CA2090649C - A method for the disposal of used ion-exchangers - Google Patents
A method for the disposal of used ion-exchangersInfo
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- CA2090649C CA2090649C CA002090649A CA2090649A CA2090649C CA 2090649 C CA2090649 C CA 2090649C CA 002090649 A CA002090649 A CA 002090649A CA 2090649 A CA2090649 A CA 2090649A CA 2090649 C CA2090649 C CA 2090649C
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- exchangers
- ion exchangers
- granular
- resins
- granular ion
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a method for the disposal of used granular organic ion-exchanges. The method comprises carbonizing the ion-exchanges in a substantially inert atmosphere at temperatures of 300°C to 900°C. The ion exchanges are thereafter actuated in an oxidizing atmosphere to convert the ion exchanges into activated carbon spherulets.
Description
'~
A METHOD FOR THE DISPOSAL OF USED ION-EXCHANGERS
SPECIFICATION
The invention relates to a method for the disposal of used up synthetic resin ion-exchangers which mostly occur in the grain form.
Synthetic resin ion-exchangers are porous polymers having numerous chemical groups with exchangeable ions. In general, they consist of a copolymer framework of styrene and divinylbenzene or styrene and acrylic acid, said framework carrying acid groups, in particular sulfonic acid groups, for cation-exchangers and basic groups (amines) for anion-exchangers. Organic ion-exchangers of the kind having a polymer resin matrix selected from the group consisting mainly of polystyrene resins, polyacrylic resins, polyalkyl amine resins or phenol-formaldehyde resins, which may be present as cation- or anion-exchange resins, depending on their functional groups, and as adsorber resins are described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Volume A 14, VCH-Verlagsgesellschaft mbH, Weinheim, Germany 1989 in the chapter "Ion Exchangers", in particular on pages 394 - 398, and are commercially available under the trade names Lewatit*, Dowex*, Kasatel*, Diaion*, Relite*, Purolite*, Amberlite*, Duolite*, Imac*, Ionac*, Wofatit*. Numerous applications of the ion-exchange resins are also described on pages 399-448 of the cited chapter.
The main purpose of using ion-exchangers is the exchange of undesirable ions present in water for less noxious ions, and the complete removal of ions. If the ions that produce hardness - basically Ca2+ and Mg2+ - are exchanged for Na+
ions, "hard~ water * Trade-Marks .,.=
~ "
A METHOD FOR THE DISPOSAL OF USED ION-EXCHANGERS
SPECIFICATION
The invention relates to a method for the disposal of used up synthetic resin ion-exchangers which mostly occur in the grain form.
Synthetic resin ion-exchangers are porous polymers having numerous chemical groups with exchangeable ions. In general, they consist of a copolymer framework of styrene and divinylbenzene or styrene and acrylic acid, said framework carrying acid groups, in particular sulfonic acid groups, for cation-exchangers and basic groups (amines) for anion-exchangers. Organic ion-exchangers of the kind having a polymer resin matrix selected from the group consisting mainly of polystyrene resins, polyacrylic resins, polyalkyl amine resins or phenol-formaldehyde resins, which may be present as cation- or anion-exchange resins, depending on their functional groups, and as adsorber resins are described in Ullmann's Encyclopedia of Industrial Chemistry, Fifth Edition, Volume A 14, VCH-Verlagsgesellschaft mbH, Weinheim, Germany 1989 in the chapter "Ion Exchangers", in particular on pages 394 - 398, and are commercially available under the trade names Lewatit*, Dowex*, Kasatel*, Diaion*, Relite*, Purolite*, Amberlite*, Duolite*, Imac*, Ionac*, Wofatit*. Numerous applications of the ion-exchange resins are also described on pages 399-448 of the cited chapter.
The main purpose of using ion-exchangers is the exchange of undesirable ions present in water for less noxious ions, and the complete removal of ions. If the ions that produce hardness - basically Ca2+ and Mg2+ - are exchanged for Na+
ions, "hard~ water * Trade-Marks .,.=
~ "
beco~es "soft" ~ter. If ~a~i~ns ~n~ anions are r~
m~ved, one o~tains deminçr~ ed water. Soft ~ter is ne~essary, for ex~mple i~ ~he texkile indus~ry, ~hd deminerali~ed wat~r in the s~eam gener~tion, in partiGI]lar in high-pressure boilers.
In general, ion-~xchan~ers become ineffective hy ob~
~truc~ion, i.e. ~heir pores get blo~ked by suspend~d p~rticles or inorganic residues~ su~h ~s iron compouhds .
