DE102013214981A1 - Process and apparatus for the treatment of valuable materials for mines - Google Patents

Abstract

The invention relates to a method (100, 200) for the treatment of water, in particular wastewater (101, 201) in mines for recovering material, in particular in mines for metal extraction comprising: a single or multi-stage filtration (102, 202, 203) of the wastewater for the recovery of process water (106, 204), wherein the obtained valuable substance concentrate (107, 225) is forwarded to at least one valuable substance recovery (234, 235); and a material recovery unit (109, 234, 235) comprising a valuable substance separation (103) from said valuable-containing concentrate (107, 225) by means of at least one selective ion exchanger (205, 206).

Description

The invention relates to a method specified in the preamble of claim 1. Art and a device specified in the preamble of claim 12 Art.

The wastewater in the metal extraction in mines, such as in copper mines, are currently mainly processed by precipitation, flocculation and subsequent sedimentation, such as in the EP 2013370 B1 described.

The precipitation is usually carried out by neutralization of the acid wastewater, usually with a high use of calcium hydroxide and often with the addition of other, partly poorly degradable precipitation chemicals and flocculants.

Sedimentation basins store the resulting sludge contaminated with heavy metals. This large amount of sludge is usually landfilled permanently on site.

This can result in a high environmental impact as e.g. Possible soil leaching from the contaminated landfilled sludge as well as groundwater in the vicinity of the mine can be heavily contaminated by possible leaching of the heavy metals.

In addition, the effectiveness of the process in terms of raw material utilization of water and remaining metals in the sludge is low and thus difficult to achieve in terms of environmental protection.

task

It is therefore an object of the invention to provide a method and a device for improving the wastewater treatment of mines for recovering valuable material, such as mines for metal extraction, in particular in terms of effectiveness, resource utilization and environmental compatibility.

solution

This is inventively achieved by a method according to claim 1 and an apparatus according to claim 12. Advantageous embodiments and further developments are the subject of the dependent claims.

An inventive method for the treatment of water, especially wastewater in mines for recovering valuable material, such as mines for metal extraction, may include a one- or multi-stage filtration of wastewater for recovery of process water, wherein obtained valuable concentrate can be forwarded to at least one resource recovery.

In addition, a method according to the invention can comprise a recycling of valuable material by separation of valuable material from said concentrate containing concentrate by means of at least one selective ion exchanger.

In this case, a recovery of various recyclables from the valuable concentrate can also be carried out by a series connection of different selective ion exchangers.

The treatment process of mine wastewater from mines for recovering valuable materials, in particular from mines for metal extraction, offers a number of advantages over the conventional treatment of wastewater in mines.

It is particularly advantageous in this case, above all, that any recyclables still present in the wastewater are separated from the wastewater or waste and can thus be recovered.

Thus, e.g. the total raw material or the total material yield of a mine by the recovery of raw materials or valuable substances, such as metals such as copper and / or manganese and / or iron, are significantly improved, which in turn can lead to that in the final to be deposited sludge or Waste product to a less polluting heavy metals remain, as well as the other that the amount of sludge to be deposited can be reduced.

The risk and the risk of leaching of environmentally unfriendly residues of mine wastewater, in particular from said waste sludge to be deposited, into soils and / or groundwater can thus be reduced.

The recovery of process water by filtration from the wastewater can also significantly reduce the fresh water requirements of the mine. With the reduction of the fresh water demand will then usually go along with a reduction in the energy needs of the mine plant.

In summary, it can be said that in addition to the better environmental compatibility of a mine wastewater treatment according to the invention as a whole a better economy of the mine can be achieved because the same raw material use more valuable materials and these can be obtained more effectively and the energy requirements can be reduced.

Said filtration of the waste water for the recovery of process water can otherwise take place by membrane filtration and comprise at least two filtration stages, wherein the first filtration stage may be microfiltration (eg with mean pore diameters of 0.1 .mu.m +/- 0.02 .mu.m) and the second filtration stage a nanofiltration ( for example, with average pore diameters of 0.001 microns +/- 0.0002 microns), in which the valuable concentrate is obtained. Any first filtration residues obtained or retained during a first filtration, for example in the case of said microfiltration, can be removed, optionally neutralized, immobilized and, for example, disposed of together with the final sludge to be disposed of.

