CA2248083A1 - Hydrogen fluoride compositions - Google Patents
Hydrogen fluoride compositions Download PDFInfo
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- CA2248083A1 CA2248083A1 CA002248083A CA2248083A CA2248083A1 CA 2248083 A1 CA2248083 A1 CA 2248083A1 CA 002248083 A CA002248083 A CA 002248083A CA 2248083 A CA2248083 A CA 2248083A CA 2248083 A1 CA2248083 A1 CA 2248083A1
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- hydrogen fluoride
- polymer
- water
- intimate mixture
- composition
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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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
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/191—Hydrogen fluoride
Abstract
The present invention provides compositions that are intimate mixtures of hydrogen fluoride and a polymer. The compositions of the invention are less hazardous and, therefore, more conveniently stored, transported, and handled in comparison to pure hydrogen fluoride. Further, the hydrogen fluoride may be readily recovered from the compositions of the invention for use.
Description
HYDROGEN FLUORIDE COMPOSITIONS
Field of the Invention 5The present invenlion relates to hydrogen fluoride cG."posilions. More particularly, the present invention provides cG~ i o~;l;nnC of l"rdr~2e~ fluoride and a polymer that are less hazardous and, Ihc,~re, more easily stored, t.~ns~o,lcd,and h~ndled in cG,l,?a ;son to pure hydrogen fluonte.
10Bac~uimdoftheIn .i.~Lion Hydrogen fluoride is a well known cornroun-i that is used in industry in a variety of ~, uccsses inrl~.ding in all~ylal,on rezctior~C as a catalyst, in fiuorination rW-tionc as a nuG,i-,aling agent, in the m~n~f~cn~re of ~o,idcs, in the sepataL.on of uranium isotopcs, and in the prod~lion of fluorine co..~ plastics. It is well1~ known that hydrogen fiuoride is a volatile, e,.l,.;."cly hazardous subst~ce the high vapor pre~ rc of which renders it rcatily acrosQli~le.
In an attempt to ~ A;sl the hazards of hytrogen fluoridc, it has been co.,.bincd with a variety of s~b~ neçs U.S. Patent No. 1,470,772 disrloses a glass etching pute of nwri~ge, sulfuric acid, and ~-.. o~ium fluoride in which the hydrogen fluoridc is forrned in s u. U.S. Patent No. 3,635,836 r~i~rlos~s disl~c.~.ons of h~drogca fluoride, particulate prot,~ reous material and a smallamount of CaIbUAIIIS~bStjtIt~d vinyl polymers useful as pickling agents, pl~mbing clcan~.~ and paint removers. U.S. Patent No. 4,383,868 di~rlosçs a method of 25 trcating an}.~dlvus l.~d~gc,~ fluoride spills by applying a particulate miAture of polyacrylamide and a polyalkyl(alk)acrylate to the surface of the spill. ~one ofthese co...~os;~;ons provides an ;.~l ;...~te mixture of hyd~ ogca fluoridc and a subsiance that ~oth reduces the hazards of hydrogen fluoride and, at the same time permits the ready recovery ofthe h~dlogen fluoride from the co...~)ûsilion Description of the Invention and the Plefe.led Embotlim.~ntc The prcsent invention provides liquid and solid hydrogen fluoride colllpos;lions that are a convenient means of using, tran~ol ling, and storing 5 I.~dlo~,cn fluoride, the cGlllpcis;l;ons being less hazardous than pure hydrogen fluorite. Further, the chemical p~op~,. Iies of the hydrogen fluoride in the cGlllpG~;lions of the present invention are s~ s~ ly ~ ch~ ~eed from those of hydrogen fluoride in its pure state and L~dio~cn fluoride may be ~ A ~t;~h/ely recovered from the co..~pos;l;Q~lc The c~-,lpos;L;ons of the invention comprise intimste mixtures of hydrogen fluoride and an effective amount of a water-soluble polymer. The term polymer, for purposes of this u~c~l;on, in~ludes hGnlopolymers, copolymers, and mixtures thereof. It has been discovered that certain polymers in ;.l1;...~te mixture with 15 hydrogen fluorite provide a colllposition in which hydrogen fluoride volatility is ~iminichf~d ,~riitio~lly, the c~,llpGs;lions of the invention are more viscous and have a greater surface tension when coll"~ar~d to pure hydrogen fluoride, hindering formation of a hydrogen ~uoride aerosol cloud.
Generally, the polymers used in the invention have mole:~ls~ weights of from about 5,000 to about lO,000,000. ~lefe...bly, polymers with molecular weights of from about 5,000 to about l,000,000 are used. The polymers useful in the c~ rG~il;o~C ofthe invention are water-soluble polyrners. By "water-soluble polymer" is meant any high mo!ec.~lsr weight compound that swells, to about twice 25 its dty volume, or dissolves with the addition of water at room te.l,p~,. alure.
Water-soluble polymer is meant to include semi-synthetic water-soluble polymers, synthetic water-soluble polymers, and mixtures thereof. Semi-syntheticwater-soluble polymers are natural water-soluble polymer derivatives. Synthetic water-soluble polymers arc not natural water-soluble polyrner derivatives and are formed only through cl~rnj~sl reactions.
F~ "~ semi-a~n~ ic water-soluble polymers include, without 5 l;...:lA~ion, c~llulose ethers, . ~o~ ed il~ches, starch derivat*es, natural gum derivatives, and ~ ures thereo~ ~llustrative synthaic watcr-soluble polymers inclute, without li ~ ;on polymcrs, related polymers, and polymer salts of acrylamide, acrylic acid, ethylene oxide, methacrylic acid, polyethyleneimine, polyvinyl ~leQhol, polyvinyl pyrrc'idonç and llu~lu.~,s thereof. By related polymer 10 is mcant that thc pol~ ,r repeat unit, or a branch thereof, is e~tten~ed by carbon atoms, preferably from one to four carbon atoms. For cxample, a related polymer of acrylic acid is one in which the vinyl group is e ~ dcd by one carbon to forrn an allyl group.
Preferably, a synthetic water-soluble pol~.. tr is used. More prcfe~ab polyacrylic acid or one of its salts is used. Most pr~fably, the water-soluble polymer is sodium polyacrylate.
