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WO2000050341A1 - Procede de concentration d'acide faisant suite a une regeneration oxydante biologique d'acide sulfurique a partir de sulfures - Google Patents

Procede de concentration d'acide faisant suite a une regeneration oxydante biologique d'acide sulfurique a partir de sulfures Download PDF

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Publication number
WO2000050341A1
WO2000050341A1 PCT/US2000/004632 US0004632W WO0050341A1 WO 2000050341 A1 WO2000050341 A1 WO 2000050341A1 US 0004632 W US0004632 W US 0004632W WO 0050341 A1 WO0050341 A1 WO 0050341A1
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WIPO (PCT)
Prior art keywords
sulfuric acid
acid
permeate
solution
concentration
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PCT/US2000/004632
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English (en)
Inventor
Dennis H. Green
Jeff Meuller
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HW Process Technologies Inc
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HW Process Technologies Inc
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Filing date
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Application filed by HW Process Technologies Inc filed Critical HW Process Technologies Inc
Priority to AU32417/00A priority Critical patent/AU3241700A/en
Publication of WO2000050341A1 publication Critical patent/WO2000050341A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/74—Preparation
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide

Definitions

  • the process of the present invention is directed generally to sulfuric acid production processes and specifically to a sulfuric acid production process recovering the acid using filtration techniques.
  • SX-EW sulfuric acid consumptive heap leach-solvent extraction-electrowin
  • the acid produced by biohydrometallurgical processing is often unfit for use by mines.
  • the acid is typically metals loaded, i.e., contaminated with dissolved and dissociated zinc, iron, copper, and arsenic, among other things, in accordance with the metals content of the feedstock and nutrient and additives used to promote the bio- oxidation of the feedstock.
  • These metals in combination with the increased acidity accruing to the progression of the biohydrometallurgical process will accumulate over time and reuse unit they constitute a fouled, or toxic (for the bacteria), solution that cannot be reused in the source bioprocess.
  • metallurgical processes must discard the fouled sulfuric acid solutions and use fresh sulfuric acid purchased from a supplier at high cost.
  • the fresh sulfuric acid represents a significant operating cost for mines, particularly for mines in remote locations.
  • the process of the present invention manufactures sulfuric acid through bio- oxidation techniques.
  • the process uses one or more filtration processes to remove dissolved impurities, such as dissolved and dissociated metals, chlorides, nitrates, and the like, from the raw sulfuric acid-containing product of the process.
  • the process includes the steps of:
  • the impurities can be multivalent, dissociated ions, such as copper, iron, zinc, nickel, manganese, and other metals from Group IIA of the Periodic Table of the Elements.
  • the pore size and electric charge of the filter is selected to retain at least most of the multivalent metals in the retentate and pass at least most (typically at least about 65%) of the monovalent compounds, such as sulfuric acid.
  • the impurities can also be both multivalent and monovalent.
  • Examples of monovalent impurities include nitrates, and chlorides, which are typically compounded with monovalent metals from Groups I A and IIA of the Periodic Table of the Elements.
  • the filter is selected to pass at least most (typically at least about 65%) of the monovalent impurities while retaining at least most (typically at least about 65%) of the sulfuric acid.
  • the process can include additional filtration steps.
  • the permeate can be filtered to produce a second retentate and second permeate.
  • at least most of any remaining metals and at least most of the sulfuric acid in the permeate are contained in the second retentate.
  • the sulfuric acid concentration in the second retentate is more than the sulfuric acid concentration in the second permeate.
  • the second permeate can be recycled to step (a) for use in producing more sulfuric acid.
  • the process promotes rapid bio-oxidation rates by maintaining the acid concentration in the second permeate at low levels through the removal of excess acid in the second filtering step, thereby promoting bacterial production of more sulfuric acid.
  • the process also permits sulfuric acid produced on site in biohydrometallurgical mining processes to be reused in bio-oxidation at a considerable cost savings to the mine operator and/or sold at a substantial profit as a byproduct.
