US20140069873A1 - Acidic Mine Water Remediation - Google Patents
Acidic Mine Water Remediation Download PDFInfo
- Publication number
- US20140069873A1 US20140069873A1 US13/978,592 US201213978592A US2014069873A1 US 20140069873 A1 US20140069873 A1 US 20140069873A1 US 201213978592 A US201213978592 A US 201213978592A US 2014069873 A1 US2014069873 A1 US 2014069873A1
- Authority
- US
- United States
- Prior art keywords
- drainage water
- gel
- mine drainage
- acidic
- acidic mine
- 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
Links
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 24
- 238000005067 remediation Methods 0.000 title description 5
- 239000003657 drainage water Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000010909 process residue Substances 0.000 claims abstract description 21
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 238000011109 contamination Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 7
- 238000011282 treatment Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000003914 acid mine drainage Methods 0.000 description 4
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical class C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 4
- 229910052683 pyrite Inorganic materials 0.000 description 4
- 239000011028 pyrite Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- -1 calcium chloride) Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000548 poly(silane) polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000736285 Sphagnum Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical class C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000013056 hazardous product Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001367 organochlorosilanes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4893—Residues derived from used synthetic products, e.g. rubber from used tyres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/203—Iron or iron compound
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/911—Cumulative poison
- Y10S210/912—Heavy metal
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S210/00—Liquid purification or separation
- Y10S210/902—Materials removed
- Y10S210/911—Cumulative poison
- Y10S210/912—Heavy metal
- Y10S210/913—Chromium
Definitions
- This invention relates to mine water remediation and in particular to the treatment of acidic mine drainage water to remove heavy metal ions.
- the treatment is particularly applicable to acidic mine drainage water from an abandoned or closed mine, but can also be used to treat acidic mine drainage water from a working mine.
- Acid mine drainage is mainly caused by oxidation of pyrite (iron sulphide mineral). Pyrite oxidises to produce acidic water often having a pH below 3. The presence of water promotes oxidation of the pyrite.
- pyrite iron sulphide mineral
- Pyrite oxidises to produce acidic water often having a pH below 3.
- the presence of water promotes oxidation of the pyrite.
- a mine for example a coal mine, iron ore mine or other metal ore mine
- Pyrite is exposed in many mines, and the build-up of water produces a drainage stream of acidic water.
- the pH of the water is sufficiently low, metal deposits within the mine may dissolve into the acidic water. This acidic metal laden solution can then overflow the mine and pollute the local environment.
- the heavy metal ions present in the mine water may for example include ions of iron, manganese, chromium, copper, zinc, cadmium and lead, amongst others.
- EP-A-765842 describes contacting an aqueous system containing heavy metal contaminants with an organically modified smectite clay.
- WO99/19523 describes removing metal ions from a fluid stream by placing a liquid having an affinity for the metal ions on a mat of hollow wicking fibres, and directing the fluid stream through the mat into contact with the liquid along the channels within the hollow wicking fibres.
- U.S. Pat. No. 5,695,882 describes producing a material for extracting heavy metal ions from aqueous solutions, for example lead from drinking water, by silanizing the hydrated surface of a solid extraction material with a silane, and reacting the silanized surface with a polyamine.
- U.S. Pat. No. 6,296,760 describes a device for removing metal ions such as cadmium, copper, nickel, lead or zinc ions from water comprising a nonporous polymer membrane for capturing the metal ions and a hydrophobic sequestration medium contained by the membrane which changes the metal ions into a complexed, non-mobile metal species.
- the acidic mine drainage water is contacted with direct process residue gel.
- Direct process residue gel is derived from the production of methylchlorosilanes.
- Methylchlorosilanes are commercially produced by what is commonly called “the direct process”, in which silicon metal is reacted with methyl chloride (CH 3 Cl) in the presence of a catalyst. The reaction takes place in a fluid bed reactor in which finely ground silicon metal powder is fluidised by passing methyl chloride gas there through at a temperature of between 200° C. and 500° C.
