Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
  • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C11/00—Aliphatic unsaturated hydrocarbons
  • C07C11/02—Alkenes
  • C07C11/08—Alkenes with four carbon atoms
  • C07C11/09—Isobutene
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/04—Purification; Separation; Use of additives by distillation
  • C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
  • C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C7/00—Purification; Separation; Use of additives
  • C07C7/20—Use of additives, e.g. for stabilisation
• • 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 invention relates to a process for the production of high-purity isobutene from technical methyl tert-butyl ether (MTBE) and the economical use of the secondary streams.
• MTBE technical methyl tert-butyl ether
• Isobutene is a raw material for the production of butyl rubber. Polyisobutylene, isobutene oligomers, branched C 5 aldehydes and C 5 carboxylic acids. It is also used as an alkylating agent and intermediate for the production of peroxides.
• Isobutene can be obtained by dehydrating isobutane. However, not enough large amounts of pure isobutane are available.
• isobutene In technical streams, for example in the C section of a steam cracker or an FCC unit, isobutene is present together with saturated and unsaturated hydrocarbons. Isobutene cannot be economically separated from these mixtures because of the low boiling point difference or because of the very low separation factor between isobutene and 1-butene by distillation.
• the isobutene can be separated from these C 4 cuts in various ways, depending on which other olefins are to be obtained.
• the first step that all work-up processes have in common is the removal of most of the butadiene and other polyunsaturated hydrocarbons. If butadiene can be marketed well or if there is a need for it, it is separated by extraction or extractive distillation. Otherwise, it is selectively hydrogenated to linear butenes up to a residual concentration of approximately 2000 mass ppm.
• 2-butene or a mixture of linear butenes with a high 2-butene content is also to be obtained in addition to isobutene
• the above-mentioned mixture which typically contains no more than 1% butadiene (C 4 stream from FCC, raffinate I or hydrogenated crack-C 4 ) hydrogenated and hydroiso erized, ie residual butadiene still present is selectively hydrogenated to a residual content of below 5 ppm and isomerized to 1-butene to give 2-butenes.
• the equilibrium position between 1-butene and the two 2-butenes for example, is around 1/17 at 80 ° C, i.e. far on the side of the 2-butenes.
• Isobutene can be separated from a C -olefin mixture via the steps of selective derivatization, separation of the derivative from the remaining hydrocarbon mixture and cleavage of the derivative.
• TBA tert-butanol
• an isobutene-containing C-cut is usually converted to MTBE with methanol, this is purified and split again to give isobutene and methanol.
• the difficulty of this process is to produce isobutene in a purity greater than 99.9%.
• Technical MTBE fuel quality
• C 4 and C 5 hydrocarbons C 4 oligomers (C 8 , C 12 hydrocarbons)
• MSBE 2-mefhoxybutane
• methanol methanol
• TBA 2-mefhoxybutane
• isobutene-containing C streams are first etherified with methanol, so that depending on the conversion, a mixture of MTBE, MSBE, unreacted C hydrocarbons, methanol, water, DME, C 4 oligomers and C 3 and C 5 hydrocarbons as impurities of the C 4 stream is obtained.
• This product mixture is separated by distillation into a low boiler fraction containing the C 3 , C and C 5 hydrocarbons, methanol and DME and a high boiler fraction containing C oligomers.
• the high boiler fraction (MTBE, methanol, MSBE) obtained from the cleavage reaction is fractionated in such a way that methanol is obtained as the high boiler and an azeotrope of methanol, MTBE and MSBE as the low boiler. These fractions are each returned before the neretherification or the cleavage stage.
• This process is complex in that the target product isobutene has to be freed of the accompanying substances of the C feed stream or unreacted reaction products or by-products from the etherification and cleavage reaction in several columns and washing stages. Furthermore, an integrated process should enable unconverted substances such as MTBE or isobutene-containing C 4 streams to be separated off easily and returned to the corresponding reaction stages. In the ideal case, isobutene-containing C 4 hydrocarbons and recovered methanol would be separated off at one point in the process and again used to produce MTBE. MTBE that is not implemented should, however, be used as a separate one Material stream obtained and returned to the ether cleavage reaction. The object of the present invention was therefore to provide a process for producing isobutene from MTBE which can be operated with as few separation stages and recycle streams as possible.
• the present invention is accordingly a process for the preparation of isobutene by acid-catalyzed cleavage of methyl tert-butyl ether (MTBE), in which a feed mixture containing MTBE, C -, C 5 -hydrocarbons, methanol,
• MTBE methyl tert-butyl ether
• the MSBE contained in the feed mixture is found unspecifically in both fractions a) and b), but is expediently removed by a discharge flow from fraction a).