  • the bio-oxidation reaction in step (a) can be performed in a suitable reactor or in a heap or pile of the sulfide-containing material.
  • suitable reactors are trickle bed reactors, continuous stirred or air sparged, agitated reactors, and open air piles.
  • Most of the acid in the acid-containing solution preferably reports to the permeate and later to the second retentate.
  • the acid-containing solution typically has an acid content ranging from about 5 to about 50 g/1.
  • the acid concentration in the retentate is typically the same as the acid concentration in the permeate because the acid readily passes through the first filter. Because the permeate represents a larger volume than the retentate, the permeate typically contains more of the acid in the solution than the retentate.
  • the second retentate preferably includes at least about 50 and more preferably from about 75 to about 97% of the acid in the acid-containing solution while the second permeate preferably has no more than about 50% and more preferably from about 10 to about 15% of the acid in the acid-containing solution.
  • the second retentate typically has an acid concentration of at least about 100 g/1 acid.
  • the second permeate typically has an acid concentration of no more than about 5 g/1 acid and more typically ranging from about 0.1 to about 2 g/1 acid.
  • the first filter preferably has a larger pore size than the second filter such that the sulfuric acid (but not multivalent metal impurities) passes through the first filter. The sulfuric acid and any remaining impurities are retained by the second filter.
  • the first and second filters are preferably a nanofilter membrane, a reverse osmosis membrane, and combinations thereof.
  • the first filter preferably has a pore size ranging from about 20 to about 100 angstroms.
  • the second filter preferably has a pore size ranging from about 1 to about 20 angstroms.
  • the permeate preferably constitutes at least most of the volume of the acid-containing solution.
  • the permeate preferably constitutes at least about
  • the retentate preferably constitutes from about 20 to about 10% by volume of the solution.
  • the second permeate preferably also constitutes at least most of the volume of the acid-containing solution.
  • the second permeate preferably constitutes at least about 50 and more preferably from about 80 to about 90% by volume of the acid-containing solution while the second retentate preferably constitutes from about 20 to about 40% by volume of the solution.
  • the process can include additional steps to remove dissolved multivalent metal impurities such as arsenic, copper, iron, nickel, calcium, magnesium, manganese and other di- and tri- valent metal ions, or metal ion complexes from the first and/or second retentate.
  • the metal can be recovered by precipitation, electrolysis, ion exchange resins, cementation, and solvent extraction.
  • Figure 1 is a flow schematic depicting a first embodiment of the process; and Figure 2 is a flow schematic depicting a second embodiment of the process.
  • a first embodiment of a process according to the present invention is directed to the bio-oxidation of a sulfide-containing material to form sulfuric acid, and more particularly to enhanced production of sulfuric acid using an acid-resistant, nanofiltration membrane to remove multivalent impurities and an acid-resistant, reverse osmosis membrane process to concentrate sulfuric acid for sale in a second retentate, while permeating a lean acid solution for return to the bacterial sulfuric acid production step.
  • the acid rich or concentrated acid product is a dilute (10-50 g H 2 SO 4 /L) sulfuric acid produced by bio-oxidation of the sulfur component of the sulfidic material. This process improves the value of the product from the bacterial sulfuric acid production step, and may enhance the production process by continually removing a portion of the sulfuric acid, thus accelerating or assisting the further bacterial production of sulfuric acid.
  • a sulfide-containing material or sulfide-coated substrate 10 are placed in a vat or column reactor 14 (or pile), inoculated with bacteria and bacteria nutrients 18.
  • the bacteria can be any suitable bacteria, such as Thiobacillus bacteria (e.g. , ThiobacillusFerroxidants, Thiobacillus Thiooxidan, etc.), LeptospirillumFerrooxidans, SulfobacillusThermosulfidooxidans, Sulfolobusbacte ⁇ a, and/ 'or Acidianus.
  • the nutrients are typically ammonium sulfate (e.g., from about 0.1 to about 0.5 gpl), phosphate (e.g., about 40 ppm), and iron (e.g., from about 0.4 to about 30 gpl of Fe +3 ), carbon and oxygen.
