CN1772848A - Etbe mixture, its producing method and apparatus - Google Patents
Etbe mixture, its producing method and apparatus Download PDFInfo
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- CN1772848A CN1772848A CNA2004101013448A CN200410101344A CN1772848A CN 1772848 A CN1772848 A CN 1772848A CN A2004101013448 A CNA2004101013448 A CN A2004101013448A CN 200410101344 A CN200410101344 A CN 200410101344A CN 1772848 A CN1772848 A CN 1772848A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/046—Alkyl tert-alkyl ether, e.g. CH3OC(CH3)3
Abstract
To obtain an ETBE (ethyl-tert-butyl ether) mixture useful as a high-performance fuel having a high octane number. The ETBE mixture is composed of a reaction product obtained by reacting hydrated ethanol with isobutene and comprises 60-90 vol.% of ethyl-tert-butyl ether, 5-20 vol.% of tert-butyl alcohol, 5-20 vol.% of ethanol and 0-3 vol.% of water. The invention also produces the ETBE mixture.
Description
Technical field
The device that the present invention relates to a kind of ETBE (Ethyl Tertisry Butyl Ether) mixture and manufacture method thereof and be used to make, particularly a kind of ETBE mixture that can replace MTBE (methyl tertiary butyl ether) to can be used as high performance fuel effectively being used, and the device making the method for this ETBE mixture effectively and preferably use when making.
Background technology
At present, from vehicles such as automobiles, in agricultural machine such as tractor or cultivator, chain saw and various fields such as various industrial machine or building machinery, oil engine is widely used as propulsion source.In addition,, use gasoline, to the raising of global environment problem awareness, require to develop effective alternative fuel of gasoline replacing along with in recent years as fossil oil as the high performance fuel of above-mentioned oil engine.In order to satisfy above-mentioned requirements, beginning is a large amount of uses the MTBE (methyl tertiary butyl ether) that obtained by following chemical equation (1) direct reaction by IB (iso-butylene) and MeOH (methyl alcohol) to contain the oxygen octane enhancer as motor benzine.
Each physics value of the MTBE that makes thus is as shown in table 1 below.In addition, except each physics value of gasoline, also provide ETBE (Ethyl Tertisry Butyl Ether), TBA (trimethyl carbinol), EtOH (ethanol), H in the lump in the table 1 as other materials
2Each physics value of O (water) and IB (iso-butylene).
Table 1
| Material | |||||||
| MTBE | ETBE | TBA | EtOH | H 2O | IB | Gasoline | |
| Molecular formula | C 5H 12O | C 6H 14O | (CH 3) 3COH | C 2H 5OH | H 2O | i-C 4H 8 | C4～C8 |
| Molecular weight (g/mol) | 88 | 102 | 74 | 46 | 18 | 56 | 100～ 105 |
| Density (30 ℃) (g/cm 3) | 0.73 | 0.73 | 0.75 | 0.79 | 1 | 0.59 | 0.72～ 0.78 |
| Boiling point (℃) | 55.2 | 72 | 82.8 | 78.5 | 100 | -6.9 | 30～220 |
| Flash-point (℃) | -26 | -19 | 11 | 11 | -43 | ||
| Research octane number (RON) (RON) | 117 | 118 | 106 | 111 | R91 P100 | ||
| Motor-method octane number (MON) | 101 | 102 | 89 | 92 | R81 P88 | ||
| Vapour pressure Rvp (psi) | 8 | 4.7 | 12 | 18 | |||
| Oxygen level (wt%) | 18.2 | 15.7 | 21.6 | 34.7 | 89 | 0 | |
| Solubleness in the water (25 ℃) (wt%) | 5 | 1.2 | 100 | 100 | |||
| Net thermal value (kcal/kg) | 8,400 | 8,600 | 7,800 | 6,400 | 10,500 | ||
| Chemically correct fuel (Air-kg/Fuel-kg) | 11.7 | 12.1 | 11.1 | 9 | 15.1 | ||
RON: the low speed research octane number (RON) (＜3000rpm)
MON: high-speed motor method octane value (＞3000rpm)
R: common
P: senior
But, each physics value that provides by his-and-hers watches 1 compares as can be known, among MTBE, ETBE, TBA and the EtOH any is high-octane material, wherein, MTBE is water white strong smelly liquid at normal temperatures, soluble in water, in addition, also there is the problem of drinking the unhappy aroma and flavor of glassware for drinking water of sneaking into this material.And the carinogenicity of MTBE is also troubling, therefore also exists after discharging to cause environmental pollution problems.