The latter a~e re~ularly flu~hed out, ~t wit~ time, more pores heco~e progress~vely blo~ked and fin~lly ~he ~ed has to be replaced. At ~his point, the problem of disposal arises. As long as no ions that polu~
the environment are present, ~he used up ion-~xchan-gers Gan ~e disposed of in waste dumps.
Ina~ive gxanulous organi~ ioh-exc~ange~ resins ~re con~aminat~d with larg~ amoun~s of inorg~nic or orga-~ f~reign ma~t~r, su~h as sus~ended parti~les of ~11 kinds, slud~e, ~icroorganisms ~ ~lg2e and vaxious ca-tions, e.q. sodium, pot~s~ium, iron, and ~alci~m ions The a~ount of these impurlties is usu~lly up to ~ y weight, ~ased on the dry su~stan~e The granular ion-ex~h~nge re~ins ~o be disposed ~f have in ~ost Gas~s a ~a~er ~onte~ which may amount to up to S0~ by weight.
Sub ject ma~teL of the inv ntion is a me~hod for the dispos~l o~ used up granular or~ant c ion-exchangexs of ~h~ afore~entione~ kind ~o~prising c~r~onizing 1~ ~re-dominantly inert a~mosphere at temper~ture$ of ~rom 300~~ t~ gO~~~ ~nd subseq~entl~ acti~ating in ~n oxi.c~
~in~ a~mosphere~ t~s co~ve~ting said ~ exc~an~c~rs in~o acti~ted car~on spherul~ts.
-It is known in the ar~ to convext specifically d~fined poly~lfon~ted ~a~roporous ~ross-linked vinyl aromatic poly~ers into carbonaceous adsorber par~i~les by ~e~tinq to ~emperatures of up to 1200~ 5~PS 4,9$7,897)~ The ul~onic a~id groups are xeleased during pyrolysis, ra~
di~al sites are genexated whi~h le~d to str~ngly cross-link~d stru~tures that ~re not meltable and c~ontain little volatile ~arbo~.
Howe~er, i~ ~s surprisin~ that hi~h qualit~ a~rasion-pro~f aGtiv~ted ~arbo~ ~herule~s c~n be produ~ed also from strongly cont~minat~d ~sed up synth~ti~ resin ion~
exchan~e~s ~y pyrolysis and ~h~t the various foreign s~bstan~es do not impair the quality and st~bility of ~e adsorbe~ Surpri~inqly enough, th~ macro- ~nd m~-sopore struc~ure of ~he feed~ock is m~intained d~rin~
the disi~tegra~ion of the impurities ~nd ~he c~rboni-zation. The accummul~ed org~nic and biolo~ical pro-duc~s are de~troyed or escape wi~hou~ ~orming ~ny pro-nounced ~ar~on residues, in parti~ular if the ca~bo-nlzation is ~ondu~ted in weakly oxidiziny atmosphere~
In the used up cation-exçh~nger xesins r the ca~ion~
are usually ~onded to sulfonic ~cid groups ~d a~e su~stantially con~erted into sulfates at temperatures ~f up to 40~ t higher ~emperatures, they are re-duced by carbon r resulting in con~ider~ble amoUFIts of s~lfld~. It is, therefore, advantageous to firs~
convert catio~-exchan~er resi~s into th~ ~ ~orm prior to c~r~onization. This is prefer~bly done L~y washing the still moist materi~l with an acid~ i e. prior ~o dryin~.
20906~9 -- s ~
In order ~ rem~e the wa~er con~ent, whi~h as ~lready ~en~ione~ ~y ~moun~ to up to ~0~ o~ the ~ranul~r org~-n~ ion-~xcha~ge resin, i~ is recommend~d to dry the used up granular xesin to ~ disposed of, preferably in a rot~ry drier or in a fluidized bed. Prio~ to ining the softening point and usually after dry-ing, the syn~h~tic resin ion-ex~han~ers ~re prefer~ly powdered with an iner~ inorg~ic powde~, preferably carbon powder, to prev~nt agglomeration and ~o main-t~in the gran~l~r structure during the entire treat-ment .
~p to d te~peratur~ of 400~C, pre~erably ~p to about 300~ to 350~C, the iner~ ~tmosphexe of the carb~ni~~-~ion step ~n co~t~in 0.2 ~o ~ Yolume~ oxygen. The oxygen content is prefex~bly controlled by the addi ~ tion of air~ This preoxid~tion is ~e~ommended not only in ~iew of the des~ruction of the or~nic imp~ri~ie~, bu~ also, t~gether with the powdering and/or slow rise in temper~ture, i~ view of reduction of vol~tile c~r-b~n by oxygen ~ridg~s ~nd r~di~l sites, and ( ih view of) preventing meltin~ or sticking toge~h~r. In par-~icul~r, ~he preoxidation i5 ~ery l~port~nt when he resins do no~ ~ontain sulfonic acid grGups, e.g.
anion-ex~han~ex resins or ~dsorber resins. It iS re-~ommended ~o pro~ess ~h~se resin types ~ogether with ~tion-exch~nger resins co~ ining sulfonic ~id groups.
