WO2002085875A1 - Procede integre de production d'oxydes d'olefines - Google Patents

Procede integre de production d'oxydes d'olefines Download PDF

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Publication number
WO2002085875A1
WO2002085875A1 PCT/EP2002/003299 EP0203299W WO02085875A1 WO 2002085875 A1 WO2002085875 A1 WO 2002085875A1 EP 0203299 W EP0203299 W EP 0203299W WO 02085875 A1 WO02085875 A1 WO 02085875A1
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WO
WIPO (PCT)
Prior art keywords
stream
process according
olefin
unit
ranging
Prior art date
Application number
PCT/EP2002/003299
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English (en)
Inventor
Ugo Romano
Ernesto Occhiello
Renato Paludetto
Original Assignee
Polimeri Europa S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polimeri Europa S.P.A. filed Critical Polimeri Europa S.P.A.
Publication of WO2002085875A1 publication Critical patent/WO2002085875A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to an integrated process for the production of olefin oxides. More specifically, the present invention relates to an integrated process for the production of olefin oxides starting from a C 2 -C 5 al yl stream.
  • the present invention relates to an integrated process for the production of propylene oxide from propane, by the direct oxidation of propylene with hydrogen peroxide.
  • Olefin oxides are useful intermediates for the preparation of a wide variety of compounds.
  • olefin oxides can be used for the production of gly- cols, condensation polymers such as polyol polyethers or polyesters which can be used as such or as useful intermediates in the synthesis of polyurethane resins, elastomers, sealants, etc.
  • the object of the present invention therefore relates to an integrated process for the production of olefin oxides which comprises : a) feeding in continuous to a dehydrogenation unit, a par- affinic stream essentially consisting of at least one C 2 -C 5 alkyl hydrocarbon; b) sending the stream leaving the dehydrogenation unit to a separation unit to produce a stream consisting of hy- drogen, a stream essentially consisting of the non- reacted alkyl hydrocarbon, which is recycled to the dehydrogenation, and a stream essentially consisting of the dehydrogenated alkyl hydrocarbon (olefin stream) ; c) feeding the stream of hydrogen together with a stream of oxygen, to a hydrogen peroxide synthesis unit; d) feeding a part of the olefin stream, together with the hydrogen peroxide produced in step (c) , to an oxidation unit, the rest of the olefin stream being sent to a storage tank; e) recovering the o
  • the paraffinic stream fed to the dehydrogenation can be selected from one or more of the C 2 -C 5 alkyl hydrocarbons even if it is pref- erable to operate with a stream of ethane and/or propane or, even more preferably, with a stream of propane alone.
  • the paraffinic stream coming from a refinery with a purity degree higher than or equal to 95%, is fed to the dehydrogenation unit which effects a catalytic dehydrogena- tion at a temperature ranging from 450 to 800°C, preferably from 550 to 650°C, and at an absolute pressure ranging from 10 to 300 kPa.
  • Any dehydrogenation catalyst for light paraffins can be used in the process, object of the present invention, even if catalysts based on platinum, gallium, chromium, vanadium supported on silica and/or alumina are preferred.
  • the separation of the hydrogen also generally takes place in two steps.
  • a stream of hydrogen is recovered, still containing significant quantities of impurities, whereas in the second step a purification is effected, for example by means of membrane separa- tion or PSA (Pressure Swing Adsorption) , which allows a stream of hydrogen to be obtained with a purity suitable for the subsequent hydrogen peroxide synthesis reaction.
  • PSA Pressure Swing Adsorption
  • the hydrogen, together with a stream of oxygen, is fed to a hydrogen peroxide synthesis unit which operates with well-defined operating conditions.
  • the hy- drogen peroxide can be prepared by feeding in continuous to a stirred reactor containing, in dispersion, a heterogeneous catalyst based on platinum and palladium, a stream consisting of: - a liquid stream containing an alcohol or an alcohol- water mixture with an alcohol content higher than 50% by weight, and an acid or halogenated promoter; and a gaseous stream containing hydrogen, oxygen and an inert gas, wherein the concentration of hydrogen is lower than 4.5% by volume and the concentration of oxygen is lower than 21% by volume, the complement to 100 being the inert gas, for example nitrogen or a noble gas such as helium or argon.
  • a liquid stream is extracted in continuous from the synthesis reactor, containing the hydrogen peroxide produced in a concentration ranging from 2 to 10% by weight and a gaseous stream essentially consisting of non-reacted hydrogen and oxygen and the inert gas, which is recycled.
