CN101497548B - Method for producing n-butene-oligomers and 1-butene from mixture-I made of hydrocarbons having four carbon atoms - Google Patents
Method for producing n-butene-oligomers and 1-butene from mixture-I made of hydrocarbons having four carbon atoms Download PDFInfo
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- CN101497548B CN101497548B CN200910003703.9A CN200910003703A CN101497548B CN 101497548 B CN101497548 B CN 101497548B CN 200910003703 A CN200910003703 A CN 200910003703A CN 101497548 B CN101497548 B CN 101497548B
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- butylene
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- hydrocarbon
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- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 53
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 52
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title description 3
- 125000004432 carbon atom Chemical group C* 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 163
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 84
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 82
- 239000000203 mixture Substances 0.000 claims abstract description 74
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 68
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 31
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001273 butane Substances 0.000 claims abstract description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 99
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 54
- 238000004821 distillation Methods 0.000 claims description 50
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 28
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- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 17
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical class COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
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- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 9
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
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- FVNIMHIOIXPIQT-UHFFFAOYSA-N 2-methoxybutane Chemical compound CCC(C)OC FVNIMHIOIXPIQT-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
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- 150000002830 nitrogen compounds Chemical class 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
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Abstract
The invention relates to a method of preparing n-butene low polymer and 1-butylene from industrial mixture I of C4 hydrocarbon. In particular, the invention relates to a method of preparing n-butene low polymer and 1-butylene from industrial mixture I of C4 hydrocarbon comprising at least 1-butylene, isobutene, butane, 2- butylene and polyunsaturated C4 hydrocarbon.
Description
Technical field
The present invention relates to a kind of from C
4the cuts I of hydrocarbon prepares the method for n-butene oligopolymer and 1-butylene, and described mixture at least comprises 1-butylene, iso-butylene, butane, 2-butylene and polynary unsaturated C
4hydrocarbon.
Background technology
Except other C
4hydrocarbon is as outside iso-butylene and 2-butylene, and 1-butylene is from industrial C
4cut (C
4-Schnitt), for example, from the C of steam cracking device or FCC unit
4cut obtains in a large number.These C
4cut is mainly made up of divinyl, monoolefine iso-butylene, 1-butylene and two kinds of 2-butylene and stable hydrocarbon Trimethylmethane and normal butane.Because the boiling point difference of described inclusion is little little with their separation factor, therefore (Aufarbeitung) difficulty and uneconomical is processed in distillation.Therefore in most cases obtain linear butenes and other products by the combination of chemical conversion and physical sepn operation.
The first step that all operations flexible program of standard has is jointly to remove contained most of divinyl.This removes by means of extractive distillation or selective hydration becomes butylene.Remaining in two kinds of situations is hydrocarbon mixture (cracking (the Cracker)-C of so-called raffinate I (Raffinat I) or hydrogenation
4), it contains alkene iso-butylene, 1-butylene and 2-butylene (cis and trans) except stable hydrocarbon normal butane and Trimethylmethane, and in described hydrocarbon mixture polynary unsaturated C
4hydrocarbon generally exists to be less than 1% share.
Because the boiling point of 1-butylene and iso-butylene is very approaching, can not from these mixtures, isolate 1-butylene economically by simple distillation.Therefore, transform from the cracking-C of raffinate I or hydrogenation by selective chemical
4in remove as far as possible fully iso-butylene.Remove after iso-butylene the remaining hydrocarbon mixture (raffinate II) that contains linear butenes and stable hydrocarbon Trimethylmethane and normal butane.This mixture can further separate by distillation, for example, be separated into the mixture of Trimethylmethane and 1-butylene and two kinds of 2-butylene and normal butane.In further distilation steps, can from the cut that contains 1-butylene, obtain highly purified 1-butylene, it contains a small amount of iso-butylene.This is necessary, because 1-butylene is undesirable vinyl polymerization for iso-butylene impurity wherein as comonomer in a large number.Therefore, the exemplary illustration of 1-butylene defines the content of iso-butylene in 1-butylene and is less than 2000ppm.
Selective chemical about iso-butylene transforms, known several different methods.A kind of method of isobutylene separation is to become corresponding tertbutyl ether with for example methyl alcohol of alcohol or ethanol synthesis.The advantage of this reaction is, iso-butylene can almost transform completely with highly selective under linear butenes exists, and transforms and there is not obvious n-butene.Developed the flexible program of several different methods technology for this reason.The technology that confirms reactive distillation at this is useful especially for reaching higher isobutene conversion.
The most significant industrial method is that iso-butylene and methyl alcohol are reacted into a large amount of methyl tertiary butyl ethers (MTBE) that use mainly as fuel dope.
The another possibility method of iso-butylene chemical conversion is to be reacted into the trimethyl carbinol (TBA) with water.Because water is at C
4solubleness in hydrocarbon is low, and this approach is synthetic more complicated than ether technically.
Another possibility method is to make the low coalescence of iso-butylene that oligopolymer is separated and removed.The shortcoming of this situation is, by oligomeric remove iso-butylene completely in the situation that, most of linear butenes of existence also changes into copolymerization or homopolymerization oligopolymer.Another shortcoming is that 1-butylene part isomery turns to 2-butylene.
There are other C
4under the condition of hydrocarbon, the another possibility method of iso-butylene chemical conversion is and the reacting of formaldehyde.Products therefrom is further processed precedent as isoprene.
A lot of known iso-butylenes transform, and for example changing into the trimethyl carbinol (TBA) or isobutylene oligomer does not provide iso-butylene completely to transform, or only provide poor selectivity in high conversion situation under the condition that has linear butenes.As a solution, simultaneously (EP 0 048 893, DE 29 44 457) or downstream change into the combination of tertbutyl ether for example to implement these methods and residue iso-butylene.
US 4,797,133 has described a kind of method especially, and wherein in the first reaction zone, iso-butylene for example separates and removes by being reacted into the trimethyl carbinol (TBA) from starting hydrocarbon mixture, and remaining resistates was converted in the etherificate stage.
DE 103 02 457 has described a kind of from the C containing iso-butylene
4material stream is prepared the method for isobutylene oligomer and tertbutyl ether, and wherein iso-butylene can be from not containing the C of divinyl substantially
4in hydrocarbon flow, remove completely and only lose on a small quantity linear butenes.In the method, a part of iso-butylene in the first reactions steps on an acidic catalyst oligomerization, and remaining iso-butylene is removed by being reacted into tertbutyl ether with alcohol in reactive distillation tower in the second reactions steps.
DE 25 21 964 has described a kind of dual stage process of preparing alkyl-tert-butyl ether, wherein reacts with alcohol at first stage iso-butylene, separates and removes formed ether, and remaining resistates is imported to the second step of reaction to transform remaining iso-butylene.
DE 10 2,005 062 700 has described a kind of from least containing the C of 1-butylene, iso-butylene, normal butane and 2-butylene
4in the cuts of hydrocarbon, separate the dual stage process of 1-butylene, wherein, be chemically converted at first stage iso-butylene the product that boiling point is higher than 1-butylene.The mixture that contains 1-butylene of gained is distilled and is separated into the cut that contains 1-butylene and optional iso-butylene and the cut that contains 2-butylene and normal butane, and described in contain 1-butylene cut be chemically converted in subordinate phase the product that boiling point is higher than 1-butylene, make it from 1-butylene, separate and remove by distillation.Be mentioned to use and separate the possibility that the 2-butylene of removing is prepared n-butene oligopolymer.
EP 1 029 839 has described a kind of method that makes oligomerization of butenes under the condition that has transition-metal catalyst, wherein, as charging, use all or part of hydrocarbon flow being formed by hydrocarbon flow (1), this hydrocarbon flow (1) mainly contains butylene, and it by separating and remove and obtain from the hydrocarbon flow (2) with lower butene content, and wherein hydrocarbon flow (1) obtains as follows: contain saturated and unsaturated C with polarity extracting agent extractive distillation
4the material stream (2) of hydrocarbon and the tower bottom distillate (4) that obtains the overhead fraction (3) of enrichment stable hydrocarbon and enrichment unsaturated hydrocarbons and contain polarity extracting agent, tower bottom distillate (4) is distilled to be separated into and contains butylene as the overhead fraction (5) of unsaturated hydrocarbons and the tower bottom distillate (6) that contains polarity extracting agent, water or solution washing at least a portion overhead fraction (5), and by dry this part overhead fraction (5) of processing in step (c) and obtain the substantially anhydrous hydrocarbon flow (1) containing butylene.