- a by-product of the direct process is direct process residue (DPR).
- the remainder of the direct process residue comprises a variety of materials, typically including iron, silicon metal, copper, organic materials, and salts (e.g.
- DPR is a chemically active, hazardous material, whose activity must be reduced prior to transportation and/or disposal.
- DPR is neutralised with an alkaline aqueous solution and optionally dewatered, resulting in a gel-solids mixture, referred to hereinafter as “direct process residue gel” or “DPR gel”.
- direct process residue gel or “DPR gel”.
- the invention includes the use of direct process residue gel to reduce the heavy metal ion content of acidic mine drainage water.
- DPR gel is a hydrolysis product of the constituents of DPR (i.e. the hydrolysis product of e.g. silicon compounds such as disilanes, larger polysilanes and silmethylenes) which are hydrolysed into a highly cross-linked gel.
- the precise composition of the DPR gel produced as described above may vary dependent on the relative amounts of the constituents in the DPR from which the gel is obtained but typically the major components of DPR gel are the products of the hydrolysis of disilanes (the amount of disilanes in direct process residue may for example be from 50 to 80 wt %).
- the DPR gel that is the gel-solids mixture produced after dewatering, usually has a water content in the range 35 to 60% by weight.
- the DPR gel can be used in the form in which it is produced as described above or can be modified, for example by the separation of ungelled solids and/or by removal of salts.
- the higher boiling point silicon compounds can be filtered before they are hydrolysed; this removes ungelled solid materials such as silicon metal, iron and copper derived from the direct process reaction vessel.
- the DPR gel can be washed after it is formed to remove at least partly soluble salts such as calcium chloride.
- DPR gel as produced as a commercial by-product in the form of a solid highly cross-linked structure is highly effective in removing heavy metal ions from mine water, and the DPR gel is preferably used without filtration or washing.
- the DPR gel can be contacted with the acidic mine drainage water in any of a number of different methods.
- the acidic mine drainage water or a stream contaminated with acidic mine drainage water can be passed through a bed of DPR gel.
- the contaminated water can for example be pumped out of the mine and passed (pumped or trickled) through the DPR gel, either as a packed cartridge of DPR gel or a loose bed of DPR gel.
- the loose bed of DPR gel can be used similarly to the way filter aid powders are deployed in industrial filtration using a plate-and-frame filter press.
- the mine causing acidic mine drainage water contamination (usually an exhausted coal or metal mine) is surrounded by a lining filled with DPR gel so that rainwater entering the mine has to pass through the DPR gel on its path to the environment.
- a large ‘catch-all’ lining can be dug around the contamination zone and filled with the DPR gel.
- Rainwater enters the mine and picks up contamination but in its path back into the environment it has to pass through the DPR gel, where the contaminants are removed.
- the heavy metal contaminants may be any heavy metal ions detrimental to the environment and present in mine water for example ions of iron, manganese, chromium, copper, zinc, cadmium and lead and mixtures thereof.
- the acidic mine drainage water or a stream contaminated with acidic mine drainage water can be fed to a pond lined with direct process residue gel.
- a single pond or a plurality of such ponds arranged in series can be used. Water leaving the pond, or the last of a series of ponds, passes to the environment.
- the DPR gel can be added to a stream of acidic mine drainage water or a stream contaminated with acidic mine drainage water.
- the DPR gel can be added to the flowing stream or the stream can be fed to a pond to which the DPR gel is added.
- the DPR gel can for example be added at 0.1 to 40 g per litre of acidic mine drainage water.
- Typical amounts of DPR gel may be 1 to 20 g per litre to treat heavily polluted acidic drainage water from a disused mine or 0.1 to 2 g per litre to treat less polluted acidic drainage water or drainage water from an active mine.