Minor amounts of ç~tions, su~h ~s alkal7 me~ nd ~1-~aline e~r~h me~al ions r ~le~ted f~om the group ~o~-sistin~ o~ sodium, pot~ssium et~. ur cal~um, ~hich were alre~dy con~erted into sulf2~es ~t t~le ~in~ing of the- pyrolysis, dcl not ~istur~ ~he ~ar~oni~a~l~n and ~ctivati~n, s~-~prisirlgly ~nQu~h, they ev~n pr~mote the ac~ tiQn step.
_ ~;
The activation o~ ~he ~rbonized material follo~s upon ~h~ c~r~onization a~ about 700~. Analogo~s to t~e car~oni~tion, i~ eah be conducted in a rotary drier or e~en better in a f luidized ~ed . To ~ctivate the materi~l, steam and/or ~arbon dioxide is ~dded in ~n ~mo~nt of 3 to 50, preferably 3 ~o 15 ~olume%, to the su~s~antially inert atmosphere. The ac~ivation tem-per~ture can be up to 900 ~C . ~o save energy, $he a~-tivation ~an be ~ondu~ed in the same app~ratus ~f~er the car~onization~ Howe~er, it mi~t be advantageous for spe~ific ~echnical and pro~dural ~easons t~ con-du~t ~he ~tivati~n in ~n independ~nt separate step, ~ll the more sin~e the ~arbonizati~n up to ~emperatures of a~out 5Q0~~ already entail~ a consider~ble ~hrinkage and a wei~ht loss of ~he feedstock of from ~0 to ~0~.
The ~r~on ~anten~ of the a~lvated ~rbon spherule~s after ac~ivation is more than 90~ by weiqht, Example 1:
1 kg of an m~cxoporous ion-exchAnger consisting mainly of ~yre~e ahd divinylbenzene~ which ~s present ih the H form ~nd was ~sed in ~he synthesls of f~el addi~ives (MTBE~ an~ had hec~me inactive, was ~rie~ in ~ r~ta~y drier at 110~~. Th~ loss in weigh~, c~used by vaporiza-tion of hydroca~bons and so~e moisture, was approxi~tel~
13%. T~ere~fter~ it w~ heated up to 30~~~ in an atmos-phere consis~ing of BQ~ inert ~as and 15~ ~ir and m~
~ined th~rein f~r on~ hour. The ~in in weight w~s a~out ~. Wher~p~n ~he tempe~ture w~ r~ised to 700~C
in inert ~tmosph~re with~n 3 hour~. 5~ ste~m were added in the r~n~e of 700~ to 900~~. The temperature rise from 700~ to ~0~¢ lasted for ~hirt~ ~inute~, the ~00~~ were ~a~hed in ~en fur~her mi~ut~s~
The y~eld w~s ~ b, b~ed on the feeds~ock. An agglorn~-ration of the spherule~ did not occux at any time.
A shrin}~ge of d}~met~r of from approximately ~ . 8 mm ~o O . ~ to O ~ 7 nnm, was o~ser~ed. The app~rent densi~y cf th~ spheru1et~ was l . 08 ~ m3 ~t a po~e volume of more th~n 0.9 ~ g, of which 0~55 mll~ w~re micropo~es~
A spe~ sur~ace of 10~ Itl2J~ was determined };~y ~he BET me~h~d~ ~ O . 5~ sphexul et could be loaded p~ncti-form with 3 0 0 ~ without bre~kage .
m~l~ ~ 2 -1 3cg of a gel-~ype cation-exchanqe~ ~hi~h had been us~d for ~he so~nin~ ~f wate~ and had no suffi~ient ac~ivi~y w~s ~onvex~ed into ~he H+ form l~y means of a hydrochlori~ a~i d solu~ion. Af~er superficial air-dryin~, the mois~uxe w~s about 50~. Af~er drying a~
1104C, oxidatio~ was carried ou~ in air ~t 300~C fo~
6 h~urs. The pro~edure of E~mple 1 was ~ereafter ~pli~d. The yield was 31~, based on the feeds~oc~.
~he spherulets were partly ~gglomerat~d.
ExaInpl~ 3:
The proçess of ~xa~nple ~ was applied in ~he s~me manner arld with the same feeds~ock, ~owever, a~ter oxida~iorl at ~00~C, powdering was ~onducetd with 5% carbor~ powder ~nd the temper~tUL~ was r~ised to 700 ~C with~n 6 hours .
