CA1200778A - Recovery of organic and heavy metal components from aqueous dispersions - Google Patents

Abstract

TITLE
RECOVERY OF ORGANIC AND HEAVY METAL
COMPONENTS FROM AQUEOUS DISPERSIONS

INVENTORS
Abdul Majid A. Frederick Sirianni John A. Ripmeester ABSTRACT OF THE DISCLOSURE

Dispersed organic and, in many cases, heavy metal components are recovered from aqueous tailings or effluents by steps comprising, (a) adding a hydrophobic collecting agent to the aqueous effluent or tailings, (b) providing that the solids content of the resulting aqueous mixture is within from about 10 to about 75% by wt., and selected to allow fluid agitation, (c) agitating the resulting mixture until the collecting agent, organic components and hydrophobic heavy metal components become agglomerated into discrete solid masses, (d) separating these masses from the aqueous medium, (e) washing the masses with a selected organic solvent to extract organic material, and (f) recovering organic material from the loaded solvent.
Preferably, at least in the case of tar sands processing effluents, heavy metal minerals are recovered from the washed masses and the minerals treated to recover e.g., Ti and Zr.

Description

~1)7~

This invellt-ioll is directed to tln;~ recovery o~ dispers~d orS~ ir components and any llydrophobtc lleavy metal-cvntainirlg components from aqueous effluent~s or tailin~rs by contrt)lled a~,gLorneratton with a llydro~
phobic collector. The agglomerates are processed for tlle separate recovery of the organic comporlellts and, i[ presellt in economic amolJr hydroplloblc heavy metal compollents.
Backgroulld alld Prior Art Both from econornic alld environmental consideratiolls tllere exists a need to provide more e~fective alld sirnpler processes to recover small amounts of or~anics and, in some ~ases, hydrophobic heavy metal-containln~ components from aqueous ~astes. nne of the prime areas wllere waste streams are gencrated which contaln both organic components and heavy metal mineral components is in ~Iherta tar salld processJng.
The ilOt water process is in use in Alberta to treat tar sands for recovery of bitumen. The tar sallds ale slurrled with hot water alll3 steam, the pulp is agitated and Led to a separatioll vessel. Entrained air causes the bitumell to rtse to tlle top of tlle vessel as a Eroth. Tile separated froth i~q usually furtl-ler treated as by centrLLugc to rclDove addltional mineral solids. The aqueous ~hase contaills hydrophilic solt~is and free as well as emulsi~ied b~tumen~ ~lucll of the sand settles out from the aqueous phase hut very fine hy~lropht~ic sollds, such as clays, and entrained or emulsified ~itumen material are very difficult to remove frorm the aqueous tailings. Even prolo~l~ed settlin& in ponds will not completely separate the clays, etc., and tlle lost b-ltumen matertals from the aqueous phase. Total loss of orgallLcs in e~luents has bcen esti-mated at about 11--12~.
Many efforts have been ma~le to separate the suspended solids from the aqueous phase, and to re-use the tatltnKs water. UnLted States Patent 3,816,305, Schutte, descrLhes the addlt~on of acid to tatlings and 30 middlings water to accelerate clarification. U.S~ Patent 3,607,720, Paulson, utilizes hot ~lue Kases to treat pond watee from tar sands pro-cessing. U.S. I'atent 3,526,585, Camp, adds a ~olatile organlc fluid immiscible wlth water to the pond wn~er to ~orm all fllterlace layer lligl~er in clay content. U.S. Patent 3,487,003, Baillic et al, treats the pond water with a Flocr~ulAtLIlg aS~ellt, pll ch;lllge nl~ entriFIIglng.