How all methods of mentioning in the prior art can be with plain mode from industrial C if all not showing
4in hydrocarbon mixture, not only obtain 1-butylene but also obtain n-butene oligopolymer.
Summary of the invention
Therefore, the object of this invention is to provide a kind of method of preparing n-butene oligopolymer and 1-butylene, the method does not have the defect of art methods.
Surprisingly find now, can be with plain mode as follows from C
4the cuts I of hydrocarbon prepares n-butene oligopolymer and 1-butylene, and this mixture at least contains 1-butylene, iso-butylene, butane, 2-butylene and polynary unsaturated C
4hydrocarbon: thus optionally detergent industry mixture I obtains cuts II, obtains cuts III thereby remove divinyl from cuts I or II, identical with cuts III or by mixtures III and C
4hydrocarbon flow mix and in the cuts IIIa that obtains the iso-butylene that contains remove by reacting in two stage methyl tertiary butyl ethers are synthetic with methyl alcohol, and gained methyl tertiary butyl ether (MTBE) is removed, thereby obtain cuts IV, polynary unsaturated C
4removing of hydrocarbon is by 0 to 75 DEG C of temperature, be under 0.05 to 10 quality ppm carbon monoxide exists in the quality based on cuts IV, in liquid phase, on carrier, contain on the fixed bed catalyst of 0.1 to 2 quality % palladium, with this polynary unsaturated C of hydrogen selective hydration
4hydrocarbon is implemented, thereby obtain cuts V, be the low high-boiling fraction S1 that boils cut L1 and contain 2-butylene and normal butane that contains 1-butylene and Trimethylmethane and substantially do not contain normal butane and 2-butylene by cuts V fractionation by distillation, be 1-butylene and Trimethylmethane by the low cut L1 fractionation by distillation of boiling, optionally under 0.1 to 5MPa pressure and at 20 to 160 DEG C of temperature, process high-boiling fraction S1 with the molecular sieve that mean pore size is 0.4 to 1.5nm, thereby obtain cuts VI, with at 0 to 200 DEG C of temperature He under 0.1 to 7MPa pressure, containing nickel, on the solid catalyst of silicon and aluminium, make the n-butene containing in high-boiling fraction S1 or cuts VI carry out oligomeric, thereby obtain oligopolymer O.
According to the flexible program of the inventive method, can reach multiple advantages.Initial according to the inventive method, extremely early stage from the method, by optionally washing C
4the mixture I of hydrocarbon and separating removes the catalyzer poison that both may also may cause interference in the time removing polynary unsaturated hydrocarbons in the time that MTBE is synthetic and oligomeric.Not only avoid thus the inactivation of catalyzer separately, and avoid can react with one of charging thing (Edukt) by catalyzer poison producing or reacting each other forming of the by product that produces by the charging thing by the catalysis of one of catalyzer poison.
Because the heat of multiple operation stages is integrated, can be optimized for the required energy of whole process, for example by the other places in present method, the heat of derivation is used for heating object.
Brief description of the drawings
Be explained in more detail method of the present invention by Fig. 1 below, but the method should be limited to the flexible program in this exemplary drafting.
Fig. 1 schematically shows h) preferred flexible program of method steps.Fig. 1 method for expressing step two stage embodiments h).There is distillation D1 and the D2 in reactive moieties or reactor R1 and R2 and every kind of situation in each stage.First cuts S1 or VI1 arrive reactive moieties R1, wherein n-butene oligomerization.The reaction mixture 2 obtaining from reactive moieties R1 imports the distillation D1 of first stage, and is separated into there and contains unreacted C
4the top stream 3 of hydrocarbon and the tower bottoms stream 4 that contains oligopolymer.Before the shunting 3a of top stream 3 can be returned to reactor R1.The remaining material stream 3b of top stream 3 imports the reactive moieties R2 of subordinate phase.The reaction mixture 5 obtaining from reactive moieties R2 imports the distillation D2 of subordinate phase.The same importing in distillation D2 of tower bottoms stream 4 obtaining in distillation D1.In distillation, D2 obtains top stream 6, and it contains unreacted C
4hydrocarbon, and before can be used as shunting 6a being partly returned to reactive moieties R2.The remaining part 6b of top stream 6 can feed in other application.As bottom product 7, in distillation, D2 obtains oligopolymer O.For the purpose of clearer, omit in the figure common material in industrial technology and flowed for example cooling-water flowing and/or common for example interchanger of equipment or separator.
Embodiment
Exemplary description the method according to this invention below.
From at least containing 1-butylene, iso-butylene, butane, 2-butylene and polynary unsaturated C
4the C of hydrocarbon
4the cuts I of hydrocarbon prepares the inventive method of n-butene oligopolymer and 1-butylene, it is characterized in that, the method at least comprises following methods step:
A) detergent industry mixture I optionally, thus cuts II obtained,
B) from cuts I or II, remove divinyl, thereby obtain cuts III,
C) identical with cuts III or by mixtures III and C
4hydrocarbon mixture mix and in the cuts IIIa that obtains the iso-butylene that contains remove by reacting in two stage methyl tertiary butyl ethers are synthetic with excessive methanol, and gained methyl tertiary butyl ether and unreacted methyl alcohol are removed, thereby obtain cuts IV, wherein, the synthetic first stage of methyl tertiary butyl ether carries out at least two fixed-bed reactor, and the synthetic subordinate phase of methyl tertiary butyl ether has on sulfonic solid acid ion exchange resin, in the reactive distillation tower with 0.5 to 1.5MPa pressure range and the operation of the reflux ratio between with 0.5 and 1.5 under the reaction zone temperature of 50 DEG C to 90 DEG C, carry out,
D) from cuts IV, remove polynary unsaturated C
4hydrocarbon is by 0 to 75 DEG C of temperature, be under 0.05 to 10 quality ppm carbon monoxide exists in the quality based on cuts IV, in liquid phase, on carrier, contain on the fixed bed catalyst of 0.1 to 2 quality % palladium, with this polynary unsaturated C of hydrogen selective hydration
4hydrocarbon is implemented, thereby obtains cuts V,
E) by cuts V fractionation by distillation be the low high-boiling fraction S1 that boils cut L1 and contain 2-butylene and normal butane that contains 1-butylene and Trimethylmethane and substantially do not contain normal butane and 2-butylene,
F) be 1-butylene and Trimethylmethane by the low cut L1 fractionation by distillation of boiling,
G) optionally, under 0.1 to 5MPa pressure and at 20 to 160 DEG C of temperature, process high-boiling fraction S1 with thering is 0.4 molecular sieve to 1.5nm mean pore size, thereby obtain cuts VI, and
H), at 0 to 200 DEG C of temperature and 0.1 under 7MPa pressure, on the heterogeneous catalyst that contains nickel, silicon and aluminium, the n-butene that makes to contain in high-boiling fraction S1 or cuts VI carries out oligomeric, thereby obtains oligopolymer O.
Charging
In the method according to the invention, can use all general operational industrial C
4hydrocarbon mixture.The suitable C containing iso-butylene
4material stream be for example from the primary flash distillate of refinery (Raffinerien), for example, from the C of cracker (steam cracking device, hydrocracking device, cat cracker)
4cut, from the synthetic mixture of Fischer-Tropsch, from the mixture of butane dehydrogenation, from the mixture of linear butenes skeletal isomerization and by alkene replace form mixture.These technical descriptions are in technical literature (K.Weissermel, H.J.Arpe, Industrielle OrganischeChemie, Wiley-VCH, the 5th edition, 1998, the 23 to 24 pages; The 65th to 99 pages; The 122nd to 124 pages) in.
Preferably use the C from steam cracking device
4cut, steam cracking device mainly operates for the production of ethene and propylene, and the raw material wherein using is for example refinery gas, petroleum naphtha, gas and oil
lPG (liquefied petroleum gas (LPG)) and NGL (natural gas liquids), or from the C of cat cracker
4cut.The C producing as by product
4iso-butylene, 1,3-butadiene, 1-butylene, cis-2-butene, Trans-2-butene, normal butane and iso-butane that cut contains different amounts depending on cleavage method difference.
The hydrocarbon mixture that contains iso-butylene and linear butenes for the inventive method preferably has following composition.
Table 1: the typical case's composition that can be used in the industrial hydrocarbon mixture of the inventive method.
Steam cracking device cat cracker
Component CC
4(S) CC
4(K)
Trimethylmethane [quality %] 0.6-6 37
Normal butane [quality %] 0.5-8 13
1-butylene [quality %] 9-25 12
Iso-butylene [quality %] 10-35 15
2-butylene [quality %] 4-20 23
1,3-butadiene [quality %] 25-70 < 1
Explain:
-CC
4(S): to C
4mixture is typical, from the cracking-C of steam cracking device (high severity)
4obtain.