The agglomer~tion of ~h~ spherulets and the fo~ ti on of ~ ~listered stru~tur~ could ~hus be preven~ed. ~he in~er surface of the ob~ined a~ivated ~a~ on p~xti~les 2mounted to ~pproa~ima~el~r lOQOm~J~r ~B;E~T) ~nd ~he yield w~,s 40~; b~sed on 1~hA~ feedstock. The ~ver~ge ~urst~ng pressur~ was 2~0 g at ~ di~e~er of O . 5 mm.
~ 2090649 Also macropor~us ~ds~r~er resins ~on~istin~ ~ainly of ~ di~inyl~enzenP-~opolymer w~re pro~ssed in the $ame manner to yi~ld ac~i~ated c~rbon, said resins had been ~lready used up and 5~ con~ained adsor~ed organic su~s~ances. Sin~e these prod~cts do not c~nt~in any sulfoni~ acid g~oups t a preoxidation is particul~rly iml?ort~nt .
m~ved, one o~tains deminçr~ ed water. Soft ~ter is ne~essary, for ex~mple i~ ~he texkile indus~ry, ~hd deminerali~ed wat~r in the s~eam gener~tion, in partiGI]lar in high-pressure boilers.
In general, ion-~xchan~ers become ineffective hy ob~
~truc~ion, i.e. ~heir pores get blo~ked by suspend~d p~rticles or inorganic residues~ su~h ~s iron compouhds .
The latter a~e re~ularly flu~hed out, ~t wit~ time, more pores heco~e progress~vely blo~ked and fin~lly ~he ~ed has to be replaced. At ~his point, the problem of disposal arises. As long as no ions that polu~
the environment are present, ~he used up ion-~xchan-gers Gan ~e disposed of in waste dumps.
Ina~ive gxanulous organi~ ioh-exc~ange~ resins ~re con~aminat~d with larg~ amoun~s of inorg~nic or orga-~ f~reign ma~t~r, su~h as sus~ended parti~les of ~11 kinds, slud~e, ~icroorganisms ~ ~lg2e and vaxious ca-tions, e.q. sodium, pot~s~ium, iron, and ~alci~m ions The a~ount of these impurlties is usu~lly up to ~ y weight, ~ased on the dry su~stan~e The granular ion-ex~h~nge re~ins ~o be disposed ~f have in ~ost Gas~s a ~a~er ~onte~ which may amount to up to S0~ by weight.
Sub ject ma~teL of the inv ntion is a me~hod for the dispos~l o~ used up granular or~ant c ion-exchangexs of ~h~ afore~entione~ kind ~o~prising c~r~onizing 1~ ~re-dominantly inert a~mosphere at temper~ture$ of ~rom 300~~ t~ gO~~~ ~nd subseq~entl~ acti~ating in ~n oxi.c~
~in~ a~mosphere~ t~s co~ve~ting said ~ exc~an~c~rs in~o acti~ted car~on spherul~ts.
-It is known in the ar~ to convext specifically d~fined poly~lfon~ted ~a~roporous ~ross-linked vinyl aromatic poly~ers into carbonaceous adsorber par~i~les by ~e~tinq to ~emperatures of up to 1200~ 5~PS 4,9$7,897)~ The ul~onic a~id groups are xeleased during pyrolysis, ra~
di~al sites are genexated whi~h le~d to str~ngly cross-link~d stru~tures that ~re not meltable and c~ontain little volatile ~arbo~.
Howe~er, i~ ~s surprisin~ that hi~h qualit~ a~rasion-pro~f aGtiv~ted ~arbo~ ~herule~s c~n be produ~ed also from strongly cont~minat~d ~sed up synth~ti~ resin ion~
exchan~e~s ~y pyrolysis and ~h~t the various foreign s~bstan~es do not impair the quality and st~bility of ~e adsorbe~ Surpri~inqly enough, th~ macro- ~nd m~-sopore struc~ure of ~he feed~ock is m~intained d~rin~
the disi~tegra~ion of the impurities ~nd ~he c~rboni-zation. The accummul~ed org~nic and biolo~ical pro-duc~s are de~troyed or escape wi~hou~ ~orming ~ny pro-nounced ~ar~on residues, in parti~ular if the ca~bo-nlzation is ~ondu~ted in weakly oxidiziny atmosphere~
In the used up cation-exçh~nger xesins r the ca~ion~
are usually ~onded to sulfonic ~cid groups ~d a~e su~stantially con~erted into sulfates at temperatures ~f up to 40~ t higher ~emperatures, they are re-duced by carbon r resulting in con~ider~ble amoUFIts of s~lfld~. It is, therefore, advantageous to firs~
convert catio~-exchan~er resi~s into th~ ~ ~orm prior to c~r~onization. This is prefer~bly done L~y washing the still moist materi~l with an acid~ i e. prior ~o dryin~.