- --Can.ldL.ln ~atent 982,966, i~el~ru;3ry 3, 1976, Maloney, descrLhr~q recycling tar sslllds IIOt water proces~s eE~Lnellt to contact fresh tar .sarlrls in a kn~ading ag~lomerattng ~one, and recovering t.lr agglomerates, s~ d and an effluent stream o~ reduced clay, s-i~t alld biturnen content. No amourlts o bltumell recovered from the c~luellt ;3re gtven.
Two of us have recently dtscovered ((:alla(lian Yatent 1,0~
October 28, 1980, A.~. .Sirlalllli arld J.~. Ripmr-~l?.ster) that improved rr-coverLes of waste bltumen rrom tar s~3nds prncess a(lueol.1s effluent carl hr.
achieved by incorporattng l1ydrol)hoblc carl70ll as scrubbing or nucl.eatLng agent togetller with ~1dded raw tar sands 11-l tlle e~fluent.
Canadian Patent 927,983, June 5, 1973, S. Penzes, deals with separating heavy metal material.s from tar .sands hot water process frr>th, treatLng solLds ~ith alkall metaI hydro~ide, thell subjecting to Elotatlon to concentrate heavy metal materials in the non-Floated residue.
CanadLall Patent 1,01~,696, July 12, 1977, ~.A. Baillie et al, describes adding a liquid hydrocarbon solvent to a tar sands mineral waste product stream to Form a so1vellt-mineral ~aste product mtxture and rerrloving the solvent to ~orm a mtlleral concelltrate.
Canadian Patent l,(:)76,504, AprLl 29, 1980, V.P. Kamirltlky et al, beneiciates tar sands hot water process froth treatment tallings by heatlng to 800-1400F to crack and volatLlize some of the bitumen, coking other of the bit-1men, burning to p~oduce cIeall particles and then COlI-centrating residual heavy metal minerals by wet gravlty concentrating Ineans .
It wouId be desirabLe to prov:~le an ecoll-)mlcAl e~EL~Iellt or tailings treatment which wou1(J give lltgl1 recoveries o~ orgar1ic materi.al.s and any heavy metal materials, in wh;.cll any add:it:lves9 solvents, etc., can be recycled or generated in sit11.
Su~mar~ of the Invention According to the present -lnvellt~oll there Ls provLded a process for recoverlng dispersed organtc compollellts arld any heavy metal compon-ents present, ~rom aqueous eff1uerlts or talltng.4 conLainlng same, com-prising:
(a) adding hydroyhohic collector. fiolidt. I1.1VI11g an ,3fE:LnlLy for sald coln-ponents, to the aqueo~s effl~lerlt or tall;rn.~s t<- rOrm an a(lueous ml~t~ e.

7~7l~3 (b) providlng that the soLids content ot tl1e aqueous mixture is wLtllin from about 10 to about 75% by wt., and ~elected to allow fluid agitation, (c) agitatlng the resultlrlg mlxture until the collector, organic compon-ents and any hydrop11obic l1e~vy metal cnm1-onerlt~ become agg10merated ~nto discrete solld rnasses, (d) separating these masses from the aqueou~ med1um, (e) contacting the masses wlth a selected organic solvent to extract organic material and leave a resldue, (f) recovering organic materlal from the loaded roLvent, and (g) recoverlng any heavy metal compor1ents present ~n econorrlic amounts from said residue.
Descriptiorl of Drawin~
The single drawing is a flowsheet of a preferred effluent treatment process where the eEfluel1t contains bnth organic material al1d heavy metal minerals.
Detailed Description and Preferred Embodiments The effluenta or tailings amenable to thls treatment are any aqueous systems containing dispersed organic material. In many cases, particularly where tl-e effluents derive from tar sands, oil shale or in situ oil recovery processes, heavy metal materials will be present which have hydrophobic surfaces. EfEluents from son1e sewage treatment or in-dustrial Ot food processing plants, or ~rom coal or peat processing also may be suitable for tl1is treatrnent.
The hydrophobic collector solids are selected to have an affinity for the dispersed organic material and pre~erably comprise solids generated in the process or in al11ed processes. In most cases, the collector solids wlll be chosen ~rom among ~olid bi~umen materials, hydrophobic residues ~rom sLeps (e) or (g), coal rr~terials, coke, reduced stlll bottoms, dried pea~, carbonaceous adsorbents and mixturefi t11ereoE.
The particle size of the collector solids is not critlcal: preEerably the size will be withln tlle approximate range -50 to -~100 mesh. At least part of the collector solids can be oE composite nature, e.g. they can have a non-hydrophobie eore or substrate ~rith a hydrophobic coati11g thereon. The amount of collector solid~s should be sufficient to provide surface collectton ~tes for the ~Itsper~f~(l organLc materia1 al1d tn ~2()~77~3 lnitiate csgglomeration into dLscrete solid masses. Normally thLs amoullt will be at least about 20% by wt. based on tlle weigllt of total orgfll~l(s, preferably srom 30 to 400% by wt.
The solids content of the aqueous sssi~ture after additton oE tlle collector should be ad~usted i~ necessary to be wLthin about 10 to ~bout 75% by wt. and selected to facilltate the flu;d s~itat~on, the contactlng and agglomeratlon.
The type asld extent of contact or agitation necessary to effect agglomeration can vary conslderably. The solid-liqutd contacting should continue until substantlally all oE Llle dispersed organic sssaterial has been brougllt into contact wlth the collector solids. The exa~ples below indicate some effectLve contact modes but others ~7111 be evident to those skilled in the art.
The agglomerated Issasses can be separated Erom the aqueous medium, for example, by screenlng, centrifugLng, decanting and cycloning.
Preferably, the masses are washed wlth water or aqueous medLum to remove hydrophilic mineral matter whlcll may remain. The aqueous medium remain-ing after step (d) usually i9 treated to remove waste solids and the water recycled.
The solvent used to extract the organics from the agglomerate masses is selected to have a good solvent actLon on t'he particu1ar orgarS-ic cQSmsp~nents present. When the organic c~m,s~onents are bitumen and the like, suitable ~sol~ent~cs lnclude aromatics such a~s benzene, toluene9 xylene and mixture~s thereof, allphatic ~solventcs such a~s C5-ClO hydrocar-bons, petroleum naphthas (particularly those derived from bLtumen upgrad-ing), chlorlnated hydrocarbon solvents, and any other liqs~sid hydrocarbon stream boiling in the range of about lO0 to 600F. The loaded solvens~
phase is separated frosn the residue by decantLng, screening, centrifug-ing, filterlng, etc., or combinationS thercof.
3~ Normally t'sle or~anic ssk~terla1 w-LIl be recovered Erom the loacled solvent, for example by varLous dist-LllatLoll techniques familiar to thocse slcilled in the art, and the solveslt recycled to btep (e). Solld portions of the recovered organic components advantageously are recycled as collector solids to step (a)~
In s~ny cases, the recovered or~ansc sslaterials are v~luab1e a9 ~IC3~7~