  • the synthesis reaction is carried out at a temperature ranging from -10 to 60°C, preferably from 0 to 40°C, at a pressure ranging from 1 to 300 bars, preferably from 40 to 150 bars, and with residence times of the liquid medium in the reactor ranging from 0.05 to 5 hours, preferably from 0.1 to 2 hours .
  • the hydrogen peroxide synthesis catalyst contains pal- ladium in a quantity ranging from 0.1 to 3% by weight and platinum in a quantity ranging from 0.01 to 1% by weight, with an atomic ratio between platinum and palladium ranging from 1/500 to 100/100.
  • the palladium is preferably present in a quantity ranging from 0.4 to 2% by weight and the platinum in a quantity ranging from 0.02 to 0.5% by weight, with an atomic ratio between platinum and palladium ranging from 1/200 to 20/100.
  • the catalytic system can comprise one or more promoters selected from metals of groups VIII or IB, such as ruthenium, rhodium, iridium and gold, in a concentration generally not higher than that of the palladium.
  • the catalyst can be prepared by dispersing the active components on an inert carrier by means of precipitation and/or impregnation starting from precursors, for example salts or soluble complexes.
  • the inert carrier can be selected from silica, alumina, silica-alumina, zeolites, activated carbon. Activated carbon with a surface area ranging from 300 to 1400 m 2 /g is preferred.
  • the catalyst is normally dispersed in the reaction medium at a concentration ranging from 0.1 to 10% by weight, preferably from 0.3 to 3% by weight.
  • the liquid stream consists of one or more C ⁇ -C 4 alcohols or a mixture of these alcohols with water.
  • the alcohols methanol is preferred.
  • the acid promoter can be any substance capable of generating hydrogen ions in the liquid reaction medium and is generally selected from inorganic acids such as sulfuric, phosphoric, nitric acids or from organic acids such as sul- fonic acids. ' Sulfuric acid and phosphoric acid are preferred.
  • the concentration of the acid generally ranges from 20 to 1000 mg per kg of liquid medium and preferably from 50 to 500 mg per kg of liquid medium.
  • the halogenated promoter can consist of any substance capable of generating halogen ions in the liquid reaction medium. These substances are generally capable of generating bromide ions such as hydrobromic acid and its salts soluble in the reaction medium, for example alkaline bro- mides .
  • the concentration of halogenated promoter generally ranges from 0.1 to 50 mg per kg of liquid medium and preferably from l to 10 mg per kg of liquid medium.
  • the reaction product containing hydrogen peroxide after filtration for recovering the catalyst dispersed therein, is fed directly to the epoxidation unit of the olefin together with the latter.
  • the fraction of olefin capable of being oxidized by the hydrogen peroxide produced with the hydrogen coming from the de- hydrogenation unit is fed to the epoxidation unit.
  • the re- maining olefin is sent for storage .
  • the reagent streams are fed to the epoxidation reactor under such conditions as to have a molar ratio olefin/H 2 0 2 inside the reaction container, ranging from 10/1 to 1/10, preferably from 6/1 to l/l.
  • the epoxidation reaction is carried out under stirring, in the presence of the same solvent used in the hydrogen peroxide synthesis, at a pH ranging from 5.5 to 8 and in the presence of a catalyst used in a quantity ranging from 1 to 15% by weight with re- spect to the reaction mixture, preferably from 4 to 10%.
  • Any epoxidation catalyst can be used in the process, object of the present invention even if titanium-silicalite having the general formula: xTi0 2 - (1-x) Si0 2 is preferred, wherein x represents a number ranging from 0.0001 to 0.04, preferably from 0.01 to 0.025.
  • This catalyst is described in the patents U.S. 4,410,501, 4,824,976, 4,666,692, 4,656,016, 4,859,785, 4,937,216.
  • the epoxidation reaction of the olefin is carried out at a temperature ranging from 20 to 150°C, preferably from
  • the stream leaving the epoxidation reactor is sent to a purification section from which the olefin oxide produced is recovered and sent for storage, together with the solvent which is recycled both to the hydrogen peroxide synthesis reactor and to the oxidation reactor of the olefin.
  • the most critical section is the separation section of the olefin from the corresponding alkyl hydrocarbon as the products to be separated, for example ethane/ethylene or propane/propylene have very similar boiling points and also because the separation may require the use of a cryogenic unit whose running involves problems of a technological/economic nature.
  • the epoxidation unit as an additional partial separation section of the hydrocarbon mixture leaving the dehy- drogenation unit.
