CN103261129A - Production of fuel additives via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by etherification - Google Patents
Production of fuel additives via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by etherification Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
- C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
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- C07C11/08—Alkenes with four carbon atoms
- C07C11/09—Isobutene
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2767—Changing the number of side-chains
- C07C5/277—Catalytic processes
- C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
Abstract
The present invention relates to a process for the production of fuel additives in which in a first step isobutanol is subjected to a simultaneous dehydration and skeletal isomerisation to make substantially corresponding olefins, having the same number of carbons and consisting essentially of a mixture of n-butenes and isobutene and in a second step the butene mixture is subjected to etherification. The process comprises: a)introducing in at least one reactor a stream (A) comprising at least 40wt% isobutanol, optionally an inert component, b)contacting said stream with at least one catalyst in said reactor(s) at conditions effective to simultaneously dehydrate and skeletal isomerise at least a portion of the isobutanol to make a mixture of n-butenes and iso-butene, c)removing the inert component if any, recovering from said reactor(s) a stream (B) comprising a mixture of n-butenes and isobutene, d)sending the stream (B) to at least one etherification reactor and contacting stream (B) with at least one catalyst in said etherification reactor(s), in the presence of ethanol and/or methanol, at conditions effective to produce ETBE and/or MTBE respectively, e)recovering from said etherification reactor a stream (E) comprising essentially ETBE and/or MTBE, unreacted butenes, heavies, optionally unreacted ethanol and/or methanol respectively, f)fractionating stream (E) to recover ETBE and/or MTBE.
Description
Technical field
The present invention relates to prepare fuel dope from renewable energy source, time dehydration and skeletal isomerization prepare and have basic identical carbonatoms accordingly but the alkene of different skeleton structures by isopropylcarbinol for it, are etherification step then.Isopropylcarbinol can obtain by the fermentation of carbohydrate or by the condensation than light alcohol that is obtained by the carbohydrate fermentation.The biomass that are made of the organic substance from the organism that lives are the main renewable energy sources in the world.
Background technology
Isopropylcarbinol (2-methyl isophthalic acid-propyl alcohol) application in history is limited, and its purposes and 1-butanols are similar.It has been used for the additive of China ink and polymkeric substance as solvent, thinner, wetting agent, detergent additive and conduct.Recently, (skellysolve E R+M/2 is that (R represents research octane number (RON) to 102-103 because isopropylcarbinol shows high octane value, M represents motor-method octane number, these numerical value are used for calculated octane number)) and low vapour pressure (the RVP-Reid vapor pressure-be 3.8-5.2psi), so it acts as a fuel or fuel element has obtained concern.
Isopropylcarbinol is often thought the by product (Liv Ullmann industrial chemistry encyclopaedia (Ullmann ' s encyclopedia of industrial chemistry) of industrial preparation 1-butanols, sixth version in 2002).It is prepared via carbonylation (Co is catalyst based) via hydroformylation (Rh is catalyst based) or in Lei Pafa in oxidizing process by propylene.Hydroformylation or carbonylation make the ratio from 92/8 to 75/25 of butyraldehyde-n and isobutyric aldehyde.For obtaining isopropylcarbinol, isobutyric aldehyde is hydrogenation on metal catalyst.Isopropylcarbinol also can be by synthetic gas (CO, H
2And CO
2Mixture) by being similar to the method preparation of Fischer-Tropsch method (Fisher-Tropch), although the formation of preferential isopropylcarbinol usually takes place in this method, but that obtain is mixture (the Applied Catalysis A of higher alcohol, general, 186,407 pages, 1999 and Chemiker Zeitung, 106,249 pages, 1982).Another route that obtains isopropylcarbinol is base catalysis Ge Er baud (Guerbet) condensation (the J.of Molecular Catalysis A:Chemical200 of methyl alcohol and ethanol and/or propyl alcohol, 137,2003 and Applied Biochemistry and Biotechnology, 113-116,913 pages, 2004)
Recently, develop new biological chemistry route cause carbohydrate selectivity and prepared isopropylcarbinol.This New Policy uses the amino sour biosynthesizing path of the high reactivity of microorganism and its 2-ketone acid intermediate is diverted to the synthetic of alcohol.The 2-ketone acid is the intermediate in the amino acid bio synthesis path.These metabolites can change into aldehyde by 2-keto acid decarboxylase (KDC), change into alcohol by alcoholdehydrogenase (ADH) then.By the preparation that will turn to alcohol from the intermediate of amino acid bio synthesis path need two steps prepare alcohol (Nature, 451,86 pages, 2008 and United States Patent (USP) 2008/0261230).Need recombinant microorganism to improve carbon towards the synthetic conversion of 2-ketone acid.In the Xie Ansuan biosynthesizing, the 2-ketoisovaleric acid is intermediate.The sugared solution of carbohydrate obtains pyruvic acid, and pyruvic acid is converted into acetylactis by acetolactate synthestase.2,4-dihydroxyl isovaleric acid is formed via heterogeneous reductase catalysis by acetyl-lactic acid ester.Dehydratase changes into the 2-ketoisovaleric acid with 2,4-dihydroxyl isovaleric acid.In next step, keto acid decarboxylase prepares isobutyric aldehyde by the 2-ketoisovaleric acid.Final step is to be isopropylcarbinol by desaturase with isobutyric aldehyde hydrogenation.
For above-mentioned route towards isopropylcarbinol, the condensation of Ge Er baud, synthetic gas hydrogenation and be to use biomass as the route of main charging by the 2-ketone acid path of carbohydrate.The synthetic gas that gasifying biomass obtains changing into methyl alcohol or directly changes into isopropylcarbinol.Become ethanol under very large scale, to prepare ethanol by the fermentation of carbohydrate or by synthetic gas direct fermentation.Therefore, biomass-derived methyl alcohol and ethanol can further be condensed into isopropylcarbinol.Directly 2-ketone acid path can prepare isopropylcarbinol by isolated carbohydrate from biomass.Simple carbohydrate can obtain from plant such as sugarcane, beet.Complicated carbohydrate can obtain from plant such as corn, wheat and other cereal grass.More complicated carbohydrate can be from isolating by untiing (unlocking) from Mierocrystalline cellulose and the hemicellulose of lignocellulose any biomass basically.
In the mid-90, the more iso-butylenes of preparation are attempted for the preparation of MTBE (methyl tertiary butyl ether) by many oil companies.Therefore, developed many for the skeletal isomerization catalyzer that n-butene is converted into iso-butylene (Adv.Catal.44,505 pages, 1999; Oil ﹠amp; Gas Science and Technology, 54 (1), 23 pages, 1999 and Applied Catalysis A:General212,97,2001)).Wherein catalyzer likely is 10 yuan of ring zeolites and modified aluminas.The reverse skeletal isomerization of not mentioned iso-butylene changes into n-butene.