chemical or petrochemicaL feedfitocks. In tlle case of b~tumen components from tar sands ef~luents, at least part oE the recovered bltumell can be fed to a coker or re~inery or otherwl~e upgraded. When fed to a coker, some of the resulting coke is advantageous as collector in step (a).
The residue ~roln the agglolnerace ma~3sefi aFter solvent extrac--tion wlll contain a~y hydrophoblc heavy metal-contailling component~.
When economlcally feasible to recover the heavy metal content, these residues ~or example can be washed wlth hot aqueolls media to remove fiOI.-vent, drled and fed to a heavy metal recovery operation. Sucll drled heavy metal mtnerals have heen found to contaln ahout 15-40% W/w of adsorbed organic matter. This adsorbed m.3teriaL can be of bene~it in some direct high temperature ch]orinat lon renc~tons where coke normally is added, e.g. in chlorlnatillg Tl minerals for conversion to Ti metal or TiO2. Alternatively, the adsorbed orgnllLc n~tter can be bu~ned to provide some process heat. These res~dlle~ W~ttl adsorbed organlc matter can be ufied to Eorm part, or ln some cases all, of the collector fiolld~.
When the adsorbed organlc matter is pre~ent ln about 30-40~, the resi(lue solids can function as sole coLlectoc solids.
The flow~heet illustrates a preferred treAtment of an effll~ent feed containing bltumen-type organic ~terial as well as hydrophobic heavy metal minerals. Recycle modes for collector, solvent and water are illù6trated. Suitable contacting equip~ent Eor tlle agglo~eratlon step would be blending or countercurrent mixing devLces, greafie kettle~; and paddle mixers. Solid-liquid ~eparatLon after agglomeratlon may be effected hy screening, e.g. with a 50 mesh screen. Solvent strippillg normally is carried out by distillatLon and steam stri~ping technlques.
For the solid-liquid separations after solvent extraction, and a~ter hot water washing, mixer-settlers or vacuum l~lt ~ilters would be suitable.
Some of the bitumen solids or products therefrom and/or hydrophobic heavy 30 minerals can he recycled to ~orm tlle c(lllector solld~ as shown.
Tlle procesfi can be by hatch mode or cemi-contlnuou~ or contin-uous. For continuous operation, the type of apparatus shown in CanadLan Patent No. 1,151,575, dated August 9, Ig83, Figs. 1-4, would be effect~e for the initial cont~cting, agglomeratlon alld solid-liquid separatic)ll.

77~3 The Eollowing examples are illIIstratLve.