To preparc thc compositions of the inventionl an effective amount of a 20 water-soluble pol~ is mixcd with l~llogen fluoride in any suitable corrosion r~ t vessel to fonn an intimate mixture. An effec~ive arnount of polymer is an amount capable of ttCI ea~u~g the volatility and increasing the surface tension of the hydrogen ûuoride to the levd desired for the end use. ~dition of the polymerand hydrogen ~IUGlltC may be p~.,f~nacd in any sequence. Mixing may be 25 accG...?li~hrd by any means convenient, i~C~ ing without lim~ on stirring or dispersing the polyrner into a pool of hydrogen fluoride or passing hydrogen fluoride gas over the polymer. The hydrogen fluoride may be co.,une.c;ally available anhydrous h~rd-o~,cn fluoride having a water content of 0.1 % or less or aqueous hydrogen fluoride. Preferably, anhydrous hydrogen fluoride is used. The W O97/32810 PCT~US97/02897 -4-polymer may be in any forrn suitable for mixing with the hydrogen fluoride jnrllltlin~ without li,.~ilalio4 granules, beads, pellets, fibers, or mats. Mixing will occur faster for smaller particle sizes of the polymer snd slower for larger sizes.
Typically mixing is pe.ro.l"ed at t.,.n~:c.a~ures from about 0 to about 100~ C.,5 ~referably from about 10 to about 40~ C. Pi es~ is not critical.
The amount of hytrogcn fluoride and po~ e~ used will tcpend in part on the polyrner s~ tcd and the desired end-use for the co""~)osilion. If the polymer has a relatively low moleculqr weight, the r~sl~ting HFlpolyrner composition will lO be a viscous 1i4uid. If the polyrner has a relatively high molec~llqr weight, the resulting co,nposition will be a solid or gel-like solid. Ad~ onqlly~ the arnount of polymer used will dct~ linc ~ elh~r or not the I~Jll; ~8 co.l.pcsilion is a solid or liquid. Generally, when up to about 20 percent by weight, based on the total weight of the c0..l?03.lio4 of polymer is used the composition will be a viscous15 liquid. CG. ~PG~ ~;One in which the amount of polymer is at least about 25 weight percent, generally, will take a gel-like solid form.
It should be noted further that the higher the weight pcr~c ~lAge of polymer used, the greater the rcduction in hydrogen fluoride ~e rosol~lion. However, with 20 qn ;ncleasc in weight percenldge of polymer, the weight p~ c~nl~ge of hydrogen fluoride in the composition decreases which may affect the compGs;lion's suitability for a desired end-use. Thcrefole, the effective amount of hydrogen fluoride and pol~lllcr used will depend on a col~s;d..alion of a number of factors.
Generally, ~om about 2 to about 99.9 weight percent of polymer and from about 25 98 to about 0.1 weight percent of hydrogen fluoride is used. P~f._.ably, fromabout 2 to about 50 weight percent polymer and from about 98 to about 50 weight percent hydrogen fluoride, more plefe~ly from about 5 to about 25 weight percent of pol~mer and from about 95 to about 75 weight percent of hydrogen fluoride is used.
Without dcp~ ling from the scope of the invention, it will be recogni~Pd that other co"lpon- .~ts may be included in the CGll.po~;lions of this invention. The specific nature ofthese CO~pOt~r~ will depend on the desired end use ofthe co..~po~;l;onC In general, any col,.pone~l that does not deleteriously effect the 5 surface tension ofthc c~mpr 2;t;or~ or ul.des;r~bly increase the volatility of the h~lo~cn fluoride cG~ one~t~ may be uscd.
The l.~d-~g~h fluoride may be recovered readily from the cG,nl~os;tion of the invention by lrealirlg the composition so as to liberate hydrogen fluoride 10 vapors. One means of 1. eati.lg the compositions in order to liberate hydrogen fluoride vapor is by heating the colllpG3ilion at elevated t~ c~alures, generally from about 0 to about 200~ C, preferably from about 80 to about 150~ C, resulting in the libc~ ~tion of hydrogen fluoride vapor. The vapor may then be condenced by any convenient means. Alternativeiy, the hydrogen fluoride may be liberated by 15 dec,lea~ g the pressure over the co~T os;l;~rl or i...,leasing both the pressure and t.,...pc.~ture and then co~r~ 8 the vapors. This alternative means for recovering hydrogen ~uoride may be accomplished at prcssures of from about 60 to about 1 psia and t-~np-~alur~s offrom about 20 to about S0~ C. As yet anotheralternative, hydrogen n~G.;tt value may be recovered from the compositions by 20 use of the co~ ~po~ ons in any of the wide variety of pr~cesses that use hydrogen ~uoride.
The co ~pGs;liorlC ofthe invention provide a convenient and safe method for storing L)rd~o~n huoride. Because the cG..lposi~ions exhibit little or no 25 vol~tili7~ti~ of hydrogen fluoride, the hazards of storing the hydrogen fluoride are cignific.an~ly reduced. Further, the hydrogen fluoride may be recovered from thestored cG-l-posilion by the means de~,ibed herein. Additionally, the stored material may be safely ~la..s~o.led.
WO 97t32810 PCTAUS97/02897 -6-The cG~npos;lions of the invention may be prepared and then placed in a storage contA;~.P by any convenient means. Alternatively, the co."?os;lions may be p.~,ared in the storage co..~ e;. Suitable storage CGI~ F ~ are those cGnLaine.s made of, or lined vith, a hydrogen fluoride resis~ t material such as5 carbon steel, polymers, MONELTM, and the like. Storage of the compositions maybe for any length oftime ~ videt that the co~ o~;l;ons are not ~ ,osed to air orother chemicals. Preferably, storage is under ambient cor ~ ionc The stored colnpoe:lion may be safely and effiri~n11y llar,spo.led to a 10 dc,l;--~;on T-~s~o-lin~ ofthe composition may bc by any conventionql means such as by rail car or tmck. Once delivered to the d~ I;on the stored cor,~pos lion may be treated to recover the hydrogen fluoride from the composition for use.
The invenlion will be clarified further by a cor ~ del .. lion of the following examples that are i~ ed so be purely e~e~pl5~.
E~a..,~les F,cq-mrle 1 7 g sodium polyacrylate, m. wt. 1,000,000, were ~. e;gl.ed in a perBuoro~koxy ("PFA") cylinder into which 28 g anhydrous hydrogen fluoride were ch~h g,cd. At ambient t~ ~llpC~ alule, the mixture turned into a viscous solid with a gd-like consistency. The PFA cylinder co.~tA: ~;n8 the mixture was heatedto 90~ C libc. ~ing HF vapors and the HF collected into another cooled cylinder.F.ssenti~lly all of the HF was recovered.