The dehydration reaction of alcohol prepares alkene known (J.Catal.7,163 pages, 1967 and J.Am.Chem.Soc.83,2847 pages, 1961) for a long time.Many available solid acid catalysts can be used for the dehydration (Stud.Surf.Sci.Catal.51,260 pages, 1989) of alcohol.Yet gama-alumina is in particular for the most frequently used in the long-chain alcohol (having three above carbon atoms).This is because have more highly acid catalyzer, can promote two key transfers, skeletal isomerization and other alkene mutual exchange reaction as silica-alumina, molecular sieve, zeolite or resin catalyst.The primary product of the acid-catalyzed dehydration of isopropylcarbinol is iso-butylene:
The dehydration of alcohol on acid catalyst with four or more carbon estimates to be accompanied by two key shift reactions of olefin product.This is because these two kinds reactions take place and speed suitable (Carboniogenic Activity of Zeolites, Elsevier Scientific Publishing Company, (1977) 169 pages of Amsterdam) easily.Because have the two keys that are connected to tertiary carbon, so the primary product iso-butylene is very active in the presence of acid catalyst.Because the tertiary carbon structure of gained carbocation is best a kind of (tertiary carbon＞secondary carbon＞primary carbon positively charged ion) in possible carbocation structure, it is protonated that this is easy to it.Gained tertiary butyl cation easily is in carrying out oligomeric/polymerization, and perhaps other is to the electrophilic substitution of aromatics or fatty compounds, or electrophilic addition reaction.The cationic rearrangement of the tertiary butyl is not direct reaction, do not wish to be subject to any theory, it relate to sec-butyl positively charged ion or Bai Dingji cationic intermediates formation and thereby the possibility of secondary reaction (replace or addition) very high and can reduce the expectation product selectivity.
Described at alumina catalyst and carried out butanols dehydration (Applied Catalysis A, General, 214,251 pages, 2001).Two keys shift and skeletal isomerization all corresponding to less than 1gml
-1Hour
-1The low-down air speed (or very long reaction times) of GHSV (ratio of the weight (ml) of gas hourly space velocity=feeding rate (g/ hour) and catalyzer) obtain down.
The US7473812 patent disclosure method of from butene mixture, removing iso-butylene by the technology of common generation butene low polymers and tertbutyl ether, it is by making the iso-butylene part oligomeric to obtain butene low polymers at an acidic catalyst, make subsequently remaining iso-butylene under acidic catalyst with pure etherificate to obtain tertbutyl ether.
US4469911 discloses in the presence of the fixed bed cation exchange resin, under 30 ℃ to 60 ℃ temperature and 2.5 hours
-1To 12 hours
-1LHSV under make the oligomeric method of iso-butylene.
US5895830 has described the saturated materials flow of heavy that contains the paraffinic hydrocarbons with at least 8 carbon atoms by utilization and has diluted butene feed, uses SPA (load phosphoric acid) catalyzer, improves optionally oligomerization of butenes technology of dimer.
US5877372 discloses iso-butylene in the presence of octane-iso thinner and the trimethyl carbinol (1wt% and preferred 5wt% to 15wt% at least), on sulfonic acid ion exchange resin such as AmberlystA-15, Dowex50 etc., under 10 ℃ to 200 ℃ the temperature and the dimerization under the pressure of 50psig to 500psig.Think that the trimethyl carbinol has improved the selectivity that dimer forms and the formation that has reduced tripolymer and higher oligomer.
US6689927 has described low temperature oligomerization of butenes method, it has the selectivity of improvement for dimerization reaction and for preferred 2,4,4-2,4,4-Trimethyl-1-pentene isomer has the selectivity of improvement, its reason be oligomerization in the presence of the SPA catalyzer, be lower than under 112 ℃ the temperature, have at least 6 carbonatomss saturated hydrocarbon diluent in the presence of carry out.
WO2007/14399 and WO2008/016428 disclose the isopropylcarbinol that is derived from fermented liquid to the conversion of butylene, and described butylene can change into aromatic hydrocarbon, isooctyl alcohol and the Octyl Ether that isoparaffin, alkyl replace, and can be used for transport fuel.
US2008/0220488 has described the method for the preparation of the isooctene of the additive that acts as a fuel, and it uses the dry 1-butanols from fermented liquid.In an embodiment, Chun dehydration and dimerization use an acidic catalyst to carry out in a step.
Now found that the dehydration of isopropylcarbinol and the isobutyl-skeletal isomerization partly of isopropylcarbinol can side by side carry out, and the mixture of the iso-butylene of gained and n-butene can be used for etherification reaction effectively with preparation MTBE/ETBE.Randomly, Can Yu butylene (mainly being n-butene) can be heavy component (gasoline, middle runnings) by alkylation (formation of many alkylate oils) or oligomeric recycling.
For instance, dehydration and skeletal isomerization have the crystalline silicate that a lot of advantages: Si/Al is higher than 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type when having found following material for isopropylcarbinol,
Perhaps Si/Al is higher than the dealuminzation crystalline silicate of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Perhaps Si/Al is higher than the crystalline silicate of the phosphorus modification of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
The perhaps aluminosilicophosphate type molecular sieve of AEL type,
Or silicic acid salinization, zirconic acid salinization or titanation or the aluminum oxide fluoridized.
Described dehydration can be at least 1 hour
-1The WHSV ratio of catalyst weight (weight hourly space velocity=feed rate (g/ hour) with) under, under 200 ℃ to 600 ℃ temperature, use the isopropylcarbinol diluent composition of 30wt% to 100wt% isopropylcarbinol, under total working pressure of 0.05MPa to 1.0MPa, finish.
For instance, be to make n-butene and iso-butylene, at Si/Al than being on 10 to 90 the ferrierite, at 2 hours
-1WHSV under, in isopropylcarbinol dehydration/isomerization, it usually is 99% also that the transformation efficiency of isopropylcarbinol is at least 98%, advantageously, the yield of butylene (iso-butylene and n-butene) is at least 90%, and the selectivity of n-butene is between 5% thermodynamic(al)equilibrium to the given reaction conditions.
The isopropylcarbinol transformation efficiency is following ratio: (introduce the isopropylcarbinol of reactor-leave the isopropylcarbinol of reactor)/(introducing the isopropylcarbinol of reactor)
The yield of n-butene is based on the following ratio of carbon: (leaving the n-butene of reactor)/(introducing the n-butene of reactor).
The selectivity of n-butene is based on the following ratio of carbon: (leaving the n-butene of reactor)/(propyl carbinol that transforms in reactor).
Dehydration/isomerization obtains the mixture of n-butene (but-1-ene and but-2-ene) and iso-butylene (2-methacrylic) in the time of isopropylcarbinol.According to the present invention, often obtain the composition close to thermodynamic(al)equilibrium, keep the high yield of total olefin simultaneously.According to reaction conditions, the thermodynamic(al)equilibrium of n-butene changes between 50% to 65%, is between 35% to 50% for iso-butylene.The important advantage of the present invention is that the composition of products therefrom is similar to from the C4 fraction of the raffinate I of steam petroleum naphtha cracking unit acquisition.Raffinate I obtains by remove 1,3-butadiene from the rough C4 fraction for preparing steam petroleum naphtha cracking unit.The composition of typical raffinate I is: the iso-butylene of 35-45wt%, the n-butene of the 52-40wt% of the butane of 3-15wt% and remainder.According to the present invention, dehydration/isomerized product can easily replace the purposes of raffinate I in the existing petrochemical plant in the time of from isopropylcarbinol.The result can minimize fund input, and by utilizing product of the present invention to replace fossil raffinate I simply, therefore can be by renewable resources rather than mineral wealth preparation from the derivative of this iso-butylene/n-butene mixture.
