Cr participated in
hydrating reaction and formed new compounds,which was similar with Afm in
structure.The heavy metals of Co,Cd can exchanged with Ca in hydrated production
and be trapped in C-S-H,which formed new Co-containing calcium silicates and
Cd-containing calcium silicates.
本文根据我国水泥厂利用回转窑焚烧危险废弃物的现状及今后废弃物处理
的发展目标确定了三种不同的水泥配料方案。首先从废弃物焚烧量、侵蚀性溶
液、混凝土孔结构三个方面对重金属元素在水泥混凝土中的浸出性进行了对比
分析。然后运用 X 射线衍射、电子探针、扫描电镜、核磁共振等方法对重金属
元素在水泥中的固化机理做了进一步的研究。结合以上两方面研究客观地评价
了利用水泥回转窑焚烧危险废弃物同时制备水泥的可行性，不仅实现了水泥的
生态化制备，而且为危险废弃物的处理开辟了新的途径。
本文研究结果表明，利用水泥回转窑焚烧危险废弃物后制备的水泥应用于
混凝土后 99%以上的重金属元素均可以固化在混凝土基体内部。这些微量重金
属元素既可以通过水泥水化产物的物理包容、吸附和化学结合的形式固化于硬
化浆体内，也可以通过混凝土结构的密实性降低其渗出，达到稳定化、无害化
的目的。不同的重金属离子在水泥中的存在形式和分布不同，铅、镍元素以化
合物的形式吸附在水泥颗粒表面。铬元素参与水泥水化反应生成类似于单硫型
水化硫铝酸盐结构的含铬结晶相。钴、镉元素取代水泥水化产物中的钙离子，
不会使原水化产物的结构发生晶格畸变，形成了相应的含钴、镉硅酸盐结晶相
和凝胶相。
Based on the analysis of the actuality and the target in future of the waste
disposal, this paper adopted three kinds of cement clinker system .And analyzed the
impact of the quantity of waste ,the causticity solution and the pore structure on the
lixiviation of heavey metals.Using XRD,EPMA,SEM and NMR to determine the
composition of hydrated production, the distribution of heavy metals, through which
solidified mechanism is discussed in detail.Accoring to two studies above, the
feasibility of using cement kiln to deal with hazardous waste and produce cement
was evaluated externally.Which not only realized entironment but also exploited an
new way to deal with hazardous waste.
In this paper , the conclusion showed that more 99%heavy metals could be
solidified in concrete by means of denseness,physical pack, adsorption and chemical
combination.The heavy meatal of Pb,Zn and Ni were adsorbed on surface of the
cement grains by means of compounds in the course of hydrating.Cr participated in
hydrating reaction and formed new compounds,which was similar with Afm in
structure.The heavy metals of Co,Cd can exchanged with Ca in hydrated production
and be trapped in C-S-H,which formed new Co-containing calcium silicates and
Cd-containing calcium silicates.
引文
1. 王世忠.生态水泥—以城市废弃物为原料的环境协调性水泥.中国建材科
技.1997，6(2)：5～9
2. 刘春英等.综合处理城市垃圾建立环保水泥产业.水泥技术.2002，(1)：
25～28
3. 王超群.水泥回转窑处理工业（城市）垃圾技术研究.2002，(7)：42～44
4. 施惠生.利用水泥窑处理污水厂污泥的应用研究.水泥.2002，(7)：8～10
5. 鲍强.中国城市垃圾出路问题待解决.环境保护.1995，(12)：10～11
6. 朱建平等.利用城市垃圾、污泥烧制生态水泥.硅酸盐通报.2003，(2)：58～
59
7. 李湘洲.国外生态水泥发展的若干动向.中国建材.2002，(9)：35～36
8. 乔龄山.水泥厂利用废弃物的有关问题（一）.水泥.2002，(10)：1～5
9. 王春云.废弃物生态水泥工艺及实例.中国资源综合利用.2002,(2):15～18
10.岳鹏等.城市生活垃圾焚烧灰渣胶凝活性的初步研究.水泥.2003，(15)：
12～15
11.M.Murat*.F.Sorrentino, Effect of large additions of Cd,Pb,Cr, Zn to
cement raw meal on the composition and the properties of the clinker
and the cement. Cement and Concrete Research. 1996,26:377～385
12.D.Stephana,*.R.Mallmannb, D.Knofelb. R.Hardtla, High intakes of Cr、
Ni and Zn in clinker partⅠ.Influence on Burning Process and Formation
of Phases. Cement and Concrete Research.1999,29:1949～1957
13.乔龄山.水泥厂利用废弃物的有关问题（二）.水泥.2002,(12): 11～16
14.崔素萍，兰明章等.生活垃圾焚烧灰在水泥工业中的资源化分析.水泥基材料
论文集.2003,344～347
15.I.Fernandez.Olmo*,E.Chacon,A.Irabien,Influence of lead,zinc,
iron(Ⅲ)and chromium(Ⅲ)oxides on the setting time and strength
development of Portland cement. Cement and Concrete Research.
