'US009663427B2 «2 United States Patent (10) Patent No: US 9,663,427 B2 Krafft et al (4s) Date of Patent: May 30, 2017 (64) PROCESS FOR PRODUCING BEBO A | 70H Me a _ eiaceaeeeiiaiaiaaaa 2319876 AS19493 Moss. (75) Inventors: Philippe Kraff, Rhode Sein Ginese paeoer sien come (BE); Patrick Gidea Shae A 21988 Herma raine-e-Conte (BE, Benoit Gosen, Hanus A 1956 Miler Twas FR) ass O'eonaor "ES Napa 7 Se libs Rima et swoisat (73) Assignee: SOLVAY (Socété Anonyme), Brussels 0 11388 finan (Be) 2 Hoeo Gree 2 Attseo Sars et a (*) Notice: Subject to any disclaimer, the tem ofthis 3 "3368 tine patent is extended or adjusted under 35 S99 ener a USC. 1540) by 751 days 2 oie vita a RLsfos A bet Manteo (21) Appl. No. 124502,296 LUG) A N19 Vandenbers SUSRSHE AUIS Sanders (22) Fie: Su 14, 2009 Savon A ‘toee whe 2a A F19ee Rows ta S3u1ao1 Aber Robinson sa © raceme S3SS,5IL A 1VI967 Schwareer US 200010275726 A1 Now. 5, 2009 2assoot A ‘Sto Schwan Xusior A Stow eh sa Related U.S. Applicaton Data Soitaos Alor Gare (62) Division of application No. 10'58,003, filed as pee t application No. PCU/EP20040S3008 on” Now. 18 Sawin & 2004, now Pat, No, 815,509. estes A Sorts A (60). Provisional application No, 60560,676, fied on Apt ssi A 8.2004, Couinws 0) Foreign Applicaton Priority Data FOREIGN PATENT DOCUMENTS Nov. 20, 2003 (FR) 03 13005 BE uy 7 ch Sinn a Soot 5, 2004 555 a ee ross (Continued) G1) Int. Ch C86 65724 (2006.01) OTHER PUBLICATIONS, CoD wi24 (200601) core 9182 Gooeal} EMikhen ct al, “nsiliion for the Resvery of co wins (200601) Diealoropropanls aad Epcrsyin fom the Waste Water ia cose sot (200601) Fpichloriin Production”, Pol. AppL Chem, vo. 4p coun 707 (2008.01) isisa97, cue a0 (200601) Klaus Wetmore of al, “Indatial One Chemin” (32) USC. Comply Revised Baia): VCH 1997p. 93-98 dau Wensermel a, indi Organi Chemisty” (9 ce core 29762 (201301), C018 rar1a Ki ; rami Chemisty {GorSo1y carp Sov (orsony conc — Comets evict tony VCH 197 paar $9704 2013.01; CHIC 3003 (2013.01), YO2E Comply Revie! Bn) VCH I997-p.347.385 50/13 (2013.00); YORP 205582 2015.11); US "apph No 6086067 led Ape 8 30 YO2P 20584 2015.11) US. Appt No. 74465, fil Now: 8 2008 8) Search US. APL No. co74a7 lad Nov. & 200 US. ADDL No. 60734657 al Nov. & 2008 See application file for complete search history. (Continued) 6) References Cited Primary Examiner — Rosalyn Keys USS, PATENT DOCUMENTS. 280.599 A TSS Baya Ses727 A 91907 Quenens Lsm076 A + 11920 Frohne sss 260.718 A LL1986 Arvin Mes91 A 121936 Dress 2612 ‘11930 Briton tab 29R600 A 41940. Baton eta 2a1s279 A * 101980 Clayton 20077 (74) Attorney, Agent, oF Firm —Oblon, McClelland, Maier & Neusiadl, LLP. on ABSTRACT Process for producing epichlorobyrin comprising subjet- ing to a dehydrochlorination operation, dichloropropanol produced from glycerol comprising aldehydes. 20 Claims, 3 Drawing SheetsUS 9,663,427 B2 Page 2 erences C1 04010123 AL £200 sue e C3) Ref Cited 20040179987 AL 92004 Oku etal US PATENT DOCUMENTS Goosootitts Ale 12a Kale 4401 ; 3oosurisor A300 Heer agseenl A S76 Cain Sigua At 1120 Baler Aaa 2006'0082272 Al 3/2006 Meli etal oot A Lon Seber sta dpicoosnn Al ‘3306 Maa fouasl A ig Yuinetal Soguisiea At Goa Soke Pe He Zoriasss AL Samer eat ea TA lea Soymssiat At 11200 Reem Pian walt tal 2007/0293707 AL 122007 Wolfert et al. bow A thoy shies araovor At 23am We ‘oso A tsa. 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AN pd BP pad ae osoowos7 "T1986 iP 3003 @ e509 1996 i Taner 3008 ae eos AL 997 13805 at 22007 ® S938 ib 326 AL 33007 ar 1998 i {e000 A 3.3007 a 2000-34462 122000 iP tease “3007 ae doorosrass "3001 i (700s! al 4007 ® 2001-21387 B trae AL 43007 @ 2001-261308 Bp Us 278 AL 43007 Sea -t261581 EP does 36t | $2008 ae 2001276872 rR Soe 251101961 @ 2002-02033 He gives oes ae 2002-088195 FR tameon “ates ® 3002 265986 ie 1% Sse ae dooo.aestss Fe 219 Bs S197 @ 2003-81991 Fe bay dis @ 200-9680 FR 246529 2988 @ 2008-13191 FR 27232 ‘Dips ® 2003-20687 Fe dime S200 a 2oousisio2 FR 2eos4i9 10 208 @ 2ooe-216246 FR dao 6i2 11208 @ 2o0s-o0rsa1 FR 2400613112008 @ aoosav7177 FR Dap Sot 13006 ® 76021635 Fe basi T2000 @ 205513064 Fe dasso0s 112000 ® doos.issm2 Fe 301273 ‘A208 2 2007-00808 FR Doi368 —Sa8 @ 2.263338 FR dois 122008 ke 0006513 Fe dora ‘63000 st ust FR Doom Sau wv nas226 FR deme 102009 x uso7is FR doisos% 112000 st sss059 FR poise ‘2010 Wo wo sst4as Fe doysse 200 WO WOdsia19 ey ter Lilt WO Wo s6076I7 oh sane 71982 WO WO sexs oe “oo UE WO WO 9948067 cB agrasl—ort938 wo Wooes7m4 ch Sis? tbat WO WOW LOK a nna ‘esse Wo Wo s932307 c ase 9952 WO wo uO2a74 o Restt F983 WO WooLaII9 cB. 