W 097/3~810 PCTrUSg7/02897 Fy~mple 2 The proccdure of FY~mple I was repeated 1 S times with thc same sample of sodium polyac~ylate. FSsentislly all of the HI: was recovered each time.
F.Y~mple 3 The procedurc of Example 1 was used except tha~ 7 g polyacrylamide, m.
wt. 100,000, were substitoted for the sodium polyacrylate of FYPmple 1.
Recovery of HF was 70 % from the gel-like viscous solid.
Example 4 The proced~lre of F--- rl~ 1 was used cxcept that 7 g polyacrylic acid, m.
wt. 1,250,000, were substi~uted for the sodium polyacrylate of Example 1.
F.s3~ ;s~1y all of the HF was recovered from the gel-like viscous solid.
FY~mr'e 5 The p~cedu~e of E~umple 1 wa used except that 5 g polyacrylic acid, m.
wt.. 250,000, were subs~it~ d for the sodium polyacrylate of FY~mple 1. The resultant mixture was a viscous liquid from which eCs~nti~lly all of the ~ was recovcred.
Example 6 The ~occ.lule of Example 1 was used except that 7 g sodium salt of polyacrylic acid copol~...c.,zed with 50 wt percent maleic acid, 50,000 m. wt.
available from Aldrich Chemical Co. were substihlted for the sodium polyacrylate25 of Fy~lnple 1. The resultant mixture was a viscous liquid from which essent~ y all of the HE~ was rccovered.
WO g7132810 PCT/US97tO2897 Example 7 The procedure of Example 1 was used except that 2 g sodium polyacrylate copolyll.c.iLcd with 20 wt percent, 50,000 m. wt acrylamide available from Aldrich Chcmical Co. were sul3stitut~d for the sodium polyacrylate of F :r ,- le I .
5 The reY~ nt mixture was a viscous liquid from which ccs~ ~;AIIy all of the HF was recovered.
r.~..,plc 8 The procedure of Example I was used except that 7 g acrylic acid copol~me.;~c~ with lO wt percent, 200,000 m. wt acrylamide available from Aldrich Chcmical Co. were sub~~inlted for the sotium polyacrylate of FY~nrle 1.
The r~ mixture was a viscous liquid from which ~scc~ ~;slly all ofthe H~
was recovercd.
lS Example 9 The ~ocedurt of Example 1 was used except that 2, lO0 m. wt. sodium polyacrylate was substituted for the sotium polyacrylate of FY~rle 1. The resultant mi~nure was a viscous liquid from which esc~ntislly all of the ~ was recoveret.
FYs-nple 10 The IJrOCedUI e of Example 1 was used except that sodium acrylate copolylllc~d with 10 wt percent, 15,000 m.wt. I.~ h~' ~t~-~rylate available from Aldrich Chemical Co. was substituted for the sodium polyacrylate of Example25 1. The result-snt mixture was a viscous liquid from which essenti~lly all of the ~:
was recovered.
CA 02248083 1998-os-o~
g _ FY~nlrle 1 1 7 g sodium polyaclylate, 1,000,000 m. wt., were weighed in a PFA cylinder into which 30 g of a 40:60 perccnt by weight H~ and water mixture were charged.
The mixturc turned into a gel-like viscous solid. The PFA cylinder con~ini~g the5 ~b~lule was heated to 120~ C libC-dth~g HF and water vapors and the a~ueo~s HFcoll~ct~d into anotber cooled cylinder. FcePn-istly all of the HF and water wererecovered.
FY~nlr'~ 12 The vapor pressures of a number of HF/sotium polyacrylate mixtures were ",tas-Jrcd. For each cxample, ~ hed ~nlolJnts of the polymer and HF were mixed together in a MONEL~M e~l;ndt~ and the cylinder was tepestedly deg~ssed by freeze and thaw cycles for apl,ru~ ely 4 cycles. The cylinder was placed in ate".pe~ reg l~ed bath and a pressure gauge ~Anth a range of 0 to 1000 mm Hg 15 was co~ d to the cylinder. The vapor pressures were read ~om the gauge at various bath t.,..,~,c.~t~,es and the rcsults are shown on Table 1. The vapor pressures of the .,~lu~s werc found to be lower than that of pure HF.
Table I
HF wt pe~ent vP at 2s~ C vP at sOo C vP at 7so C vP at looo C
436 626 1003 over range S02 overnnge ovcr~nge overrange C31 over~nge over~nge overrange loo' 914 2049 4146 7~43 20L~lu-Example 13 The surface tensions of several HF/polyrner mixtures were measured using a DuNouy interfacial tenriorn~ter In this method a plstinum ring was drawn upwardly through the mixture. The force needed to lift the ring off of the liquid 5 surface was l~eas.llcd by the tensiometer and is l"~,pG,Iional to the surface tension of the liquid The results obt&l~et at 15~ C are shown on Table 2 The HF/polymer l~--AIUl es' tensions were found to be higher than that of pure HF which is 8 6 dyne/cm Table 2 Polymer wt o/. PolymerSwf~cc Tension (dyne/cm) Example 1 10 5 lg 3 Example 4 lo o 13 4 Example 7 9.8 1~ 1 Example 8 lo o lS.2 Exarnple 14 A ~ u~c of 30 wt percent sodium polyacrylate and 70 wt percent HF is p-epar. d as in FY~mrle 1 and the mixture is stored in a vessel equipped with a valve The l~ .UI ~ formed is a solid as in Example 1 The rnixture is stored at room tc~ ,e.~l"re for a week with no apl,arenl visual changPs A~er that time thevalve is opened to vent for 1 minute at arnbient ten.p~.~lure and pressure The 20 arnount of HF vented to Al .,os~ h~ e is det~ ned by the .i;~x.lce in weight before and after venting The fraction of ~ vented is dete ...h~ed to be signific~ntly les~ than the HF that would be vented from a vessei of 100 % HF
under identical conditions W O97/32810PCTrUS97/02897 Example 15 A mixture of 30 wt percent sodium polyacrylate uld 70 wt percent HF is prepared as in Example 1 and stirred in a valved vessel. The mixture is a solid as in Fx~tnple 1. The vessel Co~\~A; ~ g the mixture is packed in an ap~,~ot";ate S co~ r and tl~l3pG~ led over a ~;C1 ~.nl~e The vessel containing thc HFlpolymer mixture is unpacked and heatcd and the HF collect~d as in Example 1.