Summary of the invention
The present invention relates to a kind of for the method that for example prepares fuel dope (ETBE/MTBE, gasoline, middle runnings) from renewable energy source, wherein in the first step, isopropylcarbinol dewaters with skeletal isomerization simultaneously to make corresponding alkene basically, described alkene has identical carbonatoms and is made up of the mixture of n-butene and iso-butylene basically, in second step, the mixture of butylene carries out etherificate, and described method comprises:
A) introduce materials flow (A) at least one reactor, described materials flow (A) comprises 40wt% isopropylcarbinol at least, optional inert component,
B) make described materials flow (A) and at least a catalyzer in described reactor, under at least a portion that makes described isopropylcarbinol is effectively dewatered condition with skeletal isomerization simultaneously, contact, making the mixture of n-butene and iso-butylene,
C) if remove any inert component that exists, the materials flow (B) of reclaiming the mixture that comprises n-butene and iso-butylene from described reactor,
D) at least one methyltertiarvbutyl ether reactor is delivered in described materials flow (B), and under the condition for preparing ETBE and/or MTBE effectively, in the presence of ethanol and/or methyl alcohol, materials flow (B) is contacted in described methyltertiarvbutyl ether reactor with at least a catalyzer,
E) retrieve materials flow (E) from described methyltertiarvbutyl ether reactor, described materials flow (E) comprises ETBE and/or MTBE, unreacted butylene (mainly being n-butene) basically, optional heavy component, and optional unreacted ethanol and/or methyl alcohol,
F) fractionation materials flow (E) to be reclaiming ETBE and/or MTBE, and randomly makes unreacted butylene and unreacted ethanol and/or methyl alcohol be recycled to methyltertiarvbutyl ether reactor.
Advantageously, be used for the materials flow (A) of step a), and/or derive from renewable energy source for methyl alcohol and/or the ethanol of step d).
Randomly, bulk stream (A) was carried out purification process before step b).This purification process is intended to for example remove pollutent by common separation method (distillation, absorption ...), as oxycompound.
In the first embodiment, the WHSV of isopropylcarbinol was at least 1 hour
-1
In second embodiment, the temperature of dehydration and skeletal isomerization is 200 ℃ to 600 ℃ scope in the time of isopropylcarbinol.
Advantageously, dehydration/isomerization catalyst is the crystalline silicate that Si/Al is higher than 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Perhaps Si/Al is higher than the dealuminzation crystalline silicate of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Perhaps Si/Al is higher than the crystalline silicate of the phosphorus modification of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
The perhaps silicoaluminophosphamolecular molecular sieve of AEL type,
Or silicic acid salinization, zirconic acid salinization or titanation or the aluminum oxide fluoridized.
If the isopropylcarbinol charging comprises one or more of other C4 alcohol, as the 2-butanols, the trimethyl carbinol and propyl carbinol then can not depart from scope of the present invention yet.
In the method for the invention, isopropylcarbinol is the main component in the charging (stream A).It should be noted that materials flow (A) can comprise other C4 alcohol.
The ratio that this means all other compositions (for example with charging in C4 alcohol) of isopropylcarbinol and materials flow (A) is more than the 40wt%.More advantageously, above-mentioned ratio is more than 70% and preferred more than 80%.
If the ratio of isopropylcarbinol is low excessively, then the present invention is not attractive, because dehydration should be finished when skeletal isomerization not taking place better at that time, and exists many catalyzer that can dewater isopropylcarbinol, 2-butanols and propyl carbinol to prepare corresponding butylene in the prior art.Having described trimethyl carbinol dehydration in WO 2005110951 is the iso-butylene skeletal isomerization of at least a portion trimethyl carbinol subsequently.
Randomly, the fractionation materials flow (E) of reclaiming from step e) is to reclaim unreacted butylene and/or unreacted ethanol and/or methyl alcohol.
Then, the unreacted ethanol of the unreacted butylene of the described recovery of at least a portion and/or the described recovery of at least a portion and/or methyl alcohol can be recycled to methyltertiarvbutyl ether reactor.
Alternatively or in combination, the unreacted butylene of the described recovery of at least a portion can be delivered to the zone purification, deliver at least one oligomerization reactor and/or at least one alkylation reactor then, with preparation heavy component (namely greater than the hydrocarbon materialization compound of 4 carbon atoms, as isooctene, middle runnings or many alkylate oils).
Advantageously, described unreacted butylene can carry out purification step before delivering to oligomerization reactor and/or alkylation reactor.
In a specific embodiment, the remaining butylene (mainly being n-butene) that comes out from methyltertiarvbutyl ether reactor is optionally changed into by oligomeric or alkylation can segregative product (isooctene, middle runnings).
Detailed Description Of The Invention
About materials flow (A), isopropylcarbinol can dewater and skeletal isomerization separately or with the mixture with inert media simultaneously.Inert component is any component, and prerequisite is that it does not transform on catalyzer substantially.Because dehydrating step is absorbed heat, so inert component can be used as energy carrier.Inert component can reduce the dividing potential drop of isopropylcarbinol and other reaction intermediate, and therefore reduces the side reaction as oligomeric/polymerization.Inert component can be selected from water, nitrogen, hydrogen, CO
2And stable hydrocarbon.Already in the isopropylcarbinol, this is because they have been used in the isopropylcarbinol preparation process or have produced jointly to some inert component.The example that can be present in the inert component in the isopropylcarbinol is water and CO
2Inert component can be selected from has the stable hydrocarbon of 10 carbon atoms at the most, naphthenic hydrocarbon.Advantageously, it is to have 3 to 7 carbon atoms, more advantageously has stable hydrocarbon or the saturated hydrocarbon mixtures of 4 to 6 carbon atoms, and preferred pentane.An example of inert component can be the synthetic mixture of arbitrarily independent saturated compound, independent saturated compound and refinery's stream of some balances, as virgin naphtha, butane etc.Advantageously, inert component is the stable hydrocarbon with 3 to 6 carbon atoms, and preferred pentane.Isopropylcarbinol and inert component part by weight separately is, for example 30-100/70-0 (summation is 100).Materials flow (A) can be liquid or gas.
About being used for dehydration/isomerized reactor simultaneously, it can be fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor.Typical fluidized-bed reactor is the FCC type that is used for fluid catalystic cracking in a kind of refinery.Typical moving-burden bed reactor is the continuous catalytic reforming type.Dehydration/isomerization simultaneously can be carried out in the fixed-bed reactor structure of using a pair of parallel " waving " reactor continuously.This makes dewatering process carry out continuously in two parallel " waving " reactors, and wherein when a reactor operation, other reactor carries out catalyst regeneration.Catalyzer of the present invention is renewable several also.
Dehydration/isomerization simultaneously can be carried out in moving-burden bed reactor continuously, and wherein catalyzer is recycled to the breeding blanket and returns from reaction zone, and catalyzer was at least 12 hours in the residence time of reaction zone.In each district, catalyzer is similar basically with performance in fixed-bed reactor, but catalyzer is by gravity or pneumatically pass each district and slowly move.Use moving bed reaction to make to realize operate continuously and need not charging and regeneration gas are switched to another from a reactor.Reaction zone receives charging continuously, and the breeding blanket receives regeneration gas continuously simultaneously.
Dehydration/isomerization simultaneously can be carried out in fluidized-bed reactor continuously, and wherein catalyzer is recycled to the breeding blanket and returns from reaction zone, and the residence time of catalyzer in reaction zone is less than 12 hours.In each district, catalyzer is fluidized state and shows shape and the size that keeps fluidized state in charging and reaction product or flow of regeneration gas.The use of fluidized-bed reactor makes the catalyzer of inactivation very rapidly regenerate by the regeneration in the breeding blanket.