- the mine drainage water which has been treated with DPR gel can be tested for acidity and/or for heavy metal ion content. Such testing may be carried out continuously or on samples taken intermittently. Once the water is tested and shown to meet standards, it is returned to the environment.
- DPR gel is highly effective in removing heavy metal ions from mine water; it is much more effective than clay minerals such as zeolites. We believe that the alkaline nature of the DPR gel causes metals dissolved in the acidic mine drainage water to precipitate out. Furthermore, the DPR gel is an extremely porous solid and thus has a high surface area to trap the metals. The DPR gel can readily be ground to a desired particle size if required, for example when adding the DPR gel to the mine drainage water or for forming a filtration cartridge of DPR gel.
- the invention is illustrated by the following Example, in which parts and percentages are by weight.
- the Example includes FIGS. 1 to 3 of the accompanying drawings:
- FIG. 1 is a graph of the pH of mine drainage water against time after addition of DPR gel
- FIG. 2 is a graph of the concentration of zinc, iron and manganese in mine drainage water against time after addition of DPR gel;
- FIG. 3 is a graph of the concentration of zinc, iron and manganese in mine drainage water against time after addition of zeolite in a comparative experiment.
- DPR gel was added to 200 mL acidic mine drainage water from an abandoned metal ore mine in Cornwall, England. This mine has highly contaminated drainage water of pH 2.47 containing 30 parts per million (ppm) zinc, 34 ppm manganese and 78 ppm iron.
- the DPR gel was a gel of water content 45 to 50 wt. %, produced by hydrolysing with lime solution higher boiling point organochlorosilanes produced in the manufacture of methylchlorosilanes by the direct process in which silicon metal was reacted with methyl chloride.
- the DPR gel was mixed with the acidic mine drainage water in a tumbling mill for 3 hours. Samples were taken for analysis after 15 min, 30 min 1 hour, 2 hours and 3 hours. The analysed samples were filtered and the metal content was determined by atomic adsorption spectrophotometry.
- FIG. 1 is a graph of the pH of the mine drainage water against time after addition of the DPR gel. It can be seen that the pH rises above pH 8 within ten minutes of addition of the DPR gel, and after an hour reaches a steady pH of about 10.
- FIG. 2 is a graph of the concentration of zinc, iron and manganese in the mine drainage water against time after addition of the DPR gel. It can be seen that the concentration of each of these metals is reduced to below 5 ppm within 15 minutes and remains below this level.
- FIG. 3 shows the concentration of zinc, iron and manganese in the mine drainage water against time after addition of zeolite (clionptilolite).
- zeolite clionptilolite
- the zeolite has a considerable effect in removing metals from the water, but the concentration of iron remains above 25 ppm and the concentration of zinc above 15 ppm even after 150 minutes.
- the DPR gel is clearly more effective than zeolite in remediation of the mine drainage water.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
A process for treating acidic mine drainage water to remove heavy metal ions is described in which acidic mine drainage water is contacted with direct process residue gel.
Description
- This invention relates to mine water remediation and in particular to the treatment of acidic mine drainage water to remove heavy metal ions. The treatment is particularly applicable to acidic mine drainage water from an abandoned or closed mine, but can also be used to treat acidic mine drainage water from a working mine.
- Acid mine drainage is mainly caused by oxidation of pyrite (iron sulphide mineral). Pyrite oxidises to produce acidic water often having a pH below 3. The presence of water promotes oxidation of the pyrite. When a mine, for example a coal mine, iron ore mine or other metal ore mine, is abandoned, there is usually a build-up of water because pumping of water from the mine has ceased. Pyrite is exposed in many mines, and the build-up of water produces a drainage stream of acidic water. When the pH of the water is sufficiently low, metal deposits within the mine may dissolve into the acidic water. This acidic metal laden solution can then overflow the mine and pollute the local environment. Reduction of pH in water leads to less dissolved oxygen and reduces enzyme activity, while certain microorganisms such as Sphagnum flourish removing essential ions from other organisms. The decrease in pH also results in the precipitation of iron salts as Fe(OH)3 (ochre) causing a red stain and acting as a site for co-precipitation of other metals. The heavy metal ions present in the mine water may for example include ions of iron, manganese, chromium, copper, zinc, cadmium and lead, amongst others.