Example 16 The procedure of Fx- ,r~ 1 is repcaled except that I g l~ol~_th~lene oxide, m. wt. 10,000,000 and 19 B H~ are s~bstin~ted for the sodium polyacrylate and HFof Example I .
Example 17 The procedure of Example 1 is repeated except that 7 g poly(methacrylic acid), m. wt. 2,500,000 and 13 g HF are substituted for the sodium polyacrylate and HF of F~ rlc I.
FY~-nple 18 The proc~l~le of Example I is repeated except that 17 g polymethacrylamidc, m. wt. 250,000 and 3 g HF ue substit~ted for the sodium polyacrylate and HF of Fy~np~e 1 Example 19 The p~occl~.~ of Example 1 is r~ peated except that 50 g polyvinyl alcohol, m. wt. 500,000 and 1 g HF are s~lbstituted for the sodium polyacrylate and HF ofExarnple 1.
FY~ 20 The proc~lu...................... of Examplc 1 is rcp~alcd exccpt that 5 g polyvinyl pyrrolidor.P, m. wt. 50,000 and 15 g HF are substituted for the sodium polyacrylate and ~ of Example 1.
Example 2 1 The procedurc of Example 1 is l~p~te~ except that 5 g polyethyl~ A~ AC, m. wt. '.750,000 and 15 g HF are s,JIs~ cd for the sodium polyacrylate and ~ of r.A..~l-le 1.
Field of the Invention 5The present invenlion relates to hydrogen fluoride cG."posilions. More particularly, the present invention provides cG~ i o~;l;nnC of l"rdr~2e~ fluoride and a polymer that are less hazardous and, Ihc,~re, more easily stored, t.~ns~o,lcd,and h~ndled in cG,l,?a ;son to pure hydrogen fluonte.
10Bac~uimdoftheIn .i.~Lion Hydrogen fluoride is a well known cornroun-i that is used in industry in a variety of ~, uccsses inrl~.ding in all~ylal,on rezctior~C as a catalyst, in fiuorination rW-tionc as a nuG,i-,aling agent, in the m~n~f~cn~re of ~o,idcs, in the sepataL.on of uranium isotopcs, and in the prod~lion of fluorine co..~ plastics. It is well1~ known that hydrogen fiuoride is a volatile, e,.l,.;."cly hazardous subst~ce the high vapor pre~ rc of which renders it rcatily acrosQli~le.
In an attempt to ~ A;sl the hazards of hytrogen fluoridc, it has been co.,.bincd with a variety of s~b~ neçs U.S. Patent No. 1,470,772 disrloses a glass etching pute of nwri~ge, sulfuric acid, and ~-.. o~ium fluoride in which the hydrogen fluoridc is forrned in s u. U.S. Patent No. 3,635,836 r~i~rlos~s disl~c.~.ons of h~drogca fluoride, particulate prot,~ reous material and a smallamount of CaIbUAIIIS~bStjtIt~d vinyl polymers useful as pickling agents, pl~mbing clcan~.~ and paint removers. U.S. Patent No. 4,383,868 di~rlosçs a method of 25 trcating an}.~dlvus l.~d~gc,~ fluoride spills by applying a particulate miAture of polyacrylamide and a polyalkyl(alk)acrylate to the surface of the spill. ~one ofthese co...~os;~;ons provides an ;.~l ;...~te mixture of hyd~ ogca fluoridc and a subsiance that ~oth reduces the hazards of hydrogen fluoride and, at the same time permits the ready recovery ofthe h~dlogen fluoride from the co...~)ûsilion Description of the Invention and the Plefe.led Embotlim.~ntc The prcsent invention provides liquid and solid hydrogen fluoride colllpos;lions that are a convenient means of using, tran~ol ling, and storing 5 I.~dlo~,cn fluoride, the cGlllpcis;l;ons being less hazardous than pure hydrogen fluorite. Further, the chemical p~op~,. Iies of the hydrogen fluoride in the cGlllpG~;lions of the present invention are s~ s~ ly ~ ch~ ~eed from those of hydrogen fluoride in its pure state and L~dio~cn fluoride may be ~ A ~t;~h/ely recovered from the co..~pos;l;Q~lc The c~-,lpos;L;ons of the invention comprise intimste mixtures of hydrogen fluoride and an effective amount of a water-soluble polymer. The term polymer, for purposes of this u~c~l;on, in~ludes hGnlopolymers, copolymers, and mixtures thereof. It has been discovered that certain polymers in ;.l1;...~te mixture with 15 hydrogen fluorite provide a colllposition in which hydrogen fluoride volatility is ~iminichf~d ,~riitio~lly, the c~,llpGs;lions of the invention are more viscous and have a greater surface tension when coll"~ar~d to pure hydrogen fluoride, hindering formation of a hydrogen ~uoride aerosol cloud.
Generally, the polymers used in the invention have mole:~ls~ weights of from about 5,000 to about lO,000,000. ~lefe...bly, polymers with molecular weights of from about 5,000 to about l,000,000 are used. The polymers useful in the c~ rG~il;o~C ofthe invention are water-soluble polyrners. By "water-soluble polymer" is meant any high mo!ec.~lsr weight compound that swells, to about twice 25 its dty volume, or dissolves with the addition of water at room te.l,p~,. alure.
Water-soluble polymer is meant to include semi-synthetic water-soluble polymers, synthetic water-soluble polymers, and mixtures thereof. Semi-syntheticwater-soluble polymers are natural water-soluble polymer derivatives. Synthetic water-soluble polymers arc not natural water-soluble polyrner derivatives and are formed only through cl~rnj~sl reactions.
F~ "~ semi-a~n~ ic water-soluble polymers include, without 5 l;...:lA~ion, c~llulose ethers, . ~o~ ed il~ches, starch derivat*es, natural gum derivatives, and ~ ures thereo~ ~llustrative synthaic watcr-soluble polymers inclute, without li ~ ;on polymcrs, related polymers, and polymer salts of acrylamide, acrylic acid, ethylene oxide, methacrylic acid, polyethyleneimine, polyvinyl ~leQhol, polyvinyl pyrrc'idonç and llu~lu.~,s thereof. By related polymer 10 is mcant that thc pol~ ,r repeat unit, or a branch thereof, is e~tten~ed by carbon atoms, preferably from one to four carbon atoms. For cxample, a related polymer of acrylic acid is one in which the vinyl group is e ~ dcd by one carbon to forrn an allyl group.
Preferably, a synthetic water-soluble pol~.. tr is used. More prcfe~ab polyacrylic acid or one of its salts is used. Most pr~fably, the water-soluble polymer is sodium polyacrylate.