20906~9 -- s ~
In order ~ rem~e the wa~er con~ent, whi~h as ~lready ~en~ione~ ~y ~moun~ to up to ~0~ o~ the ~ranul~r org~-n~ ion-~xcha~ge resin, i~ is recommend~d to dry the used up granular xesin to ~ disposed of, preferably in a rot~ry drier or in a fluidized bed. Prio~ to ining the softening point and usually after dry-ing, the syn~h~tic resin ion-ex~han~ers ~re prefer~ly powdered with an iner~ inorg~ic powde~, preferably carbon powder, to prev~nt agglomeration and ~o main-t~in the gran~l~r structure during the entire treat-ment .
~p to d te~peratur~ of 400~C, pre~erably ~p to about 300~ to 350~C, the iner~ ~tmosphexe of the carb~ni~~-~ion step ~n co~t~in 0.2 ~o ~ Yolume~ oxygen. The oxygen content is prefex~bly controlled by the addi ~ tion of air~ This preoxid~tion is ~e~ommended not only in ~iew of the des~ruction of the or~nic imp~ri~ie~, bu~ also, t~gether with the powdering and/or slow rise in temper~ture, i~ view of reduction of vol~tile c~r-b~n by oxygen ~ridg~s ~nd r~di~l sites, and ( ih view of) preventing meltin~ or sticking toge~h~r. In par-~icul~r, ~he preoxidation i5 ~ery l~port~nt when he resins do no~ ~ontain sulfonic acid grGups, e.g.
anion-ex~han~ex resins or ~dsorber resins. It iS re-~ommended ~o pro~ess ~h~se resin types ~ogether with ~tion-exch~nger resins co~ ining sulfonic ~id groups.
Minor amounts of ç~tions, su~h ~s alkal7 me~ nd ~1-~aline e~r~h me~al ions r ~le~ted f~om the group ~o~-sistin~ o~ sodium, pot~ssium et~. ur cal~um, ~hich were alre~dy con~erted into sulf2~es ~t t~le ~in~ing of the- pyrolysis, dcl not ~istur~ ~he ~ar~oni~a~l~n and ~ctivati~n, s~-~prisirlgly ~nQu~h, they ev~n pr~mote the ac~ tiQn step.
_ ~;
The activation o~ ~he ~rbonized material follo~s upon ~h~ c~r~onization a~ about 700~. Analogo~s to t~e car~oni~tion, i~ eah be conducted in a rotary drier or e~en better in a f luidized ~ed . To ~ctivate the materi~l, steam and/or ~arbon dioxide is ~dded in ~n ~mo~nt of 3 to 50, preferably 3 ~o 15 ~olume%, to the su~s~antially inert atmosphere. The ac~ivation tem-per~ture can be up to 900 ~C . ~o save energy, $he a~-tivation ~an be ~ondu~ed in the same app~ratus ~f~er the car~onization~ Howe~er, it mi~t be advantageous for spe~ific ~echnical and pro~dural ~easons t~ con-du~t ~he ~tivati~n in ~n independ~nt separate step, ~ll the more sin~e the ~arbonizati~n up to ~emperatures of a~out 5Q0~~ already entail~ a consider~ble ~hrinkage and a wei~ht loss of ~he feedstock of from ~0 to ~0~.
The ~r~on ~anten~ of the a~lvated ~rbon spherule~s after ac~ivation is more than 90~ by weiqht, Example 1:
1 kg of an m~cxoporous ion-exchAnger consisting mainly of ~yre~e ahd divinylbenzene~ which ~s present ih the H form ~nd was ~sed in ~he synthesls of f~el addi~ives (MTBE~ an~ had hec~me inactive, was ~rie~ in ~ r~ta~y drier at 110~~. Th~ loss in weigh~, c~used by vaporiza-tion of hydroca~bons and so~e moisture, was approxi~tel~
13%. T~ere~fter~ it w~ heated up to 30~~~ in an atmos-phere consis~ing of BQ~ inert ~as and 15~ ~ir and m~
~ined th~rein f~r on~ hour. The ~in in weight w~s a~out ~. Wher~p~n ~he tempe~ture w~ r~ised to 700~C
in inert ~tmosph~re with~n 3 hour~. 5~ ste~m were added in the r~n~e of 700~ to 900~~. The temperature rise from 700~ to ~0~¢ lasted for ~hirt~ ~inute~, the ~00~~ were ~a~hed in ~en fur~her mi~ut~s~
The y~eld w~s ~ b, b~ed on the feeds~ock. An agglorn~-ration of the spherule~ did not occux at any time.