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Soc’ Chim (1943), 10, pp. 52-5, with Enlish Transation. Schroder etal. "Glycerol asa By-Prdt of Boies Production in Dit for Raminaat” Insitute of Animal Nutiton, Physiology ‘and Metabolism, University of Kil, 24008 Kiel, 199. “Chemical Propetes and Derivatives of Geert (1965), pub- lished by Glyeerine Pouce GW. Busby and DE Gosven Ton-Exchange" The Furl ofthe American Oil Chemists Scie. VoL 29, NUN, pp 318-120 (1082), LL. Lamborn, "Modem Sonps, Caniles and Giyesrin” D. Van NOwrand. Company, London. third etition 191%, pp. 542-50, smusta G. Kote, “Historical perspectives on vegetable oibased dicsel Tels Inform, vol 12, Now 2001- pp. 1103-1107 Us Schuchandt tal, “Tranesteifiction of Vegctable Oils & Rovio” I Braz Chom. Soe, vol 9, N- 199-210, 1098 S. Claude, “Reseateh of new outlet for plyeerlrecent developers in France," Fest Lipid 101 (1999), Nr 3,8 101-104, (CB Prakash" crite view of Biodiesel as 4 Transportation Fuel in Canad.” forthe Transportation Systems Branch Ai Pl Inon Peveaion Ditetoate Favioement Canals, Ma. 28, 198, pp. I-04 1D Fukada tal, “Biodiesel Fue Prodston by trnsestericaion of Os”, Joumal of Bioscience and Hoenginering, vol. 92, No 5, fp. a0S-416 (001), ‘iu, Guoying. cal, “Preparation of Biodiesel and Glycerol by ‘Mesiy Ester fiaton of Cottonseed Oi” China Oi and Fa, 2003), vol 28,884, 70-73, pp. 19. ‘2 Stiyong, "Production and. Prospects ofthe World's Natural ‘Giyeerin:” Cereals and Oil (1997), sate O1, 33-38, pads [15 Arthur 3 Hill al"A Symes of Betz-Chloro-Aly Chr Sournal American Chemical Society, 192, 44(11), 2882-2595 ‘Physical and Chemical Distionzy (th Fton), Feb 20, 1998 wth aatached English iramltion of exces). Eneyloptetia Chimica No.X, 1" Eaton, Feb 26, 19621, ith atachod English tramlation of exce), Encylopaoiia Chica, No.2, 1" Ellon Jun. 30, 1960, 1-2, th aatached English ination of exces) Kins Gotti, etal, “Glycerine--A Sustainable Ravy Materia” Chem. Ing Tech 66 (1994) Nel, S, 64-66 (with atached English ‘aslo. Milbert et, ~Dehydochornation of Glycerol Dichlobyin to pichlorohyins” Chem. Papers. 49 3) 133-136 (1995), * cited by examinerU.S. Patent May 30, 2017 Sheet 1 of 3 US 9,663,427 B2U.S. Patent May 30, 2017 Sheet 2 of 3 US 9,663,427 B2 31 26 28 27 29 30: 241 \ 4 | 22: yy) 23 25 20 32U.S. Patent May 30, 2017 Sheet 3 of 3 US 9,663,427 B2US 9,663,427 B2 1 PROCESS FOR PRODUCING EPICHLOROHYDRIN REPERENCE TO PRIOR APPLICATIONS, ‘This application is @ Divisional application of US. appli= ‘ation Sex. No. 10/580,003, fled Dee. 19, 2006, now pend ing: which is a National Stage application of PCT/EPOS! 33008, filed Nox. 18, 2004, which claims benefit of US. Provisional application Ser. No, 60560,676, filed Apr: 8, 2004; and claims priority to French patent applications 03 13625, filed Nov. 20, 2003 and 4 03555, fled Apr. S, 2004, The present invention relates to processes for producing ‘an onganie compound, in particular to a process for produc ing dichloropropano tis known that natural petrochemical resources, for ‘example oil or natural gas, that are available on earth are Timited, Now, these resources are used for producing fuels and as a starting product for producing a large varity of Uwsell omzanie compounds suelt as monomers oF reactants or producing. plastics, for example epichlorohydrin oF sichloropropanol (see, for example, Ullmana’'s Eneyelope- dia of Industrial Chemistry, 5. ed. Vol. A9, p. 530-540), Documents Chemistry and Industry, Nov. 20, 1931, Pact Il, pages 949 to 984, and Nov. 27, 1931, Par I, pages 970 10 975, describe a process forthe synthesis of dicloropropanol from glycerol and hydrochloric acd in the presence of acetic acid a acid