Alberta Tar Sands Hot Water Process ~ffLuent Suncor plant 4 tail-Lngs (com~)o~ltLnn: miner;lls 73%, wat~r 23%
and toluene extractables 4.0X) were gro~ d in a b~ll mill to mo~tly -325 mesh size. lO0 gram sampLes of this n~3terlal (average solld content 46.5~) were treated w-Lth varying ainolInts oE elther reduced still bottoms or Syncrude Elexi coke (lO0 mesh size). rhe conteIltfi were then agltated on a paint shaker (except in one case wI~ere a grease kettle was ust?d).
After agglomerates forIlled~ they were separated by screening aIld an~lyzed.
The resultfi are shown in Table l. The recovery oE organics was almost quantitative.

(a) The agglomerate sample wa9 Eirst dried at 110C to con-stant weight. The dried sample was then used to extract the organics using hot toluene in a Soxhlet apparatus. The amount o~ organic material recovered was then calculated as iEollows:
wt. of the dried ~ample before extraction = ~ ~ms wt. of the drled sample after extractLoII = y gms wt. of water collected = A ~ms wt. of organlcs recovered from the original sample _ x-(y+A) 46.5 = B
where 46.5 ls the ~ of mineral water in the origLnal sample.
Percentage recoveries based on toluene extractabIes are slIo~ in paren-theses (recoveries exceeding 1()0% lndicate pL~k-~Ip of solvent).
(b) Calc~lated as ~ollows:
Let the wt. of dry res~due after tolueIle extractIon be = A gm.
Ash ~rom above = n gms.
Organlcs in the above residue l.e. = A - B = C gms.
Ash from coke added = D gms.
toluene insoluble organis recovered ~ C - D ~ E gmg.
(c) Ash Eree basis.

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:~20~778 EXA~IPLE 2 Alherta Tar Sands Hot l~ater Process EfElllent Syncrude plant #6 tailings (compositlon: minerals 16.5%, water 82.6%, and toluene extractables 0.9%) were treated as in Example I except that the grlnding step was omitted. 'rhe agglomerates were separated an(i analyzed. The results are sllown in TQble 2. Cood recoveries of orgallics from the effluent was acllleved.
Explanations for Table 2 (1) Wetght in parentlle~qes t-~S % of total organLcs

(2) Based on the origLIlilL volume of the tatling.s

(3) Orgall-Lc pha~e was weighe~d and ti~en extracted u~sLIlg llOt:
toluene in a Soxhlet apparatus coLlecting water in a ~ean ~nd Stark tube.
The total organics were thell calculated a8 ~OIloWs:
Let the wt. oE the organic pl~ase be = ~ gms wt. of still bottoms added = y gms water collected = z, gms wt. of the dried mLneral residue = ~ gms total organics = x - (Z+A) = ~ gms wt. of the organics recovered = B-Y = C gms.
Amount of total organics recovered in e-)ch of the Examples ls consider-ably greater than the amollnt extracted Erom drLed tailings using llot toluene (0.9%). This clearly indicates the recovery of solvents Erom the tailings along with the bitu~len. The organicæ recovered were greater than comparative sample lB processed accordLng to Canadian Patent No.
1,088,445.

Alberta Tar Sands Hot Water Yro .. . . _ The experLment oE ~x. 2 was repeated wltll tlle Suncor a~ueollssludge (composLtion: minerals = 16.0%, water 71.2%, toluene extractahles 3~ 10.8%). The amount o~ tlle sludge Lnvolved ln eacll sa~ple was 10~ gmæ~
The results are shown in Tahle 3.

Tar sands processing effluents an(l eEfluent sludgeæ were agglomerated as in Ex. 2 wLtll reduced still bottoms as collecting agent using gre~se kettles. The agglomerates were separated from the sand- and 7~1 3 g --~u~ - 'I

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Colle(~ting(l) Solid ~ r~e Total Org<lni SampLe agentResidue (2) Recovero(l No. (70 added) wt.% C i'PI'l (% total e~fluellt) . , __ 1_____,_ _____,___._ ,___ ___ 1 _ 30.1S 338 2 Extracted using 6.32 _ lO.8 hot toluene 3 R.S.3./Cre.lse 3.3] 38 N.D.
Kettle 4 R.S.B. (22.6) 28.32 125 10.7 Coke (134.6)23.44 115 6.5

