EP0763588B1 - Procédé pour éliminer des i-alcènes à partir de mélanges d'hydrocarbures - Google Patents
Procédé pour éliminer des i-alcènes à partir de mélanges d'hydrocarbures Download PDFInfo
- Publication number
- EP0763588B1 EP0763588B1 EP96113986A EP96113986A EP0763588B1 EP 0763588 B1 EP0763588 B1 EP 0763588B1 EP 96113986 A EP96113986 A EP 96113986A EP 96113986 A EP96113986 A EP 96113986A EP 0763588 B1 EP0763588 B1 EP 0763588B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkenes
- treated
- butene
- process according
- mixture
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/08—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one sorption step
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G70/00—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00
- C10G70/04—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes
- C10G70/046—Working-up undefined normally gaseous mixtures obtained by processes covered by groups C10G9/00, C10G11/00, C10G15/00, C10G47/00, C10G51/00 by physical processes by adsorption, i.e. with the use of solids
Definitions
- the invention relates to a method for a special residual removal of C 4 -C 8 -i-alkenes from mixtures of hydrocarbons in which n- and i-alkenes are contained.
- Such mixtures are treated according to the invention with a cation exchanger in the H + form; the material to be treated is then separated by distillation.
- the process is important in the production of pure n-alkenes.
- C 5 cuts (benzene feed) or from higher-boiling fractions after the aromatics removal
- these hydrocarbon cuts primarily contain the 1-alkene corresponding to the respective number of carbon atoms, the as valuable monomer or comonomer and for the preparation of various alkylates is sought.
- the lowest possible content of the associated i-butene is required in order to ensure trouble-free (co) polymerization.
- this maximum permissible content of i-butene is set at less than 200 ppm.
- a distillative separation for example of i-butene and butene-1, fails in many cases due to the boiling points being too close together; this is particularly pronounced in the example of the C 4 -alkenes mentioned. Therefore, attempts have been made to convert i-butene into a higher-boiling substance by chemical conversion, which is then easier to separate by distillation.
- the reaction with methanol or other lower alcohols to form methyl t-butyl ether (MTBE) or its higher homologues in the presence of acidic catalysts lends itself to this.
- MTBE methyl t-butyl ether
- the raffinate with the remaining butene-1 which is formed by distillation from such a reaction mixture, is contaminated by oxygen compounds in the same boiling range, for example by dimethyl ether. Such oxygen compounds then have to be removed again, for example by an ORU system.
- ORU Oxygen Removal Unit
- oxygen compounds are removed from carbon water streams by adsorption on an active material, such as molecular
- the invention relates to a process for removing C 4 -C 8 -i-alkenes from mixtures thereof containing hydrocarbons with essentially the same number of C atoms, which is characterized in that such mixtures at 0-30 ° C and 1- 25 bar, preferably 10-20 ° C. and 10-20 bar, are treated with a cation exchanger in the H + form and the material to be treated is then distilled into a top product largely free of i-alkenes and into a bottom product containing the conversion products of the i-alkenes is separated.
- the mixture of hydrocarbons to be treated is preferably a C 4 -, a C 5 -C 6 - or a C 4 -C 6 distillation fraction.
- the mixture of hydrocarbons to be treated is a C 4 fraction.
- the outflowing mixture of cracked hydrocarbons is subjected to a distillative separation, in which a C 4 hydrocarbon stream is generally collected separately. This C 4 cut is generally subjected to the extraction of the valuable material butadiene.
- the C 4 -hydrocarbon mixture flowing out here is known as raffinate I.
- raffinate I is used for the chemical conversion of i-butene either Dimerization, including further oligomerization, or t-alkyl ether formation subjected.
- a resulting distillate, freed from i-butene, is in the generally referred to as raffinate II.
- Raffinate II is used for further extraction of the valuable materials butene-1 and butene-2.
- Cation exchangers for the process according to the invention are polymers made from acrylic compounds or styrene which are reacted with crosslinking agents, such as divinylbenzene, to give insoluble resins, or crosslinked phenol-formaldehyde condensates which contain sulfonic acid groups, carboxyl groups or phosphonic acid groups.
- crosslinking agents such as divinylbenzene
- ion exchangers with inorganic carrier material such as functionalized siloxanes can also be used.