A shrin}~ge of d}~met~r of from approximately ~ . 8 mm ~o O . ~ to O ~ 7 nnm, was o~ser~ed. The app~rent densi~y cf th~ spheru1et~ was l . 08 ~ m3 ~t a po~e volume of more th~n 0.9 ~ g, of which 0~55 mll~ w~re micropo~es~
A spe~ sur~ace of 10~ Itl2J~ was determined };~y ~he BET me~h~d~ ~ O . 5~ sphexul et could be loaded p~ncti-form with 3 0 0 ~ without bre~kage .
m~l~ ~ 2 -1 3cg of a gel-~ype cation-exchanqe~ ~hi~h had been us~d for ~he so~nin~ ~f wate~ and had no suffi~ient ac~ivi~y w~s ~onvex~ed into ~he H+ form l~y means of a hydrochlori~ a~i d solu~ion. Af~er superficial air-dryin~, the mois~uxe w~s about 50~. Af~er drying a~
1104C, oxidatio~ was carried ou~ in air ~t 300~C fo~
6 h~urs. The pro~edure of E~mple 1 was ~ereafter ~pli~d. The yield was 31~, based on the feeds~oc~.
~he spherulets were partly ~gglomerat~d.
ExaInpl~ 3:
The proçess of ~xa~nple ~ was applied in ~he s~me manner arld with the same feeds~ock, ~owever, a~ter oxida~iorl at ~00~C, powdering was ~onducetd with 5% carbor~ powder ~nd the temper~tUL~ was r~ised to 700 ~C with~n 6 hours .
The agglomer~tion of ~h~ spherulets and the fo~ ti on of ~ ~listered stru~tur~ could ~hus be preven~ed. ~he in~er surface of the ob~ined a~ivated ~a~ on p~xti~les 2mounted to ~pproa~ima~el~r lOQOm~J~r ~B;E~T) ~nd ~he yield w~,s 40~; b~sed on 1~hA~ feedstock. The ~ver~ge ~urst~ng pressur~ was 2~0 g at ~ di~e~er of O . 5 mm.
~ 2090649 Also macropor~us ~ds~r~er resins ~on~istin~ ~ainly of ~ di~inyl~enzenP-~opolymer w~re pro~ssed in the $ame manner to yi~ld ac~i~ated c~rbon, said resins had been ~lready used up and 5~ con~ained adsor~ed organic su~s~ances. Sin~e these prod~cts do not c~nt~in any sulfoni~ acid g~oups t a preoxidation is particul~rly iml?ort~nt .
Claims (13)
1. A method for treating used granular organic ion-exchangers comprising the steps of drying the used granular organic ion exchangers and subsequently heating the granular ion exchangers in an inert atmosphere at temperatures in the range of 300°C to 900°C to carbonize the granular ion exchangers, adjusting the temperature of the carbonized granular ion exchangers to a temperature below 400°C and adding to an inert atmosphere in contact with the carbonized granular ion exchangers 0.2 to 4% by volume of oxygen, thereafter activating the carbonized granular ion exchangers by heating thereof to a temperature above 700°C in an inert atmosphere to which steam and/or carbon dioxide has been added in an amount of 3 to 50% by volume to change the granular ion exchangers into activated carbon spherulets.
2. A method as claimed in claim 1 wherein said step of adjusting the temperature of the carbonized granular ion exchangers adjusts the temperature to be in the range of 300°C to 350°C.
3. A method as claimed in claim 1 or claim 2 wherein the amount of steam and/or carbon dioxide added to the inert atmosphere is in the range of 3 to 15% by volume.
4. A method as claimed in claim 1, 2 or 3 wherein said used granular ion exchangers are cation exchangers.
5. A method as claimed in claim 4 wherein said cation exchangers are made of sulfonated styrene-divinylbenzene copolymers or styrene-acrylic acid copolymers.
6. A method as defined in claim 4 or 5, wherein the cation-exchangers are in the H+ form.
7. A method as claimed in claim 1, 2 or 3 wherein said used granular ion exchangers are anion-exchanger resins.
8. A method as claimed in claim 7 wherein said anion-exchanger resins are made of polystyrene resins or polyacrylic resins with tertiary or quaternary amine groups.
9. A method as claimed in claim 1, 2 or 3 wherein said used granular ion exchangers include granular organic adsorber resins.
10. A method as claimed in claim 1, 2 or 3 wherein the step to activate the carbonized granular ion exchangers is an independent step in the method.