-CC
4(K): cracking-C
4typical case composition, obtain from cat cracker.
Method steps is a): the washing of cuts I
The optional washing of cuts I can water or the aqueous solution complete as washing medium.Preferably use softening water or tap water as washing medium.
Can from cuts I, completely or partially remove hydrophilic component by washing.These hydrophilic compounds are such as being nitrogen compound or oxygen compound.The example of nitrogen compound is such as being can be from the acetonitrile of 1,3-butadiene extractive distillation or N-Methyl pyrrolidone.An example of oxygen compound is such as being can be from the acetone of FC cracker.This washing can complete with one-phase or multistage.Correspondingly regulate industrial design, for example, as extraction tower or as the combination of mixing tank-settling vessel.C is preferably passed through in one-phase washing
4hydrocarbon mixes with washing medium and is then separated to carry out.Being separated can be by using certain filter support.
The mass ratio of washing medium and cuts I is preferably 1: 1 to 1: 100, preferably 1: 3 to 1: 30.
After use washing medium is washed, cuts I water saturation.For fear of two-phase (Zweiphasigkeit) occurs in method steps subsequently in reactor, the temperature of reaction in reactor should be higher than approximately 10 DEG C of washing temperature.
Method steps is b): the removing of divinyl
Can in many ways divinyl be removed from cuts I, or, if carry out optional method steps a), from cuts II, remove, thereby obtain cuts III.
For example, divinyl especially can pass through as US 6,337, and passing through described in 429 for example removed with N-Methyl pyrrolidone extracting and separating 1,3-butadiene, or removes by the selective hydration of 1,3-butadiene.Preferably remove divinyl by selective hydration.Other contained polynary unsaturated compounds, for example 1，2-butadiene, ethyl acetylene and butenyne are in this equally also partly or entirely hydrogenation at least in part.
Divinyl selective hydration is that butylene preferably in liquid phase, carry out with hydrogen on solid catalyst.Preferably, described in DE 195 24 971, in the recirculation reactor (Schlaufreaktor) of multiple series windings, carry out selective hydration.Particularly preferably in carrying out this technique with two stages in two reactors, wherein in two stages of this technique, all supply hydrogen.Preferably use adiabatic fixed-bed reactor as reactor.
According to its source, cuts I used or II can contain for example 30 to 75 quality %, preferably the polynary unsaturated hydrocarbons (mehrfach of 30 to 60 quality %
kohlenwasserstoffen).For example,, at the C of steam cracking device
4in cut, the content of 1,3-butadiene is often about 45 quality %.Cuts I or II can use with dried forms, or optionally use with the form that wets.
The highly selective forming in order to reach linear butenes, maybe advantageously, method for limiting step is the polynary unsaturated hydrocarbons in first stage charging b), is mainly the concentration of 1,3-butadiene.Polynary unsaturated C in cuts I or II
4the input concentration of compound is preferably less than 20 quality %, preferably 3 to 15 quality %, particularly preferably 5 to 10 quality %.When use has the polynary unsaturated C of higher concentration
4when the cuts I of compound or II, the reaction output of first stage is preferably returned (Zur ü ckgef ü hrt), this means that the first reactor (first stage) operates in a looping fashion.
In subordinate phase, adiabatic fixed-bed reactor preferably operate under product is returned situation.Be returned with the ratio of fresh feed and be preferably 50/1 to 2/1, be preferably 35/1 to 5/1.
In the flexible program of the inventive method, selective hydration, preferably at 10 to 100 DEG C, preferably carries out under the reaction zone temperature of 25 to 80 DEG C.In the time using multiple reactor, the average hydrogenation temperature in these reactors can be identical or different.
Be the liquid phase in three-phase system as the material that the contains divinyl stream (cuts I or II) of charging thing.Therefore this hydrogenation, preferably 0.5 to 5MPa, preferably 0.5 is arrived 3MPa, the most particularly preferably under 0.5 to 2.5MPa pressure, carries out, and described pressure records in the ingress of reactor respectively.
Method steps b) the blank pipe speed of middle liquid phase can change in wide region.Especially blank pipe speed can obviously expand and exceedes laminar flow (laminar) scope.Preferred blank pipe speed (the inventive method step b) can be carried out taking this speed) is 50 to 700m
3/ m
2/ h, preferably 100 arrives 450m
3/ m
2/ h.Exist in multiple reactor situations, the blank pipe speed in different reactor can be identical or different.
In the case of the gas (hydrogen) of input reactor than be dissolved in the gas feeding in liquid many, can separate this gas by means of static mixer.Suitable mixing tank is the mixing tank of for example applying for description in DE 10 2,004,021 128.
Gas for hydrogenation can be pure hydrogen or hydrogen-containing gas, for example, contain neither reacting and also not changing the hydrogen of the rare gas element of catalyst activity with charging thing and/or product up to 50 volume %.Rare gas element can be for example nitrogen or methane, but is not carbon monoxide.Because the carbon monoxide in gas often causes the reduction of catalyst activity, therefore its content should be in the scope of a little volume ppm, is preferably less than 10 volume ppm.In technique according to the present invention, preferably use hydrogen that purity is greater than 99.5 volume % as gas.
About selectivity butadiene hydrogenation, preferably use palladium-catalyst-loaded (Palladium-
).Palladium concentration in catalyst-loaded is preferably 0.01 to 1.0 quality %, preferably 0.05 to 1.0 quality %.As Substrates, can use for example MgO, Al
2o
3, SiO
2, TiO
2, SiO
2/ Al
2o
3, CaCO
3or gac or their mixture.Preferred Substrates is Al
2o
3and SiO
2.About hydrogenation, can use especially shell catalyst, wherein hydrogenation activity material is present in the catalyzer of the fringe region of catalyst body.
Catalyzer is preferably so that wherein they bring the form of low flow resistance to use, for example, use as the form of lamellar body, right cylinder, spheroid, strand extrudate (Strangextrudat) or ring bodies with particle, bead or formed body.In each reactor or reaction zone, can use identical or different catalyzer.
Method steps is c): MTBE is synthetic
Method steps c) in, by means of synthetic cuts III b) obtaining from method steps of MTBE or by mixtures III and C
4hydrocarbon mixture mix and obtain mixtures III a in remove iso-butylene.For obtaining the C of cuts IIIa
4the content of the contained 1,3-butadiene of hydrocarbon mixture is preferably less than 1 quality %, is particularly preferably less than 0.5 quality %.Can be mixed into cuts III the typical C of mixtures III a
4hydrocarbon mixture is for example raffinate I and raffinate II.
Raffinate I generally refers to by from containing divinyl, alkene if iso-butylene, 1-butylene and 2-butylene and stable hydrocarbon are as the C of Trimethylmethane and normal butane
4hydrocarbon mixture (for example cracking-C
4) in remove 1,3-butadiene (the maximum residual concentration of 1,3-butadiene is 1 quality %, is preferably less than 0.2 quality %) completely or substantially and obtain C
4hydrocarbon mixture.Raffinate II for example generally refers to be become methyl tertiary butyl ether or Ethyl Tertisry Butyl Ether and separated the raffinate I that removes this ether and iso-butylene is therefrom removed completely or substantially by iso-butylene and methyl alcohol or ethanol synthesis.The method steps of the inventive method c) in, at C
4the iso-butylene containing in the mixtures III of hydrocarbon or IIIa is by separating and remove with two stage methyl tertiary butyl ethers synthetic (MTBE is synthetic) with excessive methanol.MTBE is synthetic can carry out in principle described in DE 101 02 082.
The inventive method step c) in the synthetic first stage of MTBE in fixed-bed reactor, carry out; The subordinate phase of this reaction is carried out with reactive distillation.Synthetic first stage of methyl tertiary butyl ether, preferably at least two, particularly preferably carries out in three fixed-bed reactor.React as wherein methyl alcohol and iso-butylene until approach the reactor of thermodynamic(al)equilibrium, can use conventional fixed-bed reactor (tube bundle reactor
adiabatic fixed-bed reactor, recirculation reactor).They can have or not have part and are returned and operate, and now optionally can coolingly be returned logistics.
In the first stage, iso-butylene transforms until set up the thermodynamic(al)equilibrium of MTBE, methyl alcohol and iso-butylene, and the transformation efficiency that preferably reaches iso-butylene is greater than 94%, is particularly preferably greater than 96%.As catalyzer, preferably use the catalyzer identical with the catalyzer using in subordinate phase.The reactor of first stage is preferably at 20 to 110 DEG C, preferably at 25 to 70 DEG C of temperature, and 0.5 to 5MPa, preferably under 0.7 to 2MPa pressure, operate.
