CN112608044A - 水泥窑协同处置污染土壤混合材及其制备方法和应用 - Google Patents
水泥窑协同处置污染土壤混合材及其制备方法和应用 Download PDFInfo
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- 239000004568 cement Substances 0.000 title claims abstract description 98
- 239000002689 soil Substances 0.000 title claims abstract description 80
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000012545 processing Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002893 slag Substances 0.000 claims abstract description 29
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000010881 fly ash Substances 0.000 claims abstract description 18
- 239000010440 gypsum Substances 0.000 claims abstract description 14
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011777 magnesium Substances 0.000 claims abstract description 13
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 13
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 230000001105 regulatory effect Effects 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 8
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 238000011278 co-treatment Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 12
- 230000036571 hydration Effects 0.000 abstract description 7
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- 230000009467 reduction Effects 0.000 abstract description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 17
- 239000002994 raw material Substances 0.000 description 6
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 5
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
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- 230000005284 excitation Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000006835 compression Effects 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/085—Acids or salts thereof containing nitrogen in the anion, e.g. nitrites
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/12—Acids or salts thereof containing halogen in the anion
- C04B22/124—Chlorides of ammonium or of the alkali or alkaline earth metals, e.g. calcium chloride
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/143—Calcium-sulfate
- C04B22/145—Gypsum from the desulfuration of flue gases
-