About dehydration/isomerized pressure simultaneously, it can be any pressure, but operation is more prone to and is economical under the pressure of appropriateness.For instance, the pressure of reactor is in the scope of 0.5 bar to 10 bar absolute pressure (50kPa to 1MPa), advantageously being 0.5 bar to 5 bar absolute pressure (50kPa to 0.5MPa), more advantageously is that 1.2 bar to 5 cling to absolute pressure (0.12MPa to 0.5MPa) and are preferably 1.2 bar to 4 bar absolute pressure (0.12MPa to 0.4MPa).Advantageously, the isopropylcarbinol dividing potential drop is 0.1 bar to 4 bar absolute pressure (0.01MPa to 0.4MPa), more advantageously is 0.5 bar to 3.5 bar absolute pressure (0.05MPa to 0.35MPa).
About dehydration/isomerized temperature simultaneously, it is 200 ℃ to 600 ℃ scope, advantageously is 250 ℃ to 500 ℃, more advantageously is 300 ℃ to 450 ℃.
These temperature of reaction relate to average catalytic bed temperature substantially.Isopropylcarbinol dehydration is thermo-negative reaction and needs input reaction heat to keep enough height and dehydration fever mechanical balance turned to sufficiently high level of conversion of activity of such catalysts.
Under the situation of fluidized-bed reactor: (i) for the fixed fluidized bed that does not have catalyst recirculation, temperature of reaction is uniform substantially in whole catalytic bed; (ii) in the situation of circulating fluidized bed, wherein catalyzer circulates between conversion reaction section and catalytic regeneration section, according to the degree of catalyzer back-mixing, the temperature of catalyst bed is near uniform condition (back-mixing is more) or near the condition (almost not having back-mixing) of piston flow and therefore will carry out temperature lowering curve and set along with conversion.
Under the situation of fixed bed or moving-burden bed reactor, will transform with isopropylcarbinol and carry out the temperature lowering curve setting.For equalising temp descends and the catalyst activity that therefore causes or near the reduction of thermodynamic(al)equilibrium, can pass through a plurality of series-connected catalyst beds of use and introduce reaction heat, the effluent after heating also will be heated from the extremely higher temperature of first reactor effluent in the middle of the described series-connected catalyst beds is introduced second catalyst bed etc.When using fixed-bed reactor, can use multitubular reactor, wherein catalyzer is loaded in the pipe that is installed in the minor diameter in the reactor enclosure.At shell-side, introduce heating medium, it provides required reaction heat by passing reactor tube walls to the heat exchange of catalyzer.
About being used for the WHSV of dehydration/isomerized isopropylcarbinol simultaneously, it advantageously is 1 hour
-1To 30 hours
-1, more advantageously be 2 hours
-1To 21 hours
-1, preferred 5 hours
-1To 15 hours
-1, more preferably 7 hours
-1To 12 hours
-1
About from dehydration/isomerized materials flow (B) simultaneously, it comprises water, alkene, inert component (if existence) and unconverted isopropylcarbinol basically.Described unconverted isopropylcarbinol should be few as much as possible.Alkene reclaims by common fractionating method.Advantageously, inert component (if existence) and unreacted isopropylcarbinol (if existence) circulation in materials flow (A).Unreacted isopropylcarbinol (if existence) is recycled to the reactor in the materials flow (A).
About being used for dehydration/isomerized catalyzer simultaneously, advantageously, it is the crystalline silicate of FER (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-11) or TON (ZSM-22, Theta-1, NU-10) type
The perhaps crystalline silicate of the dealuminzation of FER (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-11) or TON (ZSM-22, Theta-1, NU-10) type
The perhaps crystalline silicate of the phosphorus modification of FER (ferrierite, FU-9, ZSM-35), MWW (MCM-22, PSH-3, ITQ-1, MCM-49), EUO (ZSM-50, EU-1), MFS (ZSM-57), ZSM-48, MTT (ZSM-23), MFI (ZSM-5), MEL (ZSM-11) or TON (ZSM-22, Theta-1, NU-10) type
The perhaps silicoaluminophosphamolecular molecular sieve of AEL (SAPO-11) type,
Or silicic acid salinization, zirconic acid salinization or titanation or the aluminum oxide fluoridized.
About the crystalline silicate of FER structure (ferrierite, FU-9, ZSM-35), it can be the lamellar precursor that becomes FER by roasting.
Advantageously, the Si/Al of crystalline silicate ratio is higher than 10.
The Si/Al of crystalline silicate is than more advantageously in 10 to 500 scope, and is preferred 12 to 250, and more preferably 15 to 150.
The acidity of catalyzer can be determined by the amount of ammonia residual on the catalyzer, it makes catalyzer contact with ammonia on the acidic site that is adsorbed on catalyzer, desorption of ammonia is at elevated temperatures measured by the concentration of ammonia in differential thermogravimetric analysis or the analytical solution adsorbed gas subsequently.
Crystalline silicate can carry out various processing before being used for dehydration, comprise ion-exchange, with metal-modified (in nonrestrictive mode, be alkali, alkaline earth, transition or rare earth element), the outside surface passivation, with P-compound modification, decatize, acid treatment or other dealumination process, or its combination.
In a specific embodiment, crystalline silicate by decatize from the crystalline silicate framework, to remove aluminium.It is to carry out at elevated temperatures and under the water partial pressure of barometric point and 13kPa to 200kPa that decatize is handled, and the temperature of described rising is preferably in 425 ℃ to 870 ℃ scope, more preferably in 540 ℃ to 815 ℃ scope.Preferably, decatize is handled and is carried out in the atmosphere that comprises 5 volume % to 100 volume % steam.Steam atmosphere preferably comprises the steam of 5 volume % to 100 volume % and the rare gas element of 0 volume % to 95 volume %, described rare gas element preferred nitrogen.Decatize is handled the time period of preferably carrying out 1 hour to 200 hours, more preferably 4 hours to 10 hours.As mentioned above, decatize is handled and is tended to by forming the amount that aluminum oxide reduces tetrahedral aluminium in the crystalline silicate framework.
In a more particular embodiment, crystalline silicate is by following method dealuminzation, namely in steaming step, heatable catalyst is to remove aluminium from the crystalline silicate framework in steam, and contact from catalyzer by the complexing agent that makes catalyzer and be used for aluminium and extract aluminium from the hole of skeleton, removing the aluminum oxide that is deposited on wherein, thereby increase the silicon/al atomic ratio of catalyzer.Advantageously, commercially available crystalline silicate is by decatize process modification, the octahedra aluminium that it has reduced the tetrahedral aluminium in the crystalline silicate framework and the aluminium atom has been changed into the amorphous alumina form.Though the aluminium atom removes to form alumina particle with chemical mode from the crystalline silicate skeleton construction in steaming step, these particles can cause hole or the channel part in the skeleton to block.This can suppress dewatering of the present invention.Therefore, after steaming step, crystalline silicate carries out extraction step, wherein removes amorphous alumina from the hole, and recovers the volume of micropore at least in part.By the lixiviate step, obtain the whole dealuminzation effect of crystalline silicate by formation physical removal amorphous alumina from the hole of water-soluble aluminum complex compound.In the method, by remove aluminium from the crystalline silicate framework, remove the aluminum oxide of this formation then from the hole, this method is intended to obtain basic dealuminzation uniformly at the whole hole surface of catalyzer.This has reduced the acidity of catalyzer.Substantially equably take place in the hole that acid reduction limits in whole crystalline silicate framework ideally.After decatize is handled, carry out leaching process with by lixiviate so that the catalyzer dealuminzation.Aluminium preferably extracts from crystalline silicate by the complexing agent that tends to form with aluminium soluble complexes.Complexing agent is preferably in its aqueous solution.Complexing agent can comprise organic acid, as the salt (for example sodium salt) of citric acid, formic acid, oxalic acid, tartrate, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, toxilic acid, phthalic acid, m-phthalic acid, fumaric acid, nitrilotriacetic acid(NTA), hydroxy ethylene ethylenediamine triacetic acid, ethylenediamine tetraacetic acid (EDTA), trichoroacetic acid(TCA), trifluoroacetic acid or this acid or mixture or the salt of two or three this acid.Complexing agent can comprise mineral acid such as nitric acid, haloid acid, sulfuric acid, phosphoric acid or these sour salt or these sour mixtures.Complexing agent also can comprise these organic and mixture or their corresponding salt mineral acid.The complexing agent that is used for aluminium preferably forms water soluble complex with aluminium, and removes the aluminum oxide that forms in decatize treatment step process especially from crystalline silicate.