  • a further object of the present invention therefore relates to an integrated process for the production of olefin oxides which comprises: a) feeding in continuous to a dehydrogenation unit, a par- affinic stream essentially consisting of at least one
  • object of the present invention in order to keep the material balance under conditions of self-sufficiency, a fraction of mixed hy- drocarbon stream which contains a quantity of olefin capable of being oxidized by the hydrogen peroxide produced with the hydrogen coming from the dehydrogenation unit, is fed to the epoxidation unit.
  • Figure 1 represents a block scheme of the present process wherein a fraction of the olefin produced after the dehydrogenation phase is fed to the epoxidation unit;
  • Figure 2 represents a block scheme of the present process wherein a fraction of the mixed stream still containing both the olefin and non-dehydrogenated corre- sponding paraffin is fed to the epoxidation unit.
  • D represents the dehydrogenation unit
  • H represents the hydrogen peroxide synthesis unit
  • E represents the epoxidation unit
  • S1-S3 are three separation units
  • P represents a purification unit of the hydrogen stream
  • R is a recovery unit of the solvent
  • PR and PO represent the storage tanks of the olefin and epoxide respectively.
  • the outgoing stream is subjected to a first separation, for example in a distilla- tion system of the cold box type SI, to recover the hydro- gen (2) which, after purification in P (membrane separation or PSA) , is fed, by means of line (3) , to the hydrogen peroxide synthesis unit H together with the stream of oxygen and inert gas (9) .
  • the stream (5) leaving SI goes to the separation section S2, to recover the non-dehydrogenated paraffin (6), which is recycled to the unit D, and the olefin (8) which, according to the scheme of figure 1, is partly stored in PR and is partly sent, by means of line (7) , to the oxidation unit E.
  • the light products or impurities (methane, ethane, ethylene, heavy products) , which are discharged from sections SI, S2 and P are sent to the torch by means of line (4) .
  • the stream (14) containing hydrogen peroxide in solu- tion is fed to the oxidation unit E, together, as already mentioned, with the olefin (7) .
  • the solvent is recovered in the unit E from the stream (11) , which is separated in R and recycled both to the hydrogen peroxide synthesis, by means of (12) , and to the oxidation unit, by means of (13) , as diluent of the hydrogen peroxide solution (10) leaving the synthesis.
  • the olefin oxide produced (16) goes to the separation/purification section S3 from which the non- reacted olefin (17) is recovered, which is recycled to E, and the epoxide (18) stored in PO.
  • the excess water formed during the cycle is separated from the solvent in R, treated with means not illustrated in the figures, and discharged to the sewage by means of line (15) .
  • the hydrocarbon stream (7) is fed to the oxidation unit.
  • the stream is fed to the oxidation unit.
  • the stream is fed to the oxidation unit.
  • the procedure is adopted according to the scheme of Figure 1.
  • the dehydrogenation step is carried out using a fixed bed reactor and a chromium catalyst on alumina.
  • the dehydrogenation temperature is 650°C, the pressure 70 kPa.
  • the hydrogen peroxide synthesis is effected in a solvent (methanol) in which a catalyst consisting of palladium and platinum on coal, is dispersed at a concentration of 1% by weight. 200 mg of H 2 S0 4 per kg of liquid medium and 6 mg of HBr per kg of liquid medium, are used as reaction promoters. The reaction temperature is 25°C, the pressure is 10 MPa. A hydrogen peroxide solution at 7% is obtained, which, after dilution to 3.5%, is fed to the epoxidation unit .
  • a solvent methanol
  • a catalyst consisting of palladium and platinum on coal
  • the latter is effected using titanium silicalite dispersed in a concentration of 6% by weight in the aqueous reaction medium kept at a pH of 6.5 by the addition of NH 4 0H.
  • the reaction temperature is 50°C, the pressure 1.3 MPa.
  • the material balances are indicated in the following table .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé intégré de production d'oxydes d'oléfines comportant une unité de déshydrogénation, une unité de synthèse de peroxyde d'hydrogène et une unité d'époxydation d'oléfines C2-C5 qui sont intégrées les unes aux autres. Selon ce procédé, l'hydrogène provenant des formes déshydrogénées compose une matière première permettant la préparation de peroxyde d'hydrogène qui est ensuite apportée à l'unité d'époxydation avec l'oléfine produite.
PCT/EP2002/003299 2001-04-24 2002-03-21 Procede integre de production d'oxydes d'olefines WO2002085875A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT2001MI000859A ITMI20010859A1 (it) 2001-04-24 2001-04-24 Procedimento integrato per la produzione di ossidi olefinici
ITMI2001A000859 2001-04-24