- 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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/14—Acids or salts thereof containing sulfur in the anion, e.g. sulfides
- C04B22/142—Sulfates
- C04B22/149—Iron-sulfates
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/02—Alcohols; Phenols; Ethers
- C04B24/026—Fatty alcohols
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/21—Mixtures thereof with other inorganic cementitious materials or other activators with calcium sulfate containing activators
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/364—Avoiding environmental pollution during cement-manufacturing
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/52—Grinding aids; Additives added during grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
水泥窑协同处置污染土壤混合材及其制备方法和应用，按重量份由以下物质组成：水泥窑协同处置污染土65‑85份、脱硫石膏2‑5份、粉煤灰5‑25份、高炉矿渣5‑15份、镁渣1‑10份、水化氯铝酸钙1‑6份、硫酸亚铁0.1‑0.5份，调节助剂0.5‑5份。本发明为水泥窑协同处置污染土提供了一个安全高效的后续利用的路径。而且，本发明的混合材具有较高水化活性，能够增加掺混合材水泥的强度，为水泥制造拓展了优质混合材，促进水泥生产的节能减排。
Description
技术领域
本发明涉及用于水泥生产的混合材，特别是涉及一种水泥窑协同处置污染土壤混合材及其制备方法和应用。
背景技术
污染土壤包括由工业污水、农业污水引起的有机物污染和无机物污染，当土壤中含有过多有害物质，超过土壤的自洁净能力，导致生产、生活环境污染，则会严重影响人体健康。如何妥善处置污染土已经成为迫在眉睫的问题。目前国内对于污染废弃物处理有只进行简单焚烧、填埋的方式，不仅未能合理利用、造成资源浪费，甚至可能形成二次危险废弃物、造成更大危害，通过处理、填埋等方式成本较大，且资源利用率不高，容易产生二次污染。此外，还有原固化/稳定化+填埋的处理方法，由于未能根除重金属元素，污染土去向成问题，植物修复适用污染物浓度低，浅层污染土处理，且处理效率不高。电动修复技术成本昂贵、条件苛刻，国内尚无应用工程，异位洗涤需处理废水、成本较高，原位淋洗二次污染风险大，对地下水污染控制及其重要。上述污染土壤处理的使用适用性等均受一定限制，为此，近年来，人们逐渐开发使用一种水泥窑协同处置污染土壤，但处理后的污染土壤仍面临去处问题。
发明申请号201911266093.1提供一种陶粒生产协同处置污染土壤的处理剂及制备方法，通过处理剂调理可降低污染土壤脱水难度，提高固含率，保证原料粘度减少团聚，提高污染土壤应用于陶粒生产的高温发胀，益于增加参烧比例，获得多孔微观形貌，降低陶粒生产成本，达到环保、资源有效利用。发明申请号201911114313.9将污染土作为原料配料与水泥原料共同煅烧，水泥窑高温煅烧水泥熟料的同时焚烧处置污染土，使重金属元素通过与生料中的矿物发生复杂反应产生“矿物晶格取代”从而固定在熟料矿物相中，处理完毕污染土后无废渣残留物产生，从而能够大大降低产品中重金属的含量。
我国是水泥制造大国，产量位居世界第一。水泥生产过程中消耗大量的资源，因此常利用工业固废如粉煤灰、矿渣等来替代部分水泥熟料。水泥中混合材的掺量一般为5％～50％，因此水泥工业对固废混合材的消纳量巨大。而且，随着水泥生产和消耗量持续增加，一些传统的优质混合材如粒化高炉矿渣、粉煤灰都逐渐减少，致使水泥工业面临寻找量大面广、价格低廉、活性好的新混合材以满足水泥生产需要的问题。一般而言，污染土中含有各类重金属如汞、铅、铬、砷等，含有的有机污染物有多环芳烃、有机氯、苯酚、胺类等，经水泥窑高温煅烧后有机污染物被去除，处置后污染土壤主要化学成分有钙、硅、铝、铁、钠、钾以及各种重金属等。若能将协同处置污染土壤用作水泥熟料生产的原材料或者水泥混合材则可以解决协同处置污染土壤去处问题。但是，将污染土直接用作原料煅烧水泥熟料时，若协同处置污染土量大或者所含重金属量大，则可能对水泥品质造成影响，如造成水泥熟料组成和性能波动、水泥六价铬超标等。将协同处置污染土直接用作水泥混合材，则能够根据水泥性能的变化和污染土成分变化来比较灵活的调整协同处置污染土混合材的掺量。但是，这种方法也面临因水泥窑协同处置污染土壤水化活性不高，且含有重金属、氯等有害组分而限制了其作为混合材的掺量问题。