2001,31:1213～1219
- 62 -
参考文献
16.D.Stephana,*.R.Mallmannb, D.Knofelb. R.Hardtla, High intakes of Cr、
Ni and Zn in clinker partⅡ.Influence on the hydration properties.
Cement and Concrete Research.1999,29:1959～1967
17.袁玲等.生态水泥—都市水泥工业可持续发展的方向.2002，(5)：1～4
18.冯乃谦等.生态水泥及应用.混凝土于水泥制品.2000，(6)：18～21
19.张射墟等.生态水泥的特性与应用.中国建材.2002，(1)：36～37
20.刘艳霞.水泥生产过程中有毒有害元素的流向及其环境影响.北京工业大学
硕士论文.2002：42～43
21.Juan Carlos Urcelay Gordóbil,Eleannt. Juan Carlos Urcelay Gordó
bil,Elean Guede. Secondary Fuels and Raw Materials in the Spa
1997,3:40～43
22.HeratS.protecting the environment from waste disposal:the cement
kiln option.Environmental Protection Engineering,1997,23:25～352
23.乔龄山.水泥厂利用废弃物的有关问题（五）.水泥.2003,(5):14～21
24.朱桂珍 利用水泥回转窑焚烧处置危险废物的评价研究.环境保护.2000，
(3)：14～16
25.余其俊等.水泥和粉煤灰中重金属和有毒离子的溶出问题及思考.水
泥.2003，(1)：8～15
26.AndacM,GlasserFP.Long-term leaching mechanisms of Portland
cement-stabilized municipal solid waste fly ash in carbonated
water[J]. Cement and Concrete Research.1999, 29:179～186
27.HohnergI,GrootGJde,Veenam Hvander,WassingW. Development of a
leaching protocol for concrete[A].In:Waste Materials in
Construction,Putting Theroy into Practice[M].Press of Elsevier
ScienceB.V.1997,217～228
28.S. Nagataki and Q. Yu et al., Leachability of Heavy Metals in Fly Ash
Incorporated Cement Mortars and Cement-solidified Fly Ashes under
Different Leaching Conditions, in Cement Science and Concrete
- 63 -
北京工业大学工学硕士学位论文
Technology, Japan Cement Association.2000,54:180～187
29.赵霄龙等.普通强度高耐久性混凝土的配制技术.建筑技术.2004,(1):12～16
30. [美]P·梅泰.混凝土的结构、性能与材料.同济大学出版社.1991:75～76
31.吴中伟.高性能混凝土.中国铁道出版社.1999:103
32.陆平.水泥材料科学导论.同济大学出版社.1991:120～126
33.袁润章.胶凝材料学.武汉工业大学出版社.1991:45～60
34.沈威等.水泥工艺学.武汉工业大学出版社.1990:76～80
35.G.Kakali,1S.Tsivilis,and A.Tsialtas.Hydration of ordinary cement
made from raw mix containing transition element oxides. Cement and
Concrete Research.1998, 28: 335～340
36.V.Alunno Rossetti,F.Mdici.Inertization of Toxic Metals in Cement
Matrices:Effects on Hydration,Setting and Hardening. Cement and
Concrete Research.1995, 25:1147～1152
37.S.Komarneti+,E.B.reval,D.M.Roy and R.Roy. Reaction of some Calcium
Silicates with Metal Cations. Cement and Concrete Research.1988,
18:204～220
38.H.Akhter,F.k.Cartledge(1),A.ROY* and M.E.Tittlebaum*.A study of the
effects of niuckel chloride and calcium chloride on hydration of
Portland cement. Cement and Concrete Research.1993, 23:833～842
39.K.Kolovos,S.Tsivilis,G.Kakali*.The Effect of Foreingn Ions On the
Reactivity of the CaO-SiO2-Al2O3-Fe2O3 System PartⅡ:Catioins. Cement
and Concrete Research.2002, 32:463～469
40.Sridhar Komarneni*,Rustum Roy# and Della M. Roy+.Pseudomorphism in
xonotlite and tobermorite with Co2+ and Ni2+ exchange for Ca2+ at 25
℃. Cement and Concrete Research.1986, 16: 47～58
41.I Odler, S. Abdul-Maula,. Effect of Mineralizers on the burning
process of Portland cement clinker: Part II. Mode of action of the
mineralisers, Zem.-Kalk-Gips.1980, 33:278～282
- 64 -
参考文献
42.Kuen-Sheng Wang*,Kae-Long Lin,Zuh-Quia Huang.Hydraulic activity of
municipal solid waste incinerator fly-ash-slag-blend eco-cement.
