‘US 20071 cu») United States 97835A1 2) Patent Application Publication co) Pub. No.: US 2007/0197835 A1 Zaher et al. (54) MANUEACTURE OF OXALI DINYDRATE, AcID (76) Inventors: Joseph J. Zaher, Newark, DE ( Bryan C. Frityer, Newark, DE (US), Scott N. Hutchison, Wilmington, DE ws) Comesponlence Address: ET DU PONT DE NEMOURS AND COMPANY, LEGAL PATENT RECORDS CENTER BARLEY MILL PLAZA 28/1128 4417 LANCASTER PIKE WILMINGTON, DE. 19805 (US) 124.720 (21) Appl. No. (22) Filed Mar. 16, 2007 HCI Na,C,0, (43) Pub. Date: Aug. 23, 2007 Related U.S. Application Data (63) Continuation-in-part of application No, 11/2287, fled on Sep. 16, 2005, Publication Classification (51) Int. COC 5142 (200601) (2) US. C1 ‘Sonat; 562/503 on ABSTRACT A process for the manufacture of oxalie acid diydate in ‘which an aqueous solution of sodium oxalate is contacted ‘with hydrochloric aed and the resulting mixture then cooled to precipitate oxalic sid, followed by optional recovery and recycling ofthe sodium oxalate and hytdrochlorie ack into the reaction chamber HyC,0,*2H,04 NaClPatent Application Publication Aug. 23,2007 Sheet 1 of 4 US 2007/0197835 A1 HCI Na,C,0, H,C,04*2H,04 NaCl FIG. 1 Hel NaOH Na,C,0, + H,C,0,*2H,01 Na,C;0, recycle FIG. 2Patent Application Publication Aug. 23,2007 Sheet 2 of 4 US 2007/0197835 AI i HCI, oxalic acid recycle >} na H,C,0,*2H,OL + NaCl FIG. 3 Hel HCI, oxalic acid recycle NaOH Lf | Na,C,0, > LI _,] |_| H,C,0,+2H,01 Na,C,0, recycle FIG. 4Patent Application Publication Aug. 23,2007 Sheet 3 of 4 US 2007/0197835 AI BL é 3: I 2 + 6 +8 a of ar eo 3 — 4.38 3 +32 a & & 1000 + 5000 4000 3000 2000 4 (syunop)AysueyuPatent Application Publication Aug. 23,2007 Sheet 4 of 4 US 2007/0197835 AI A g i 3 a ee = de g tna © ag Te 10 4000 2000 1000 (sjunog)Aisuayu|US 2007/0197835 Al MANUFACTURE OF OXALIC ACID DIIYDRATE [0001] ‘This application is a continvation-in-pan of, and ‘luims the benefit of, U.S. pplication Ser. No. 11/228,378, filed Sep. 16, 2005, which is incorporated in its entirety as ‘a part hereo! forall purposes FIELD OF THE INVENTION [0002] The present invention relates to the manufacture of ‘oxalic acid dihydrate. ‘TECHNICAL BACKGROUND [0003] Oxalie acid (or ethanedive acid) [HOOCCOOHT] dihydrate is curently manulactured by many different routes, One of the most common routes reaets sodium ‘oxalate with lime (ealeium oxide) to precipitate calium, ‘oxalate monohydrate and form an aqveots solution of sodium hydroxide. The caleium oxalate monohydrate is Separated from the caustic solution and in another reaction sep sulfuric acid is used to precipitate calcium sulfate ‘dihydrate and form an aqueous solution of oxalie seid. This ‘aqueous solution of oxalic acid is separated from the cal- ‘ium sullite dihydrate and cooled to induce erystallization ‘of oxalic acid diydrate. The final Mirae is then typically returned tothe sulfuric acid addition step since much of the ‘unused sulfori acid is sil contained in this solution, The ‘calcium sulfate dihydrate forms solid waste byproduct that ‘often requires landil disposal [0004] Oxalie acid or its dihydrate is used curently inthe following commercial applications: in textile finishing as & bleach of stain remover, as 4 metal cleaning agent, as Wood blesch or wood stain lightener and in the tanning and finishing of eater. Iti also used a8 an aditve to inerease {ertlzers and in artillery ammunition to suppress flashing. These relatively limited commercial uses have not spurred 3 ‘commercial demand for finding a more efficient method for ‘oxalic acid. manufacture; and. production by the current ‘manufacture methods has kept pace withthe modest world- ‘wide demand forthe aid [0005] Specifically needed to improve the efficiency of ‘oxalic acid dihydrate production isa process made in one reaction chamber, ic, a one-pot process, and ane that is ‘more environmentally benjgn, such as when the dischanse ‘vaste salt of such a process is sodium ebloride, which need not be disposed in a landil SUMMARY OF THE INVENTION [0006] Disclosed herein is « process comprising: ‘8 contacting an aqueous solution of hydeochlorie acid with soditm oxalate ina reaction zane a a temperature between about 35° C. and