- Various treatments have been suggested for mine water remediation. These can be active treatments, in which a neutralising agent is added to the source of the acid mine drainage or to a stream which has been polluted, or passive treatments. Neutralising agents which have been suggested for active remediation of acid mine drainage include calcium carbonate, calcium oxide or hydroxide, ammonia, sodium hydroxide or sodium carbonate. In passive treatments the acid mine drainage is passed through drains, channels or ponds, generally of limestone, or to aerobic or anaerobic wetlands.
- EP-A-765842 describes contacting an aqueous system containing heavy metal contaminants with an organically modified smectite clay.
- WO99/19523 describes removing metal ions from a fluid stream by placing a liquid having an affinity for the metal ions on a mat of hollow wicking fibres, and directing the fluid stream through the mat into contact with the liquid along the channels within the hollow wicking fibres.
- U.S. Pat. No. 5,695,882 describes producing a material for extracting heavy metal ions from aqueous solutions, for example lead from drinking water, by silanizing the hydrated surface of a solid extraction material with a silane, and reacting the silanized surface with a polyamine.
- U.S. Pat. No. 6,296,760 describes a device for removing metal ions such as cadmium, copper, nickel, lead or zinc ions from water comprising a nonporous polymer membrane for capturing the metal ions and a hydrophobic sequestration medium contained by the membrane which changes the metal ions into a complexed, non-mobile metal species.
- In a process according to the present invention for treating acidic mine drainage water to remove heavy metal ions, the acidic mine drainage water is contacted with direct process residue gel.
- Direct process residue gel is derived from the production of methylchlorosilanes. Methylchlorosilanes are commercially produced by what is commonly called “the direct process”, in which silicon metal is reacted with methyl chloride (CH3Cl) in the presence of a catalyst. The reaction takes place in a fluid bed reactor in which finely ground silicon metal powder is fluidised by passing methyl chloride gas there through at a temperature of between 200° C. and 500° C. A by-product of the direct process is direct process residue (DPR). DPR comprises between 50-90% the higher boiling point methylchlorodisilanes (boiling point higher than methylchlorosilanes) with the general formula Si2(CH3)xCly where x+y=6. The remainder of the material substantially comprises silmethylenes SiCH2Si(CH3)Clk where j+k=6 and higher boiling polysilanes, where the general formula is Sin(CH3)mClp where m+p=6+(2(n−2)). The remainder of the direct process residue comprises a variety of materials, typically including iron, silicon metal, copper, organic materials, and salts (e.g. calcium chloride), DPR is a chemically active, hazardous material, whose activity must be reduced prior to transportation and/or disposal. Thus, once separated from the other reaction products, DPR is neutralised with an alkaline aqueous solution and optionally dewatered, resulting in a gel-solids mixture, referred to hereinafter as “direct process residue gel” or “DPR gel”. Methods for neutralising DPR are described for example in U.S. Pat. No. 4,408,030 and U.S. Pat. No. 5,876,609.
- The invention includes the use of direct process residue gel to reduce the heavy metal ion content of acidic mine drainage water.
- DPR gel is a hydrolysis product of the constituents of DPR (i.e. the hydrolysis product of e.g. silicon compounds such as disilanes, larger polysilanes and silmethylenes) which are hydrolysed into a highly cross-linked gel. The precise composition of the DPR gel produced as described above may vary dependent on the relative amounts of the constituents in the DPR from which the gel is obtained but typically the major components of DPR gel are the products of the hydrolysis of disilanes (the amount of disilanes in direct process residue may for example be from 50 to 80 wt %). The DPR gel, that is the gel-solids mixture produced after dewatering, usually has a water content in the range 35 to 60% by weight.