After aluminium lixiviate step, crystalline silicate can be used for example distilled water wash subsequently, and preferably for example dry under about 110 ℃ at elevated temperatures subsequently.
In addition, if used alkali or alkaline-earth metal in being used for the present invention's Preparation of catalysts process, then molecular sieve can carry out the step of ion-exchange.Routinely, ion-exchange uses ammonium salt or mineral acid to carry out in the aqueous solution.
After the dealuminzation step, catalyzer subsequently under 400 ℃ to 800 ℃ temperature for example under barometric point 1 hour to 10 hours time period of roasting.
The another kind of appropriate catalyst that is used for the inventive method is AEL type silicoaluminophosphamolecular molecular sieve, and typical example is the SAPO-11 molecular sieve.The SAPO-11 molecular screen base is in ALPO-11, and having is the Al/P ratio of 1 atom/atom substantially.In building-up process, the interpolation of silicon precursor and in the ALPO framework insertion of silicon obtain acid position at the micropore surface place of 10 yuan of ring grizzlies.Silicone content is 0.1 atom % to 10 atom % scope (Al+P+Si is 100).
In another specific embodiment, crystalline silicate or silicoaluminophosphamolecular molecular sieve mix with the preferred inorganic adhesive of tackiness agent, and the shape that is configured as expectation particle for example.Temperature in the selection tolerance dewatering process of the present invention and the tackiness agent of other condition.Tackiness agent is to be selected from clay, silicon oxide, metal silicate, metal oxide such as ZrO
2And/or the inorganic materials of metal, perhaps comprise the gel of silicon-dioxide and metal oxide mixture.If the tackiness agent that is used in combination with crystalline silicate itself is catalytic activity, this may change transformation efficiency and/or the selectivity of catalyzer.The non-active material that is used for tackiness agent can in order to can obtain product economical and in an orderly manner, and need not to adopt the method for other control speed of reaction suitably as the amount of thinner with the control conversion.Expectation provides the catalyzer with good crushing strength.This is because in commercial use, and expectation prevents that catalyzer is broken into powder mass.This clay or oxide adhesive only are used for usually improving the purpose of catalyzer crushing strength and use.Particularly preferred tackiness agent for catalyzer used in this invention comprises silicon-dioxide.The relative proportion of the inorganic oxide matrix of finely divided crystalline silicate material and tackiness agent can change in very wide scope.Usually, the content of tackiness agent is 5% to 95% scope by weight, more generally is by weight 20% to 75%, and it is based on the weight of composite catalyst.The mixture of this crystalline silicate and inorganic oxide adhesive is called the crystalline silicate of preparation.With in the mixing of catalyzer and tackiness agent, catalyzer can be mixed with particle, is extruded into other shape, or forms sphere or spray-dried powders.Usually, tackiness agent and crystalline silicate are admixed together by hybrid technique.In this technology, the tackiness agent of gel form (for example silicon-dioxide) mixes with crystalline silicate material, and the gained mixture is extruded into the shape that needs, for example cylindrical or leafy.Can make spherical by rotary pelleting machine or oil droplet technology.Bead can further prepare by spray-dried catalyst-tackiness agent suspensoid.Then, the crystalline silicate of preparation roasting 1 hour to 48 hours in air or in the rare gas element under 200 ℃ to 900 ℃ temperature usually.
In addition, catalyzer and tackiness agent both mix can before decatize and the extraction step also can after carry out.
The another kind of suitable catalyst family that is used for dehydration simultaneously and skeletal isomerization is by the aluminum oxide with silicon, zirconium, titanium or fluorine surface treatment modification.The general feature of aluminum oxide is that quite wide strength of acid distributes, and has Lewis type and Bronsted type acid position simultaneously.Existing wide strength of acid distribution to make needs the catalysis of several reactions of different strength of acid to become possibility separately.This can cause the low selectivity of required product usually.The deposition of silicon, zirconium, titanium or fluorine allows catalyzer to present significantly higher selectivity on the surface of aluminum oxide.For the preparation of alumina base catalyst, can use suitable aluminum oxide commonly used, preferably have 10m
2/ g to 500m
2The surface-area of/g and less than η or the gama-alumina of 0.5% alkali content.The catalyzer that is used for the present invention for example prepares by adding 0.05% to 10% silicon, zirconium or titanium.The adding of these materials can be finished in the preparation process of aluminum oxide, maybe can join the existing aluminum oxide that has finally activated.The interpolation of metal can be finished by before final precipitation of alumina metal precursor being dissolved with aluminum precursor in the aluminum oxide preparation process, perhaps by metal precursor is added in the aluminum hydroxide gel.Preferable methods is that metal precursor is added in the aluminum oxide of shaping.Metal precursor is dissolved in the suitable solvent (water-based or organically), and by beginning profit pickling process or wet dipping, perhaps removes excessive solute then and contacts with aluminum oxide by contact one given period with excessive solute.Aluminum oxide also can contact with the steam of metal precursor.Suitable metal precursor is the halogenide of silicon, zirconium or titanium, the oxyhalogenide of zirconium or titanium; The hydrocarbon oxy compound of silicon, zirconium or titanium, the oxalate of zirconium or titanium or Citrate trianion or said mixture.Solvent is selected according to the solvability of metal precursor.Contact can be under 0 ℃ to 500 ℃, most preferably finish under 200 ℃ at 10 ℃ in temperature.After the contact, finally wash aluminum oxide, dry and final roasting with the surface reaction between promotion silicon, zirconium or titanium and the aluminum oxide, and promote the removal of metal precursor part.The use of silicic acid salinization, zirconic acid salinization or the titanation of dehydration and skeletal isomerization or the aluminum oxide fluoridized is preferably finished in the presence of water when being used for isopropylcarbinol.The weight ratio of water and isopropylcarbinol is in 1/25 to 3/1 scope.The aluminum oxide of fluoridizing itself is known, and can be according to prior art for preparing.
About being derived from the purposes of dehydration/isomerized product simultaneously, the mixture of n-butene and iso-butylene can replace the purposes of raffinate I in refinery or petrochemical plant.The main purposes of n-butene and iso-butylene is as described below.