Said filtration may also comprise a prefiltration stage, which may be preceded by, for example, a micro- or nanofiltration and can filter out substances> 100 microns.

Thanks to an ion-specific retention capacity of the nanofiltration used, ions of different valences can advantageously be separated, and, for example, polyvalent ions (eg valent ions such as Cu ²⁺ , Mn ²⁺ , Fe ³⁺ ) accumulate in the valuable-containing concentrate, while monovalent (eg Na ⁺ ) ions in the Filtrate for process water recovery can remain.

Among other things, the ion-specific retention capacity of the nanofiltration used can be based on membrane filtration, for example on the utilization of convection and diffusion effects due to pressure differences and / or concentration gradients, as well as on the utilization of steric or electrochemical effects.

The yield is defined as the ratio of filtrate to fed volume flow (feed) under stable operation and can therefore be considered constant and e.g. at least 95% for microfiltration and at least 80% for nanofiltration.

The recovered from the wastewater after filtration process water can then be reused and, for example, fed to a selective ion exchanger. It may also be used, for example, to dilute any treatment chemicals that may be added to the selective ion exchanger so as to allow for pH adjustment and / or regeneration of the selective ion exchanger.

As mentioned, recovery from a valuable concentrate may involve the use of a selective ion exchanger, e.g. a cation exchanger, wherein a Wertstoffionenseparation can be carried out with the addition of one or more treatment chemicals, and wherein the valuable material ions can be dissolved in the regenerate of the selective ion exchanger or can be dissolved.

Suitable treatment chemicals may be used to adjust the pH and / or to regenerate the selective ion exchanger.

As a treatment chemical, for example, sulfuric acid can be used. However, other acidic treatment chemicals such as hydrochloric acid, phosphoric acid or nitric acid can also be used.

The selective ion exchangers may be in the form of a DC ion exchanger or, preferably, a countercurrent ion exchanger, and for example, as an ion exchange material, an exchange resin, e.g. Polystyrene resin or polyacrylate resin, especially with a functional group such as IDA (iminodiacetic acid). The selective ion exchangers can be designed both as a membrane or, preferably, as a column.

The selectivity of the ion exchanger can be influenced in particular by adjusting the pH and choice of the ion exchange material.

For example, different ion exchange materials can have different ion exchange material molecule sizes and / or have different ion affinities, and thus the selectivity of the ion exchanger can be controlled or optimized with regard to the valuable substance ions to be exchanged, for example as a function of the valuable ion radius.

From the concentrate containing valuable material, obtained for example from a previous nanofiltration, eg sulfuric acid H ₂ SO ₄ can be dissolved or dissolved in concentrated form in the form of a sulfate in the regenerate of the ion exchanger as a treatment chemical for the regeneration and thus the valuable substance be recovered.

For example, copper sulphate (or iron or manganese sulphate) dissolved in this manner can be recovered from the reclaimed material containing valuable material and sent to any further recovery processes, such as e.g. Electrolysis process, where, for example, the valuable material, e.g. Copper, iron or manganese, can be obtained in solid form.

As already mentioned, among other things, the selectivity of the ion exchanger, for example, can be optimized by adjusting the pH and, for example, the optimum pH range for copper recovery is 2 +/- 0.5.

For example, a plurality of selective ion exchangers with different parameters, in particular with respect to different pH ranges and / or different ion exchange materials, can be connected in series to different recyclables, in particular copper and / or manganese and / or iron from the valuable concentrate or regenerate win.

The number and type of possible selective ion exchange processes may be e.g. according to the type of chemical composition of the waste water to be treated.

In addition, the filtrate from the selective ion exchanger or filtrate may be subjected to further membrane filtration after passing through a series of selective ion exchangers (or a series of selective ion exchange processes) for at least partial recovery of the added treatment chemicals, with membrane filtration being nanofiltration and the recovered chemical can be recycled back to a selective ion exchanger.

The concentrate remaining after recovery and / or treatment chemical recovery may be precipitated or flocculated in a conventional manner, for example with metal hydroxides such as calcium hydroxide and addition of calcium chloride.