catalyst ‘According to known processes for producing dichlono- propanol, the product is generally obtained in highly diluted olution with a ttre of 3 to 15% by weight, It is then Particularly expensive to purify it. Moreover, the major ‘somer oblained uoconding to such processes is 23-dichlo- Fopropane-1-o Tt was desirable to find uses and provesses making it possible to reduce the consumption of natural petrochemical Fesources, in particular for the abovementioned uses, BRIEF Di {CRIPTION OF THE DRAWING FIG. 1 shows a panicular scheme for a plant that ean be used for carrying out the process for producing a chlorinated ‘organic compound aecoeing to the invention. TIG.2 shows a prefered particular schene for plant at ‘ean be used for eatrying out the process for producing Jichloropropanol according to the iavention, FIG. 3 shows a more prefered seheme fora plant that ean be used for carrying out the process for producing dichlo- ropropanol according to the invention twas also desimible to find processes for re-using by= products of other production provesses so as to minimize the ‘overall amount of by-products having to be eliminated oF destroyed. ‘Consequently, the invention relates to the use of glycerol ‘obtained from renewable aw materials, a # starting procict {or producing organie compounds. The use according to the invention makes it possible to ‘obtain a large number of organi compounds while atthe same time minimizing the consumption of natural oil resources. The glycerol derived from renewable raw mate- rials ean be readily and effectively used in reactions for produeing organic compounds, in particular organic com pounds comprising a niimber of carbon atoms which is @ multiple of 3. IPnecessary, the crude glycerol can be readily purified with a view to it being used in the production of ‘organic compounds, 0 o 2 The expression “glycerol obtained from renewable raw materials” is intended 10 denote in particular glycerol ‘obtained in the couse of the production of biodiesel, or else ‘ycerol obtained during conversions of fats or oils of plant ‘or animal origin ia general, such a saponification, tans- ‘esterification or hydrolysis reactions. A particularly stable alyeerol can be obisined during the conversion of animal fats. Another particularly suitable glycerol can be obtained during the production of biodiesel. In contrast, synthetic glycerol is generally obtained from petrochemical resources Ta the use according 1 the invention, the glyeerol ean be a crude product or a purified product, When the glycerol is 4 erude product, it can compris, for example, water and a ‘metal salt, in particular a metal ebloide, which is preferably chosen from NaCl and KCI. The meial salt ea also be selected from metal sulphates such as sodium sulphate and potassium sulphate. The eride product can also contain ‘organic impurities such as carbonyl compounds, in parieu- Jar aldehydes, fatty acids, or esters of fatty acids, such a in particular monoglycerides or diglycerides, optionally in ‘omination with water andlor the metal chloride Tn the use according tothe invention, the erade product generally comprises at least 40% by weight of glycerl Often, the erace product comprises at least 50% by weight of alycerol. Preferably, it comprises atleast 70% by weight of glycerol. Often, the crude product comprises at most 99% by weight of glycerol. Typically it comprises at most 95% by weight of glycerol. In the use accortng to tho invention, the crude product generally comprises at least 5% by weight of water of, in the absence of other compounds, at least Mey weight of water In the use according to the invention, the enile product generally comprises at most 50% by weight of water of, the absence of other compounds, at most 60% by weight of ater, Often, the erude product comprises at most 30% by weight of water, preferably at most 21% by weight of water ‘In another embodiment, the eruce product comprises at most 89% by weight of glycerol. In that embodiment, the trade product comprises at most 85% by weight of glycerl In that embodiment, the crude product comprises generally atleast 