- The DPR gel can be used in the form in which it is produced as described above or can be modified, for example by the separation of ungelled solids and/or by removal of salts. The higher boiling point silicon compounds can be filtered before they are hydrolysed; this removes ungelled solid materials such as silicon metal, iron and copper derived from the direct process reaction vessel. The DPR gel can be washed after it is formed to remove at least partly soluble salts such as calcium chloride. We have however found DPR gel as produced as a commercial by-product in the form of a solid highly cross-linked structure is highly effective in removing heavy metal ions from mine water, and the DPR gel is preferably used without filtration or washing.
- The DPR gel can be contacted with the acidic mine drainage water in any of a number of different methods. The acidic mine drainage water or a stream contaminated with acidic mine drainage water can be passed through a bed of DPR gel. The contaminated water can for example be pumped out of the mine and passed (pumped or trickled) through the DPR gel, either as a packed cartridge of DPR gel or a loose bed of DPR gel. The loose bed of DPR gel can be used similarly to the way filter aid powders are deployed in industrial filtration using a plate-and-frame filter press.
- In an alternative process the mine causing acidic mine drainage water contamination (usually an exhausted coal or metal mine) is surrounded by a lining filled with DPR gel so that rainwater entering the mine has to pass through the DPR gel on its path to the environment. A large ‘catch-all’ lining can be dug around the contamination zone and filled with the DPR gel. Rainwater enters the mine and picks up contamination but in its path back into the environment it has to pass through the DPR gel, where the contaminants are removed. The heavy metal contaminants may be any heavy metal ions detrimental to the environment and present in mine water for example ions of iron, manganese, chromium, copper, zinc, cadmium and lead and mixtures thereof.
- In a further alternative the acidic mine drainage water or a stream contaminated with acidic mine drainage water can be fed to a pond lined with direct process residue gel. A single pond or a plurality of such ponds arranged in series can be used. Water leaving the pond, or the last of a series of ponds, passes to the environment.
- Alternatively the DPR gel can be added to a stream of acidic mine drainage water or a stream contaminated with acidic mine drainage water. The DPR gel can be added to the flowing stream or the stream can be fed to a pond to which the DPR gel is added. The DPR gel can for example be added at 0.1 to 40 g per litre of acidic mine drainage water. Typical amounts of DPR gel may be 1 to 20 g per litre to treat heavily polluted acidic drainage water from a disused mine or 0.1 to 2 g per litre to treat less polluted acidic drainage water or drainage water from an active mine.
- The mine drainage water which has been treated with DPR gel can be tested for acidity and/or for heavy metal ion content. Such testing may be carried out continuously or on samples taken intermittently. Once the water is tested and shown to meet standards, it is returned to the environment.
- We have found DPR gel to be highly effective in removing heavy metal ions from mine water; it is much more effective than clay minerals such as zeolites. We believe that the alkaline nature of the DPR gel causes metals dissolved in the acidic mine drainage water to precipitate out. Furthermore, the DPR gel is an extremely porous solid and thus has a high surface area to trap the metals. The DPR gel can readily be ground to a desired particle size if required, for example when adding the DPR gel to the mine drainage water or for forming a filtration cartridge of DPR gel.
- The invention is illustrated by the following Example, in which parts and percentages are by weight. The Example includes
FIGS. 1 to 3 of the accompanying drawings: -
FIG. 1 is a graph of the pH of mine drainage water against time after addition of DPR gel; -
FIG. 2 is a graph of the concentration of zinc, iron and manganese in mine drainage water against time after addition of DPR gel; -
FIG. 3 is a graph of the concentration of zinc, iron and manganese in mine drainage water against time after addition of zeolite in a comparative experiment. - In a laboratory test, 8 g DPR gel was added to 200 mL acidic mine drainage water from an abandoned metal ore mine in Cornwall, England. This mine has highly contaminated drainage water of pH 2.47 containing 30 parts per million (ppm) zinc, 34 ppm manganese and 78 ppm iron. The DPR gel was a gel of water content 45 to 50 wt. %, produced by hydrolysing with lime solution higher boiling point organochlorosilanes produced in the manufacture of methylchlorosilanes by the direct process in which silicon metal was reacted with methyl chloride. The DPR gel was mixed with the acidic mine drainage water in a tumbling mill for 3 hours. Samples were taken for analysis after 15 min, 30 min 1 hour, 2 hours and 3 hours. The analysed samples were filtered and the metal content was determined by atomic adsorption spectrophotometry.