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WO2002085875A1 true WO2002085875A1 (fr) 2002-10-31

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004020423A1 (fr) * 2002-08-30 2004-03-11 Basf Aktiengesellschaft Procede integre pour la synthese d'oxyde de propylene
WO2005092874A1 (fr) * 2004-03-17 2005-10-06 Lyondell Chemical Technology, L.P. Procede de preparation d'oxyde de propylene
WO2005108285A1 (fr) * 2004-05-11 2005-11-17 Degussa Ag Procede destine a la synthese directe de peroxyde d'hydrogene
EP1943237A2 (fr) * 2005-10-25 2008-07-16 University Of Kansas Processus d'oxydation selective d'olefines en resines epoxydes
WO2009129355A1 (fr) * 2008-04-18 2009-10-22 Dow Global Technologies Inc. Procédé intégré pour la production d'époxydes chlorés tels que l'épichlorhydrine
WO2011118823A1 (fr) * 2010-03-26 2011-09-29 Sumitomo Chemical Company, Limited Procédé de production d'oxyde de propylène
WO2011152268A1 (fr) * 2010-05-31 2011-12-08 Sumitomo Chemical Company, Limited Procédé de production d'un oxyde d'oléfine
US8080677B2 (en) 2005-10-25 2011-12-20 University Of Kansas Process for selective oxidation of olefins to epoxides
CN106478351A (zh) * 2015-08-28 2017-03-08 中国石油化工股份有限公司 异丁烷和/或丙烷脱氢的方法
TWI730093B (zh) 2016-05-17 2021-06-11 德商贏創運營有限公司 自丙烷製備丙烯和1,2-環氧丙烷之整合方法
WO2022238145A1 (fr) 2021-05-10 2022-11-17 Evonik Operations Gmbh Installation intégrée et procédé intégré pour produire un oxyde de propène

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599956A (en) * 1996-02-22 1997-02-04 Uop Integrated process for the production of propylene oxide
WO2000020404A1 (fr) * 1998-10-07 2000-04-13 Arco Chemical Technology L.P. Production d'oxyde de propylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5599956A (en) * 1996-02-22 1997-02-04 Uop Integrated process for the production of propylene oxide
WO2000020404A1 (fr) * 1998-10-07 2000-04-13 Arco Chemical Technology L.P. Production d'oxyde de propylene

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7173143B2 (en) 2002-08-30 2007-02-06 Basf Aktiengesellschaft Integrated method for synthesis propylene oxide
DE10240129A1 (de) * 2002-08-30 2004-05-19 Basf Ag Integriertes Verfahren zur Synthese von Propylenoxid
DE10240129B4 (de) * 2002-08-30 2004-11-11 Basf Ag Integriertes Verfahren zur Synthese von Propylenoxid
WO2004020423A1 (fr) * 2002-08-30 2004-03-11 Basf Aktiengesellschaft Procede integre pour la synthese d'oxyde de propylene
CN100569763C (zh) * 2004-03-17 2009-12-16 利安德化学技术有限公司 制备环氧丙烷的方法
WO2005092874A1 (fr) * 2004-03-17 2005-10-06 Lyondell Chemical Technology, L.P. Procede de preparation d'oxyde de propylene
US7241908B2 (en) 2004-05-11 2007-07-10 Degussa Ag Process for the direct synthesis of hydrogen peroxide
WO2005108285A1 (fr) * 2004-05-11 2005-11-17 Degussa Ag Procede destine a la synthese directe de peroxyde d'hydrogene
US7649101B2 (en) 2005-10-25 2010-01-19 University Of Kansas Process for selective oxidation of olefins to epoxides
EP1943237A4 (fr) * 2005-10-25 2009-10-21 Univ Kansas Processus d'oxydation selective d'olefines en resines epoxydes
EP1943237A2 (fr) * 2005-10-25 2008-07-16 University Of Kansas Processus d'oxydation selective d'olefines en resines epoxydes
US8080677B2 (en) 2005-10-25 2011-12-20 University Of Kansas Process for selective oxidation of olefins to epoxides
WO2009129355A1 (fr) * 2008-04-18 2009-10-22 Dow Global Technologies Inc. Procédé intégré pour la production d'époxydes chlorés tels que l'épichlorhydrine
WO2011118823A1 (fr) * 2010-03-26 2011-09-29 Sumitomo Chemical Company, Limited Procédé de production d'oxyde de propylène
WO2011152268A1 (fr) * 2010-05-31 2011-12-08 Sumitomo Chemical Company, Limited Procédé de production d'un oxyde d'oléfine
CN102918032A (zh) * 2010-05-31 2013-02-06 住友化学株式会社 用于制备烯烃氧化物的方法
CN106478351A (zh) * 2015-08-28 2017-03-08 中国石油化工股份有限公司 异丁烷和/或丙烷脱氢的方法
CN106478351B (zh) * 2015-08-28 2019-02-19 中国石油化工股份有限公司 异丁烷和/或丙烷脱氢的方法
TWI730093B (zh) 2016-05-17 2021-06-11 德商贏創運營有限公司 自丙烷製備丙烯和1,2-環氧丙烷之整合方法
WO2022238145A1 (fr) 2021-05-10 2022-11-17 Evonik Operations Gmbh Installation intégrée et procédé intégré pour produire un oxyde de propène

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Publication number Publication date
ITMI20010859A1 (it) 2002-10-24
ITMI20010859A0 (it) 2001-04-24

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