Because the thermodynamic(al)equilibrium between methyl alcohol/iso-butylene and ether at low temperatures is mainly positioned at ether side, therefore for compared with the object of high reaction rate, preferably operating this first reactor higher than wherein utilizing at the temperature of downstream reactor of equilibrium theory of tide.Preferably, the first reactor operates at 35 to 70 DEG C of temperature, and downstream reactor operates at 25 to 50 DEG C of temperature.
Method steps c) mol ratio of the methyl alcohol in the charging of the first reactor of first stage and iso-butylene preferably at 10: 1 to 1: 1, particularly preferably in 5: 1 to 1.1: 1 scopes, particularly preferably in the scope of 1.8: 1 to 1.2: 1.
The synthetic subordinate phase of methyl tertiary butyl ether is carried out in reactive distillation tower, described tower has 0.5 to 1.5MPa, preferably 0.75 in the pressure range of 1.0MPa overvoltage, with in reaction zone 50 DEG C to 90 DEG C, preferably at the temperature of 55 to 70 DEG C, between 0.5 and 1.5, preferably the reflux ratio between 0.7 and 0.9 operates on acidic ion exchange resin.According to definition, reflux ratio refers to the ratio of the distillating stream that is returned stream and derives that enters tower.Relatively low backflow specific energy is brought significant steam saving, thereby makes the inventive method have low energy requirement.Surprisingly, although the reflux ratio in catalyst filling is relative with temperature low, still reach relatively high isobutene conversion.This is surprising especially, because for example Lawrence A.Smith of document, D.Hearn, in Catalytic Distillation Proc.Intersoc.Energy Convers.Conf. (1984) 19
th, (the 2nd volume), the contrary content of document description of quoting in 998-1002 page and this external DE 10102082.Best reflux ratio can depend on composition and the pressure tower of turnout, tower charging.But it is always preferably in above-mentioned scope.
Synthetic by two stage MTBE, the residual concentration that especially can obtain iso-butylene in cuts IV is less than 1000 quality ppm, and preferably 800 quality ppm, are particularly preferably less than 500 quality ppm, based on the C in distillment
4mixture meter.
Reaction pressure in the temperature of tower charging and its composition, tower and turnout are irrelevant, preferably between 50 DEG C and 90 DEG C, preferably between 60 DEG C and 75 DEG C.
Can be above or below the catalyst zone to the charging of reactive distillation tower, preferably below carry out.To the charging of reactive distillation tower preferably below reactive filler, preferably 3 to 13 below reactive filler, particularly preferably 4 to 10 theoretical levels (Trennstufen) that separate are carried out.
In the tower charging of subordinate phase, can contain than the iso-butylene still existing and transform required more methyl alcohol completely.But methyl alcohol is excessive should be subject to following restriction: on the one hand, for methyl alcohol and C
4there is the methyl alcohol of q.s in the azeotrope that hydrocarbon forms, is not again so many on the other hand, to such an extent as to methyl alcohol can enter in bottom product, therefore preferably obtains the MTBE that methanol content is less than 5000wppm.Iso-butylene residual content in subordinate phase charging is preferably less than 2 quality %, is preferably less than 1 quality %.
Optionally extra methyl alcohol can be added in subordinate phase.This can with together with first stage reinforced, carry out, or carry out at a place or some places of reactive distillation tower, for example at tower top and/or on catalyst bed, middle and/or under carry out.
Reactive distillation tower is preferably at rectifying tower
contain catalyzer, and below catalyst filling and above preferably exist spacer plate or distillation filler.Catalyzer or can be integrated for example, in filler (Packung),
filler (EP 0 428 265),
filler (EP 0 396 650) or
in filler (German utility model number 298 7 007.3), as described in the document of quoting, or can be aggregated to (US 5,244,929) on formed body.Preferably use
filler.
Reactive distillation tower preferably has pure fractionation by distillation region above catalyst filling.The region of catalyst filling top preferably has 5 to 20, and particularly 10 to 15 separate level (Trennstufen).The disengaging zone of catalyzer below is contained 12 to 36, and particularly 20 to 30 separate level.Catalyst zone can be evaluated by 1 to 5 theoretical distillment that separates level/packed height (rice).The height of catalyst zone/reactive zone can depend on the isobutene conversion of hope and try to achieve by simple preliminary test.Preferably select so large catalytic amount, make the transformation efficiency of iso-butylene reach 75 to 99%, preferably 85 to 98%, particularly preferably 95 to 97%, the iso-butylene content meter in the charging based on reactive distillation.
The method steps of the inventive method c) the reactive distillation tower in subordinate phase preferably taking the hydraulic pressure load (hydraulischer Belastung) of catalyst filling as 10% to 110% of its flooding point load, preferably 20% operate to 70%.The hydraulic pressure load of distillation tower refers to by the vapor quality stream rising and the liquid mass refluxing and flows the uniform stress of fluidity that tower cross section is produced.Upper load limit represents the maximum load being produced by steam and withdrawing fluid, more than it, because withdrawing fluid is because of the carrying secretly or gathering of the steam flow that rises, causes separating effect to decline.Load lower limit represents minimum load, below it, for example, due to the idle running of Non-Uniform Flow or tower (column plate), separating effect declines or slump (Vauck/M ü ller, " Grundoperationen chemischerVerfahrenstechnik ", 626 pages, VEB Deutscher Verlag f ü rGrundstoffindustrie).
When spotting out (Flutpunkt), so large to the shear-stress of liquid from gas transfer, to such an extent as to all the liquid of amount is carried secretly with the drop form with gas, or in tower, there is inversion of phases (J.Mackowiak, " Fluiddynamik von Kolonnen mit modernen
und Packungen f ü r Gas/Fl ü ssigkeitssysteme ", Otto Salle Verlag 1991).
As catalyzer, in MTBE is synthetic, uses and contain sulfonic solid acid ion exchange resin.Suitable ion exchange resin is for example those by the copolymerized oligomer of phenol/aldehyde condensate or aromatic vinyl compound being carried out to sulfonation makes.Example for the preparation of the aromatic vinyl compound of copolymerized oligomer is: vinylbenzene, Vinyl toluene, vinyl naphthalene, vinyl ethylbenzene, vinyl toluene, vinyl chlorobenzene, vinyl-dimethyl benzene and Vinylstyrene.Especially react with Vinylstyrene by vinylbenzene form copolymerized oligomer as precursor for the preparation of containing sulfonic ion exchange resin.This resin can be made into gel, coarse pored or spongy.The character of these resins, especially specific surface area, porosity, stability, swelling or contraction and exchange capacity, can change by preparation technology.
In the methods of the invention, can use the ion exchange resin of H form.The highly acidic resin of styrene-divinylbenzene type is especially sold with following trade(brand)name: Duolite C20, Duolite C26, Amberlyst 15, Amberlyst 35, Amberlite IR-120, Amberlite200, Dowex 50, Lewatit SPC 118, Lewatit SPC 108, K2611, K2621, OC 1501.As ion exchange resin, preferably use
15,
35 (respectively from Rohm & Haas) or
k2621 (Lanxess) type.
The pore volume that is used as the ion exchange resin of catalyzer is preferably 0.3 to 0.9ml/g, especially 0.5 arrives 0.9ml/g.The granularity of resin is preferably 0.3mm to 1.5mm, and especially 0.5mm is to 1.0mm.Can select narrower or wider size-grade distribution.Therefore for example can use granularity ion exchange resin (monodisperse resin) very uniformly.Based on supply form meter, the capacity of ion-exchanger is preferably 0.7 to 2.0eq/l, especially 1.1 arrives 2.0eq/l, or is preferably 0.5 to 5.5mol/kg, especially 0.8 arrives 5.5mol/kg.Capacity data (mol/kg) based in every kind of situation at the ion exchange resin meter that is for example dried to constant weight at 105 DEG C in hot nitrogen gas stream.
The reaction mixture obtaining from the synthetic subordinate phase of MTBE separates removes obtained methyl tertiary butyl ether and unreacted methyl alcohol, thereby obtains cuts IV.From reaction mixture, separate and remove MTBE and in reactive distillation tower, carry out, wherein MTBE produces as bottom product.As the overhead product of reactive distillation tower, obtain the stream of the material containing methyl alcohol that contains 1-butylene, 2-butylene and butane.