- The effect of the DPR gel on the pH of the acidic mine drainage water is shown in
FIG. 1 , which is a graph of the pH of the mine drainage water against time after addition of the DPR gel. It can be seen that the pH rises abovepH 8 within ten minutes of addition of the DPR gel, and after an hour reaches a steady pH of about 10. - By comparison, when the same amount of the zeolite clinoptilolite is added to the acidic mine drainage water from the abandoned metal ore mine, the pH only rises to 2.81 after an hour and 2.87 after 3 hours.
- The effect of the DPR gel on the heavy metal content of the acidic mine drainage water is shown in
FIG. 2 , which is a graph of the concentration of zinc, iron and manganese in the mine drainage water against time after addition of the DPR gel. It can be seen that the concentration of each of these metals is reduced to below 5 ppm within 15 minutes and remains below this level. - By comparison,
FIG. 3 shows the concentration of zinc, iron and manganese in the mine drainage water against time after addition of zeolite (clionptilolite). The zeolite has a considerable effect in removing metals from the water, but the concentration of iron remains above 25 ppm and the concentration of zinc above 15 ppm even after 150 minutes. The DPR gel is clearly more effective than zeolite in remediation of the mine drainage water.
Claims (18)
1. A process for treating acidic mine drainage water to remove heavy metal ions, characterised in that the acidic mine drainage water is contacted with direct process residue gel.
2. A process according to claim 1 , characterised in that acidic mine drainage water or a stream contaminated with acidic mine drainage water is passed through a bed of direct process residue gel.
3. A process according to claim 2 , characterised in that the bed of direct process residue gel is packed in a cartridge and the acidic mine drainage water is pumped through the cartridge.
4. A process according to claim 2 , characterised in that the acidic mine drainage water or stream contaminated with acidic mine drainage water is trickled through a loose bed of direct process residue gel.
5. A process according to claim 1 , characterised in that the mine causing acidic mine drainage water contamination is surrounded by a lining filled with direct process residue gel so that rainwater entering the mine has to pass through the direct process residue gel on its path to the environment.
6. A process according to claim 1 , characterised in that acidic mine drainage water or a stream contaminated with acidic mine drainage water is fed to a pond lined with direct process residue gel.
7. A process according to claim 1 , characterised in that direct process residue gel is added to a stream of acidic mine drainage water or a stream contaminated with acidic mine drainage water.
8. A process according to claim 1 wherein the heavy metal ions include iron, manganese, chromium, copper, zinc, cadmium and lead and mixtures thereof.
9. A process comprising using direct process residue gel to reduce the heavy metal ion content of acidic mine drainage water.
10. A process of claim 9 wherein the heavy metal ions include iron, manganese, chromium, copper, zinc, cadmium and lead and mixtures thereof.
11. The process of claim 1 , where the DPR gel is added at 0.1 to 40 g per litre of acidic mine drainage water.
12. The process of claim 11 , where the DPR gel is added at 1 to 20 g per litre to treat heavily polluted acidic drainage water from a disused mine.
13. The process of claim 11 , where the DPR gel is added at 0.1 to 2 g per litre to treat less polluted acidic drainage water or drainage water from an active mine.