Cement and Concrete Research.2001, 31: 97～103
43.Marie-Pierre Pomies*,Nicolas Lequeux,Philippe Boch.Speciation of
cadmium in cement PartⅠ.Cd2+ uptake by C-S-H. Cement and Concrete
Research.2001, 31:563～569
44.Marie-Pierre Pomies*,Nicolas Lequeux,Philippe Boch.Speciation of
cadmium in cement PartⅡ.C3S hydration with Cd2+ solution. Cement and
Concrete Research.2001, 31:571～576
45.苏慕珍.第八届国际水泥化学会议论文集（三）—水泥化学主报告.中国建筑
材料科学研究院技术情报中心.1989:20～26
46.Takayuki Maeshimaa,*, Hiroaki Nomab,Masato Sakiyamac,Takeshi
Mistudad.Natural 1.1 and 1.4 nm tobermorites from
Fuka,Okayam,Japan:Chemical analysis,cell dimensions,29SiNMR and
thermal behavior.Cement and Concrete Research.2003, 33:1515～1523
47.Anupama Goswami,AjaiK.Singh*.1,8-Dihydroxyanthraquinone anchored
on silica gel:synthesis and application as solid phase extractant for
lead(II), zinc(II) and cadmium(II) prior to their determination by
flame atomic absorption spectrometry.A.Goswami,A K.Singh/Talanta.
2002,(58):669～678
48.P.BARNES 等.水泥的结构和性能.中国建筑工业出版社，1991:203～221
技.1997，6(2)：5～9
2. 刘春英等.综合处理城市垃圾建立环保水泥产业.水泥技术.2002，(1)：
25～28
3. 王超群.水泥回转窑处理工业（城市）垃圾技术研究.2002，(7)：42～44
4. 施惠生.利用水泥窑处理污水厂污泥的应用研究.水泥.2002，(7)：8～10
5. 鲍强.中国城市垃圾出路问题待解决.环境保护.1995，(12)：10～11
6. 朱建平等.利用城市垃圾、污泥烧制生态水泥.硅酸盐通报.2003，(2)：58～
59
7. 李湘洲.国外生态水泥发展的若干动向.中国建材.2002，(9)：35～36
8. 乔龄山.水泥厂利用废弃物的有关问题（一）.水泥.2002，(10)：1～5
9. 王春云.废弃物生态水泥工艺及实例.中国资源综合利用.2002,(2):15～18
10.岳鹏等.城市生活垃圾焚烧灰渣胶凝活性的初步研究.水泥.2003，(15)：
12～15
11.M.Murat*.F.Sorrentino, Effect of large additions of Cd,Pb,Cr, Zn to
cement raw meal on the composition and the properties of the clinker
and the cement. Cement and Concrete Research. 1996,26:377～385
12.D.Stephana,*.R.Mallmannb, D.Knofelb. R.Hardtla, High intakes of Cr、
Ni and Zn in clinker partⅠ.Influence on Burning Process and Formation
of Phases. Cement and Concrete Research.1999,29:1949～1957
13.乔龄山.水泥厂利用废弃物的有关问题（二）.水泥.2002,(12): 11～16
14.崔素萍，兰明章等.生活垃圾焚烧灰在水泥工业中的资源化分析.水泥基材料
论文集.2003,344～347
15.I.Fernandez.Olmo*,E.Chacon,A.Irabien,Influence of lead,zinc,
iron(Ⅲ)and chromium(Ⅲ)oxides on the setting time and strength
development of Portland cement. Cement and Concrete Research.
2001,31:1213～1219
- 62 -
参考文献
16.D.Stephana,*.R.Mallmannb, D.Knofelb. R.Hardtla, High intakes of Cr、
Ni and Zn in clinker partⅡ.Influence on the hydration properties.