about 140" C. to form # mixture, ‘wherein the molar ratio of the water to the sodium oxalate js between 20 to 1 and 350 to 1 and the molae ratio of the hydrochloric acid to the sodium oxalate is areater than 3 10 Vand les than 45 10 1 ») cooling the mixture toa temperature between about ~10° C. and about 25° C. wo form precipitated oxalic acid diy rate in a slurry; and ©) separating the precipitated oxalic ac dihydrate from the slurry, thereby leaving a frst residual solution, Aug. 23, 2007 Steps a and b [0007] ‘The disclosed method may further comprise the ‘steps of recovering both the unreacted hydrochloric acl and the unprecipitated oxalie acid from a residual solution and recycling the recovered hydrochloric cid and the recovered oxalic acid hack (o the rection zone. Alternatively, either the unreacted hydmehlrie acid othe unprecpitated oxalic acid may be recovered and recycled back to the reaction ‘ane. In any ease, the unrecovered oxalic acid may be ‘neutralized with 2 sodium-contaning base solution to form precipitated sodium oxalate, which, after separation from a residual sotution, may be reeyeled back to the reaction zone. yy be carried out in one reaction ebamber. BRIEE DESCRIPTION OF THE DRAWINGS [0008] FIG. 1 shows » generalized process of manufacture ‘by reacting sodium oxalate an hydrochloric acid to result in oxalic acid. [0009] FIG. 2 shows a recyeting variant of FIG. 1, in ‘whieh the sodium oxalate reagent is transfered back to the beginning of the process. [0010] FIG. 3 shows 4 recyeting variant of FIG. 1, in whieh hydrochloric acid and/or oxalic acid are recovered and reeyeled back to the reaction step [0011] FIG. 4 shows a recycling variant of FIG. 3, in \Whiel the sodium oxalate reagent is transfered back to the beginning of the process [0012] FIG. § shows an X-ray diffsction patter of the separated solid of Example 1 indicating the presence of oxalic acid dihydrate [0013] FIG. 6 shows an X-ray diffsetion patter of the separated solid of Example 2 indicating the presence of sodium hydrogen oxalate monohydrate DETAILED DESCRIPTION [0014] Described herein is process forthe manufactore ‘of oxalic acid dihydrate by reacting together hydrochloric ‘acid and sodium oxalate in @eertain rao of molar amounts ofthese reagents and under certain reaction conditions. This racess may be performed in single reation chamber as a ingle reaction step. Both sodium oxalate and hydrochloric ‘cid are inexpensive reagents prodoced in excess of demand by other incistrial processes. Their conversion in a single reaction sep into useful oxalie acid dihydrate ean reduce the waste streams of other industrial processes, Pls, the waste steam of the curently described oxalic acid dihydrate ‘mantfactare is # sodinim chloride solution that may be environmentally benign enough for discharge into large bodies of water [0015] Reacting hydrochloric acid with sodium oxalate ‘may take place in one reaction chamber. Either or both reagents may be recycle back tothe beginning or front-end ‘step of the process to fther reduce costs and provide an ‘increased amount of starting material. In addition to the novelty ofthis manufacture, the process of recycling hydro- chlori acid and sodium oxalate in this manufacture has not heretofore been practicedUS 2007/0197835 Al Delinitons [0016] The following definitions explain, illuminate and ‘larify elements recited inthe claims and used herein. [0017] As used herein, “reeyeling” means sending mate~ Fial from the back end of the manufacture process tothe fot end, [0018] As used herein, “recovery” isthe physical sopara- tion of a chemical from a residual solution for the purpose ‘of being recycled [0019] As used herein, “molar ratio” is the quantitative ‘comparison between the amounts of oo chemicals in & mixture, solution, et. which identities their stoichiometric relationship to each other aad which is typically given as @ ‘quotient [0020] As used herein, “residual solution” is @ general term to indicate the solution that remains after the product Jormed by a separation ora prevpitate-forming reaetion, has ben removed! from the restion mixtre [0021] _As used herein, “oxalic aid” refers to oxalie acid