The MTBE producing as bottom product in reactive distillation tower can be for multiple objects.Due to its methyl sec-butyl ether (MSBE) that contains minute quantity, therefore be applicable to preparing high-purity isobutylene by MTBE dissociate again (R ü ckspaltung), because in fact can not form linear butenes by dissociating again of methyl sec-butyl ether.MTBE dissociates and for example can carry out according to DE 100 20943.2.Due to by product (MSBE and C
8-alkene) content little, like this obtain MTBE after residual alcohol is removed in separation, can be used as solvent for analyze or organic synthesis.In addition it can also be as the composition of Fuel Petroleum.
Preferably carry out like this method steps of the inventive method c), make to obtain and contain methyl alcohol and C in subordinate phase
4the overhead product of hydrocarbon mixture, described C
4the iso-butylene content of hydrocarbon mixture is less than 1000 quality ppm, based on C
4hydrocarbon mixture meter, and the bottom product that contains MTBE, and overhead product is separated into cuts IV and methyl alcohol.In the time that MTBE is used as the composition of Fuel Petroleum, no longer need to be further purified MTBE.Can from overhead product, separate and remove methyl alcohol, for example, by being adsorbed on molecular sieve, membrane method, entrainer distillation or extraction, preferably undertaken by extraction, thereby obtain low levels methyl alcohol or do not contain the cuts IV of methyl alcohol.
From overhead product, separate and remove methyl alcohol and especially can extract to realize by the water or the aqueous solution that are used as washing medium.Preferably use pH value to be more than or equal to 8, preferably 8 to 12 the aqueous solution.For example can be by adding aqueous sodium hydroxide solution and/or sulfuric acid to regulate pH value.This extraction is carried out according to known standard industry methods, for example, can carry out at extraction tower or in the cascade of mixing tank and separation vessel.Compared with other method, this has multiple advantages, and for example less investment and running cost are low.
Be used as the water of washing medium or the aqueous solution separates and removes methyl alcohol and preferably in extraction tower, carry out from the overhead product of reactive distillation tower.Now the residual content of alcohol is preferably reduced to below 0.2 quality %, is particularly preferably reduced to below 500 quality ppm, is more particularly preferably reduced to below 50 quality ppm.Extraction tower preferably has 2 to 25, particularly preferably 5 to 15 theoretical levels that separate, and preferably at the temperature of 10 to 90 DEG C and C
4under the pressure of the above at least 0.1MPa of vapor pressure of hydrocarbon, operate.The mass ratio of the overhead product (cuts IV adds methyl alcohol) of washing medium and infeed is preferably 1: 5 to 1: 40.
The washing water that are loaded with alcohol from extraction are preferably processed in independent unit, and are returned at least partly in extraction.This processing example, as undertaken by distillation, does not in fact contain the aqueous distillate of alcohol and the methyl alcohol as overhead product thereby obtain at the bottom of tower.Methyl alcohol can lead back again MTBE synthetic in.
Preferably the overhead product of reactive distillation tower is transferred in extraction tower, be convection current input extraction agent, for example water by the opening for feed that is arranged in tower top to this extraction tower.This extraction agent can take out by the outlet at the bottom of tower.Top at extraction tower can obtain cuts IV as extraction product.
Method steps is d): selective hydration
By using the polynary unsaturated C of hydrogen selective hydration
4hydrocarbon and remove this polynary unsaturated C the industry mixture IV that c) obtains from method steps
4hydrocarbon, thus cuts V obtained.This hydrogenation preferred class is similar to the method for describing in DE 31 43 647 and carries out.
In liquid phase, containing on the fixed bed catalyst of palladium, add carbon monoxide as negative catalyst situation under, carry out this hydrogenation with hydrogen.In the case, hydrogen and carbon monoxide are dissolved in hydrocarbon mixture completely.At least add by polynary unsaturated compound stoichiometry be hydrogenated to the required hydrogen amount of monoene.Can by want hydrogenation cuts IV form to calculate hydrogen amount.
Quality meter based on cuts IV, CO amount is at least 0.05ppm.The amount that exceedes 20ppm generally can not cause hydrogenation result further significantly to be improved, therefore preferred 0.05 to 10ppm amount.The CO optimum quantity that will be metered in each technique can easily be determined by experiment, described in DE 31 43 647.
Catalyzer contains the palladium of 0.1 to 2 quality % on carrier.Such carrier for example comprises aluminum oxide, silica gel, aluminosilicate and gac.The hydrocarbon amount of the catalyzer preferably treatment of every liter of use is 5 to 300 liters.
The temperature of carrying out hydrogenation is 0 to 75 DEG C.In order not produce free water, this hydrogenation is carried out suitably at the temperature higher than method steps extraction c).
Operation pressure must be enough large, to liquid phase is maintained at selected temperature, and the hydrogen of q.s and carbon monoxide entered in solution.Reaction pressure is less than 20MPa, is preferably less than 6MPa, is preferably less than 2MPa.Typical reaction pressure is 1.5MPa.
This hydrogenation preferably divides the multistage to carry out, and particularly preferably carries out in two stages.In the case, feed hydrogen in the upstream of each reactor, preferably carbon monoxide is fed in first reactor.Can under product circulation, operate reactor.
Method steps is e): distillation
It is mainly contain 1-butylene, Trimethylmethane and optional low-boiling-point substance and do not basically contain normal butane and the overhead fraction L1 of 2-butylene that method steps e) comprises cuts V fractionation by distillation, and at least contains the tower bottom distillate S1 of 2-butylene and normal butane.
Cuts V d) obtaining from method steps, is also usually called raffinate II in technical literature, completely or partially fractionation by distillation is removed Trimethylmethane and 1-butylene.The mixture S1 remaining, is also referred to as raffinate III, conventionally mainly contains 2-butylene, normal butane and optional 1-butylene part.Mixture S1 is the inventive method method steps incoming mixture g) or h).Fractionation by distillation can, at the equipment that is generally used for separating this hydrocarbon mixture, for example, be carried out in distillation tower or separation column.
In preferred flexible program, fractionation by distillation is carried out in superfractionator., preferably carry out at lower 1/3rd of tower preferably in the Lower Half of tower to this tower charging.Because the mixture boiling range that will separate is narrow, method steps e) preferably has more than 100, preferably more than 125, particularly preferably, more than 150 theoretical levels that separate, very particularly preferably in 150 to 200 theoretical towers that separate level, carries out.This tower can be designed to packing tower or tray column.Be preferably designed to tray column.
Reflux ratio (quantity of reflux is than distillment withdrawal amount) in tower, depends on and the sum of series working pressure of realization is preferably less than or equal to 20, is preferably less than 14, is particularly preferably less than 11.Water coolant or air carry out condensation relatively.Distil container is preferably designed to liquid liquid separator.Thereby can make the water that optionally contains in incoming flow separated the removing of second-phase as distil container, can obtain technical anhydrous bottom product S1.
Method steps separation e) is preferably 0.4 to 1.0MPa at pressure
definitely, preferred pressure is 0.5 to 0.7MPa
definitelyunder carry out.The temperature separating is preferably 35 to 80 DEG C, preferably 40 to 65 DEG C.
In order to heat the vaporizer of tower using in e) at method steps, can use conventional thermal barrier, for example steam or hot water and preferably from the used heat of other technique.In rear kind of situation, be favourable for tower is equipped with more than one vaporizer.Described tower is preferably equipped with at least one vaporizer and at least one condenser as single tower.Due to energy requirement is high and bottom and the top of tower between temperature contrast little, the connection of therefore saving energy is particularly preferred flexible program.In this for example steam compressed method of reference (Br ü denverdichtung).Another particularly preferred connection is that two pressure of being combined with second tower connects (economic benefits and social benefits distillations (double effect distillation)).Second tower can be preferably the tower in parallel with identical or different separation task.In the case, one of described tower operates under so high pressure, makes its condensing temperature be enough to heat another tower.When from there is the tower thermal technology of different separation tasks on while connecting, the tower that can make in principle any suitable tower of the inventive method and the inventive method outside be positioned at equipment installation site is connected with method steps tower e).Particularly preferably second tower is method steps C f)
4knockout tower.
Method steps is f): 1-butylene separates and removes
It will be 1-butylene and Trimethylmethane and optional low-boiling-point substance from the method steps low cut L1 fractionation by distillation of boiling e) that method steps f) comprises.
The overhead fraction L1 that mainly contains 1-butylene, Trimethylmethane and optional low-boiling-point substance e) obtaining from method steps is distilled and removes 1-butylene.Can remove 1-butylene by distillation fraction L1 in one or more distillation towers.
In preferred flexible program, in distillation tower, separate and remove 1-butylene, wherein obtain very pure 1-butylene as bottom product.As overhead product, obtain the cut that is rich in Trimethylmethane, it optionally additionally contains low-boiling-point substance (for example C
3hydrocarbon).