To preparc thc compositions of the inventionl an effective amount of a 20 water-soluble pol~ is mixcd with l~llogen fluoride in any suitable corrosion r~ t vessel to fonn an intimate mixture. An effec~ive arnount of polymer is an amount capable of ttCI ea~u~g the volatility and increasing the surface tension of the hydrogen ûuoride to the levd desired for the end use. ~dition of the polymerand hydrogen ~IUGlltC may be p~.,f~nacd in any sequence. Mixing may be 25 accG...?li~hrd by any means convenient, i~C~ ing without lim~ on stirring or dispersing the polyrner into a pool of hydrogen fluoride or passing hydrogen fluoride gas over the polymer. The hydrogen fluoride may be co.,une.c;ally available anhydrous h~rd-o~,cn fluoride having a water content of 0.1 % or less or aqueous hydrogen fluoride. Preferably, anhydrous hydrogen fluoride is used. The W O97/32810 PCT~US97/02897 -4-polymer may be in any forrn suitable for mixing with the hydrogen fluoride jnrllltlin~ without li,.~ilalio4 granules, beads, pellets, fibers, or mats. Mixing will occur faster for smaller particle sizes of the polymer snd slower for larger sizes.
Typically mixing is pe.ro.l"ed at t.,.n~:c.a~ures from about 0 to about 100~ C.,5 ~referably from about 10 to about 40~ C. Pi es~ is not critical.
The amount of hytrogcn fluoride and po~ e~ used will tcpend in part on the polyrner s~ tcd and the desired end-use for the co""~)osilion. If the polymer has a relatively low moleculqr weight, the r~sl~ting HFlpolyrner composition will lO be a viscous 1i4uid. If the polyrner has a relatively high molec~llqr weight, the resulting co,nposition will be a solid or gel-like solid. Ad~ onqlly~ the arnount of polymer used will dct~ linc ~ elh~r or not the I~Jll; ~8 co.l.pcsilion is a solid or liquid. Generally, when up to about 20 percent by weight, based on the total weight of the c0..l?03.lio4 of polymer is used the composition will be a viscous15 liquid. CG. ~PG~ ~;One in which the amount of polymer is at least about 25 weight percent, generally, will take a gel-like solid form.
It should be noted further that the higher the weight pcr~c ~lAge of polymer used, the greater the rcduction in hydrogen fluoride ~e rosol~lion. However, with 20 qn ;ncleasc in weight percenldge of polymer, the weight p~ c~nl~ge of hydrogen fluoride in the composition decreases which may affect the compGs;lion's suitability for a desired end-use. Thcrefole, the effective amount of hydrogen fluoride and pol~lllcr used will depend on a col~s;d..alion of a number of factors.
Generally, ~om about 2 to about 99.9 weight percent of polymer and from about 25 98 to about 0.1 weight percent of hydrogen fluoride is used. P~f._.ably, fromabout 2 to about 50 weight percent polymer and from about 98 to about 50 weight percent hydrogen fluoride, more plefe~ly from about 5 to about 25 weight percent of pol~mer and from about 95 to about 75 weight percent of hydrogen fluoride is used.
Without dcp~ ling from the scope of the invention, it will be recogni~Pd that other co"lpon- .~ts may be included in the CGll.po~;lions of this invention. The specific nature ofthese CO~pOt~r~ will depend on the desired end use ofthe co..~po~;l;onC In general, any col,.pone~l that does not deleteriously effect the 5 surface tension ofthc c~mpr 2;t;or~ or ul.des;r~bly increase the volatility of the h~lo~cn fluoride cG~ one~t~ may be uscd.
The l.~d-~g~h fluoride may be recovered readily from the cG,nl~os;tion of the invention by lrealirlg the composition so as to liberate hydrogen fluoride 10 vapors. One means of 1. eati.lg the compositions in order to liberate hydrogen fluoride vapor is by heating the colllpG3ilion at elevated t~ c~alures, generally from about 0 to about 200~ C, preferably from about 80 to about 150~ C, resulting in the libc~ ~tion of hydrogen fluoride vapor. The vapor may then be condenced by any convenient means. Alternativeiy, the hydrogen fluoride may be liberated by 15 dec,lea~ g the pressure over the co~T os;l;~rl or i...,leasing both the pressure and t.,...pc.~ture and then co~r~ 8 the vapors. This alternative means for recovering hydrogen ~uoride may be accomplished at prcssures of from about 60 to about 1 psia and t-~np-~alur~s offrom about 20 to about S0~ C. As yet anotheralternative, hydrogen n~G.;tt value may be recovered from the compositions by 20 use of the co~ ~po~ ons in any of the wide variety of pr~cesses that use hydrogen ~uoride.
The co ~pGs;liorlC ofthe invention provide a convenient and safe method for storing L)rd~o~n huoride. Because the cG..lposi~ions exhibit little or no 25 vol~tili7~ti~ of hydrogen fluoride, the hazards of storing the hydrogen fluoride are cignific.an~ly reduced. Further, the hydrogen fluoride may be recovered from thestored cG-l-posilion by the means de~,ibed herein. Additionally, the stored material may be safely ~la..s~o.led.
WO 97t32810 PCTAUS97/02897 -6-The cG~npos;lions of the invention may be prepared and then placed in a storage contA;~.P by any convenient means. Alternatively, the co."?os;lions may be p.~,ared in the storage co..~ e;. Suitable storage CGI~ F ~ are those cGnLaine.s made of, or lined vith, a hydrogen fluoride resis~ t material such as5 carbon steel, polymers, MONELTM, and the like. Storage of the compositions maybe for any length oftime ~ videt that the co~ o~;l;ons are not ~ ,osed to air orother chemicals. Preferably, storage is under ambient cor ~ ionc The stored colnpoe:lion may be safely and effiri~n11y llar,spo.led to a 10 dc,l;--~;on T-~s~o-lin~ ofthe composition may bc by any conventionql means such as by rail car or tmck. Once delivered to the d~ I;on the stored cor,~pos lion may be treated to recover the hydrogen fluoride from the composition for use.
The invenlion will be clarified further by a cor ~ del .. lion of the following examples that are i~ ed so be purely e~e~pl5~.
E~a..,~les F,cq-mrle 1 7 g sodium polyacrylate, m. wt. 1,000,000, were ~. e;gl.ed in a perBuoro~koxy ("PFA") cylinder into which 28 g anhydrous hydrogen fluoride were ch~h g,cd. At ambient t~ ~llpC~ alule, the mixture turned into a viscous solid with a gd-like consistency. The PFA cylinder co.~tA: ~;n8 the mixture was heatedto 90~ C libc. ~ing HF vapors and the HF collected into another cooled cylinder.F.ssenti~lly all of the HF was recovered.