solution and “oxalic ack dihydrate” refers to oxalic acid in crystallized fom, [0022] FIG. 1 outlines » generalized manufaeturing pro- ‘ess of oxalic acid. The first step is to contact an aqueous solution of hydrochloric acid with sodium oxalate. The hydrochloric acid sed should be in an amount greater than ‘about 2 moles, greater than about 3 moles, greater than about 44 moles, or greater than about 8 moles, but less than about 5 moles per mole of sodium oxalate. The amount of water present should be greater than about 20 moles, or greater than about 35 moles, but less than about 350 moles per mole ‘of sodium oxalate. In alternative embodiments the concen- teation of hydrochloric acid in the aqneous solution of hydrochloric acid may be no greater than about 18 wt %,and may alternatively be in the ange of about 3 wr % to about 18 wt %. In order to dissolve the sodium oxalate, the reaction should ects a a temperaire in the range of about 38°C. to about 140°C. and the reagents should be thor- ‘oughly sired, [0023] The solution of hydrochloric acid and sodium ‘oxalate is then cooled to precipitate solids of H,C,0..2H,0,, i. oxalic acid dihydrate as indicated by step 2 in FIG. 1 ‘A iemperature between about ~10" C. and about 25° C. achieves maximum yield. Whea the hydrochloric acid is present inthe amount of 3 moles or less per mole of soxium ‘oxalate, the precipiite formed upon cooling is not oxic id diydrate but crystals of sodium hydrogen oxalate monohydrate [0024] The third sep in FIG. 1 is the separation of the solid oxalic acid dihydrate from the residual solution, which may be accomplish by various tecnigues well known ia the art such as filtration or esntrfigation. The solid oxalic ‘acid dihydrate may then be washed, dried and packaged. [0025] After separation ofthe solid oxaie acid dinydrate, the residual solution contains unreacted hydrochloric acid ‘and unpreciptated oxalic acid. As FIG, 2 shows, that residual solution may be treated by the adlition of soxinm hydroxide to neutralize these remaining acid, thereby form- ing sodium chloride in solution and regenerating sodium oxalate. The regenerated sodium oxalate may be prec Aug. 23, 2007 tated, separated and returned to the front end or beginning of the process to be combined ith the sodium oxalate fed, [0026] Before treating the residual solution that contains ‘unreacted hydrochloric acid and unprecpitated oxalic acid ‘with sodium hydroxide, the residual solution may optionally be processed for sepanition of the hydrochloric acid and ‘oxalic acid by Various techniques well known in the art such fas distillation or extraction FIG. 3 shows that the separated ‘team of hydrochloric acid and oxalic acid may be retumed to the font end of the process to be combined with the hydrochloric acid feed. Finally, sodium oxalate canbe regenerated, precipitated, separated and recycled after hydrochloric eid or oxalic aed or both hydrochloric acid And oxalic aed are frst separated and recycled as shown in FIG. 4 [0027] Any or all ofthe reaction steps in this process may be continous, For example, the sodiia oxalate and hydro- chlorie acid may continuously feed into the reaction cham- ber by separate feed streams or may be mixed into one feed stream, which then enters the reaction chamber. Moroover, the steps Zor recovery and recycling ofthe hydrochlorie acid Andi the sodium oxalate after precipitation and removal of the oxalic acid may also be continuous. Recovery techniques from residual solution, which functions ass waste stream, {or both ofthese reactants are well known in the at, as is recycling of recovered products. Specifically, FIGS. 1 through 4 may depict a continuous manufsetur, recovery and reeyeling process. EXAMPLES [0028] The following Examples fuer illustrate the pro- fess of manufacture of oxalic acid dihydrate described herein and allow one skilled in the art to ascertain its preferred features Example 1 Sulicient HCL [0029] 108.0 grams of deionized water was placed in a lass vessel To the deionized water was added! 