11. A method as claimed in claim 7, 8 or 9 wherein the granular ion-exchanger resins are mixed with an inert powder prior to attaining the softening point of the ion exchanger resins.
12. A method as claimed in claim 11 wherein the inert powder is powdered carbon.
13. A method as claimed in claim 1, 2 or 3 wherein said method uses a fluidized bed or in a rotary drier for carrying out the step of the method.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4206132.6 | 1992-02-28 | ||
| DE4206132 | 1992-02-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2090649A1 CA2090649A1 (en) | 1993-08-29 |
| CA2090649C true CA2090649C (en) | 1999-02-02 |
Family
ID=6452779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002090649A Expired - Fee Related CA2090649C (en) | 1992-02-28 | 1993-03-01 | A method for the disposal of used ion-exchangers |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2626956B2 (en) |
| KR (1) | KR0125587B1 (en) |
| CA (1) | CA2090649C (en) |
| DE (1) | DE4304026B4 (en) |
| FR (1) | FR2687941B1 (en) |
| GB (1) | GB2265143B (en) |
| IT (1) | IT1264353B1 (en) |
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| IT1273678B (en) * | 1993-08-12 | 1997-07-09 | Bluecher Hasso Von | ACTIVATED CARBON PRODUCTION PROCESS |
| NL1000078C2 (en) * | 1994-04-19 | 1996-04-22 | Bluecher Hasso Von | Odor filter for vacuum cleaners. |
| SE515506C2 (en) * | 1994-06-17 | 2001-08-20 | Mhb Filtration Gmbh & Co Kg | Odor filter for ventilation outlet hoods |
| SE509743C2 (en) * | 1994-06-17 | 1999-03-01 | Bluecher Hasso Von | Adsorptionsfilterskikt |
| DE4446253A1 (en) * | 1994-12-23 | 1996-06-27 | Hasso Von Bluecher | Textile material of active carbon for adsorption air filters |
| JPH11501606A (en) * | 1995-01-11 | 1999-02-09 | ブリュッヒャー，ハッソ フォン | Manufacturing method of granular activated carbon |
| EP0814056B1 (en) * | 1996-06-22 | 2002-03-27 | MHB Filtration GmbH & CO. KG | Process for manufacturing activated carbon |
| DE19650414A1 (en) * | 1996-08-20 | 1998-02-26 | Bluecher Gmbh | High grade spherical adsorbents production from ion exchanger or precursor |
| DE19653238A1 (en) * | 1996-12-05 | 1998-06-25 | Bluecher Gmbh | High-grade granular activated charcoal production without sulphur di:oxide emission |
| DE19752593C5 (en) | 1997-11-27 | 2005-02-17 | Helsa-Werke Helmut Sandler Gmbh & Co. Kg | Process for the preparation of activated carbon from polymers with aromatic nuclei |
| US6143835A (en) * | 1998-04-03 | 2000-11-07 | Solutia Inc. | Polyacrylonitrile polymer treatment |
| US6277933B1 (en) | 1998-04-03 | 2001-08-21 | Solutia Inc. | Polyacrylonitrile particles by surfmer polymerization and sodium removal by chemical exchange |
| DE19912153B4 (en) | 1999-03-18 | 2004-08-19 | Carbotex Produktions-Und Veredelungsbetriebe Gmbh | Process for the production of shaped high-performance adsorbents |
| DE19930732A1 (en) * | 1999-07-05 | 2001-01-18 | Sandler Helmut Helsa Werke | Process for the controlled production of spherical activated carbon |
| DE20121506U1 (en) | 2000-04-28 | 2002-12-19 | Bluecher Hasso Von | Spherical activated carbon |
| EP1289883B1 (en) * | 2000-05-24 | 2006-01-04 | Carbotex Produktions- und Veredelungsbetriebe GmbH | Method for the production of moulded activated charcoal |
| JP2006273772A (en) * | 2005-03-30 | 2006-10-12 | Japan Organo Co Ltd | Orally administered drug and method for producing the same |
| DE102005062160A1 (en) | 2005-12-19 | 2007-06-21 | BLüCHER GMBH | Activated charcoal for medical use |
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| DE102011114132A1 (en) | 2011-08-14 | 2013-02-14 | BLüCHER GMBH | Filter material useful e.g. in or as filter for gas treatment and in filters for removing pollutants, comprises activated carbon, which is present in form of discrete activated carbon particles, preferably in spherical or granular shape |