  • the material 10 is sprayed with or immersed and/or stirred in dilute (e.g., about 1-2 g H 2 SO 4 /L) acid 26 and sparged with air. After a period of time, the sulfuric acid concentration of the solution grows to the range of about 20-40 g H 2 SO 4 /L due to the bio- oxidation process.
  • This product solution 30 is then passed through acid-resistant membrane systems 32 and 34 to produce an acid concentrate stream 38, i.e.
  • membrane concentrate of about 50-120 g H 2 SO 4 /L, and an acid lean stream 42, i.e. membrane permeate, of about 0.5-1 g H 2 SO 4 /L.
  • the membrane concentrate 38 is collected in a tank for sale as product; the membrane permeate 42 is returned to the reactor or pile for further bio-oxidation acid production.
  • the membrane process provides a way to upgrade the dilute acid to provide a superior saleable acid product.
  • the membrane systems 32 and 34 can each be configured as a single membrane or multiple membranes. The multiple membranes can treat the feed stream serially and/or in parallel.
  • Bio-oxidation of sulfides for production of sulfuric acid is accomplished by using a suitable bacteria. Air, oxygen and trace nutrients can continually or intermittently be added to the recycled solution to speed the kinetics of this bio-oxidation process.
  • the commercial process would involve placing a sulfide-containing material or sulfide coated substrates, in a vat, column, tank, or freestanding pile or heap. The sulfide is then inoculated with bacteria, nutrients, and air, and sprayed with or immersed in dilute (1 -2 g H2SO4/L) acid.
  • the solution is recirculated and oxygen or air may be blown, diffused or bubbled into the solution, and, after a period of time (typically 1-4 weeks), sulfuric acid concentration of the solution grows to the range of about 20-40 g H 2 SO 4 /L.
  • the sulfur component of the sulfide-containing material is slowly consumed during the acid generation process.
  • a heat exchanger 50 may be needed to remove this heat.
  • a typical shell and tube heat exchanger would be sufficient with heat being transferred from the regulating acid situation to process water or make-up water.
  • the bio-oxidation rate of acid production is affected by the concentration of acid in the column, tank, or heap, and the air or oxygen availability, nutrient availability, temperature, and contaminant metal concentrations (if any). These variables may conspire to optimize bio-oxidation production of sulfuric acid at a sulfuric acid concentration of about 20-40 g H2SO4/L. This acid concentration, approximately 2-4%, is fairly dilute, and thus limits the uses for this inexpensively produced acid product. For example, dilute acid such as this may add substantial water to the process, which often creates water balance problems. Also, many processes, such as electrowinning tankhouses, require more concentrated acid addition, in the 100-200 g H 2 SO 4 /L (10-20 wt% range).
  • Sulfuric acid is priced according to grade, with "technical grade” containing certain impurities and selling for less than "food grade", which contains less impurities.
  • certain impurities such as arsenic, may be toxic or inhibitory to the sulfiiric acid producing bacteria, and slow or stop the bio-oxidation process, resulting in a corresponding drop in rate of acid production.
  • the process of the present invention improves the bio-oxidation process by using the membrane system 34 to remove and concentrate acid, while maintaining the rate of biooxidation at its peak.
  • This provides a wider ranging market and more saleable sulfuric acid product. Accordingly, the invention represents an advance in the art of bio-oxidation of sulfides to sulfuric acid, as described in detail herein.
  • the process improvements claimed in the present invention will result from utilizing an acid-resistant reverse osmosis membrane system 34 and acid-resistant nanofiltration membrane system 50 to purify and concentrate the dilute sulfiiric acid product from bio-oxidation of sulfides.
  • an acid-resistant reverse osmosis membrane system 34 and acid-resistant nanofiltration membrane system 50 to purify and concentrate the dilute sulfiiric acid product from bio-oxidation of sulfides.
  • the use of a membrane process to remove and concentrate acid allows the bio-oxidation reactor to be run at maximum rate of acid production.
  • the dilute sulfuric acid product is passed through the reverse osmosis membrane system 34, after first passing through a nanofiltration membrane system 32 (to remove dissolved and dissociated multivalent metal impurities).
  • the dilute acid solution is first sent to the acid-resistant nanofiltration membrane 50 which separates the solution into two streams-permeate 54 and concentrate 58.
  • the osmotic pressure preferably ranges from about 150 to about 1,000 psi.