W 097/3~810 PCTrUSg7/02897 Fy~mple 2 The proccdure of FY~mple I was repeated 1 S times with thc same sample of sodium polyac~ylate. FSsentislly all of the HI: was recovered each time.
F.Y~mple 3 The procedurc of Example 1 was used except tha~ 7 g polyacrylamide, m.
wt. 100,000, were substitoted for the sodium polyacrylate of FYPmple 1.
Recovery of HF was 70 % from the gel-like viscous solid.
Example 4 The proced~lre of F--- rl~ 1 was used cxcept that 7 g polyacrylic acid, m.
wt. 1,250,000, were substi~uted for the sodium polyacrylate of Example 1.
F.s3~ ;s~1y all of the HF was recovered from the gel-like viscous solid.
FY~mr'e 5 The p~cedu~e of E~umple 1 wa used except that 5 g polyacrylic acid, m.
wt.. 250,000, were subs~it~ d for the sodium polyacrylate of FY~mple 1. The resultant mixture was a viscous liquid from which eCs~nti~lly all of the ~ was recovcred.
Example 6 The ~occ.lule of Example 1 was used except that 7 g sodium salt of polyacrylic acid copol~...c.,zed with 50 wt percent maleic acid, 50,000 m. wt.
available from Aldrich Chemical Co. were substihlted for the sodium polyacrylate25 of Fy~lnple 1. The resultant mixture was a viscous liquid from which essent~ y all of the HE~ was rccovered.
WO g7132810 PCT/US97tO2897 Example 7 The procedure of Example 1 was used except that 2 g sodium polyacrylate copolyll.c.iLcd with 20 wt percent, 50,000 m. wt acrylamide available from Aldrich Chcmical Co. were sul3stitut~d for the sodium polyacrylate of F :r ,- le I .
5 The reY~ nt mixture was a viscous liquid from which ccs~ ~;AIIy all of the HF was recovered.
r.~..,plc 8 The procedure of Example I was used except that 7 g acrylic acid copol~me.;~c~ with lO wt percent, 200,000 m. wt acrylamide available from Aldrich Chcmical Co. were sub~~inlted for the sotium polyacrylate of FY~nrle 1.
The r~ mixture was a viscous liquid from which ~scc~ ~;slly all ofthe H~
was recovercd.
lS Example 9 The ~ocedurt of Example 1 was used except that 2, lO0 m. wt. sodium polyacrylate was substituted for the sotium polyacrylate of FY~rle 1. The resultant mi~nure was a viscous liquid from which esc~ntislly all of the ~ was recoveret.
FYs-nple 10 The IJrOCedUI e of Example 1 was used except that sodium acrylate copolylllc~d with 10 wt percent, 15,000 m.wt. I.~ h~' ~t~-~rylate available from Aldrich Chemical Co. was substituted for the sodium polyacrylate of Example25 1. The result-snt mixture was a viscous liquid from which essenti~lly all of the ~:
was recovered.
CA 02248083 1998-os-o~
g _ FY~nlrle 1 1 7 g sodium polyaclylate, 1,000,000 m. wt., were weighed in a PFA cylinder into which 30 g of a 40:60 perccnt by weight H~ and water mixture were charged.
The mixturc turned into a gel-like viscous solid. The PFA cylinder con~ini~g the5 ~b~lule was heated to 120~ C libC-dth~g HF and water vapors and the a~ueo~s HFcoll~ct~d into anotber cooled cylinder. FcePn-istly all of the HF and water wererecovered.
FY~nlr'~ 12 The vapor pressures of a number of HF/sotium polyacrylate mixtures were ",tas-Jrcd. For each cxample, ~ hed ~nlolJnts of the polymer and HF were mixed together in a MONEL~M e~l;ndt~ and the cylinder was tepestedly deg~ssed by freeze and thaw cycles for apl,ru~ ely 4 cycles. The cylinder was placed in ate".pe~ reg l~ed bath and a pressure gauge ~Anth a range of 0 to 1000 mm Hg 15 was co~ d to the cylinder. The vapor pressures were read ~om the gauge at various bath t.,..,~,c.~t~,es and the rcsults are shown on Table 1. The vapor pressures of the .,~lu~s werc found to be lower than that of pure HF.
Table I
HF wt pe~ent vP at 2s~ C vP at sOo C vP at 7so C vP at looo C
436 626 1003 over range S02 overnnge ovcr~nge overrange C31 over~nge over~nge overrange loo' 914 2049 4146 7~43 20L~lu-Example 13 The surface tensions of several HF/polyrner mixtures were measured using a DuNouy interfacial tenriorn~ter In this method a plstinum ring was drawn upwardly through the mixture. The force needed to lift the ring off of the liquid 5 surface was l~eas.llcd by the tensiometer and is l"~,pG,Iional to the surface tension of the liquid The results obt&l~et at 15~ C are shown on Table 2 The HF/polymer l~--AIUl es' tensions were found to be higher than that of pure HF which is 8 6 dyne/cm Table 2 Polymer wt o/. PolymerSwf~cc Tension (dyne/cm) Example 1 10 5 lg 3 Example 4 lo o 13 4 Example 7 9.8 1~ 1 Example 8 lo o lS.2 Exarnple 14 A ~ u~c of 30 wt percent sodium polyacrylate and 70 wt percent HF is p-epar. d as in FY~mrle 1 and the mixture is stored in a vessel equipped with a valve The l~ .UI ~ formed is a solid as in Example 1 The rnixture is stored at room tc~ ,e.~l"re for a week with no apl,arenl visual changPs A~er that time thevalve is opened to vent for 1 minute at arnbient ten.p~.~lure and pressure The 20 arnount of HF vented to Al .,os~ h~ e is det~ ned by the .i;~x.lce in weight before and after venting The fraction of ~ vented is dete ...h~ed to be signific~ntly les~ than the HF that would be vented from a vessei of 100 % HF
under identical conditions W O97/32810PCTrUS97/02897 Example 15 A mixture of 30 wt percent sodium polyacrylate uld 70 wt percent HF is prepared as in Example 1 and stirred in a valved vessel. The mixture is a solid as in Fx~tnple 1. The vessel Co~\~A; ~ g the mixture is packed in an ap~,~ot";ate S co~ r and tl~l3pG~ led over a ~;C1 ~.nl~e The vessel containing thc HFlpolymer mixture is unpacked and heatcd and the HF collect~d as in Example 1.