The remaining after sedimentation sludge or waste can be dumped and the supernatant after sedimentation water the processing method are made available again as process water available.

A wastewater treatment method according to the invention for recovering valuable material can significantly reduce the amount to be deposited or the volume of sludge that is to be dumped in comparison with conventional treatment processes due to the recovery of water or process water and the recovery of valuable substances.

A device according to the invention for the treatment of water, in particular of wastewater in mines for recovering valuable material, in particular in metal extraction mines, can thus comprise at least one filtration device, at least one valuable matter recovery device with at least one selective ion exchanger, wherein the at least one filtration device can be configured for carrying out a one-stage or multi-stage filtration of the wastewater for the recovery of process water, and further configured for the forwarding of an active-substance-containing concentrate to a valuable substance recovery device.

Said resource recovery device may be configured to perform at least one resource recovery by at least one recycling of material from said valuable concentrate by means of the at least one selective ion exchanger.

The following figure is an example:

1 : Exemplary scheme for a process for the treatment of mine wastewater

2 : Another exemplary scheme for a process for the treatment of mine wastewater

3 : Exemplary exchange of ions of different valences

The 1 exemplifies a method 100 for the treatment of water, in particular of waste water 101 in mines for recovering valuable material, for example for metal extraction.

In this case, the wastewater to be treated 101 from the mine for the recovery of valuable material, for example, first a one- or multi-stage filtration 102 be subjected, wherein a obtained valuable concentrate 107 to a recycling of recyclables 109 is forwarded. That, in the filtration 102 of the sewage 101 obtained filtrate 108 can as process water 106 be recovered and the process 100 or other process steps (not shown) within the mine for recovering valuable material.

In said filtration 102 It may be, for example, a microfiltration and / or a nanofiltration, which can be carried out for example by means of membrane filtration process / can.

While, for example due to ion-specific retention capacity of the filtration used 102 Be separated ions of different valences, and, for example, polyvalent ions (eg recyclable materials such as Cu ²⁺ , Mn ²⁺ , Fe ³⁺ ) in the valuable concentrate 107 can collect monovalent (eg, Na ⁺ ) ions in the filtrate 108 remain for process water recovery.

The recycling of recyclables 109 can be a recyclable material separation 103 from said valuable concentrate 107 which can be carried out, for example, by means of at least one selective ion exchanger.

A possibly used or used selective ion exchanger can / can be embodied as a DC or countercurrent ion exchanger, preferably as a countercurrent ion exchanger, and, for example, as an ion exchange material, an exchange resin, in particular with functional groups from IDA (iminodiacetic acid).

In said recyclable waste separation 103 can thus valuable portions of the valuable concentrate 107 be exchanged for ions of the ion exchange material and so the valuable material (s) of the valuable concentrate 107 be separated. The recovered material 104 can be obtained for example in dissolved form.

After said recyclable material separation 103 or material recovery 109 remaining residues 110 of the sewage 101 For example, they may be neutralized, immobilized and disposed of 105 become.

The exemplary method 100 can of course be repeated several times in succession or / and by further features, as in the general part and / or as in the following example in 2 described, supplemented and / or completed.

The 2 exemplifies another method 200 for the treatment of water, in particular of waste water 201 in mines for recovering valuable material, in particular for metal extraction.

In this case, for example, the wastewater to be treated 201 a first filtration 202 , For example, a microfiltration by membrane filtration process subjected. A possible in said first filtration 202 obtained or retained Erstfiltrierungs residue 232 may optionally be neutralized, immobilized and disposed of.

Said first filtration residue 232 possibly also a precipitation / flocculation 208 supplied 233 before dumping, for example, along with final waste sludge 211 can be

The case of sedimentation 209 By the way, supernatant water can again be used as process water 210 the mine or the treatment process 200 is available.

The filtrate 217 from a first filtration 202 can then do a second filtration 203 or further filtrations. This may be, for example, a nanofiltration, which may also be carried out by means of a membrane filtration process.