14. The process of claim 1 , wherein the DPR gel has a water content in the range 35 to 60% by weight.
15. The process of claim 1 , where the process further comprises (a) forming the DPR gel by separating direct process residue from other reaction products of the direct process, neutralizing the direct process residue with an alkaline aqueous solution, and optionally dewatering, before (b) the acidic mine drainage water is contacted with direct process residue gel.
16. The process of claim 15 , further comprising (c) modifying the DPR gel after step (a) and before step (b).
17. The process of claim 16 , where step (c) is performed by separation of ungelled solids, by removal of salts, removing ungelled solid materials, and/or washing.
18. The process of claim 15 , where the DPR gel is produced as a commercial by-product of the direct process, and the DPR gel used in step (b) without filtration or washing
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PCT/EP2012/057928 WO2012156198A1 (en) | 2011-05-13 | 2012-04-30 | Acidic mine water remediation |
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CN112321049A (en) * | 2020-10-22 | 2021-02-05 | 河北工程大学 | Underground mine water treatment device for coal mine |
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US2380995A (en) * | 1941-09-26 | 1945-08-07 | Gen Electric | Preparation of organosilicon halides |
US3464920A (en) * | 1967-07-20 | 1969-09-02 | Wacker Chemie Gmbh | Method of removing oil from the surface of water using oleophilic,hydrophobic comminuted organic materials |
US4408030A (en) | 1982-03-22 | 1983-10-04 | Dow Corning Corporation | Waste chlorosilane treatment |
DE3523541A1 (en) | 1985-07-02 | 1987-01-15 | Bayer Ag | Process for working up hydrolysed residues arising in the preparation of organochlorosilanes |
DE4116925C2 (en) | 1991-05-24 | 1999-06-24 | Huels Silicone Gmbh | Process for the preparation of distillation residues from the direct synthesis of chlorosilanes and / or organochlorosilanes |
US6656360B2 (en) | 1994-12-23 | 2003-12-02 | Alliedsignal Inc. | Fibrous system for continuously capturing metals from an aqueous stream |
US5695882A (en) * | 1995-08-17 | 1997-12-09 | The University Of Montana | System for extracting soluble heavy metals from liquid solutions |
US5667694A (en) | 1995-08-28 | 1997-09-16 | Rheox, Inc. | Process for the removal of heavy metals from aqueous systems using organoclays |
US6077439A (en) | 1996-08-23 | 2000-06-20 | Mcgill University | Method for the removal of metals from solution by means of activated silica |
US5876609A (en) | 1997-03-28 | 1999-03-02 | General Electric Company | Process for treating methylchlorosilanes by-products |
BR9907795A (en) * | 1998-02-09 | 2000-10-17 | Ind Science & Technology Netwo | "chemically modified surface gel (csmg) and production process and its use in the removal of metals from the liquid system" |
US6296760B1 (en) | 1999-03-03 | 2001-10-02 | The United States Of America As Represented By The Secretary Of The Interior | Device for the removal and concentration of ionic metal species from water |
US7358318B1 (en) * | 1999-05-19 | 2008-04-15 | Syracuse University | Organo-ceramic composite materials, their use as adsorbents, and methods of making the same |
JP2001226155A (en) | 2000-01-27 | 2001-08-21 | Dow Corning Corp | Method for manufacturing fluid clay slurry |
GB0212324D0 (en) * | 2002-05-29 | 2002-07-10 | Dow Corning | Silicon composition |
DE102005057460A1 (en) | 2005-12-01 | 2007-06-06 | Wacker Chemie Ag | Crosslinkable to high-strength elastomers ionically and / or organometallic functionalized silicone polymers |
US8217131B2 (en) * | 2006-10-02 | 2012-07-10 | Abs Materials, Inc. | Method for extracting a metal particulate from an aqueous solution using a sol-gel derived sorbent |
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CA2824717A1 (en) | 2012-11-22 |
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US8679350B1 (en) | 2014-03-25 |
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CN103501892A (en) | 2014-01-08 |
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