Therefore, begin to pay close attention to the nontoxic biological ethanol that makes through fermentation and distillation procedure by reproducible biomass (biomass), replace MT reconnaissance BE to use it as the gasoline alternative fuel.But in simple distillation procedure, EtOH and water formation azeotropic mixture only can obtain concentration and be up to aqueous ethanol about 95vol%.Therefore,, must in this aqueous ethanol, further add benzene or hexanaphthene equal solvent, carry out component distillation, thereby have the problem that causes unit price to increase as the 3rd composition in order to obtain dehydrated alcohol.And also there are problems (referring to table 1) such as the high or every liter of mileage number of flash-point is low in ethanol.
Therefore, in order to address the above problem, consider to utilize the ETBE (Ethyl Tertisry Butyl Ether) that makes by following chemical equation (2) direct reaction by IB (iso-butylene) and EtOH (ethanol).This ETBE has the vapour pressure of reducing and reduces volatile advantage, also has almost non-toxic feature (referring to table 1).
Disclose the reactive distillation column that a kind of use is equipped with the fixed-bed reactor of having filled ion exchange resin in the patent documentation 1, made the C 4 fraction and the EtOH that contain IB react the method for making ETBE.In addition, in many documents, also the synthetic method of ETBE has been carried out studying (for example, referring to non-patent literature 1 etc.).But above-mentioned prior art all uses the dehydrated alcohol of high price as raw material, does not find to relate to and uses the document of the manufacture method of aqueous ethanol at a low price as described herein.
In addition, TBA (trimethyl carbinol) also has the effect (referring to table 1) as the octane enhancer of gasoline, can be by IB and H
2O synthesizes by following chemical equation (3), and this method is by many documents open (for example, referring to non-patent literature 2 etc.).
On the other hand, undersupply takes place in the IB that uses in the above-mentioned chemical equation of worries such as the inventor, just utilizes TBA to carry out the alternate method and studies, and its result is as paper publishing (non-patent literature 3 and 4).TBA is the by product when making propylene oxide, in the reactive distillation column of having filled as the storng-acid cation exchange resin of catalyzer, the big bio-ethanol of TBA and water content is reacted by following chemical equation (4).
The IB composition uses as the C 4 fraction that former oil refining obtains usually, in addition, and also can be synthetic by biomass as described below.That is, at first, biomass are carried out methane fermentation, produce CH
4And CO
2Need to prove that methane also can obtain from subterranean resource such as Sweet natural gas or methane hydrate.Shown in following chemical equation (5), use carbonic acid gas to carry out the methane modified-reaction, obtain carbon monoxide (CO) and hydrogen (H
2) (for example, non-patent literature 5), again by carbon monoxide and the synthetic iso-butylene (IB) (for example, non-patent literature 6,7) of hydrogen.
No. 5248836 specification sheets of (patent documentation 1) United States Patent (USP)
(non-patent literature 1) Y-C.Tian, F.Zhao, B.H.Bisowarno, M.O.Tade, " Pattern-based predictive control for ETBE reactive distillation ", J.Process Control, Vol.13, pp.57-67 (2003)
(non-patent literature 2) C.M.Zhang, A.A.Adesina, M.S.Wainwright, " Isobutene hydration in a countercurrent flow fixed bed reactor ", Chem.Eng.Processing, Vol.43, pp.533-539 (2004)
(non-patent literature 3) A.Quitain, H.Itoh, S.Goto, " Reactive Distillationfor Synthesizing Ethyl tert-Butyl Ether from Bioethanol ", J.Chem.Eng.Japan, Vol.32, No.3, pp.280-287 (1999)
(non-patent literature 4) A.Quitain, H.Itoh, S.Goto, " Industrial-ScaleSimulation of Proposed Process for Synthesizing Ethyl tert-Butyl Etherfrom Bioethanol ", J.Chem.Eng.Japan, Vol.32, No.4, pp.539-543 (1999)
(non-patent literature 5) A.Takano, T.Tagawa, S.Goto, " Carbon DioxideReforming of Methane on Supported Nickel Catalysts ", J.Chem.Eng.Japan, Vol.27, No.6, pp.727-731 (1994)
(non-patent literature 6) K.Maruya, T.Komiya, T.Hayakawa, L.Lu, M.Yashima, " Active sites on ZrO
2For the formation of isobutene fromCO and H
2", Journal of Molecular Catalysis A:Chemical, Vol.159, pp.97-102 (2000)
(non-patent literature 7) Y.Li, D.He, Q.Zhang, B.Xu, Q.Zhu, " Influence ofreactor materials on i-C4 synthesis from CO hydrogenation over ZrO
2Based catalysts ", Fuel Process.Technol., Vol.85, pp.401-411 (2004)
Summary of the invention
The present invention finishes under above-mentioned background, the problem that is solved for provide a kind of can be effectively as the ETBE mixture (first problem) of high-octane high performance fuel, the method (second problem) that a kind of low price makes this ETBE mixture is provided and a kind of device (the 3rd problem) that can effectively make this ETBE mixture is provided.