For example, due to an ion-specific retention capacity of the nanofiltration used ions of different valences can be separated, and there may be, for example, polyvalent ions (eg valence ions such as Cu ²⁺ , Mn ²⁺ , Fe ³⁺ ) in the valuable concentrate 225 collect while monovalent (eg, Na ⁺ ) ions in the filtrate 218 can remain for process water recovery.

So while one in the second filtration 203 Contained valuable concentrate 225 a resource recovery 234 can be fed, the resulting filtrate 218 as process water 204 the mine or the treatment process 200 to disposal 226 to be asked.

The recycling of recyclables 234 can the recovery of a valuable substance in dissolved form 223 from the valuable concentrate 225 eg by selective ion exchange 205 include.

A selective ion exchange 205 can be carried out in a selective ion exchanger, for example a selective cation exchanger, wherein valuable substance ions of the valuable concentrate 225 can be exchanged for ions of the ion exchange material.

In this case, so from the valuable concentrate 225 to be recovered valuable material ions are more strongly bound to the selective ion exchanger than the ions of the ion exchange material, and the valuable material ions on loading or operation of the ion exchanger displace the ions of the ion exchange material.

The selective ion exchange 205 is a reversible chemical process, ie, there is a chemical equilibrium between a forward reaction, eg an exchange of valuable ions for ions of the ion exchange material, and a back reaction, for example a displacement of bound in the ion exchange material valencies, before, however, the forward reaction upon inception of the selective ion exchanger can outweigh.

The removal of valuable ions bound to the ion exchange material can be carried out with the addition of one or more treatment chemicals 231 take place, the treatment chemicals 231 also for pH adjustment and / or for Regeneration of the selective ion exchanger can serve.

As a treatment chemical 231 For example, sulfuric acid can be used. However, other acidic treatment chemicals such as hydrochloric acid, phosphoric acid or nitric acid are also conceivable.

The recyclable material can thus be recycled 219 be dissolved or dissolved and so from the valuable concentrate 225 separated and concentrated.

The dissolved concentrated material 213 , For example, dissolved copper sulfate or iron or manganese sulfate, can be forwarded to a further process step (not shown), such as an electrolysis process, where, for example, the valuable material, such as copper, iron or manganese, can be obtained in solid form.

The selective ion exchangers may be in the form of a DC or countercurrent ion exchanger, preferably as a countercurrent ion exchanger, and, for example, as an ion exchange material, a replacement resin, in particular polyelectrolytes, such as e.g. Polystyrene resin or polyacrylate resin, in particular having functional groups, e.g. IDA (iminodiacetic acid).

The selectivity of ion exchange 205 for certain recyclables or recyclable materials can be done in particular by adjusting the pH and choice of ion exchange material.

For example, different ion exchange materials can have different ion exchange material molecule sizes and / or different ion affinities, and thus the selectivity of the ion exchanger can be controlled or optimized with regard to the valuable substance ions to be exchanged, for example as a function of the valuable ion radius and / or valuable ion value.

As mentioned, the selectivity of the ion exchanger can be optimized by adjusting the pH and, for example, the optimum pH range for copper recovery is 2 +/- 0.5.

Said pH adjustment can be assisted 226 of a filtration 203 recovered process water 204 carried out, which can be used, for example, for dilution purposes, for example for the dilution of treatment chemicals.

From the valuable concentrate 225 , eg obtained from a previous filtration 203 , For example, a nanofiltration, for example, when using sulfuric acid H ₂ SO ₄ as a treatment chemical of the valuable material in the form of a sulfate dissolved in the regenerate of the ion exchanger can be obtained.

Various in the concentrate 225 contained valuable substances or valuable substances can be obtained, for example, separately, for example in the context of several, eg nfach, successive recycling processes 234 . 235 , each using ion exchange processes 205 . 206 which can be selective for a given specific recyclable.

Thus, several selective ion exchangers with different parameters, in particular with respect to different pH ranges and / or different ion exchange materials, can be connected in series to the various valuable substances, in particular copper and / or manganese and / or nickel and / or iron from the valuable material To gain concentrate.