1,3-butadiene can be isolated from the thick C4 stream (comprising 40% 1,3-butadiene, 25% iso-butylene, 30% n-butene, 5% butane usually) that is derived from cracking unit.
1,3 divinyl can be used for preparation:
-styrene-butadiene rubber(SBR) (SBR),
-polyhutadiene (PB),
-nitrile-divinyl rubber (NBR),
-styrene-butadiene-styrene (SBS/SEBS),
-acrylonitrile-butadiene-styrene (ABS) (ABS),
-hexanolactam,
-1,4-butyleneglycol/THF,
-telomer etc.
Raffinate I also can isolate from the thick C4 stream that is derived from cracking unit.This raffinate I comprises 40% iso-butylene, 50% n-butene, 10% butane usually.
Isopropylcarbinol dehydration and isomerization obtain the mixture (common 40% iso-butylene and 60% n-butene) of n-butene and iso-butylene.
The dehydration of raffinate I, isopropylcarbinol and isomerized product and the C4 that is derived from the FCC materials flow can be used for preparation:
(1) MTBE/ETBE, TBA or two/three-iso-butylene can be used for preparation:
(a) high-purity iso-butylene of the decomposition by MTBE/ETBE or TBA, this iso-butylene can be used for preparation:
-isoprene-isobutylene rubber
-polyisobutene
-methyl methacrylate
-isoprene
-hydrocarbon resin
-tert-butylamine
-alkylphenol
-tert-butyl mercaptan
(b) gasoline or rocket engine fuel
(2) raffinate II (comprise usually 80-45% n-butene,＜2% iso-butylene,＞butane of 18-53%) can be used for preparation:
-sec-butyl alcohol (being used for producing MEK)
-alkylate oil
-polymerization gasoline
-oxidation synthol
-propylene
-by high-purity 1-butylene of superfractionation, it can be used for preparing LLDPE/HDPE, polybutene-1 or normal-butyl mercaptan.
The most common application of this mixture is that contained iso-butylene is changed into ether (MTBE or ETBE), changes into the trimethyl carbinol (TBA) or oligopolymer (for example dimerization/tripoly-iso-butylene), and all is gasoline component.The higher oligopolymer of iso-butylene can be used for rocket engine fuel/kerosene purposes.
In a specific embodiment, do not contain (or having only very small amount of) butane from the butene mixture of the preparation of dehydration/isomerization steps simultaneously, thereby allow to realize by accurate technology chaining the complete upgrading of olefin fraction.
Unreacted n-butene has the purposes in alkylate oil (Trimethylmethane is added butylene), polymerization gasoline (iso-butylene oligomeric) preparation in the preparation process of ether.
About etherification step, from C
4It is well-known in the art that the acid catalyzed reaction of alkene and alcohol (as methyl alcohol or ethanol) prepares the butyl alkyl oxide.
People such as etherification reaction such as St ü we A. described (Synthesis of MTBE and TAME and related reactions, Section 3.11, in handbook of heterogeneous Catalysis, n Volume 4, (Ertl G.,
H., Weitkamp J., (eds), and 1997, VCH Verlagsgesellschaft mbH, Weinheim is Germany) for the preparation of methyl tertiary butyl ether.
All business-like MTBE/ETBE/TAME methods are used similar operational condition, although use different reactor technology (EP0455029, DE2706465, DE-OS 2911077).Etherification reaction was with 1 hour
-1To 2 hours
-1Liquid hourly space velocity (LHSV) carries out under the condition of gentleness in liquid phase that (temperature is 40 ℃ to 200 ℃, be preferably 50 ℃ to 130 ℃, pressure be 0.1MPa to the scope of 20.7MPa, be preferably 6 bar to 25 bar, pressure allows to guarantee to maintain liquid phase greater than 8 bar, in the presence of solid acid catalyst.Suitable acid catalyst includes but not limited to acidic ion exchange resin.
Being reflected at respect to contained isoolefine in the hydrocarbon charging of iso-butylene and alcohol (ethanol and/or methyl alcohol) is used for carrying out under the existence of the required excessive a little alcohol of stoichiometric reaction.Make balance shift towards the generation of ether with excessive a little alcohol, to be conducive to higher per pass conversion, therefore limited side reaction such as oligomeric.
Temperature of reaction keeps low and can be in quite wide range regulation: the speed of etherificate raises with the rising of temperature really, but because thermodynamic(al)equilibrium, so lower temperature is conducive to higher ether transformation efficiency.In addition, if higher temperature is possible, but do not advise too high temperature, this is because of the resin dirt that may take place from polymkeric substance.About 130 ℃, it is unstable that sulfonic ion exchange resin becomes greatly.In lower temperature range, operate, guaranteed stable operation and long catalyst life.
Etherification reaction is heat release.From reactor, shift out reaction heat, and the balance between transformation efficiency and the speed of response has greatly influenced the development of etherificate technology.Generally speaking, two reactors in series are used-the first reactor to maintain and are realized about 80% reaction about 70 ℃, second reactor allows alkene to be converted into ether (under the situation of iso-butylene, transformation efficiency reaches and is higher than 97%) substantially 50 ℃ to 60 ℃ operations.
About the etherificate technology, first commercial MTBE factory (starting from gondola Ravenna in 1973, by the Anic/Snamprogretti operation) uses tubular reactor as the principal reaction device, follows by fixed-bed reactor.At that time, four Huels of company (Huels, Belgian856,401-Jan.2,1978), Snamprogretti (people such as Ancillotti F., US 4,071,567 or US3,979,461), Arco (Oil Gas J.76,26, June26,1978,62) and Sun (Oil Gas J., June16,1975,50-2) developed MTBE technology and for they provide permission.For example, the PEP in August, 1979 report n ° 131 and reference have wherein described contained iso-butylene manufacturing MTBE in the gaseous mixture by cracking in detail.
Now, use catalytic distillation most of ether-based devices (EP0008860 of CR﹠L in 1979 or in November, 1992 CDTech hydrocarbon processing), it used at Houston (Texas) in 1981 for the first time.
The catalyst for etherification that is used for the etherificate technology is highly acid ion exchange resin.Also reported the modification of this catalyzer, be called trifunctional catalyzer (TFC), it introduces a small amount of diolefine hydrogenation existing in the stream cracking incoming flow before the C5 on the catalyst for etherification with palladium, thereby improve catalyst life and product color (B.Schleppinghoff, S.Pritchard, Erdoel and Kohle-Erdgas-Petrochimie; In April, 41,1988, or people such as K.Rock, Hydrocarbon Technology International, 1994,42-46).
Description of drawings
Fig. 1 shows an explanation non-limiting technology in conjunction with the etherificate implementation process of the present invention.After the dehydration/skeletal isomerization, product water is separated at the same time, finally comprises the butene mixture of some heavy components (C4+) by mixing and etherificate with methyl alcohol and/or ethanol.The etherificate effluent comprises ether, unreacted n-butene and a small amount of unconverted iso-butylene.Basically unreacted butene mixture randomly is recovered and delivers to oligomerization reactor or alkylation reactor prepares heavy component (many alkylate oils, isooctene or middle runnings).
Embodiment
[embodiment]
Experiment:
The internal diameter of stainless steel reaction organ pipe is 10mm.The 35-45 purpose beaded catalyst of 10ml is loaded in the tubular reactor.Fill the silicon-carbide particle of 2mm before the catalyzer with void space afterwards.By the thermocouple monitoring temperature curve that well is positioned over inside reactor.Temperature of reactor speed with 60 ℃/hour under air is increased to 550 ℃, keeps 2 hours at 550 ℃, uses nitrogen purging then.Then, shown in replace nitrogen with charging under the operational condition.