1000 grams ‘of 37% hydrochloric seid and 3.5 grams of Aldrich sodium ‘oxalate, The hydroclorie acid to sodium oxalate molar ratio was 4 to 1. The water to sodium oxalate molar ratio was 237.3, This mixture was heated on a hotplate at 80° C, while Stiring for 60 minutes to form a colorless solution with the solids completely dissolved. After 60 minutes at 80°C, the slats vessel containing the solution was placed in an ice bat ‘ntl the temperatures as measured by a thermometer in the solution and one just outside the glass vessel were both 2° C. White solids were observed to form in the solution. [0030] ‘These solids were filtered using # 0.48 micron S00 ‘i. cellulose acetate filter funnel, The solids were washed with saturmted aquonus solution of oxalic acid using 2 sisplacements (about SO mL) and the total mass of colorless filtrate solution collected was I88.5 grams, The solids were ried overnight at 75°C. in a vacuum oven. [0031] X-ray diffraction analysis (using an X°PERT. ‘Mode 3040 automated powder dilatometer mannfactured by PANalytical of Natick, Mass.) showed the solids t0 contain 178 grims of mixed oxalic acid dihydrate and fnhydrous crystals of oxalie aed. The anhydrous crystals Traction is an arifact ofthe drying technique,US 2007/0197835 Al [0022] FIG. 5 shows the X-ray diltaction pattem of the separated solid, This correspond toa yield of at least 56% but not greater than 79% forthe production of oxalic acid dihydrate, Example 2 Insuiicient HCL [0033] 13000 grams of deionized water was placed in a tlass vestel, To the deionized water was added 75.0 grams (037% hydrochloric eid and 33.5 prams of Aldrich sodium ‘oxalate, The hydrochloric acid to sodium oxalate molar naio was 3 1, The watero sodium oxalate mola ratio was 39.4 to 1. This mixture was heated on aot plate at 80° C. while stirring for 60 minutes co form a colorless solution with the solids completoly dissolved. After 60 minutes at 80 C., the lass vessel containing the solution was placed inan ce ath tut the temperatures as measured by a thennometer in the solution and one just outside the glass vessel were both 2° C. White solids were observed to form i the solution. These solids were filtered using a 0.45 micron S00 mL. cellulose cette filter funnel. The solids were washed with deionized Water and the total mass of colorless filrate solution col- lected was 224.7 grams. The solids were dried overnight tunder nitrogen at room temperature [0034] X-ray disfoction analysis (using an X°PERT. Model 3040 automated powder diffraetometer manufactured by PANalytical of Natick, Mass.) showed the solids ‘contain 25.6 grams of sodium hydrogen oxalate monohy= ddrate. FIG. 6 shows the X-ray diflrxction pattem of the separated solid What is claimed is 1. A process comprising: 8) contacting an aqueous solution of hydrochloric acid wih sodium oxalate ina revetion zone ala temperate ‘herween about 38°C. and about 140° C. to form a mixture wherein the solids are dissolved, ‘wherein the molar ratio of the water to the sodium oxalate is between about 20 to 1 and about 350 to 1 and the ‘molar ratio of the Hydrochloric acid to the sodium oxilate is greater than about 3 fo | and less than about 4St0 1 +) cooling the mixture to a temperature between about 10° C. and about 25° C. to form precipitated oxalic acid dihydrate in a slumys and ©) separating the precipitated oxalieaeid dihydrate from the slay, thereby leaving a first resid soliton, 2. The process of claims 1, further comprising the seps of: «neutralizing the fist residual solation with a sodium= containing base to form precipitated sodium oxalate in a shu: ©) separating the precipitated sodium oxalate from the slury, thereby leaving a second residual solution; and 1) recycling the separated saium oxalate to the reaction Aug. 23, 2007 3. The process of claim 1, farther compr 8) separating the hydrochloric acid or the oxalic acid or ‘oth the hydrochloric acid andthe oxalic acid from the first residual solution, thereby leaving a third residual solution; and 1 reeling the acids separated in step gto the rection 4. The process of claim 3, farther comprising te steps of, 1) neutralizing the third residual solution with a sodium- containing base to form precipitated sodium oxalate in fe slur: the steps of ji) separating the precipitated sodium oxalate from the slurry; and ) royeling the sepamsted sodium oxalate to the reaction 8. The process of claim 1, wherein at lest one step is done continvotsl, 6. The process of claim 2, wherein at lest one sep is done continuously. 