  • the permeate 54 is greatly reduced in multivalent impurity concentration, containing a minority of the impurities. Acid concentration is approximately the same in the permeate and the concentrate, only divalent and trivalent ion impurities such as iron and copper are rejected and concentrated in the membrane concentrate.
  • the impurity clean permeate 54 is sent to the reverse osmosis membrane 34 for concentration.
  • the reverse osmosis membrane separates the acid into two streams: permeate 42 and concentrate or retentate 38.
  • the osmotic pressure preferably ranges from about 150 to about 1,000 psi.
  • the permeate 42 is greatly reduced in acid concentration, and is returned to the bio-oxidation reactor.
  • the concentrate 38 is greatly increased in acid concentration, and it is collected for sale.
  • the concentrate 58 is greatly increased in impurity concentration, containing a majority of the impurities.
  • the concentrate 58 may be removed from the sulfuric acid processing system and the metals recovered and/or disposed of through neutralization and precipitation.
  • the reverse osmosis membrane system 34 of the first embodiment would process 10 -10,000 gallons per minute of dilute sulfuric acid solution, with 65-95% of the feed flow becoming permeate product.
  • Typical reverse osmosis membranes used would be S or A series elements from Osmonics/Desalination Systems of Nista, CA. For example, SC, SE, SG, AD, AG, AK membrane elements are appropriate.
  • a typical system would process 1000 gpm of 20 g H 2 SO 4 /L sulfiiric acid solution through 600 each 8 inch diameter, 40 inches long spiral wound SE membrane elements, at 600-800 psi and 30-40 deg C.
  • the system would split the feed flow into 800 gpm of permeate containing about 0.5 g H 2 SO 4 L, and 200 gpm of concentrate containing about 98 g H 2 SO 4 /L.
  • the concentrate would be collected and sold as a high grade sulfuric acid product.
  • the permeate would be returned to the bio-oxidation reactor 14.
  • the nanofiltration membrane system 32 of the first embodiment would process 10- 10,000 gallons per minute of dilute sulfiiric acid solution, with 50-95% of the feed flow becoming permeate product.
  • the typical nanofiltration membrane used would be D or G series elements from Osmonics/Desalination Systems of Vista, CA. For example, DK, DL, GE, GH membrane elements are appropriate.
  • Atypical system would process 1000 gpm of 20 g H 2 SO 4 /L sulfuric acid solution, containing 1 g iron/L, through 500 each 8 inch diameter, 40 inches long spiral wound DK membrane elements, at 200-400 psi and 30-40 deg C.
  • the system would split the feed flow into 800 gpm of permeate containing about 20 g H 2 SO 4 /L and 0.01 g iron L, and 200 gpm of concentrate containing about 20 g H 2 SO 4 /L and 5 g iron L.
  • the concentrate 58 would be sent to a precipitation system or ion exchange system for iron removal.
  • the permeate 54 would be sent to the reverse osmosis membrane system for acid concentration.
  • Figure 2 A second embodiment of the present invention is depicted in Figure 2. Referring to Figure 2, a sulfide-containing material or a sulfide coated substrate 10 is placed in a reactor or pile 14, innoculated with bacteria and bacteria nutrients 18, sparged with air 22, and sprayed with or immersed in dilute sulfuric acid 26.
  • a product solution 30 is withdrawn and passed through a first membrane filter system 32 to form a first retentate 58 containing at least most of the multivalent impurities and a first permeate 54 containing at least most of the sulfuric acid and selected monovalent impurities, typically nitrates and chlorides.
  • the first permeate 54 is passed through a second membrane filter system 100 to form a second permeate 108 containing at least most (typically at least about 65%) of the nitrates and chlorides in the first permeate 54 and a second retentate 104 containing at least most (typically at least about 65%) of the sulfuric acid in the first permeate 54.
  • the second permeate 108 can be discarded.
  • a portion 102 of the second retentate 104 can be combined with the make-up water 112 and recycled to the reactor or pile 14.
  • the remaining portion 110 of the second retentate 104 can be further concentrated, if necessary, by a reverse osmosis filter system 118 for sale as a product 122.
  • the permeate 124 of the reverse osmosis process 118 can be combined with make-up water 112 for reuse.
  • the preferred membrane in the second filter system 100 is a G series ultrafilter manufactured by Osmonics. Chlorides and nitrates are preferentially passed through this membrane relative to sulfuric acid and the chloride to sulfuric acid and nitrate to sulfuric acid ratios of the second retentate of the G series ultrafilter are reduced.
  • the molar ratios of nitrate to acid and of chloride to acid typically are reduced from a range of from about 0.25:1 to about 5:1 to a range (in the second retentate) of from about 0.01: 1 to