In 2 are exemplary two selective ion exchange processes 205 . 206 as part of two recycling processes 234 . 235 shown. For example, in the (first) selective ion exchange process 205 the separation or recovery of copper ions (first concentrated recyclable material 213 ) from the concentrate 225 about the regenerate 219 of the first selective ion exchanger 205 respectively.

The following can analogously in a second (or n-th) ion exchange process 206 the separation or extraction of nickel or manganese ions (n-th concentrated recyclable material 215 ) about the regenerate 220 of the second (or nth) selective ion exchanger 206 respectively.

The number and type of possible selective ion exchange processes 205 . 206 may be, for example, the type of chemical composition of the wastewater to be treated 201 judge.

The ones for operation and regeneration 219 . 220 The treatment chemical (s) used in the selective ion exchanger ( 231 ) can / can from the filtrate 223 . 224 a selective ion exchange process 205 . 206 , or after passing through several possible selective ion exchange processes 205 . 206 by a suitable filtration 207 be recovered in part.

Said filtration 207 may be nanofiltration using membrane filtration techniques and the recovered treatment chemical (s) 212 may, for example, belong to the reservoir or the source of the treatment chemical (s) 231 supplied 229 be, and can / can eg so back to use 230 in a selective ion exchange process 205 . 206 come.

After recycling (s) or after passage of one or more, z. B. n, selective ion exchange processes 205 . 206 and / or concentrate remaining after regeneration chemical recovery 221 can be precipitated in a conventional manner 208 or flocculated, for example with metal hydroxides such as calcium hydroxide and addition of calcium chloride.

The one after a sediment formation 209 Any remaining sludge may be neutralized, immobilized and disposed of 211 and after the sedimentation supernatant water the treatment process again as process water 210 to provide.

The 3 exemplifies an ion exchange reaction 300 in a selective ion exchanger 310 , wherein in the forward reaction shown monovalent ions 305 . 306 the ion exchange material of the ion exchanger 310 against polyvalent, for example, as shown bivalent, valuables 307 of the wastewater to be treated can be exchanged. The first to the selective ion exchanger 310 bound ions 305 . 306 are from the recoverable recyclables 307 displaced and released 309 ,

The recoverable recyclables 307 can therefore from the selective ion exchanger 310 bound 308 be released and then (not shown) in the regeneration again, so as to regenerate the ion exchanger 310 to be concentrated and to be regained.

Said ion exchange can, for example, by means of a functional group 303 , For example, as shown iminodiacetic acid (IDA), carried out, for example, on the polymer backbone 301 the replacement resin of the ion exchanger 310 can be anchored.

This is followed by three figures on three leaves.

Dashed lines show additional options (n + 1) for the basic version (s).

The reference numerals are assigned as follows.

LIST OF REFERENCE NUMBERS

100

Process for the treatment of water, in particular of wastewater in mines for the recovery of valuable material, in particular mines for metal extraction

101

sewage

102

Filtration / filtration device (single or multi-stage)

103

Recyclable material / material separation device, for example by means of selective ion exchange / selective ion exchanger

104

recycled material

105

landfill

106

Recycled water / recovered process water

107

concentrate

108

filtrate

109

Material Recovery / valuable material recovery device

110

Residue

200

Process for the treatment of water, in particular of wastewater in mines for the recovery of valuable material, in particular mines for metal extraction

201

sewage

202

Filtration / filtration apparatus

203

Filtration / filtration apparatus

204

Recycled water / recovered process water

205

Selective ion exchange / Selective ion exchanger

206

Selective ion exchange / selective ion exchanger (n-fold)

207

Filtration / filtration apparatus

208

Precipitation and / or flocculation

209

sedimentation

210

Recycled water / recovered process water

211

landfill

212

Recovered treatment chemical (s)

213

Concentrated valuable material

215

Concentrated valuable material

217

filtrate

218

filtrate

219

regenerated

220

regenerated

221

concentrate

222

filtrate

223

filtrate

224

filtrate

225

Concentrate, valuable concentrate

226

Supply of process water

229

 Return of recovered chemical (s)

230

 Supply of treatment chemical (s)

231

 Treatment chemical (s)