• the process according to the invention can easily be connected to an existing MTBE plant, so that the return flow of the methanol and the C 4 hydrocarbons can be used again for the production of MTBE. It is also possible to use technical MTBE in fuel quality or with even lower specifications.
• the process according to the invention is distinguished from the prior art by a particularly elegant separation of impurities contained in the feed mixture and material streams to be recycled to other process stages.
• methanol and low-boiling impurities in the feed mixture are separated before the cleavage reaction.
• efficient separation of the isobutene obtained in the cleavage reaction is only possible because disruptive accompanying substances have already been removed.
• the recycling of the methanol obtained in the reaction before the Cleavage reaction or more precisely before the first distillation stage in an MTBE synthesis preceding the process according to the invention results in an efficient circulatory procedure of the methanol with simultaneous removal of by-products such as DME, C 4 oligomers, TBA or MSBE.
• FIG. 1 A block diagram for a plant in which the method according to the invention can be carried out is shown in FIG. 1.
• MTBE fuel quality
• (1) is fed into column (2) together with the bottom product (11) from column (9).
• the top product (3) a mixture of MTBE, methanol and C ⁇ and Cs hydrocarbons is drawn off.
• Part (6) is removed from the bottom product (4), which consists predominantly of MTBE, from the column (2) in order to remove high boilers (TBA, diisobutene, MSBE).
• TSA high boilers
• MSBE high boilers
• the other part (5) is moved into the cleavage reactor (7).
• the reaction mixture (8) is separated in the distillation column (9).
• the top product (10) is an isobutene, which may contain methanol, dimethyl ether and water.
• Technical MTBE in fuel quality can be used for the process according to the invention.
• This typically consists of 98 mass% of MTBE and contains approx. 0.5 mass% of C 4 to C 8 hydrocarbons, approx. 1 mass% of methanol, approx. 500 mass ppm of water and 2-methoxybutane.
• the C - and Cs-hydrocarbons in the MTBE are removed together with the MTBE-methanol minimum azeotrope by distillation.
• a distillate is obtained which contains MTBE, methanol and C 4 and C 5 hydrocarbons. This mixture is expediently driven into the synthesis stage of an MTBE plant.
• the number of separation stages in practice is from 10 to 60, in particular from 20 to 40, of which 10 to 30 are for the rectifying section and 10 to 30 for the stripping section. proven.
• the column is suitably equipped with internals consisting of trays, packing or packings.
• the fractionation in this column can be carried out at normal pressure or at elevated pressure. Since the MTBE content in the MTBE / methanol azeotrope decreases with increasing pressure in the pressure range from 1 to 25 bar and as little MTBE as possible is to be separated off with the methanol, the distillation is preferably carried out under excess pressure, in particular in the pressure range from 5 to 25 bar, especially in the pressure range 8 to 20 bar.
• the reflux ratio of the column is between 1 and 10, in particular between 2 and 7.
• the bottom product of column (2) upstream of the cleavage reactor (step a) (FIG. 1) preferably has a C 4 and Cs hydrocarbon content of less than 250 ppm by mass. It contains little methanol and, as high boilers, TBA, 2-methoxybutane and diisobutene.
• part (6) of the bottom product (4) of the column (2) can be discharged continuously.
• the discharge of the C 4 oligomers from fraction a) of the process according to the invention can be carried out either by a discharge stream or by a further distillation stage, for. B. take place as a bottom product.
• One possible use for the discharge stream is the distillative work-up to high-purity MTBE. For this, it is necessary to reduce the content of methanol in the bottom (4) of the column (2) to 50 ppm by mass, which can be achieved by increasing the distillate in the column (2).
• the bottom product which consists predominantly of MTBE, can be cleaved into isobutene and methanol on an acid catalyst arranged in a fixed bed.
• a group of acidic catalysts which can be used in the process according to the invention are solid ion exchange resins with sulfonic acid groups.
• Suitable ion exchange resins are, for example, those which are prepared by sulfonation of phenol / aldehyde condensates or of cooligomers of aromatic vinyl compounds.
• aromatic vinyl compounds for the production of the cooligomers are: styrene, vinyl toluene. Vinylnaphthalene, vinylethylbenzene, methylstyrene, vinylchlorobenzene, vinylxylene and divinylbenzene.
• the cooligomers that result from the reaction of styrene with divinylbenzene are used as a precursor for the production of ion exchange resins with sulfonic acid groups.
• the resins can be made in gel, macroporous or sponge form.