| DE102012007392A1 (en) | 2011-11-07 | 2013-05-08 | BLüCHER GMBH | Nitrogen-modified or -functionalized activated carbon, preferably activated coal with nitrogen as catalytically active heteroatom obtained by surface oxidation of activated carbon using oxidizing reagent, useful to produce e.g. filter |
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| DE102014110791A1 (en) | 2014-07-11 | 2016-01-14 | BLüCHER GMBH | Protective clothing unit with preferably textile splinter protection equipment |
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| DE202015104218U1 (en) | 2015-07-25 | 2016-07-26 | BLüCHER GMBH | New textile protection material |
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| DE202016100320U1 (en) | 2015-12-10 | 2016-12-28 | BLüCHER GMBH | Activated carbon, in particular particulate activated carbon, in particular with defined porosity properties |
| DE202016100318U1 (en) | 2015-12-22 | 2016-12-23 | BLüCHER GMBH | Device for modifying porous solids |
| WO2018059722A1 (en) | 2016-10-01 | 2018-04-05 | BLüCHER GMBH | Protective material having catalytic and/or reactive properties and the production and use of same |
| DE202017100965U1 (en) | 2016-12-23 | 2018-01-02 | BLüCHER GMBH | Protective clothing unit |
| DE202017106774U1 (en) | 2017-09-27 | 2018-10-01 | BLüCHER GMBH | Plant for the treatment and / or purification of water |
| DE102018100935A1 (en) | 2017-11-28 | 2019-05-29 | BLüCHER GMBH | Air-permeable surface filter material and its use |
| KR102178391B1 (en) * | 2018-10-15 | 2020-11-12 | 이동희 | Recycling method of deodorant using waste cation exchange resin. |
| DK3994418T3 (en) | 2019-09-03 | 2023-07-10 | Bluecher Gmbh | PROTECTIVE ITEM IN THE FORM OF PROTECTIVE CLOTHING WITH SPLINT, PUSH AND CUT PROTECTION PROPERTIES, WHERE THE PROTECTIVE ITEM AT LEAST INCLUDES OR CONSISTS OF A TEXTILE SURFACE MATERIAL WITH SPLINT, PUSH AND/OR CUT PROTECTION PROPERTIES |
| WO2021047789A1 (en) | 2019-09-09 | 2021-03-18 | BLüCHER GMBH | Head covering, in particualr a hood or balaclava, for use as protective clothing |
| DE202021100461U1 (en) | 2020-09-25 | 2022-01-07 | Blücher Gesellschaft mit beschränkter Haftung | supported catalysts |
| DE202020107404U1 (en) | 2020-11-27 | 2022-03-01 | Blücher Gesellschaft mit beschränkter Haftung | Blasting media based on granular activated carbon |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5621724B2 (en) * | 1973-12-27 | 1981-05-21 | ||
| US4040990A (en) * | 1975-02-18 | 1977-08-09 | Rohm And Haas Company | Partially pyrolyzed macroporous polymer particles having multimodal pore distribution with macropores ranging from 50-100,000 angstroms |
| US4957897A (en) * | 1988-01-29 | 1990-09-18 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
| US4839331A (en) * | 1988-01-29 | 1989-06-13 | Rohm And Haas Company | Carbonaceous adsorbents from pyrolyzed polysulfonated polymers |
-
1993
- 1993-02-11 DE DE4304026A patent/DE4304026B4/en not_active Expired - Fee Related
- 1993-02-26 GB GB9303956A patent/GB2265143B/en not_active Expired - Fee Related
- 1993-02-26 IT IT93MI000386A patent/IT1264353B1/en active IP Right Grant
- 1993-02-26 FR FR9302227A patent/FR2687941B1/en not_active Expired - Fee Related
- 1993-02-26 JP JP5062720A patent/JP2626956B2/en not_active Expired - Lifetime
- 1993-02-27 KR KR1019930002887A patent/KR0125587B1/en not_active IP Right Cessation
- 1993-03-01 CA CA002090649A patent/CA2090649C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2265143A (en) | 1993-09-22 |
| FR2687941A1 (en) | 1993-09-03 |
| GB2265143B (en) | 1995-08-16 |
| ITMI930386A0 (en) | 1993-02-26 |
| DE4304026B4 (en) | 2005-02-17 |
| IT1264353B1 (en) | 1996-09-23 |
| GB9303956D0 (en) | 1993-04-14 |
| DE4304026A1 (en) | 1993-09-02 |
| JPH0692615A (en) | 1994-04-05 |
| JP2626956B2 (en) | 1997-07-02 |
| CA2090649A1 (en) | 1993-08-29 |
| KR0125587B1 (en) | 1998-04-11 |
| FR2687941B1 (en) | 1995-07-21 |
| KR930017632A (en) | 1993-09-20 |
| ITMI930386A1 (en) | 1994-08-26 |
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