Preferably in superfractionator, separate., preferably carry out in the bottom of the first half of tower preferably at the first half of tower to this tower charging.Because the boiling range of the mixture that will separate is narrow, thus tower is designed to preferably have more than 100, preferably more than 125, particularly preferably more than 150, and more particularly preferably 150 to 200 theoretical separation grade.Described tower is preferably designed to packing tower or tray column, is preferably designed to tray column.Reflux ratio (quantity of reflux is than distillment withdrawal amount), depends on and progression (Stufenzahl) and the working pressure of realization is preferably less than or equal to 100, is preferably less than 70, is particularly preferably less than 60.More particularly preferably reflux ratio is 30 to 60.Water coolant or air carry out condensation relatively.Distil container is preferably designed to liquid liquid separator.Thereby can make the water that optionally contains in incoming flow separated the removing of second-phase as distil container, can obtain technical anhydrous bottom product.
For heating tower's vaporizer, can use conventional thermal barrier, for example steam or hot water and the preferred used heat from other technique.In rear kind of situation, be favourable for tower is equipped with more than one vaporizer.Described tower is preferably equipped with at least one vaporizer and at least one condenser as single tower.Due to energy requirement is high and bottom and the top of tower between temperature contrast little, the connection of therefore saving energy is particularly preferred flexible program.In this for example steam compressed method of reference.Another particularly preferred connection is that two pressure of being combined with second tower connects (economic benefits and social benefits distillations (double effectdistillation)).Second tower can be preferably the tower in parallel with identical or different separation task.In the case, one of described tower operates under so high pressure, makes its condensing temperature be enough to heat another tower.When from there is the tower thermal technology of different separation tasks on while connecting, the tower that can make in principle any suitable tower of the inventive method and the inventive method outside be positioned at equipment installation site is connected with method steps tower of the present invention f).Particularly preferably second tower is method steps C e)
4knockout tower.In the case, one of described tower operates under so high pressure, makes its condensing temperature be enough to heat another tower.
Except the inventive method step is f) this preferred flexible program, can also from the overhead fraction L1 of the first distillation tower, first separate the low-boiling-point substance of removing optional existence as overhead product, thereby at the bottom of tower, mainly be contained the mixture of 1-butylene and Trimethylmethane.In second tower that can be designed to as mentioned above superfractionator, at the bottom of this tower, mixture can be separated into the 1-butylene producing as bottom product and the cut (overhead product) that is rich in Trimethylmethane.
The pure 1-butylene making by the inventive method preferably contains and is less than 5000 quality ppm, is preferably less than 2000 quality ppm, is particularly preferably less than the iso-butylene of 1500 quality ppm, is required intermediate product.For example can set it as comonomer for the preparation of polyethylene (LLDPE or HDPE) and the mixed polymers of ethylene-propylene.Be used as in addition alkylating reagent, and be the raw material of preparation 2-butanols, butylene oxide ring, valeral.Another purposes that contains hardly the 1-butylene of iso-butylene making according to the present invention is to prepare n-butene oligopolymer, especially standby by Octol legal system.
Except producing 1-butylene, according to C
4the difference of the initial composition of hydrocarbon, adds and also produces the cut that is rich in Trimethylmethane man-hour in method steps distillation f).Can be further purified these, preferably the Trimethylmethane of purifying Cheng Chun.The purity of the Trimethylmethane obtaining under described processing is preferably the Trimethylmethane of at least 90 quality %, the particularly preferably Trimethylmethane of 95 quality %, and preferably contain and be less than 1000wppm, be particularly preferably less than the alkene of 200wppm.Purifying becomes pure Trimethylmethane for example can, by the alkene still containing is hydrogenated to alkane completely, then to distill to realize.
Method steps is g): molecular sieve processing
The high-boiling fraction S 1 obtaining in e) at method steps can optional method steps g) in use sorbent treatment, poison catalyzer or reduce its active trace constituent in h) thereby remove at method steps.Suitable sorbent material is for example stated in DE 198 45 857 or DE 38 25 169 or DE 39 14817.As the product of g) processing according to method steps, obtain cuts VI.
Preferably using mean pore size is that 0.4 to 1.5nm molecular sieve is as sorbent material.Molecular sieve can be both the natural aluminosilicate of crystallization, and for example layer lattice silicate can be also the synthetic molecular sieve making.Fall into the A being for example purchased in addition, X and the y-type zeolite of this scope.Molecular sieve can additionally contain other metal, for example mixture of copper, silver, zinc or these metals.The content of these metals is preferably less than 2 quality %.
Method steps of the present invention g) preferably pressure be 0.1 to 5MPa and temperature be in liquid phase, to carry out at 20 to 160 DEG C.For example sulphur compound, nitrogen compound, oxygen compound and/or halogen compounds by purify the typical trace constituent of removing with sorbent material.
Method steps is h): oligomeric
On the cuts VI that method steps obtains in g) or the n-butene that contains is containing nickel, silicon and aluminium in the cut S 1 of acquisition in e) at method steps heterogeneous catalyst, occur oligomeric, thereby obtain oligopolymer O.Method based on the method step is found as OCTOL process quilt in the literature, this is at Hydrocarbon Process., Int.Ed. (1986) 65 (2.Sect.1), the 31st to 33 pages and description to some extent in file DE 39 14 817, EP 1 029 839 and DE 10 2,004 018753.
Under the heterogeneous catalyst-loaded condition that contains nickel in existence, carry out oligomeric.As Substrates, catalyzer for example can comprise silicon-dioxide and aluminum oxide, aluminosilicate or zeolite.Described carrier optionally can be by sulphating.In addition, described catalyzer can comprise sulphur.This catalyzer is known in technical literature, for example, in DE 43 39 713 or WO 01/37989, state.
There is number of ways to prepare used nickel catalyst-loaded.For example, this catalyzer can be by nickel compound and for example aluminium of Substrates and silicon compound coprecipitation, filters and next thermal treatment (Tempern) and making.Another kind of possibility is, nickel compound is coated on to one of above-mentioned Substrates upper, for example, be coated with by flooding or spraying, then calcined catalyst precursor.For Kaolinite Preparation of Catalyst, can use nickel compound, for example nickelous nitrate, nickelous chloride or amine complex.Suitable Substrates is commercially available carrier, the aluminosilicate that for example Grace company model is GraceDAVICAT or the pyrolysis aluminosilicate of mobil oil or amorphous zeolite (MCM4).
Particularly preferably use the carrier of titaniferous not or catalyst-loaded, it is mainly made up of nickel oxide, aluminum oxide and silicon oxide in form.This catalyzer preferably contains the nickel of 5 to 50 quality %, especially 10 to 30 quality %.The content range of aluminium is 5 to 30 quality %, especially 7 to 20 quality %.The share scope of silicon is 10 to 40 quality %, especially 20 to 30 quality %, respectively the metal share meter based on all.As other composition, these catalyzer can also contain alkalimetal oxide, alkaline earth metal oxide, lanthanide oxide or the rare earth oxide of 0.1 to 2 quality % and optional shaping assistant.
Nickel catalyzator is suitably so that wherein they bring the form of low flow resistance to use, for example, use as the form of lamellar body, right cylinder, spheroid, strand extrudate or ring bodies with particle, bead or formed body.
Oligomeric in h) of method steps is 0 to 200 DEG C in (reaction) temperature, preferably 50 to 130 DEG C, and pressure is 0.1 to 70MPa, and preferably 0.1 to 10MPa, particularly preferably carry out under 0.5 to 3MPa.
The oligomeric preferred multistage operation of method steps in h).Each stage comprises reactive moieties, and it can be formed by one or more reactor or reaction zones that wherein form oligopolymer, and by oligopolymer and C
4the distillation that hydrocarbon separates.The C separating
4hydrocarbon preferably partly returns to reactive moieties as recycle stream, and resistates is transfused to next step of reaction.Number of stages is preferably 2 to 6, and preferably 2 to 4.
Industrial, oligomerization preferably carries out in one or more tube bundle reactors.In the case, C
4hydrocarbon (mixture VI or cut S1), optional and C
4together, transmission is by being equipped with the pipe of catalyzer for recycle stream.The reaction heat producing can be led away by the cooling liqs of jacket side, therefore on the catalyzer in pipe, maintains smooth temperature curve.Can use one or more reactors, they can in parallel or series connection.For limited reactions device length or in order to utilize the possibility that operates reactor under differing temps, serial operation may be for example favourable.In rear kind selection situation, between reactor, can additionally heat or reaction mixture.