• Strongly acidic resins of the styrene-divinyl type are u. a. sold under the following trade names: Duolite C20, Duolite C26, Amberlyst A15, Amberlyst A35, Amberlyst 36, Amberlite IR-120, Amberlite 200, Dowex 50, Lewatit K2431, Lewatit K2441, Lewatit K2621, Lewatit K2629, Lewatit K2641.
• the properties of these resins in particular the specific surface, porosity, stability, swelling or shrinkage and exchange capacity, can be varied by the manufacturing process.
• MTBE cleavage is carried out in one or more reactors. If several reactors are used, they are connected in series or in parallel or both in series and in parallel. Different types of reactors can be used, such as fixed bed reactors or tube bundle reactors or chain reactors.
• the reactor (s) is / are operated isothermally, polytropically or adiabatically, in a single pass or with an external recycle.
• the reaction temperature in the cleavage reactor in the process according to the invention is between 60 ° C. and 200 ° C., preferably between 80 ° C. and 120 ° C. When using several reactors, the temperatures are the same or different, independently of one another.
• the cleavage of MTBE can be carried out in the liquid phase on acidic ion exchange resins as described for example in DE 3 509 292 or DE 3 610 704 or on acidic aluminum oxides as disclosed for example in DD 240 739.
• the reaction conditions 167 ° C and 1 bar or 297 ° C and 10 bar
• the cleavage processes which are carried out in the pure liquid phase, however, it should be noted that, due to the thermodynamic equilibrium position, high MTBE conversions cannot be achieved in a single pass.
• EP 0 302 336 describes the cleavage of methanol from MTBE on an acidic ion exchange resin which is positioned in the column bottom.
• the cleavage of the Efher takes place here in the column bottom, ie the catalyst is permanently washed around by a mixture of ether, olefin and alcohol. This is disadvantageous for the production of isobutene, since on the one hand slightly higher oligomers of isobutene are formed at relatively high temperatures under the acidic conditions.
• DE 4 322 712 therefore follows a different path.
• the tertiary ether is fed there above the reaction zone of a reaction distillation column, the rectifying section of the column being used for isobutene purification, while methanol is separated from the MTBE-methanol azeotrope in the stripping section of the column.
• the azeotrope returns to the reaction zone.
• a sulfated titanium dioxide extrudate is used as the acid catalyst.
• An alternative process is known from DE 100 20 943, in which the ether to be cleaved (such as MTBE) is introduced into a reactive distillation column below the reaction zone. The actual cleavage takes place at an azeotrope of the ether with the corresponding alcohol.
• cleavage reactor (7) and the column (9) are designed as reactive distillation in the process according to the invention, preference is given to stnictured catalytic multipurpose packings, as described, for example, in US Pat. No. 5,348,710, EP 0 950 433, EP 0428 265, EP 433 222 ,
• structured packing for the purposes of the novel process are for example commercially available as Katapak ® Sulzer AG, Katamax® ® from Koch-Glitsch or Multipak ® from Montz GmbH. They are usually made from sheet metal, preferably black steel, stainless steel, Hastelloy, copper or aluminum, or structured fabric webs.
• the cleavage mixture consisting of unreacted MTBE, methanol, isobutene, low boilers and high boilers, is converted in a column ((9) in FIG. 1) into an isobutene-containing top product and a bottom product which comprises the unreacted MTBE and the major part contains the split methanol, separated.
• the bottom product from the column (9) (FIG. 1) in an additional column (not shown in FIG. 1) into an MTBE-rich bottom product and a top product, which mainly consists of an MTBE / methanol azeotrope. Part of this bottom product can be removed to separate high boilers. The other part is returned to the splitting stage.
• the bottom product from column (9) or the reactive distillation column can be fed into the synthesis stage of an MTBE plant.
• the isobutene separated off from the reaction mixture by distillation contains methanol, water and dimethyl ether. Methanol is optionally removed therefrom by extraction with water using methods known per se.
• the isobutene-containing stream can be fractionated in a purification column into a bottom product containing high-purity isobutene and a top product containing isobutene, volatile by-products and optionally water.
• a water wash to remove methanol can also be connected upstream of this cleaning column.
• a decanter a feed stream consisting of isobutene, DME and water is separated into a heavy, aqueous phase and a light, organic phase from isobutene and DME.
• a column with a decanter for separating water which is located in the side stream of the column is preferably used for this.
• the arrangement of the decanter in the side stream minimizes the isobutene losses. It is also possible to arrange the decanter in the top of the column.
• FIG. 2 shows such a procedure schematically.
• B Isobutene-containing stream obtained according to FIG. 1 (10) is washed with water (16) in the extractor (15). This isobutene stream (17) containing dimethyl ether and water is fed into the column (18), with dimethyl ether being withdrawn as the top product (19) and highly pure isobutene as the bottom product (20).