6 Coke (137.7)11.41 48 1].2

7 Coke (148.6)7.53 54 11,4 N.D. - Not Determined R.S.B. - Reduced Still Bottoms (1) Weight in parentileses ~IS % of total organics (2) Based on the ul~diluted sample (3) Asll free b~sis :3l2(~7~3 clay-containing aqueous tstlings usJng a 30 mesll si~e screen and waslled with water to remove attached clay. OrgallLcs, includlng bitumell, were recovered by toluene extractlon and the resldual solLds drled at 110C.
The dried solids were ashed ~o constant weight at 4~0C and analyzed for heavy metal content USillg:
(i) quantttatlve IC~-~ES (inductLvely coupled plasma-atomlc emission spectroscopy) methods, and (ii) atomic absorpt~on spectroscopy, except for zirconium ~hLch was tletermined gravimetrlcally as tlle pyrophosphate %rP207-The results are given in Tab1e 4. Two sampLes from Feed A and four samples from Feeds B and C (and a comparison for tar sands Feed D) were processed and analyzed. It i5 evident that sLgniEicant concentratloll of Ti, Zr, and in some cases NL, Mn and Cr, was achieved. At the same tlme, the organics from the efflllents was being recovered almost quantLtat~vely by the process of this invention.

The data show good recoveries (over 90%) of residual bltu~len, waste solvent or toluene-insoluble organics (e.g. coke~ were obtailled from oil sand tailings, using reflnery coke or reduced still bottorns as nucleating agents. The organ-lc phase Eor~ed agglomerates which were easy to separate by screening. The separated organic pha.se can he furtller processed by conventional techniq-les to recover carbon solids and hydro-carbons. The flnal aqueous phase wlll have a reduced organlc content:, usually corresponding to a carbon conte-lt of 0.2 to 3.0%. Tlle or~nic content is normally reduced by a factor of 4 to 16 on going Erom feed to flnal aqueous phase.
The process is adaptable to any type of solid or liqnid tail-ing~ or effluent containing residnal organlcs.

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Claims (11)

CLAIMS:

1. A process for recovering dispersed organic components and any heavy metal components present, from aqueous effluents or tailings con-taining same, comprising:
(a) adding hydrophoblc collector solids having an affinity for said components, to the aqueous effluent or tailings to form an aqueous mixture, (b) providing that the solids content of the aqueous mixture is within from about 10 to about 75% by wt., and selected to allow fluid agitation, (c) agitating the resulting mixture until the collector, organic components and any hydrophobic heavy metal components become agglomerated into discrete solid masses, (d) separating these masses from the aqueous medium, (e) contacting the masses with a selected organic solvent to extract organic material and leave a residue, (f) recovering organic material from the loaded solvent, and (g) recovering any heavy metal components present in economic amounts from said residue.

2. The process of claim I wherein the effluent or tailings are from tar sands hot water processing, in situ oil recovery processes, oil shale processing, sewage or industrial plant effluents, and coal or peat processing.

3. The process of claim I wherein the collector is selected from solid bitumen materials, hydrophobic residues from steps (e) or (g), coal, coke, reduced still bottoms, dried peat, carbonaceous adsorbents, and mixtures thereof.

4. The process of claim 1, 2 or 3 wherein the amount of collector added in step (a) is selected from within the range about 30 to about 400% by wt. of the organic components present to be sufficient to agglom-erate all of the organic components present.

CLAIM (cont.):

5, The process of claim 1, 2 or 3, wherein the solvent is selected from aromatic solvents, aliphatic hydrocarbon solvents, petroleum naphthas, chlorinated hydrocarbon solvents and other liquid hydrocarbon streams boiling in the range of about 100 to 600°F.

6. The process of claim 1, 2 or 3 wherein a portion of solid organic material recovered in step (f) is recycled as collector to step (a).

7. The process of claim 1, 2 or 3 wherein the solvent from step (f) is recycled to step (e).

8. The process of claim 1, 2 or 3 wherein the aqueous medium remaining after step (d) is treated to remove any waste solids and the water recycled.

9. The process of claim 1, 2 or 3 wherein the starting effluent or tailings are from tar sands processing and at least part of the bitumen recovered in step (f) is fed to a coker and some of this coke used as collector in step (a).

10. The process of claim 1, 2 or 3 wherein at least part of the residue from step (e), which is hydrophobic, is recycled as collector to step (a).

11. The process of claim 1, 2 or 3 wherein metals are recovered, and in step (g) said residue is washed to remove residual solvent, dried and fed to a metal recovery circuit.