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Abstract

Le procédé de la présente invention concerne un procédé (14) d'oxydation biologique de sulfures dans lequel de l'acide sulfurique est récupéré par filtration dans une solution d'oxydation biologique (30). La solution d'oxydation biologique est un métal de base débarrassé de ses impuretés au moyen d'un filtre (32) à membrane et l'acide est récupéré de préférence à l'aide d'un filtre (34) à membrane. La solution (42) à faible teneur en acide est recyclée et renvoyée au réacteur (14) d'oxydation biologique pour fabriquer à nouveau de l'acide sulfurique.
PCT/US2000/004632 1999-02-23 2000-02-23 Procede de concentration d'acide faisant suite a une regeneration oxydante biologique d'acide sulfurique a partir de sulfures Ceased WO2000050341A1 (fr)

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AU32417/00A AU3241700A (en) 1999-02-23 2000-02-23 Method of acid concentration following biological oxidative generation of sulfuric acid from sulfides

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US12126799P 1999-02-23 1999-02-23
US60/121,267 1999-02-23

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
WO2004013338A1 (fr) * 2002-08-01 2004-02-12 Phelps Dodge Corporation Procede d'oxydation biologique de materiaux elementaires de soufre en vue d'une production d'acide sulfurique
WO2004013337A1 (fr) * 2002-08-01 2004-02-12 Phelps Dodge Corporation Appareil de traitement de matieres de support de soufre elementaire destine a la production d'acide sulfurique
CN100395187C (zh) * 2006-10-12 2008-06-18 同济大学 一种ⅱb硫化物纳米材料的制备方法
WO2010082194A2 (fr) 2009-01-13 2010-07-22 B.P.T. Bio Pure Technology Ltd. Membranes stables aux solvants et aux acides, leurs procédés de fabrication et leurs procédés d'utilisation entre autres pour séparer des ions métalliques de courants de traitement liquides
EP2350400A1 (fr) * 2008-09-10 2011-08-03 European Space Agency Installation pour le traitement de l eau contenant de l urée, toilettes, étable et procédé
CN103318850A (zh) * 2013-07-17 2013-09-25 上海奥格利环保工程有限公司 用于硫铁矿和冶炼烟气制酸装置中的低温余热回收系统
CN106521162A (zh) * 2016-10-31 2017-03-22 长春黄金研究院 从酸性含砷、铁、硫生物氧化液中回收有价元素的方法
CN109818099A (zh) * 2019-01-31 2019-05-28 襄阳金湛技术开发有限公司 一种废旧硫酸回收再生系统及方法
CN115298136A (zh) * 2020-03-16 2022-11-04 杜邦安全与建筑公司 硫酸的浓缩

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004013337A1 (fr) * 2002-08-01 2004-02-12 Phelps Dodge Corporation Appareil de traitement de matieres de support de soufre elementaire destine a la production d'acide sulfurique
WO2004013338A1 (fr) * 2002-08-01 2004-02-12 Phelps Dodge Corporation Procede d'oxydation biologique de materiaux elementaires de soufre en vue d'une production d'acide sulfurique
CN100395187C (zh) * 2006-10-12 2008-06-18 同济大学 一种ⅱb硫化物纳米材料的制备方法
EP2350400A1 (fr) * 2008-09-10 2011-08-03 European Space Agency Installation pour le traitement de l eau contenant de l urée, toilettes, étable et procédé
US9205383B2 (en) 2009-01-13 2015-12-08 Ams Technologies Int. (2012) Ltd Solvent and acid stable membranes, methods of manufacture thereof and methods of use thereof inter alia for separating metal ions from liquid process streams
WO2010082194A2 (fr) 2009-01-13 2010-07-22 B.P.T. Bio Pure Technology Ltd. Membranes stables aux solvants et aux acides, leurs procédés de fabrication et leurs procédés d'utilisation entre autres pour séparer des ions métalliques de courants de traitement liquides
US9943811B2 (en) 2009-01-13 2018-04-17 Ams Technologies In. (2012) Ltd Solvent and acid stable membranes, methods of manufacture thereof and methods of use thereof inter alia for separating metal ions from liquid process streams
CN103318850A (zh) * 2013-07-17 2013-09-25 上海奥格利环保工程有限公司 用于硫铁矿和冶炼烟气制酸装置中的低温余热回收系统
CN106521162A (zh) * 2016-10-31 2017-03-22 长春黄金研究院 从酸性含砷、铁、硫生物氧化液中回收有价元素的方法
CN109818099A (zh) * 2019-01-31 2019-05-28 襄阳金湛技术开发有限公司 一种废旧硫酸回收再生系统及方法
CN109818099B (zh) * 2019-01-31 2019-12-17 襄阳金湛技术开发有限公司 一种废旧硫酸回收再生系统及方法
CN115298136A (zh) * 2020-03-16 2022-11-04 杜邦安全与建筑公司 硫酸的浓缩
CN115298136B (zh) * 2020-03-16 2024-07-19 杜邦安全与建筑公司 硫酸的浓缩

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