- Styrene-divinyl resins with sulfonic acid groups are preferably used.
- Such resins have long been known to the person skilled in the art.
- such resins are present in the H + form at least 50 equivalent%, preferably at least 80 equivalent%, particularly preferably at least 90 equivalent%.
- Such resins are common commercial products, for example for water desalination.
- the process according to the invention can in principle be carried out batchwise or continuously.
- the hydrocarbon mixture containing one or more i-alkenes is treated with a cation exchanger of the type described, if appropriate under such a pressure at which the hydrocarbon mixture is liquid.
- the desired removal of the i-alkenes can be checked by taking samples after specified reaction times.
- the process according to the invention is preferably carried out continuously, using shaft reactors or tubular reactors which are filled with the cation exchanger in the form of a fixed bed.
- i-butene it may be advantageous to separate the major part of i-butene in a first reactor under more stringent reaction conditions, the formation of codimer with loss of butene-1 not yet being too significant, and in a second step under milder conditions to push the remaining i-butene content down to the required specification, and under milder reaction conditions the loss of butene-1 by formation of codimer or by acid-catalytic isomerization to other alkenes can also be adequately avoided.
- the process according to the invention is preferred at a temperature of 0-30 ° C from 10-20 ° C.
- the pressure under which the method according to the invention is carried out to the extent that the mixture to be treated of Hydrocarbons taking into account the desired reaction temperature must be kept in the liquid state; otherwise the pressure is not critical.
- the pressure range to be set according to the invention is therefore 1-30 bar, preferably 10-20 bar; in a particularly preferred manner, how it sets at the desired reaction temperature worked.
- the Reaction mixture can move the reactor both from the bottom up and from the top flow downwards.
- the material to be treated is then separated by distillation.
- the top product obtained is a hydrocarbon mixture largely freed of i-alkene, which can be used in particular for further working up to alkene-1.
- the bottom product obtained is the alkenes with an internal double bond and a higher-boiling mixture which contains the oligomerization products of the removed i-alkenes.
- the distillation can also be carried out in such a way that the alkene-1 and the alkenes with an internal double bond are obtained as the top product and only the higher-boiling oligomerization product remains in the bottom.
- the oligomerization products are essentially C 8 hydrocarbons (dimers) which are 90% by weight and C 12 -, C 16 - or even higher oligomerization products which are at most 10 % By weight are present.
- the composition of the oligomer is strongly dependent on the composition of the feed mixture and the reaction conditions; in general, all possible reaction products arise from the i-alkene with the other alkenes in accordance with the associated reaction rate constants.
- the bottom product obtained can be worked up to pure recyclables.
- a raffinate which has already largely been freed from i-alkene is used as the starting point which is used to comply with the desired specifications of other i-alkene must be freed
- the bottom product represents only a small amount, the Refurbishment is not worthwhile, but this is advantageous for the feed for the steam cracker or can be fed to a catalytic cracker.
- the method according to the invention is used in an LHSV (Liquid Hourly Space Velocity) of 0.1-5 liters of hydrocarbon mixture containing i-alkenes per Liters of cation exchanger per hour, preferably 1-2 l / l ⁇ h, carried out.
- LHSV Liquid Hourly Space Velocity
- the LHSV and the reaction temperature are so dependent on the content of i-alkenes in the hydrocarbon mixture or from the desired residual content
- the i-alkene in the treatment mixture is adjusted to be as complete as possible Sales of i-alkene is achieved with as little loss of 1-alkene as possible.
- a continuous laboratory apparatus consisting of a preheater, a temperature-controlled double-jacket reactor and a separator was filled with 150 ml of cation exchanger in the H + form (Lewatit SPC 118 from Bayer AG).
- a C 4 raffinate II from a steam cracker was passed through the apparatus at a temperature and an LHSV, as indicated in the following Table 1, and at an equal pressure of 15 bar in both experiments, the removal of the i- Butene up to a value of below 200 ppm (below the detectability limit) the slight loss of butene-1 also given in Table 1 occurred.