Cement and Concrete Research.1999,29:1959～1967
17.袁玲等.生态水泥—都市水泥工业可持续发展的方向.2002，(5)：1～4
18.冯乃谦等.生态水泥及应用.混凝土于水泥制品.2000，(6)：18～21
19.张射墟等.生态水泥的特性与应用.中国建材.2002，(1)：36～37
20.刘艳霞.水泥生产过程中有毒有害元素的流向及其环境影响.北京工业大学
硕士论文.2002：42～43
21.Juan Carlos Urcelay Gordóbil,Eleannt. Juan Carlos Urcelay Gordó
bil,Elean Guede. Secondary Fuels and Raw Materials in the Spa
1997,3:40～43
22.HeratS.protecting the environment from waste disposal:the cement
kiln option.Environmental Protection Engineering,1997,23:25～352
23.乔龄山.水泥厂利用废弃物的有关问题（五）.水泥.2003,(5):14～21
24.朱桂珍 利用水泥回转窑焚烧处置危险废物的评价研究.环境保护.2000，
(3)：14～16
25.余其俊等.水泥和粉煤灰中重金属和有毒离子的溶出问题及思考.水
泥.2003，(1)：8～15
26.AndacM,GlasserFP.Long-term leaching mechanisms of Portland
cement-stabilized municipal solid waste fly ash in carbonated
water[J]. Cement and Concrete Research.1999, 29:179～186
27.HohnergI,GrootGJde,Veenam Hvander,WassingW. Development of a
leaching protocol for concrete[A].In:Waste Materials in
Construction,Putting Theroy into Practice[M].Press of Elsevier
ScienceB.V.1997,217～228
28.S. Nagataki and Q. Yu et al., Leachability of Heavy Metals in Fly Ash
Incorporated Cement Mortars and Cement-solidified Fly Ashes under
Different Leaching Conditions, in Cement Science and Concrete
- 63 -
北京工业大学工学硕士学位论文
Technology, Japan Cement Association.2000,54:180～187
29.赵霄龙等.普通强度高耐久性混凝土的配制技术.建筑技术.2004,(1):12～16
30. [美]P·梅泰.混凝土的结构、性能与材料.同济大学出版社.1991:75～76
31.吴中伟.高性能混凝土.中国铁道出版社.1999:103
32.陆平.水泥材料科学导论.同济大学出版社.1991:120～126
33.袁润章.胶凝材料学.武汉工业大学出版社.1991:45～60
34.沈威等.水泥工艺学.武汉工业大学出版社.1990:76～80
35.G.Kakali,1S.Tsivilis,and A.Tsialtas.Hydration of ordinary cement
made from raw mix containing transition element oxides. Cement and
Concrete Research.1998, 28: 335～340
36.V.Alunno Rossetti,F.Mdici.Inertization of Toxic Metals in Cement
Matrices:Effects on Hydration,Setting and Hardening. Cement and
Concrete Research.1995, 25:1147～1152
37.S.Komarneti+,E.B.reval,D.M.Roy and R.Roy. Reaction of some Calcium
Silicates with Metal Cations. Cement and Concrete Research.1988,
18:204～220
38.H.Akhter,F.k.Cartledge(1),A.ROY* and M.E.Tittlebaum*.A study of the
effects of niuckel chloride and calcium chloride on hydration of
Portland cement. Cement and Concrete Research.1993, 23:833～842
39.K.Kolovos,S.Tsivilis,G.Kakali*.The Effect of Foreingn Ions On the
Reactivity of the CaO-SiO2-Al2O3-Fe2O3 System PartⅡ:Catioins. Cement
and Concrete Research.2002, 32:463～469
40.Sridhar Komarneni*,Rustum Roy# and Della M. Roy+.Pseudomorphism in
xonotlite and tobermorite with Co2+ and Ni2+ exchange for Ca2+ at 25
℃. Cement and Concrete Research.1986, 16: 47～58
41.I Odler, S. Abdul-Maula,. Effect of Mineralizers on the burning
process of Portland cement clinker: Part II. Mode of action of the
mineralisers, Zem.-Kalk-Gips.1980, 33:278～282
- 64 -
参考文献
42.Kuen-Sheng Wang*,Kae-Long Lin,Zuh-Quia Huang.Hydraulic activity of
municipal solid waste incinerator fly-ash-slag-blend eco-cement.
Cement and Concrete Research.2001, 31: 97～103
43.Marie-Pierre Pomies*,Nicolas Lequeux,Philippe Boch.Speciation of
cadmium in cement PartⅠ.Cd2+ uptake by C-S-H. Cement and Concrete
Research.2001, 31:563～569
44.Marie-Pierre Pomies*,Nicolas Lequeux,Philippe Boch.Speciation of
cadmium in cement PartⅡ.C3S hydration with Cd2+ solution. Cement and
Concrete Research.2001, 31:571～576
45.苏慕珍.第八届国际水泥化学会议论文集（三）—水泥化学主报告.中国建筑
材料科学研究院技术情报中心.1989:20～26
46.Takayuki Maeshimaa,*, Hiroaki Nomab,Masato Sakiyamac,Takeshi
Mistudad.Natural 1.1 and 1.4 nm tobermorites from
Fuka,Okayam,Japan:Chemical analysis,cell dimensions,29SiNMR and
thermal behavior.Cement and Concrete Research.2003, 33:1515～1523
47.Anupama Goswami,AjaiK.Singh*.1,8-Dihydroxyanthraquinone anchored
on silica gel:synthesis and application as solid phase extractant for
lead(II), zinc(II) and cadmium(II) prior to their determination by
flame atomic absorption spectrometry.A.Goswami,A K.Singh/Talanta.
2002,(58):669～678
48.P.BARNES 等.水泥的结构和性能.中国建筑工业出版社，1991:203～221