• a side stream (21) is located below the educt introduction point. withdrawn in liquid form, which is separated in the decanter (22) into an aqueous phase (23) and into an organic phase (24) depleted in water. Water (23) is drawn off and the organic phase (24) is returned to the column.
• the pure isobutene column (18) preferably has a number of stages of 25 to 50, in particular 30-40.
• the isobutene to be purified is fed into the 15th to 30th separation stage, in particular into the 18th to 24th separation stage, counted from below in each case.
• the entire condensate of this separation stage is drawn off two to five separation stages below the feed point and fed into the decanter. After the water has been mechanically separated off, the organic phase is returned one to two separation stages further into the column.
• the decanter (22) is used as a decanting tray within the column, for. B. arranged in the head.
• the aqueous phase is obtained as a side draw.
• the distillation can be carried out at pressures of 8 to 20 bar, in particular at pressures of 8 to 12 bar.
• the distillation temperatures are pressure dependent.
• the head temperature at 9 bar is approximately 40 ° C.
• the isobutene obtained by the process according to the invention has a purity of from 99.90 to 99.98% by mass, in particular from 99.94 to 99.98% by mass, very particularly from 99.96 to 99.98% by mass.
• internals consisting of trays, packing elements or packings can be used for the distillation (column (2), (9) in FIG. 1; column (18) in FIG. 2).
• the following types are used for the column trays: trays with holes or slots in the base plate, trays with necks or chimneys that are covered by bells, caps or hoods, trays with holes in the base plate that are covered by movable valves.
• Random fillings with different packing elements can also be used. They can be made from almost all materials - steel, stainless steel, copper, carbon, earthenware, porcelain, glass, plastics, etc.
• Packs with regular geometry can consist, for example, of sheets or fabrics. Examples of such packs are Sulzer woven packs BX made of metal or plastic, Sulzer lamellar packs Mellapack made of sheet metal, structured packings from Sulzer (Optiflow), Montz (BSH) and Kühni (Rombopack).
• Example 1 MTBE cleavage with separation of isobutene and methanol
• the cleavage of MTBE and the separation of the produced isobutene and the methanol from the unreacted MTBE were carried out in a plant according to FIG. 1, however, without the MTBE synthesis stage (13).
• a column (2) was used which was filled with the Sulzer BX fabric packing and had 30 theoretical plates.
• the reinforcement part had an inner diameter of 50 mm and 15 separation stages and the stripping section had an inner diameter of 80 mm and also 15 separation stages.
• the isobutene was separated off in a column (9) with an inner diameter of 50 mm, which was also equipped with the Sulzer BX fabric packing and had 35 theoretical plates.
• a tube reactor (7) with an inner diameter of 21 mm and a length of 160 mm was used for the MTBE cleavage.
• the tubular reactor was operated in a thermostated oil bath at 100 ° C.
• Example 2 Separation of DME and water from the isobutene with a decanter at the top of the column
• the purification of the isobutene by removing dimethyl ether and water was carried out according to FIG. 3 in a column with a diameter of 50 mm.
• the column was equipped with a Sulzer-BX fabric packing and had 35 theoretical plates.
• the feed to the plant originates from an MTBE cleavage (such as, for example, according to FIG. 1) with subsequent methanol separation by extraction with water.
• Example 3 Separation of DME and water from the isobutene with a decanter arranged on the side
• Example 2 the same column as in Example 2 was used as shown in FIG. 2, but the decanter was arranged below the feed stage.

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• 2002
  • 2002-08-22 DE DE10238370A patent/DE10238370A1/de not_active Withdrawn
• 2003
  • 2003-07-11 CN CNB038199327A patent/CN1325444C/zh not_active Expired - Fee Related
  • 2003-07-11 US US10/524,790 patent/US7439413B2/en not_active Expired - Fee Related
  • 2003-07-11 WO PCT/EP2003/007543 patent/WO2004018393A1/de active Application Filing
  • 2003-07-11 AU AU2003246684A patent/AU2003246684A1/en not_active Abandoned
  • 2003-07-11 KR KR1020057002913A patent/KR20050058406A/ko not_active Application Discontinuation
  • 2003-07-11 PL PL373774A patent/PL206182B1/pl not_active IP Right Cessation
  • 2003-07-11 EP EP03792194A patent/EP1530556A1/de not_active Withdrawn
  • 2003-07-11 JP JP2004530017A patent/JP4499566B2/ja not_active Expired - Fee Related
  • 2003-08-18 TW TW092122658A patent/TWI307686B/zh not_active IP Right Cessation

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