232

 First filtration residue, residue from first filtration, e.g. microfiltration

233

 Optional forwarding of the residue for precipitation / flocculation

234

 (First) recycling / recycling system

235

 (nth) recycling / recycling system

300

 Ion exchange reaction

301

 Polymer scaffold of exchange resin of ion exchanger

303

 Functional group

305

 Monovalent ion of the ion exchange material of the ion exchanger

306

 Monovalent ion of the ion exchange material of the ion exchanger

307

 Recovered multivalent, e.g. divalent, valuable substance

308

 Multi-valued, e.g. divalent, valency, bound to selective ion exchanger

309

(Released) monovalent ions ( 305 and 306 ) of the ion exchange material of the ion exchanger

310

 Selective ion exchanger

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 2013370 B1 [0002]

Claims (12)

Procedure ( 100 . 200 ) for the treatment of water, in particular wastewater ( 101 . 201 ) in recovering mines, in particular in metal mining mines, comprising: single or multi-stage filtration ( 102 . 202 . 203 ) of the wastewater for the recovery of process water ( 106 . 204 ), whereby obtained wertstoffhaltiges concentrate ( 107 . 225 ) for at least one resource recovery ( 234 . 235 ) is forwarded; A recycling of recyclables ( 109 . 234 . 235 ) comprising a recyclable material separation ( 103 ) from said valuable concentrate ( 107 . 225 ) by means of at least one selective ion exchanger ( 205 . 206 ). Process according to claim 1, wherein the filtration ( 202 . 203 ) of wastewater ( 101 . 201 ) for the recovery of process water ( 106 . 204 ) by membrane filtration and comprises at least two filtration stages, wherein the first filtration stage ( 202 ) is a microfiltration, and the second filtration stage ( 203 ) is a nanofiltration, in which the valuable concentrate is recovered.  The process of claim 2 wherein the yield of microfiltration is at least 95% and the yield of nanofiltration is at least 80%. Method according to one of the preceding claims, wherein the wastewater ( 201 ) recovered process water ( 204 ) at least one selective ion exchanger ( 205 . 206 ) is supplied. Method according to one of the preceding claims, wherein the material recovery ( 234 . 235 ) a valuable material separation with the addition of one or more treatment chemicals ( 231 ) and wherein the valuable substances in the regenerate ( 219 . 220 ) of the selective ion exchanger ( 205 . 206 ) are solved. Process according to claim 5, wherein the treatment chemical (s) (s) ( 231 ) for the pH adjustment and / or for the regeneration of a selective ion exchanger ( 205 . 206 ) be used. Process according to claim 5 or 6, wherein a treatment chemical ( 231 ) Sulfuric acid or hydrochloric acid, or phosphoric acid, or nitric acid. Process according to claim 6 or 7, wherein the filtrate ( 223 . 224 ) of a selective ion exchanger ( 205 . 206 ) is subjected to membrane filtration for the at least partial recovery of the added treatment chemical (s) ( 231 ), wherein the membrane filtration is a nanofiltration and the recovered treatment chemical (s) ( 212 ) again the selective ion exchanger ( 205 . 206 ) is / are returned. Method according to one of the preceding claims, wherein the ion exchange material of the selective ion exchanger ( 205 . 206 ) is an exchange resin.  Method according to one of the preceding claims, wherein the recovered valuable materials are metals, in particular copper and / or manganese and / or iron. Method according to one of the preceding claims, wherein after recycling of material ( 234 . 235 ) and / or treatment chemical recovery remaining concentrate ( 221 ) precipitated ( 208 ) or flocculated, and after sedimentation ( 209 ) remaining sludge deposited ( 211 ) and the water which has survived after sedimentation is returned to the treatment process as process water ( 210 ) can be provided. Apparatus for the treatment of water, in particular of waste water in mines for recovering valuable material, in particular in metal extraction mines, comprising at least one filtration device, comprising at least one valuable matter recovery device with at least one selective ion exchanger, characterized in that the at least one filtration device is configured to perform a single or multi-stage filtration of the effluent for recovering process water, and further configured to forward an effluent concentrate to a resource recovery device; and the the valuable substance recovery device is configured to carry out at least one valuable substance recovery by at least one valuable substance separation from said valuable substance concentrate by means of the at least one selective ion exchanger.

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