Example 16 The procedure of Fx- ,r~ 1 is repcaled except that I g l~ol~_th~lene oxide, m. wt. 10,000,000 and 19 B H~ are s~bstin~ted for the sodium polyacrylate and HFof Example I .
Example 17 The procedure of Example 1 is repeated except that 7 g poly(methacrylic acid), m. wt. 2,500,000 and 13 g HF are substituted for the sodium polyacrylate and HF of F~ rlc I.
FY~-nple 18 The proc~l~le of Example I is repeated except that 17 g polymethacrylamidc, m. wt. 250,000 and 3 g HF ue substit~ted for the sodium polyacrylate and HF of Fy~np~e 1 Example 19 The p~occl~.~ of Example 1 is r~ peated except that 50 g polyvinyl alcohol, m. wt. 500,000 and 1 g HF are s~lbstituted for the sodium polyacrylate and HF ofExarnple 1.
FY~ 20 The proc~lu...................... of Examplc 1 is rcp~alcd exccpt that 5 g polyvinyl pyrrolidor.P, m. wt. 50,000 and 15 g HF are substituted for the sodium polyacrylate and ~ of Example 1.
Example 2 1 The procedurc of Example 1 is l~p~te~ except that 5 g polyethyl~ A~ AC, m. wt. '.750,000 and 15 g HF are s,JIs~ cd for the sodium polyacrylate and ~ of r.A..~l-le 1.
Claims (10)
1. A composition comprising an intimate mixture of hydrogen fluoride and an effective amount of a water-soluble polymer.
2. The composition of claim 1 wherein the water-soluble polymer is a synthetic water-soluble polymer.
3. The composition of claim 2 wherein the water-soluble polymer is a synthetic water-soluble polymer.
4. The composition of claim 3 wherein the synthetic water-soluble polymer is acrylamide polymer, acrylic acid polymer, ethylene oxide polymer, methacrylic acid polymer, polyethyleneimine polymer, polyvinyl alcohol polymer, polyvinyl pyrrolidone polymer, or mixtures thereof.
5. The composition of claim 4 wherein the acrylic acid polymer is sodium polyacrylate.
6. The composition of claim 1 wherein the amount of water-soluble polymer is from about 2 to about 50 weight percent based on the total weight of the composition.
7. A method of storing hydrogen fluoride comprising the steps of:
(A) preparing an intimate mixture comprising hydrogen fluoride and an effective amount of a water-soluble polymer, and (B) storing the intimate mixture in a storage container.
(A) preparing an intimate mixture comprising hydrogen fluoride and an effective amount of a water-soluble polymer, and (B) storing the intimate mixture in a storage container.
8. The method of claim 7 further comprising the step (C) recovering the hydrogen fluoride from the intimate mixture by (i) treating the intimate mixture so as to liberate a hydrogen fluoride vapor and (ii) condensing the liberated hydrogen fluoride vapor.
9. The method of claim 8 wherein the intimate mixture is treated by simultaneously heating the intimate mixture and increasing the pressure over themixture.
10. A method of transporting hydrogen fluoride comprising the steps of:
(A) preparing an intimate mixture of hydrogen fluoride and an effective amount of a water-soluble polymer, (B) storing the intimate mixture in a storage container; and (C) transporting the storage container to a destination.
(A) preparing an intimate mixture of hydrogen fluoride and an effective amount of a water-soluble polymer, (B) storing the intimate mixture in a storage container; and (C) transporting the storage container to a destination.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/610,816 | 1996-03-07 | ||
| US08/610,816 US6177058B1 (en) | 1996-03-07 | 1996-03-07 | Hydrogen fluoride compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2248083A1 true CA2248083A1 (en) | 1997-09-12 |
Family
ID=24446529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002248083A Abandoned CA2248083A1 (en) | 1996-03-07 | 1997-02-26 | Hydrogen fluoride compositions |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US6177058B1 (en) |
| EP (1) | EP0889848B1 (en) |
| JP (1) | JP2000506116A (en) |
| KR (1) | KR19990087510A (en) |
| AU (1) | AU717955B2 (en) |
| BR (1) | BR9707934A (en) |
| CA (1) | CA2248083A1 (en) |
| DE (1) | DE69706152T2 (en) |
| ES (1) | ES2163132T3 (en) |
| WO (1) | WO1997032810A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6670281B2 (en) | 1998-12-30 | 2003-12-30 | Honeywell International Inc. | HF etching and oxide scale removal |
| US6277342B1 (en) * | 1999-08-23 | 2001-08-21 | Air Products And Chemicals, Inc. | Storage and safe delivery of hazardous specialty gases by acid/base reactions with ionic polymers |
| US6677269B2 (en) * | 2001-05-17 | 2004-01-13 | George A Olah | Environmentally safe alkylation of aliphatic and aromatic hydrocarbons with olefins using solid HF-equivalent catalysts |
| US8329603B2 (en) * | 2003-09-16 | 2012-12-11 | Uop Llc | Isoparaffin-olefin alkylation |
| US7914761B2 (en) * | 2007-06-08 | 2011-03-29 | Honeywell International Inc. | Hydrogen fluoride compositions |
| US8067660B2 (en) * | 2007-06-08 | 2011-11-29 | Honeywell International Inc. | Method and system for restraining a chemical discharge |
| US8309034B2 (en) * | 2007-06-09 | 2012-11-13 | Honeywell International Inc. | Compositions, methods and devices for control and clean-up of hazardous spills |
| WO2016133895A1 (en) * | 2015-02-16 | 2016-08-25 | Schlumberger Technology Corporation | Well treatment |
| US20180093890A1 (en) * | 2016-10-04 | 2018-04-05 | Honeywell International Inc. | Aqueous hydrogen fluoride compositions |
| US10280082B2 (en) * | 2016-10-04 | 2019-05-07 | Honeywell International Inc. | Process to recover hydrogen fluoride from hydrogen fluoride-polymer compositions |