- the reaction product from the last hour was collected and examined by gas chromatography. This information can also be found in Table 1 below.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Claims (6)
- Procédé d'élimination de i-alcènes en C4-C8 de mélanges contenant ceux-ci, d'hydrocarbures de nombre d'atomes C essentiellement similaires, caractérisé en ce que de tels mélanges sont traités entre 0 et 30°C et entre 1 et 25 bar, avec un échangeur de cations sous forme H+ et en ce que le produit du traitement est ensuite séparé par distillation, en un produit de tête libéré le plus largement possible des i-alcènes et en un produit de queue contenant les produits de conversion des i-alcènes.
- Procédé suivant la revendication 1, caractérisé en ce que le mélange à traiter d'hydrocarbures est une fraction de distillation en C4, C5-C6 ou C4-C6.
- Procédé suivant la revendication 2, caractérisé en ce que le mélange à traiter d'hydrocarbures est une fraction en C4.
- Procédé suivant la revendication 1, caractérisé en ce que lors d'une conduite en continu du procédé, on ajuste une Liquid Hourly Space Velocity (LHSV) allant de 0,1-5, de préférence 1 à 2 litres du mélange à traiter par litre d'échangeur de cations par heure.
- Procédé suivant la revendication 4, caractérisé en ce que l'on ajuste une LHSV en fonction de la teneur en i-alcène (i-butène) et en fonction de la teneur en alcène-1 (butène-1).
- Procédé suivant la revendication 3, caractérisé en ce que l'on ajuste une température de réaction allant de 10 à 20°C.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19533914A DE19533914A1 (de) | 1995-09-13 | 1995-09-13 | Verfahren zur Entfernung von i-Alkenen aus Gemischen von Kohlenwasserstoffen |
DE19533914 | 1995-09-13 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0763588A1 EP0763588A1 (fr) | 1997-03-19 |
EP0763588B1 true EP0763588B1 (fr) | 1999-12-01 |
Family
ID=7772053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96113986A Expired - Lifetime EP0763588B1 (fr) | 1995-09-13 | 1996-09-02 | Procédé pour éliminer des i-alcènes à partir de mélanges d'hydrocarbures |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0763588B1 (fr) |
CZ (1) | CZ291045B6 (fr) |
DE (2) | DE19533914A1 (fr) |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4290881A (en) * | 1977-05-23 | 1981-09-22 | Deutsche Texaco Aktiengesellschaft | Process for the separation of unsaturated compounds from liquid hydrocarbon mixtures |
US4992601A (en) * | 1989-02-15 | 1991-02-12 | Energia Andina Ltd. | Process for the selective separation of alkenes and alkynes |
-
1995
- 1995-09-13 DE DE19533914A patent/DE19533914A1/de not_active Withdrawn
-
1996
- 1996-09-02 EP EP96113986A patent/EP0763588B1/fr not_active Expired - Lifetime
- 1996-09-02 DE DE59603770T patent/DE59603770D1/de not_active Expired - Lifetime
- 1996-09-12 CZ CZ19962685A patent/CZ291045B6/cs not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
CZ268596A3 (cs) | 1998-04-15 |
EP0763588A1 (fr) | 1997-03-19 |
DE59603770D1 (de) | 2000-01-05 |
CZ291045B6 (cs) | 2002-12-11 |
DE19533914A1 (de) | 1997-03-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69918017T2 (de) | Verfahren zur Herstellung eines Treibmittelbestandteils | |
DE69600826T2 (de) | Integriertes Verfahren zur Herstellung von Buten-1 | |
EP1388528B1 (fr) | Procédé pour l'oligomérisation d'isobutène contenu dans des courants d'hydrocarbures contenant du n-butène | |
DE69812693T2 (de) | Verfahren zur oligomerisierung von isobuten | |
EP1199296B1 (fr) | Procédé pour la préparation de raffinat II et de méthyl tert-butyl éther de haute pureté | |
DE3702630C2 (de) | Verfahren zur Herstellung von Benzin | |
EP1508558A1 (fr) | Procédé pour la préparation de tert.-butanol | |
EP1519906A1 (fr) | Procede pour la production de methyl-tert-butylether de grande purete | |
WO2004018393A1 (fr) | Procede de production d'isobutene a partir d'ether methyltertiobutylique technique | |
DE3148109A1 (de) | Verfahren zur herstellung von methyl-tert.-butylether (mtbe) und weitgehend von i-buten und vom methanol befreiten kohlenwasserstoff-raffinaten | |