109% by weight of water and often atleast 14% by ‘weight of water. ‘Where appropriate, the erude product penerally has ‘metal sal, in particular 1 metal ebloride content of at least 1% by weight, preferably greater than or equal to appro. mately 3% by weight. Where appropriate, the erage product generally has a metal salt, in particular a metal chloride fontent of at most 10% by weight, preferably less than oF equal fo approximately 59% by weight ‘When purified glycerol is used in the use according to the invention, said glycerol is obtained, stating with the enue product, by means of ane or more purification operations such as a distilation, an evaporation, an extraction, or else ‘concentration operation followed by separation operation such as settling ot, ilraton or centrifugation. distillation ‘operation gives good resus Its also possible to carry out ‘an operation consisting in drying the erude prod or the product derived fom the purification operations. Its also possible to carry out @ purification operation which com- ries treating the crude product ora product obtained from nother purification operation, with a resin. An example of such a treatment is a chromatography operation over an jon-exchange resin, in particular an anion exchange resin, Ta the use aeconing tothe iavention, the pried product generally comprises atleast 80 by weight of glycerol. It preferably comprises at least 908% by weight of glycerlUS 9,663,427 B2 3 ‘Oftea, the purified product comprises at most 99.9% by: ‘weight of glycerol Itean comprise at most 97% by weight ‘of glycerol. It can also comprise at most 95% by weight of alyeerl Inthe use according tothe invention, the purified product generally comprises atleast 0.1% by weight of wate. Inthe use according to the invention, the purified product gener ally comprises at most 20% by weight of water. Ofte, the purified product comprises at most 10% by weight of water Itpreferably comprises at most 5% by weight of water. In a particular Variant, the purified product comprises at most 3% by weight of water, In a preferred variant of the use according 10 the javen= tion, the purified glycerol product generally comprises at most 0.5% by weight of aldehydes. It preferably comprises ‘at most 0.1% by weight of aldehyde. Often, the purified alyeerol product generally comprises at least 1-mpkg by ‘weight of aldehydes. thas been found particularly advantageous to reduce the ‘content or totally remove aldehydes possibly present in the ‘nide product, during an evaporation step for instance. This allows to obtain less coloured products from the use accont- ing to the invention, Tn a variant of the use according to the inveation, the alyeerol contains at least one other alcohol, peeferably ‘chosen from methanol and ethanol. The aloahol content the purified product may, for example, be atleast 10 marks. ‘Geaerally, this conwat is less than oF equal 10 10% by ‘weight, A content of another aleohol of les than or equal t0 1000 mg/kg is preferred, “The use according tothe invention applies in particular to the production of organic compounds comprising 4 number ‘of earbon atoms which i multiple of 3. Ina first preferred nbodiment, the organic compound comprises 3 carbon jms Ina second prefered embodiment, the onganic com pounds comprise 6,9, 12, 15 of 18 earbou atoms, peeferably 6, 9 or 12 carbon stom. ‘The use according t0 the invention also applies in pars ticular to the production of oxygenated organic eompotinds preferably comprising a number of carbon atoms as described above, The use according fo the invention applies particularly preferably to the production of chlorinated compounds such a dichloropropanol and epichlomhydrin. Surprisingly. the use according to the invention makes it possible o econo cally obtain these compounds. stating fom renewable ‘Consequently, the invention also relates to a process for producing an organic compound, comprising the use aecord- {ng 10 the invention, ‘Consequently, the invention also relates in particular to 3 method for producing a chlorinated organic compound, ‘acconling to Which glycerol obtained from renewable