Catalytic test carries out under downstriker flows, and under the absolute pressure of 1.5 bar to 2.0 bar, in 280 ℃ to 380 ℃ temperature range, and has 7 hours
-1To 21 hours
-1Weight hourly space velocity (WHSV).
Carry out the analysis of product by using online gas-chromatography.
Embodiment 1 (according to the present invention)
The catalyzer of Shi Yonging is the crystalline silicate of FER structure herein.The Si/Al of the H-FER of pulverulence is 33.Catalyzer is roasting 4 hours under 550 ℃ air before making 35-45 purpose particle.
Mixture with isobutanol/water that 95/5wt% forms on the catalyzer under 2 bar absolute pressures, under 350 ℃ to 375 ℃ the temperature, and 7 hours
-1To 21 hours
-1The isopropylcarbinol air speed under handle.
In this group operational condition, the conversion of isopropylcarbinol almost is completely, and the selectivity of butylene surpasses 95%wt, and the selectivity of iso-butylene is about 41-43%.Form a spot of C
4 +Compound.Table 1 has been summarized the data of present embodiment.
Table 1: embodiment 1
Comparative example 2
This catalyzer be by
The column gama-alumina of preparation.The specific surface area of catalyzer is 182m
2/ g and pore volume are 0.481ml/g.The small amount of impurities that is present on the aluminum oxide is summarized as follows:
0.25％wt?Si、0.02％wt?P、0.02％wt?fe、29ppm?Na。
Mixture with isobutanol/water that 95/5wt% forms, under 2 bar absolute pressures on catalyzer, under 350 ℃ to 380 ℃ temperature, with 7 hours
-1By 12 hours
-1Isopropylcarbinol carry out air speed and handle.
Under this group operational condition, the isopropylcarbinol transformation efficiency is almost completely, and the selectivity of butylene surpasses 98%wt, and the selectivity of iso-butylene is about 90-94%.Therefore generate very small amount of n-butene at this catalyzer.Form a spot of C
5 +Compound.Table 2 has been summarized the data of present embodiment.Table 2: embodiment 2
Embodiment 3 (according to the present invention)
Catalyzer is the zeolite (P-ZSM5) according to the phosphorus modification of following formulation.The ZSM-5 zeolite sample (Si/Al=13) of H type is at 100% H
2Among the O 550 ℃ of following decatizes 6 hours.Solid after the decatize is (4ml/1g zeolite) and H under the condition that refluxes
3PO
4(85%wt) aqueous solution contact is 2 hours.Introduce the CaCO of 69.9g then
3Then, solution evaporates 3 days dryings down at 80 ℃.The sample of 750g drying is extruded with the Bindzil of 401.5g and the additive of extruding of 0.01wt%.The solid of extruding is 110 ℃ of following dryings 16 hours and 600 ℃ of roastings 10 hours.
Have isobutanol/water mixture that 95/5wt% forms under 1.5 bar absolute pressures on catalyzer, under 280 ℃ to 350 ℃ temperature, with about 7 hours
-1The isopropylcarbinol air speed handle.
Under this group operational condition, the isopropylcarbinol transformation efficiency is almost completely, and the selectivity of butylene surpasses 90%wt, and the selectivity of iso-butylene is about 66-67%.Therefore, generated the almost butylene more than 90%, wherein significant amount is changed into n-butene by skeletal isomerization.The generation of heavy component is limited in 10% or still less.Table 3 has been summarized the data of present embodiment.
Table 3: embodiment 3
Claims (15)
1. method for the preparation of fuel dope, wherein isopropylcarbinol dewaters with skeletal isomerization simultaneously to make the alkene of basic correspondence in the first step, described alkene has identical carbonatoms and is made up of the mixture of n-butene and iso-butylene basically, and carry out etherification reaction at butene mixture described in second step, described method comprises:
A) introduce materials flow (A) at least one reactor, described materials flow (A) comprises isopropylcarbinol and the optional inert component of 40wt% at least,
B) make described stream and at least a catalyzer in described reactor, under at least a portion that makes described isopropylcarbinol is effectively dewatered condition with skeletal isomerization simultaneously, contact, making the mixture of n-butene and iso-butylene,
C) if remove the inert component that exists, the materials flow (B) of reclaiming the mixture that comprises n-butene and iso-butylene from described reactor,
D) at least one methyltertiarvbutyl ether reactor is delivered in described materials flow (B), and respectively under the condition for preparing ETBE and/or MTBE effectively, in the presence of ethanol and/or methyl alcohol, described materials flow (B) is contacted in described methyltertiarvbutyl ether reactor with at least a catalyzer,
E) reclaim materials flow (E) from described methyltertiarvbutyl ether reactor, described materials flow (E) comprises ETBE and/or MTBE, unreacted butylene, heavy component basically, the unreacted ethanol of optional difference and/or methyl alcohol,
F) fractionation materials flow (E) is to reclaim ETBE and/or MTBE.
2. method according to claim 1, wherein said materials flow (A) comprises the isopropylcarbinol of 70wt% at least, and preferably at least 80% or more.
3. method according to claim 1 and 2, wherein said materials flow (A) comprises the one or more of C4 alcohol that are different from isopropylcarbinol.
4. according to each described method in the claim 1 to 3, wherein be used for the described materials flow (A) of step a), and/or derive from renewable energy source for methyl alcohol and/or the ethanol of step d).
5. according to each described method in the claim 1 to 4, purification process is carried out in wherein said materials flow (A) before step b).
6. according to each described method in the claim 1 to 5, the WHSV of wherein said isopropylcarbinol is at least 1 hour
-1
7. according to each described method in the claim 1 to 6, the temperature of dehydration and skeletal isomerization is in 200 ℃ to 600 ℃ scope in the time of wherein said isopropylcarbinol.
8. according to each described method in the aforementioned claim, the temperature of dehydration and skeletal isomerization is in 250 ℃ to 500 ℃ scope in the time of wherein said isopropylcarbinol.
9. according to each described method in the aforementioned claim, the temperature of dehydration and skeletal isomerization is in 300 ℃ to 450 ℃ scope in the time of wherein said isopropylcarbinol.
10. according to each described method in the aforementioned claim, the described catalyzer that wherein is used for dehydration simultaneously and skeletal isomerization is the crystalline silicate that Si/Al is higher than 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Or Si/Al is higher than the dealuminzation crystalline silicate of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Or Si/Al is higher than the crystalline silicate of the phosphorus modification of 10 FER, MWW, EUO, MFS, ZSM-48, MTT, MFI, MEL or TON type,
Or the silicoaluminophosphamolecular molecular sieve of AEL type,
Or silicic acid salinization, zirconic acid salinization or titanation or the aluminum oxide fluoridized.
11. according to each described method in the aforementioned claim, the pressure of the described reactor of dehydration and skeletal isomerization is in the absolute pressure scope that 0.5 bar to 10 clings in the time of wherein said isopropylcarbinol.
12. according to each described method in the aforementioned claim, wherein materials flow (E) fractionation that will reclaim from step e) is to reclaim unreacted butylene and/or unreacted ethanol and/or methyl alcohol.