DE2908426A1 (de) | Verfahren zur gewinnung von isobuten aus isobuten enthaltenden c tief 4 -kohlenwasserstoffgemischen | |
EP0068194B1 (fr) | Procédé pour la séparation de tert.-oléfines pures à partir de mélanges de hydrocarbures | |
DE3101703A1 (de) | Verfahren zur herstellung von buten-1 aus einer c(pfeil abwaerts)4(pfeil abwaerts) -kohlenwasserstoff-fraktion | |
DE2706465C3 (de) | Verfahren zur Gewinnung von Butadien bzw. n-Butenen aus diese enthaltenden Kohlenwasserstoffgemischen unter Abtrennung von Isobuten | |
DD204244A5 (de) | Verfahren zur herstellung von reinen alkyl-tert.-alkylethern und weitgehend vom isoolefin und vom alkanol befreiten kohlenwasserstoff-raffinaten | |
DE1957167B2 (de) | Verfahren zur herstellung von carbonsaeuren durch umsetzung von olefinen mit kohlenmonoxid und wasser in gegenwart eines katalysators, der aus orthophosphorsaeure, bortrifluorid und wasser erhaeltlich ist | |
DE68919805T2 (de) | Wärmeintegrationsverfahren. | |
EP0216991B1 (fr) | Procédé pour la séparation d'hydrocarbures paraffiniques en C4 d'hydrocarbures oléfiniques en C4 | |
EP0763588B1 (fr) | Procédé pour éliminer des i-alcènes à partir de mélanges d'hydrocarbures | |
EP1462433B1 (fr) | Procédé pour la séparation de 2-butanol d' un mélange tert.-butanol/eau | |
EP1911736B1 (fr) | Procédé pour la préparation d'ethers alkyls tertiobutyls par régulation de la température dans les réacteurs | |
DE69509465T2 (de) | Verfahren zur Trennung von mit Olefinen gemischten Paraffinen | |
EP1575886A1 (fr) | Procede de preparation de tert-butanol par la rectification reactive | |
DE3318301A1 (de) | Verfahren zur herstellung von tert.-butyl-alkylethern | |
DE102010022138A1 (de) | Verfahren und Anlage zur Herstellung oxygenatarmer Olefinströme |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE DE FR GB IT NL |
|
17P | Request for examination filed |
Effective date: 19970919 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17Q | First examination report despatched |
Effective date: 19990121 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE DE FR GB IT NL |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19991201 |
|
REF | Corresponds to: |
Ref document number: 59603770 Country of ref document: DE Date of ref document: 20000105 |
|
ITF | It: translation for a ep patent filed |
Owner name: SOCIETA' ITALIANA BREVETTI S.P.A. |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20111201 AND 20111207 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20140102 AND 20140108 |
|
BECA | Be: change of holder's address |
Owner name: HAWKSLEASE CHAPEL LANE,LYNDHURST HAMPSHIRE SO43 Effective date: 20140120 Owner name: INEOS SALES (UK) LTD Effective date: 20140120 |
|
BECH | Be: change of holder |
Owner name: HAWKSLEASE CHAPEL LANE,LYNDHURST HAMPSHIRE SO43 Effective date: 20140120 Owner name: INEOS SALES (UK) LTD Effective date: 20140120 |
|
BECN | Be: change of holder's name |
Owner name: HAWKSLEASE CHAPEL LANE,LYNDHURST HAMPSHIRE SO43 Effective date: 20140120 Owner name: INEOS SALES (UK) LTD Effective date: 20140120 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: TD Effective date: 20140220 Ref country code: NL Ref legal event code: SD Effective date: 20140220 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R082 Ref document number: 59603770 Country of ref document: DE Representative=s name: GODEMEYER BLUM LENZE PATENTANWAELTE, PARTNERSC, DE Ref country code: DE Ref legal event code: R082 Ref document number: 59603770 Country of ref document: DE Representative=s name: GODEMEYER BLUM LENZE PARTNERSCHAFT, PATENTANWA, DE |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20150928 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20150917 Year of fee payment: 20 Ref country code: BE Payment date: 20150928 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20150923 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20150929 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20150926 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 59603770 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MK Effective date: 20160901 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20160901 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20160901 |