raw materials is used, in accordance with the use according to the ‘invention, and said glycerol is brought into contact With at Jeast one chlornating agent. It i understood thatthe meth- ‘ds of production described hereinafter can also be carried ‘out with glyeerol in general and are not limited 10 the preferred use of glycerol obtained from renewable raw materials. In the process for producing a chlorinated organic com= pound aeconding to the invention, the chlorinating agent ‘may be an agent for oxidative chlorination of substiutive chlorination. An agent for subst Tred, "Among the agents for oxidative chlorination, mention may in particular be made of chlorine, 0 o 4 Among the ageots for substiutive eblorination, mention ‘nay in particular be made of chlorinating agent compe ing hydrogen chloride This chlorinating agen is particularly advantageous, since itis often obtained as a by-product in organic chlorination, climination or substitution reactions, or else by combustion. Te present invention makes it possible to valorize this by-product. ‘In a first variant, the chlorinating agent is substantially anhydrous hydrogen chloride. ‘This vasiat is paricularly advantageous when the peo= duction takes place on the same site as a production of hhydrogea chloride, for example a production of vinyl chlo- ride or of 4 4-methylenedipheny]disoeyanate (MDD, which provides hydmgen chloride as a by-product, In a second variant, the chlorinating agent is an aqueous solution of hydrogen chloride. In this ease, the hydrogen chloride content of the solution is generally atleast 4% by weight, Preferably, this eontent is greater than or equal 40 20% by weight In this ease, the hydrogen ehloride content of the solution is generally at most 37% by weight ‘This particular aspect makes it possihle to valorize low- quality hydrochloric aeid derived, for example, Irom the pyrolysis of chlorinated organie compounels or having been used for stripping metals. Inpparticular, itis possible to use hydrochloric acid loaded \with diehloropropanol originating, for example, from reaction for producing dichloropmopanol by hypochlorina- tion of the ally chloride, according tothe ustal process for synthesizing thie product, In a particular aspect, concentrated hydrochloric acid generally comprising from 28 to 37% by weight of hydrogen chloride, is used as a primary source of the ehlorinating agent, and said concentrated hydrochloric acid is separate {or example by evaporation, into atleast two fractions, the first consisting essentially of anhydrous hydrogen chloride ‘and the second comprising hydrogen chloride and water in proportions in which they form an szcotrope, seid azcotmope consisting, at a pressure of 1013 kPs, of 19 1 25% of hydrogen chloride and of 75 to 81% by weight of water, ia particular of approximately 20% by weight of hydrogen chloride and of epproximately 80% of wa “This particular aspect makes it possible (0 use a realy tmmspertble chlorinating agent while at the same time allowing an effective control of the water content in the reaction medium, in particular when the resetion between the glycerol and the chlorinaing. agent is carried out in several steps In a thied variant, the chlorinating agent is hydrogen chloride generated in situ within the reaction medium, lor ‘example stating with at inoganie acid such as sulphuric acid or phosphoric seid, and a suitable metal chloride such as NaCl, KCL or CaCl ‘These various variants may be combined: thus, for example, a supply of aquoous HCI can be completed with a supply of gaseous andr anhydrous HCL The process for producing a chlorinated organic com. pound according to the inveation is generally earied out reactor made of or coated with materials that are resistant, ‘under the reaction conditions, o the chlorinating agents, ia particular to hydrogen chloride, 'By way of suitable material, mention may be mado, for cxample, of enameled steel. Polymers may also be use. Among the polymers. polyolefins such as polypropylene and in partictlae Noorinated polymers such a polytetrafiuo- ethylene, poly(vinylidene fhuride) an poly(perluoropro-