13. method according to claim 12 wherein is recycled to described methyltertiarvbutyl ether reactor with at least a portion of the unreacted butylene of described recovery and/or the unreacted ethanol of described recovery and/or at least a portion of methyl alcohol.
14. according to claim 12 or 13 described methods, wherein at least a portion of the unreacted butylene of described recovery is delivered to the zone purification, deliver at least one oligomerization reactor and/or at least one alkylation reactor then, with the preparation heavy component.
15. method according to claim 14 is wherein carried out purification step with described unreacted butylene, delivers to oligomerization reactor and/or alkylation reactor then.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR1060911A FR2969147B1 (en) | 2010-12-21 | 2010-12-21 | PRODUCTION OF FUEL ADDITIVES BY DEHYDRATION AND SIMULTANEOUS SKELETAL ISOMERISATION OF ISOBUTANOL ON ACID CATALYSTS FOLLOWED BY ETHERIFICATION |
| FR1060911 | 2010-12-21 | ||
| PCT/EP2011/073413 WO2012084950A1 (en) | 2010-12-21 | 2011-12-20 | Production of fuel additives via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by etherification |
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| Publication Number | Publication Date |
|---|---|
| CN103261129A true CN103261129A (en) | 2013-08-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011800612267A Pending CN103261129A (en) | 2010-12-21 | 2011-12-20 | Production of fuel additives via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by etherification |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20130261345A1 (en) |
| EP (1) | EP2655300A1 (en) |
| CN (1) | CN103261129A (en) |
| BR (1) | BR112013011269A2 (en) |
| FR (1) | FR2969147B1 (en) |
| WO (1) | WO2012084950A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278788A (en) * | 2015-05-22 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of with mixed alcohol production methyl tertiary butyl ether(MTBE) and/or the method for isobutene. |
| CN107987898A (en) * | 2017-12-01 | 2018-05-04 | 山东滨州裕华化工厂有限公司 | A kind of ethanol petrol and preparation method thereof |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3162763A1 (en) * | 2015-10-30 | 2017-05-03 | Total Research & Technology Feluy SA | Simultaneous dehydration and skeletal isomerisation of isobutanol on ti-containing zeolite catalysts |
| FR3135265A1 (en) * | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for obtaining hydrocarbons, and associated installation |
| FR3135263A1 (en) * | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for manufacturing jet fuel comprising a step of converting a stream of alcohol in a fluidized bed, associated jet fuel and installation |
| FR3135264A1 (en) * | 2022-05-06 | 2023-11-10 | Totalenergies Onetech | Process for manufacturing jet fuel, jet fuel and associated installation |
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| US4071567A (en) | 1974-05-21 | 1978-01-31 | Snamprogetti S.P.A. | Process for the production of methyl tert-butyl ether |
| IT1012686B (en) | 1974-05-21 | 1977-03-10 | Snam Progetti | PROCEDURE FOR THE PREPARATION OF TER-ALKYL ETHERS |
| DE2629769B2 (en) | 1976-07-02 | 1980-03-13 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of pure methyl tertiary butyl ether |
| DE2706465C3 (en) | 1977-02-16 | 1980-10-02 | Deutsche Texaco Ag, 2000 Hamburg | Process for the production of butadiene or n-butenes from hydrocarbon mixtures containing them with separation of isobutene |
| NL7803135A (en) | 1978-03-23 | 1979-09-25 | Shell Int Research | PROCESS FOR PREPARING TERTIARY ALKYL ETHERS. |
| DE2967531D1 (en) | 1978-07-27 | 1985-11-21 | Chemical Res & Licensin | Catalytic distillation process and catalyst |
| US4469911A (en) | 1980-10-23 | 1984-09-04 | Petro Tex Chemical Corporation | Isobutene removal from C4 streams |
| DE4013711A1 (en) | 1990-04-28 | 1991-10-31 | Erdoelchemie Gmbh | METHOD FOR THE PRODUCTION OF HIGH-OCTANE, LOW-OILFINE FUELS AND FUEL COMPONENTS |
| ZA966107B (en) * | 1995-07-21 | 1997-02-03 | Shell Int Research | Dehydration of primary alcohols. |
| US5895830A (en) | 1995-12-15 | 1999-04-20 | Uop Llc | Process for oligomer production and saturation |
| US5877372A (en) | 1997-11-21 | 1999-03-02 | Arco Chemical Technology, L.P. | Isobutylene oligomerization using isooctane diluent |
| US6689927B1 (en) | 2001-05-07 | 2004-02-10 | Uop Lcc | Process for oligomer production and saturation |
| US6768035B2 (en) * | 2002-01-31 | 2004-07-27 | Chevron U.S.A. Inc. | Manufacture of high octane alkylate |
| 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 |
| US6977318B2 (en) | 2004-05-04 | 2005-12-20 | Equistar Chemicals, Lp | Propylene production |
| US8975047B2 (en) | 2006-06-16 | 2015-03-10 | E I Du Pont De Nemours And Company | Process for making isooctenes from dry 1-butanol |
| US20090030239A1 (en) | 2006-06-16 | 2009-01-29 | D Amore Michael B | Process for making butenes from aqueous isobutanol |
| US20080132741A1 (en) * | 2006-06-16 | 2008-06-05 | D Amore Michael B | Process for making butenes from dry isobutanol |
| KR101573775B1 (en) | 2007-04-18 | 2015-12-04 | 부타맥스 어드밴스드 바이오퓨얼스 엘엘씨 | - fermentive production of isobutanol using highly active ketol-acid reductoisomerase enzymes |
| JP2011505490A (en) * | 2007-12-03 | 2011-02-24 | ジーヴォ，インコーポレイテッド | Renewable composition |
| CA2753037A1 (en) * | 2009-02-24 | 2010-09-02 | Gevo, Inc. | Methods of preparing renewable butadiene and renewable isoprene |
-
2010
- 2010-12-21 FR FR1060911A patent/FR2969147B1/en not_active Expired - Fee Related
-
2011
- 2011-12-20 US US13/878,016 patent/US20130261345A1/en not_active Abandoned
- 2011-12-20 BR BR112013011269A patent/BR112013011269A2/en not_active IP Right Cessation
- 2011-12-20 CN CN2011800612267A patent/CN103261129A/en active Pending
- 2011-12-20 WO PCT/EP2011/073413 patent/WO2012084950A1/en active Application Filing
- 2011-12-20 EP EP11811537.7A patent/EP2655300A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278788A (en) * | 2015-05-22 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of with mixed alcohol production methyl tertiary butyl ether(MTBE) and/or the method for isobutene. |
| CN106278788B (en) * | 2015-05-22 | 2018-11-02 | 中国石油化工股份有限公司 | A method of to mix alcohol production methyl tertiary butyl ether(MTBE) and/or isobutene |
| CN107987898A (en) * | 2017-12-01 | 2018-05-04 | 山东滨州裕华化工厂有限公司 | A kind of ethanol petrol and preparation method thereof |
| CN112898121A (en) * | 2021-01-23 | 2021-06-04 | 四川上氟科技有限公司 | Preparation method of perfluoroalkyl alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012084950A1 (en) | 2012-06-28 |
| FR2969147A1 (en) | 2012-06-22 |
| EP2655300A1 (en) | 2013-10-30 |
| BR112013011269A2 (en) | 2016-11-01 |
| FR2969147B1 (en) | 2013-01-04 |
| US20130261345A1 (en) | 2013-10-03 |
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Application publication date: 20130821 |