发明内容
解决的技术问题：本发明克服现有技术中的不足之处，提供一种水泥窑协同处置污染土壤混合材及其制备方法和应用。
技术方案：一种水泥窑协同处置污染土壤混合材，按重量份由以下物质组成：水泥窑协同处置污染土65-85份，脱硫石膏2-5份，粉煤灰5-25份，高炉矿渣5-15份，镁渣1-10份，水化氯铝酸钙1-6份，硫酸亚铁0.1-0.5份，调节助剂0.5-5份。
优选的，按重量份由以下物质组成：70份水泥窑协同处置污染土，3份脱硫石膏，5份粉煤灰，10份高炉矿渣，9.9份镁渣，2份水化氯铝酸钙，0.1份硫酸亚铁，调节助剂1份。
一种水泥窑协同处置污染土壤混合材的制备方法，包括以下步骤：(1)先将水泥窑协同处置污染土、脱硫石膏、粉煤灰、高炉矿渣、镁渣、水化氯铝酸钙和硫酸亚铁均匀混合得混合物；(2)将调节助剂0.5份-5份均匀喷洒在上述混合物上；(3)将上述混合物放入球磨机，粉磨至比表面积为400m2/kg以上的微粉，即得到水泥窑协同处置污染土壤水泥混合材。
上述水泥窑协同处置的污染土是经水泥窑煅烧后的污染土。
上述调节助剂按重量份组成为磷酸盐5-25份，柠檬酸0.1-2份，亚硝酸钙5-15份，多元醇15-30份和水35-75份，调节助剂的掺量为0.5份-5份。
优选的，上述调节助剂按重量份组成为15份磷酸二氢钾，5份亚硝酸钙，10份乙二醇，70份水调配出调节助剂。
上述多元醇为化工厂产生的多元醇废弃物，为乙二醇、一缩二乙二醇中的至少一种。
上述磷酸盐为磷酸二氢钾、磷酸二氢铵、磷酸二氢钠中的至少一种。
上述水泥窑协同处置污染土壤混合材在制备水泥中的应用。
有益效果：1.本发明开发的水泥窑协同处置污染土壤水泥混合材具有高水化活性，能提高掺混合材水泥强度；2.本发明的组分水泥窑协同处置污染土壤、脱硫石膏、粉煤灰、高炉矿渣和镁渣能够形成协同激发，提高混合材水化活性的作用。水泥窑协同处置污染土壤能够提供水化用的钙、硅和铝，高炉矿渣能够提供钙和铝源，镁渣能够提供丰富的钙质成分，粉煤灰提供铝、硅和少量钙，脱硫石膏提供水化所需的钙和硫酸根离子。上述组分互为补充，为混合材发生火山灰反应提供充足的活性组分；3.本发明的组分水化氯铝酸钙具有双层结构，能够吸附固化污染土壤中所含的重金属，硫酸亚铁具有强还原作用，能够将污染土壤中所含可溶性六价铬还原成三价铬，形成三价铬氢氧化物沉淀。4.本发明的调节助剂，所述调节助剂主要由磷酸盐、柠檬酸、亚硝酸钙、多元醇和水组成。其中，磷酸盐和柠檬酸对混合材具有一定激发作用，尤其是能够稳定固化污染土壤中所含的重金属如铅。多元醇具有一定的助磨作用，更容易将混合物磨成细微颗粒，降低混合材粉磨的能耗，对水泥早期和后期强度的发展均有利。亚硝酸钙具有激发作用，有利于促进混合材和水泥的水化。5.本发明为污染土壤以及工业固废脱硫石膏、粉煤灰和高炉矿渣的资源化利用提供良好的路径，为水泥的生产制造拓宽了混合材料的原料来源。
具体实施方式
下面就本发明举例说明，但不是对本发明的限制。为了更好的解释本发明，通过以下具体实施方式对本发明进行解释和说明。
实施例1
首先，按重量份，将85份水泥窑协同处置污染土，2份脱硫石膏，5份粉煤灰、5份高炉矿渣、1.9份镁渣、1份水化氯铝酸钙、0.1份硫酸亚铁。按照份数均匀混合，其次，称取5份磷酸二氢钾、5份亚硝酸钙、20份乙二醇、70份水调配出调节助剂；然后将1份的调节助剂按照质量比例或者份数均匀喷洒在上述粉体物料上；将粉体物料在球磨机中粉磨至比表面积为400±10m2/kg的微粉，得到所述的用于水泥的水泥窑协同处置污染土水泥混合材。
实施例2
首先，按重量份，将65份水泥窑协同处置污染土，5份脱硫石膏，10份粉煤灰、15份高炉矿渣、2.9份镁渣、2份水化氯铝酸钙、0.1份硫酸亚铁。按照份数均匀混合，其次，称取5份磷酸二氢钾、5份亚硝酸钙、20份乙二醇、70份水调配出调节助剂；然后将1份的调节助剂按照质量比例或者份数均匀喷洒在上述粉体物料上；将粉体物料在球磨机中粉磨至比表面积为400±10m2/kg的微粉，得到所述的用于水泥的水泥窑协同处置污染土水泥混合材。
实施例3
首先，按重量份，将70份水泥窑协同处置污染土，5份脱硫石膏，10份粉煤灰、10份高炉矿渣、2.9份镁渣、2份水化氯铝酸钙、0.1份硫酸亚铁。按照份数均匀混合，其次，称取15份磷酸二氢钾、5份亚硝酸钙、5份乙二醇、5份一缩二乙二醇、70份水调配出调节助剂；然后将3份的调节助剂按照质量比例或者份数均匀喷洒在上述粉体物料上；将粉体物料在球磨机中粉磨至比表面积为400±10m2/kg的微粉，得到所述的用于水泥的水泥窑协同处置污染土水泥混合材。
实施例4
首先，按重量份，将70份水泥窑协同处置污染土，3份脱硫石膏，5份粉煤灰、10份高炉矿渣、9.9份镁渣、2份水化氯铝酸钙、0.1份硫酸亚铁。按照份数均匀混合，其次，称取15份磷酸二氢钾、柠檬酸0.5份、5份亚硝酸钙、10份乙二醇、70份水调配出调节助剂；然后将3份的调节助剂按照质量比例或者份数均匀喷洒在上述粉体物料上；将粉体物料在球磨机中粉磨至比表面积为450±10m2/kg的微粉，得到所述的用于水泥的水泥窑协同处置污染土水泥混合材。