The reaction mixture being obtained by reactor is all separated into C in distillation tower at every one-phase
4hydrocarbon and the cut that contains oligopolymer O.Preferably, 0.1 to 2.0MPa, preferably under 0.2 to 0.5MPa pressure, distill.
, import the distillation tower of final stage from previous stage at the oligopolymer O producing at the bottom of the tower of distillation tower h) in preferred flexible program at method steps, and distill with together with reaction output that in the end stage produces there.Method steps h) this preferred flexible program is illustrated in Fig. 1.The advantage of the inventive method step this flexible program h) is, separation of C accurately in all other stages
4hydrocarbon and oligopolymer, that is still have residual C
4hydrocarbon is still retained in oligopolymer and/or residual oligopolymer is still retained in C
4in hydrocarbon.Therefore reduced the required vapor volume of operational tower.But preferably no more than 1 quality %, particularly preferably the oligopolymer O of 5000ppm stays C
4in hydrocarbon, and the C of no more than 5000ppm
4hydrocarbon is stayed in oligopolymer.
Undertaken oligomericly by the n-butene containing in S1 or VI, as oligopolymer O, especially obtain thering are eight, the alkene of 12,16,20 or more carbon atoms.These alkene for example can be for the preparation of plasticizer alcohol (C
9or C
13alcohol) or be used for the alcohol (C of making detergent raw material
13, C
17or C
21alcohol).Before further processing, they are preferably distilled and are treated to one or more cuts, are preferably separated into that to contain dibutene (be mainly C
8-alkene) cut, contain three butylene (C
12-alkene) cut and contain higher oligomer (C
16+-alkene) cut.By hydroformylation, hydrogenation and distillation, obtain in a large number the isononyl alcohol as plasticizer alcohol from dibutene.By similar reaction, can obtain isotrideyl alcohol from three butylene.By by C
16+cut is hydrogenated to paraffinic hydrocarbons, can obtain the mixture of high-purity paraffinic hydrocarbons.
In preferred flexible program, in the tower operating, oligopolymer distillation is separated into respectively to dibutene cut, three butene fraction and C under two decompressions
16+cut.In first tower, 100 to 800hPa
definitelypressure under obtain as the dibutene of overhead product.Bottom product arrives 300hPa 10 in second tower
definitelypressure under be separated into three butylene (overhead product) and C
16+cut (bottom product).
While needs, described cut further can be separated, for example, by C
16+cut is separated into four butylene and C
20+alkene.Dibutene also can further be separated for application-specific, for example, in EP 1 029 839, described such separation.
Except oligopolymer, obtain cuts VII at method steps in h), its contain method steps h) in unreacted C
4hydrocarbon, for example butane and optional n-butene.Therefore the inventive method can be supplemented optional method steps i) with the C of residual processing
4hydrocarbon VII.
Method steps is i): the C of optional further residual processing
4hydrocarbon VII
Due to oligomeric (method steps h) in butylene transform completely and say conventionally nonsensically from economic angle, if therefore produce the mixture of n-butene and butane as mixture VII, can not make economically its separation by distillation separately.This mixture VII can directly further use, for example, as the raw material of hydrocracking device.But this mixture VII preferably or be processed to normal butane or be separated into and be rich in the cut of butylene and the butylene cut through dilution by extractive distillation.
Being processed into normal butane can be by realizing complete the butylene still containing hydrogenation.Industrial this hydrogenation is preferably carried out according to prior art on fixed bed catalyst.Preferably use palladium-catalyst-loaded at this.
The normal butane obtaining from this hydrogenation can be further processed, for example, remove Trimethylmethane or C by fractionation by distillation
5hydrocarbon.
Separate butylene and normal butane is prior art equally by extractive distillation, for example, in DE 10,242 923 and DE 10 2,005 023 549, state.
Claims (20)
1. from least containing 1-butylene, iso-butylene, butane, 2-butylene and polynary unsaturated C
4the C of hydrocarbon
4the cuts I of hydrocarbon prepares the method for n-butene oligopolymer and 1-butylene, it is characterized in that following methods step:
A) detergent industry mixture I optionally, thus cuts II obtained,
B) from cuts I or II, remove 1,3-butadiene, thereby obtain cuts III,
C) identical with cuts III or by mixtures III and C
4hydrocarbon mixture mix and in the cuts IIIa that obtains the iso-butylene that contains remove by reacting in two stage methyl tertiary butyl ethers are synthetic with excessive methanol, and gained methyl tertiary butyl ether and unreacted methyl alcohol are removed, thereby obtain cuts IV, wherein, the synthetic first stage of methyl tertiary butyl ether carries out at least two fixed-bed reactor, and the synthetic subordinate phase of methyl tertiary butyl ether has on sulfonic solid acid ion exchange resin, in the reactive distillation tower with 0.5 to 1.5MPa pressure range and the operation of the reflux ratio between with 0.5 and 1.5 under the reaction zone temperature of 50 DEG C to 90 DEG C, carry out,
D) from cuts IV, remove polynary unsaturated C
4hydrocarbon is by 0 to 75 DEG C of temperature, be under the condition of carbon monoxide of 0.05 to 10 quality ppm there is the quality based on cuts IV, in liquid phase, on carrier, contain on the fixed bed catalyst of 0.1 to 2 quality % palladium the polynary unsaturated C containing with hydrogen selective hydration in this cuts
4hydrocarbon is implemented, thereby obtains cuts V,
E) by cuts V fractionation by distillation be the low high-boiling fraction S1 that boils cut L1 and contain 2-butylene and normal butane that contains 1-butylene and Trimethylmethane and substantially do not contain normal butane and 2-butylene,
F) be 1-butylene and Trimethylmethane by the low cut L1 fractionation by distillation of boiling,
G) optionally under 0.1 to 5MPa pressure and at 20 to 160 DEG C of temperature, process high-boiling fraction S1 with thering is 0.4 molecular sieve to 1.5nm mean pore size, thereby obtain cuts VI, and
H), at 0 to 200 DEG C of temperature and 0.1 under 7MPa pressure, on the heterogeneous catalyst that contains nickel, silicon and aluminium, the n-butene that makes to contain in high-boiling fraction S1 or cuts VI carries out oligomeric, thereby obtains oligopolymer O.
2. according to the method for claim 1, it is characterized in that, make water or the aqueous solution as washing medium at method steps in a).
3. according to the method for claim 1 or 2, it is characterized in that, the mass ratio of washing medium and the cuts I using in a) at method steps arrives 1:100 for 1:1.
4. according to the method for claim 1 or 2, it is characterized in that, from cuts I or II, obtain 1 by selective hydration at method steps in b), 3-divinyl, wherein selective hydration 0.5 at the temperature of the pressure of 2.5MPa and 25 to 80 DEG C, under the condition that has hydrogen, at the Al containing as carrier
2o
3and SiO
2and count on the palladium of 0.05 to 1 quality % palladium-catalyst-loaded and carry out based on carrier.
5. according to the method for claim 4, it is characterized in that, selective hydration carried out with two stages, and wherein at least the reactor of first stage operates in a looping fashion.
6. according to the method for claim 1 or 2, it is characterized in that, method steps c) first fixed-bed reactor in the first stage at the temperature of 35 to 70 DEG C, operate, the fixed-bed reactor in downstream operate at the temperature of 25 to 50 DEG C.
7. according to the method for claim 1 or 2, it is characterized in that c) in subordinate phase, thering is the temperature of 50 to 90 DEG C to the tower charging of reactive distillation tower at method steps.
8. according to the method for claim 1 or 2, it is characterized in that, method steps c) in, separate and remove methyl alcohol from the overhead product of the reactive distillation tower of subordinate phase by extraction, wherein the mass ratio of washing medium and overhead product is that 1:5 is to 1:40.
9. according to the method for claim 1 or 2, it is characterized in that, the reactive distillation tower of method steps in c) operates under 0.7 to 0.9MPa pressure.
10. according to the method for claim 1 or 2, it is characterized in that, the reactive distillation tower of method steps in c) operates as 10% to 110% taking the hydraulic pressure load of catalyst filling.
11. according to the method for claim 1 or 2, it is characterized in that, the pressure of method steps in d) is less than 20MPa.
12. according to the method for claim 1 or 2, it is characterized in that, method steps d) carries out with two stages.
13. according to the method for claim 1 or 2, it is characterized in that, method steps e) carries out in the towers with 150 to 200 theoretical separation levels.
14. according to the method for claim 1 or 2, it is characterized in that, method steps e) middle distillation tower operates to be less than 11 reflux ratio.