Family Cites Families (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1470772A (en) | 1922-08-21 | 1923-10-16 | Henry L Greenbaum | Paste for etching glass |
| US2903345A (en) | 1957-11-15 | 1959-09-08 | American Cyanamid Co | Etching of barium glass |
| US4373050A (en) | 1966-06-01 | 1983-02-08 | Amchem Products, Inc. | Process and composition for coating metals |
| US3635836A (en) | 1969-11-10 | 1972-01-18 | Gen Mills Inc | Thickened compositions and the process of preparing same |
| US3692581A (en) * | 1971-02-23 | 1972-09-19 | Peter J Ferrara | Acid modification of flour and starch with hci and hf |
| US3947558A (en) * | 1973-08-16 | 1976-03-30 | Dow Chemical (Nederland) B.V. | Method of recovering HF from mixtures containing C1 -C3 halocarbon compounds |
| SU665932A1 (en) * | 1973-11-05 | 1979-06-05 | Государственный научно-исследовательский институт цветных металлов | Method of purifying gases from accompanying admixtures |
| US3927717A (en) * | 1973-12-20 | 1975-12-23 | Texaco Inc | Secondary recovery process utilizing polyvinylpyrrolidones |
| US4079011A (en) * | 1974-09-03 | 1978-03-14 | Texaco Inc. | Composition containing a polyvinylpyrrolidone and method for stimulating well production |
| US4004996A (en) * | 1974-12-23 | 1977-01-25 | Merck & Co., Inc. | Fluorination of organic compounds |
| JPS51147486A (en) * | 1975-06-12 | 1976-12-17 | Dai Ichi Kogyo Seiyaku Co Ltd | Thickener for inorganic acid |
| GB1572032A (en) | 1977-01-31 | 1980-07-23 | Hoechst Uk Ltd | Gels comprising silica and an aqueous acid |
| JPS546820A (en) | 1977-06-18 | 1979-01-19 | Nishiyama Sutenresu Kemikaru K | Acidic cleaning agent for stainless steel |
| US4157376A (en) * | 1977-10-04 | 1979-06-05 | Alovyainikov Alexandr A | Process for purification of gases |
| US4383868A (en) | 1979-05-02 | 1983-05-17 | Braley Gordon K | Treatment of spillages of hazardous chemicals |
| US4297257A (en) | 1980-04-17 | 1981-10-27 | Dart Industries Inc. | Metal stripping composition and method |
| JPS5792502A (en) | 1980-11-28 | 1982-06-09 | Asahi Glass Co Ltd | Method for storage and transportation of hydrofluoric acid |
| US4466893A (en) * | 1981-01-15 | 1984-08-21 | Halliburton Company | Method of preparing and using and composition for acidizing subterranean formations |
| JPS6039169A (en) * | 1983-08-12 | 1985-02-28 | Nippon Light Metal Co Ltd | Hydrophilic surface treating agent for metal |
| US4923753A (en) * | 1987-03-26 | 1990-05-08 | The Dow Chemical Company | Controlled-release compositions for acids |
| US4807703A (en) * | 1987-08-19 | 1989-02-28 | Mobil Oil Corporation | Fracture acidizing sandstone formations |
| US5458674A (en) * | 1993-08-24 | 1995-10-17 | E. I. Du Pont De Nemours And Company | Organic separation from HF |
| US4938935A (en) | 1988-08-08 | 1990-07-03 | Mobil Oil Corporation | Alteration of the character of hydrogen fluoride droplets rendering them more susceptible to a water drench |
| CA1338709C (en) * | 1988-09-06 | 1996-11-12 | Nobuo Totsuka | Electrolytic process and apparatus for forming pattern on surface of metallic object |
| JPH02209795A (en) * | 1989-02-09 | 1990-08-21 | Kawasaki Steel Corp | Manufacture of circuit board |
| JPH03243392A (en) * | 1989-04-19 | 1991-10-30 | Toyo Shigyo Kk | Surface treatment method and planographic printing plate |
| US5073363A (en) | 1989-10-06 | 1991-12-17 | Pellico Michael A | Foamable fluoride gels and method |
| RU2013406C1 (en) | 1991-10-28 | 1994-05-30 | Юлия Алексеевна Щепочкина | Etching solution |
| JPH06264003A (en) * | 1993-03-11 | 1994-09-20 | Nippon Light Metal Co Ltd | Method of surface treatment for imparting mildewproofness and hydrophilicity to aluminum material |
| US5344504A (en) * | 1993-06-22 | 1994-09-06 | Betz Laboratories, Inc. | Treatment for galvanized metal |
| WO1995016740A1 (en) | 1993-12-16 | 1995-06-22 | Mobil Oil Corporation | Hydrogen fluoride composition |
| CA2141492C (en) | 1994-04-28 | 1999-07-27 | Bruce B. Randolph | Transportation of hydrogen fluoride |
| US5663474A (en) * | 1996-03-07 | 1997-09-02 | Alliedsignal Inc. | Alkylation process using hydrogen fluoride-containing alkylation catalysts |
| US5705717A (en) * | 1996-03-07 | 1998-01-06 | Alliedsignal Inc. | Fluorination process using hydrogen fluoride-containing fluorinating agents |
-
1996
- 1996-03-07 US US08/610,816 patent/US6177058B1/en not_active Expired - Lifetime
-
1997
- 1997-02-26 CA CA002248083A patent/CA2248083A1/en not_active Abandoned
- 1997-02-26 EP EP97907829A patent/EP0889848B1/en not_active Expired - Lifetime
- 1997-02-26 ES ES97907829T patent/ES2163132T3/en not_active Expired - Lifetime
- 1997-02-26 BR BR9707934A patent/BR9707934A/en not_active Application Discontinuation
- 1997-02-26 AU AU19727/97A patent/AU717955B2/en not_active Expired
- 1997-02-26 JP JP9531808A patent/JP2000506116A/en not_active Ceased
- 1997-02-26 KR KR1019980706942A patent/KR19990087510A/en not_active Application Discontinuation
- 1997-02-26 DE DE69706152T patent/DE69706152T2/en not_active Expired - Lifetime
- 1997-02-26 WO PCT/US1997/002897 patent/WO1997032810A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69706152D1 (en) | 2001-09-20 |
| ES2163132T3 (en) | 2002-01-16 |
| AU717955B2 (en) | 2000-04-06 |
| DE69706152T2 (en) | 2002-04-18 |
| KR19990087510A (en) | 1999-12-27 |
| JP2000506116A (en) | 2000-05-23 |
| EP0889848A1 (en) | 1999-01-13 |
| BR9707934A (en) | 1999-07-27 |
| WO1997032810A1 (en) | 1997-09-12 |
| EP0889848B1 (en) | 2001-08-16 |
| US6177058B1 (en) | 2001-01-23 |
| AU1972797A (en) | 1997-09-22 |
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