采用江南小野田生产的P.II 52.5水泥作为对照组1。采用浙江某电厂生产的II级粉煤灰作为对照组2。将水泥窑协同处置污染土壤放在在球磨机中粉磨至比表面积为400±10m2/kg的微粉，得到的混合材作为对照组3。将实施例、对照组2分别代替30％对照组1所述的水泥，测3天、7天和28天的抗压强度，其结果见表1所示。
表1掺实施例和对照组混合材的水泥的抗压强度/MPa
| 编号 | 3d | 7d | 28d |
| 对照组1 | 40.1 | 52.4 | 56.7 |
| 对照组2 | 26.2 | 35.8 | 43.4 |
| 对照组3 | 23.1 | 31.5 | 38.0 |
| 实施例1 | 25.6 | 36.3 | 44.2 |
| 实施例2 | 33.8 | 44.2 | 50.3 |
| 实施例3 | 30.3 | 41.1 | 47.9 |
| 实施例4 | 34.6 | 46.2 | 52.1 |
针对对比组3和实施例1-4，参照标准HJ557-2010《固体废物浸出毒性浸出方法》对混合材所含重金属进行浸提，测取重金属含量，重金属主要包括Pb、Cd、Hg、Cr、Ni、Cu、Zn、As。测试结果如表2。
表2浸出重金属含量
| 编号 | 浸出重金属含量(mg/L) |
| 对照组3 | 11.2 |
| 实施例1 | 3.8 |
| 实施例2 | 3.1 |
| 实施例3 | 1.3 |
| 实施例4 | 0.6 |
由表1可以看出，本发明中掺对照组3水泥窑协同处置土壤的水泥强度低于掺对照组2的水泥强度，说明水泥要协同处置污染土壤的活性低于对照组2。但是实施例1-4的水泥窑协同处置污染土壤混合材的活性均要明显好于对照组2和对照组3。尤其是实施例4在3d、7d、28d的强度均达到对照组1硅酸盐水泥强度的86.3％、88.2％和91.9％。也就是说实施例4在28天的活性指数是91.9％，显著高于对照组2粉煤灰在28天的活性指数76.5％。由表1可以看出，实施例1-4浸出重金属含量均明显低于对照组3，其中实施例4具有最低的重金属浸出量，对比对照组3，重金属浸出量降低了94.6％。上述结果表明，本发明水泥窑协同处置污染土壤作为水泥混合材表现出高活性，表明其可作为一种优质的水泥混合材。
本发明方案所公开的技术手段不仅限于上述实施方式所公开的技术手段，还包括由以上技术特征任意组合所组成的技术方案。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也视为本发明的保护范围。
Claims (9)
1.一种水泥窑协同处置污染土壤混合材，其特征在于，按重量份由以下物质组成：水泥窑协同处置污染土65-85份，脱硫石膏2-5份，粉煤灰5-25份，高炉矿渣5-15份，镁渣1-10份，水化氯铝酸钙1-6份，硫酸亚铁0.1-0.5份，调节助剂0.5-5份。
2.根据权利要求1所述一种水泥窑协同处置污染土壤混合材，其特征在于，按重量份由以下物质组成：70份水泥窑协同处置污染土，3份脱硫石膏，5份粉煤灰，10份高炉矿渣，9.9份镁渣，2份水化氯铝酸钙，0.1份硫酸亚铁，调节助剂1份。
3.根据权利要求1所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于包括以下步骤：（1）先将水泥窑协同处置污染土、脱硫石膏、粉煤灰、高炉矿渣、镁渣、水化氯铝酸钙和硫酸亚铁均匀混合得混合物；（2）将调节助剂0.5份-5份均匀喷洒在上述混合物上；（3）将上述混合物放入球磨机，粉磨至比表面积为400m2/kg以上的微粉，即得到水泥窑协同处置污染土壤水泥混合材。
4.根据权利要求2所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于，所述水泥窑协同处置的污染土是经水泥窑煅烧后的污染土。
5.根据权利要求2所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于，所述调节助剂按重量份组成为磷酸盐5-25份，柠檬酸0.1-2份，亚硝酸钙5-15份，多元醇15-30份和水35-75份，调节助剂的掺量为0.5份-5份。
6.根据权利要求5所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于，所述调节助剂按重量份组成为15份磷酸二氢钾，5份亚硝酸钙，10份乙二醇，70份水调配出调节助剂。
7.根据权利要求5所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于，所述的多元醇为化工厂产生的多元醇废弃物，为乙二醇、一缩二乙二醇中的至少一种。
8.根据权利要求5所述一种水泥窑协同处置污染土壤混合材的制备方法，其特征在于，所述的磷酸盐为磷酸二氢钾、磷酸二氢铵、磷酸二氢钠中的至少一种。
9.权利要求1或2所述水泥窑协同处置污染土壤混合材在制备水泥中的应用。
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