7.The process of claim 3, wherein at lest one sep is done continuously. 8. The process of claim 4, wherein at lest one step is done continously. 9. The process of claim 1, wherein steps a and b are carried out in one reation chamber. 10, 4 process comprising 8) contacting an aqueous solution of hydrochloric avid ‘with sodium oxalate in reaction zone ata temperature between about 35° C. and about 140° C. to form 3 mixture, ‘wherein the molar ratio of the water to the sod oxalate is between about 38 to 1 and about 350 to 1 and the molar ratio of the hydrochloric acid 0 the sodiu ‘shout 2to Land les than about ») cooling the mixture to a temperature between about “10° C. and about 25° C, to form peeipitated oxalic ‘acid diydrate ina Slurry: and ©) separating the precipitated oxalic aid dihydrate from the slury, thereby leaving a fist residual solution, 11. The process of claim 10, furher comprising the steps of 4) neutralizing the first residual solution with sodium- ‘containing base to form prepitated sodium oxalate in a slury: ©) separating the prccipitated sodium oxalate from the slurry, thereby leaving a second residual sofution; and 1 recycling the separated sodium oxalate o the reaction 12, The process of claim 10, further comprising the steps of 8) separating the hydrochloric acid or the oxalic acid or ‘oth the hydrochloric acid andthe oxalic acid from the first residual solution, thereby leaving a thind residual solution; and fb) recycling the acids separated in step to the reactionUS 2007/0197835 Al a slur: i) separating the precipitated sodium oxalate from the slury; and e reeyeling the separated sodium oxalate 0 the reaction 14. The process of claim 10, wherein atleast one step is done continuously. 15. The process of claim 11, wherein atleast one step is done continuously. 16. The process of claim 12, wherein atleast one step is done continuously. 17. The process of lsim 13, wherein atleast one step is done continuously. 18, The process of claim 10, wherein steps a and are ceartied out in one reaction chamber. 19. A process comprising 8) contacting an aqueous solution of hydrochloric acid ‘with sodium oxalate ina revetion zone ata temperature between about 38° C. and about 140° C. to form a mixture, wherein the molar ratio of the hydrochloric acid to the sodium oxalate is preater than about 20 1 and ess than about 45 10 1, and the concentration of hydrochloric Acid in the aqueous solution of hydrochloric aid is no treater than about 18 wt %: ») cooling the mixture to a temperature between about “10° C. and shout 25° C, to form precipitated oxalic acid dihydrate in a Surry: and ©) separating the precipitated oxalic seid dihydrate fom the slurry, thereby leaving a first residual solution Aug. 23, 2007 20. The process of laim 19, further comprising the steps of «) neutralizing the first residual solution with a sodium- Containing base to form precipitated sodium oxalate in slur: ©) separating the precipitated sodium oxalate ftom the slurry, thereby leaving a second residual solution; and 1 recycling the separated sc 21. The process of claim 19, further comprising the steps of mn oxalate to the rection 2) separating the hydrochloric acid or the oxalic aid or bol the hydrochloric acid and the oxalic seid from the first residual solution, thereby leaving a third residual solution; and 1) recycling the acids separated in step g to the reaction 22, The process of elaim 21, further comprising the steps a slury; {) separating the precipitated sodium oxalate from the slurry and reveling the separated sodium oxalate to the reaction 23. The process ofelaim 19, wherein a last one step is done continuously. 24, The process of claim 20, wherein at least one step is done continuously. 25, The process of claim 21, wherein at last one step is done coatiavously. 26. The process of elaim 22, wherein at least one step is done coatinvously. 27. The process of claim 19, wherein stops a and b are catred out in one reation chamber