15. according to the method for claim 1 or 2, it is characterized in that, method steps f) carries out in the towers with 150 to 200 theoretical separation levels.
16. according to the method for claim 1 or 2, it is characterized in that, method steps f) middle distillation tower operates with 30 to 60 reflux ratio.
17. according to the method for claim 1 or 2, it is characterized in that, method steps uses A, X or y-type zeolite as molecular sieve in g).
18. according to the method for claim 1 or 2, it is characterized in that, method steps h) in use contain 5 to 50 quality % nickel, the catalyzer of the silicon of the aluminium of 5 to 30 quality % and 10 to 40 quality %, the metal share meter based on all.
19. according to the method for claim 1 or 2, it is characterized in that, method steps is h) taking the multistage operation of number of stages as 2 to 4.
20. according to the method for claim 19, it is characterized in that, every one-phase at method steps in h) comprises reactive moieties and distillation, import the distillation tower of final stage from one or more previous stages at the oligopolymer O producing at the bottom of the tower of one or more distillation towers, and distill together with the reaction output producing with the reactive moieties in stage in the end there.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102008007081.5A DE102008007081B4 (en) | 2008-01-31 | 2008-01-31 | Process for the preparation of n-butene oligomers and 1-butene from technical mixtures I of C4-hydrocarbons |
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Families Citing this family (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1392673B1 (en) * | 2009-01-13 | 2012-03-16 | Saipem Spa | PROCEDURE FOR OBTAINING HIGH PURITY 1-BUTENE FROM HYDROCARBURIC MIXTURES C4 |
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| PL3170805T3 (en) | 2015-11-19 | 2019-02-28 | Evonik Degussa Gmbh | Influencing the viscosity of n-butene based esters mixtures by targeted use of ethene in the production of the esters precursors |
| US10227279B2 (en) | 2016-09-12 | 2019-03-12 | Evonik Degussa Gmbh | Dehydrogenation of LPG or NGL and flexible utilization of the olefins thus obtained |
| CN108559010B (en) * | 2018-04-08 | 2023-05-12 | 合润科技有限公司 | Production device for producing poly alpha olefin by Fischer-Tropsch synthesis olefin polymerization |
| EP3677610B1 (en) | 2019-01-07 | 2021-09-22 | Evonik Operations GmbH | Preparation of polyurethane foam |
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| EP3693356B1 (en) | 2019-02-07 | 2022-01-12 | Evonik Operations GmbH | Flexible manufacture of mtbe or etbe and isononanol |
| CN110846065B (en) * | 2019-10-31 | 2022-11-04 | 中国石油天然气集团有限公司 | Isobutene polymerization system and polymerization method |
| CN113929550B (en) * | 2020-06-29 | 2023-12-08 | 中国石油化工股份有限公司 | Mixed carbon four superposition reaction method and device |
| WO2023222400A1 (en) | 2022-05-17 | 2023-11-23 | Evonik Operations Gmbh | Production of polyurethane foam |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990438A (en) * | 2005-12-28 | 2007-07-04 | 奥克森诺奥勒芬化学股份有限公司 | Process for the preparation of 1-butene from technical mixtures of C4-hydrocarbons |
Family Cites Families (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1012686B (en) | 1974-05-21 | 1977-03-10 | Snam Progetti | PROCEDURE FOR THE PREPARATION OF TER-ALKYL ETHERS |
| DE2944457A1 (en) | 1979-11-03 | 1981-05-14 | EC Erdölchemie GmbH, 5000 Köln | METHOD FOR PRODUCING A MIXTURE, CONSISTENTLY OF ISO BUTEN OLIGOMERS AND METHYL-TERT.-BUTYL ETHER, ITS USE AND FUELS, CONTAINING SUCH A MIXTURE |
| DE3036481A1 (en) | 1980-09-27 | 1982-05-19 | EC Erdölchemie GmbH, 5000 Köln | METHOD FOR THE SIMULTANEOUS PRODUCTION OF C 4-OLIGOMERS AND ALKYL-TERT.-BUTYL ETHERS |
| DE3143647A1 (en) * | 1981-11-04 | 1983-05-11 | Chemische Werke Hüls AG, 4370 Marl | METHOD FOR SELECTIVELY HYDROGENATING MULTIPLE UNSATURATED HYDROCARBONS IN HYDROCARBON MIXTURES |
| US4797133A (en) | 1986-12-29 | 1989-01-10 | Uop Inc. | Process for recovery of butene-1 from mixed C4 hydrocarbons |
| DE3825169A1 (en) | 1988-07-23 | 1990-02-01 | Huels Chemische Werke Ag | METHOD FOR FINE DESULFURATION OF HYDROCARBONS |
| WO1990002603A1 (en) | 1988-09-02 | 1990-03-22 | Gebrüder Sulzer Aktiengesellschaft | Device for carrying out catalytic reactions |
| DE3914817C2 (en) | 1989-05-05 | 1995-09-07 | Huels Chemische Werke Ag | Process for oligomerizing olefins |
| US5244929A (en) | 1989-09-13 | 1993-09-14 | Veba Oel Aktiengesellschaft | Molded bodies comprised of macroporous ion exchange resins, and use of said bodies |
| US5073236A (en) | 1989-11-13 | 1991-12-17 | Gelbein Abraham P | Process and structure for effecting catalytic reactions in distillation structure |
| US5169824A (en) * | 1991-01-22 | 1992-12-08 | Exxon Chemical Patents Inc. | Catalyst comprising amorphous NiO on silica/alumina support |
| DE4339713A1 (en) | 1993-11-22 | 1995-05-24 | Basf Ag | Process for oligomerization of olefins to highly linear oligomers and catalysts therefor |
| DE19524971A1 (en) | 1995-07-08 | 1997-01-09 | Huels Chemische Werke Ag | Process for the catalytic selective hydrogenation of polyunsaturated organic substances |
| DE19818810A1 (en) | 1998-04-27 | 1999-10-28 | Basf Ag | Separation of 4 carbon hydrocarbon mixture with recovery of highly pure 1,3-butadiene fraction |
| DE19845857A1 (en) | 1998-10-05 | 2000-04-06 | Basf Ag | Process for the catalytic oligomerization of monoolefins |
| DE19906518A1 (en) | 1999-02-17 | 2000-08-31 | Oxeno Olefinchemie Gmbh | Dibutene fractionation process |
| DE19957173A1 (en) | 1999-11-27 | 2001-05-31 | Basf Ag | Production of catalyst, for oligomerization of olefin, especially 1- and 2-butene, by charging alumina with nickel and sulfur compounds uses low sulfur to nickel molar ratio |
| DE10020943A1 (en) | 2000-04-28 | 2001-10-31 | Oxeno Olefinchemie Gmbh | Process for the cleavage of alkyl tert-alkyl ether to obtain iso-olefins and alkanols on acidic catalysts |
| DE10102082A1 (en) | 2000-10-19 | 2002-05-02 | Oxeno Olefinchemie Gmbh | Process for the preparation of high-purity raffinate II and methyl tert-butyl ether |
| DE10242923A1 (en) | 2002-09-16 | 2004-03-18 | Oxeno Olefinchemie Gmbh | Separation of butenes and butanes by extractive distillation with a polar extractant comprises extractive distillation of a butene and butane containing stream with a polar extractant with recycle of the polar extractant |
| DE10302457B3 (en) | 2003-01-23 | 2004-10-07 | Oxeno Olefinchemie Gmbh | Process for the preparation of butene oligomers and tert-butyl ethers from isobutene-containing C4 streams |
| DE102004018753A1 (en) | 2004-04-17 | 2005-11-03 | Oxeno Olefinchemie Gmbh | Production of 16C alkane mixtures useful as solvents (e.g. in cosmetics), extractants or hydraulic fluids involves nickel-catalyzed oligomerization of low isobutene-content 4C stream, followed by hydrogenation |
| DE102004021128A1 (en) | 2004-04-29 | 2005-11-24 | Oxeno Olefinchemie Gmbh | Apparatus and method for the continuous reaction of a liquid with a gas on a solid catalyst |
| DE102005023549A1 (en) | 2005-05-21 | 2006-11-23 | Oxeno Olefinchemie Gmbh | Transition metal-catalyzed butene oligomerization uses a butene-rich stream obtained by extractive distillation, distillative separation, washing and drying from a stream containing saturated and unsaturated 4C hydrocarbons |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1990438A (en) * | 2005-12-28 | 2007-07-04 | 奥克森诺奥勒芬化学股份有限公司 | Process for the preparation of 1-butene from technical mixtures of C4-hydrocarbons |
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| DE102008007081B4 (en) | 2018-12-06 |
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