In order to solve above-mentioned first problem, main points of the present invention are a kind of ETBE mixture, form by the reaction product that aqueous ethanol and isobutene reaction obtain, it is characterized by, wherein contain the Ethyl Tertisry Butyl Ether of 60～90vol%, the trimethyl carbinol of 5～20vol%, the ethanol of 5～20vol% and the moisture of 0～3vol%.
One of preferred version of the ETBE mixture of the invention described above is that raw material is made for making the first at least in described aqueous ethanol and the described iso-butylene with biomass (biomass).
In addition, main points of the present invention also are a kind of oil engine superoctane fuel of being made up of this ETBE mixture.
In addition, in order to solve above-mentioned second problem, main points of the present invention are a kind of ETBE mixture manufacture method, it is characterized by, with aqueous ethanol and iso-butylene is raw material, the fixed-bed reactor that solid catalyst has been filled in use react raw material, contained at least the Ethyl Tertisry Butyl Ether and the trimethyl carbinol, with unreacted alcoholic acid reaction product.
One of preferred version of ETBE mixture manufacture method of the present invention is, along with the cooling reaction system that carries out of reaction, makes the temperature of reaction of last stage reaction be lower than the temperature of reaction of initial reaction stage.
In addition, other preferred versions of manufacture method of the present invention are to use storng-acid cation exchange resin as solid catalyst, and then the azeotropic mixture of use ethanol and water is as aqueous ethanol.
And, in order to solve above-mentioned the 3rd problem, main points of the present invention are a kind of manufacturing installation of ETBE mixture, described manufacturing installation makes aqueous ethanol and isobutene reaction, make contain at least Ethyl Tertisry Butyl Ether and the trimethyl carbinol, with unreacted alcoholic acid reaction product, it is characterized by, described manufacturing installation has with the lower section: be used to make multitube multistage fixed bed reactor aqueous ethanol and isobutene reaction, that equipped heating-cooling device; With distillation effusive reacting coarse product in this reactor, will contain the distillation tower that the Ethyl Tertisry Butyl Ether that above-mentioned reaction generates and the trimethyl carbinol and unreacted alcoholic acid raffinate together take out.
The preferred version that is fit to ETBE mixture manufacturing installation of the present invention is for constituting manufacturing installation in the following manner: use a plurality of unit that are made of above-mentioned reactor and above-mentioned distillation tower, configured in series, connect above-mentioned reaction member, in addition, in a plurality of reaction members of configured in series, the unitary reactor of initial reaction is linked to each other with above-mentioned iso-butylene feedway, and the unitary reactor of end reaction is linked to each other with described aqueous ethanol feedway, the raffinate that takes out from the distillation tower of specific reaction member is back in the reactor of previous reaction member.
In addition, other preferred versions of ETBE mixture manufacturing installation of the present invention make to be present in the reactive distillation column that the unreacted reactant in this reacting coarse product reacts for above-mentioned distillation tower being constituted effectively in the above-mentioned reacting coarse product of distillation.
Thus, the present invention with the IB composition in or the C 4 fraction that in oil factory, generates synthetic by methane and carbonic acid gas or by MTBE decompose pure IB that (reversed reaction of above-mentioned formula (1)) generate through the pressurized liquefied composition that obtains (below, above-mentioned two kinds of compositions are collectively referred to as the C4 composition) and aqueous ethanol be raw material, by above-mentioned formula (2) and above-mentioned formula (3), carry out liquid phase reaction adding to depress, so that synthetic TBA in synthetic ETBE, in addition, unreacted EtOH also becomes a moiety of ETBE mixture simultaneously.
Because the EtOH as raw material among the present invention uses hydrate, therefore needn't carry out processed to aqueous ethanol fully, or the product after the rectifying of use height, can use low price raw material, in addition, because the liquid phase reaction that adopted can be carried out under the mild conditions of medium temperature and medium pressure (below 100 ℃ or 100 ℃, 2MPa or 2MPa below), so also can further reduce the manufacturing cost of ETBE mixture.
And, shown in above-mentioned table 1, all higher with the octane value of the TBA of ETBE together synthetic (the secondary generation) and unreacted EtOH, therefore, the present invention does not separate mentioned component, use as the ETBE mixture containing under the state of mentioned component directly, thus can be effectively as oil engine superoctane fuels such as automobile fuels.In addition,, can both be used as good fuel no matter this ETBE mixture with which kind of ratio mixes with gasoline, and, not only can be used for automobile, also can be effective to automotive fuel as the power use of other mechanisms such as chain saw.
Description of drawings
Fig. 1 is the concept map that one of the reactor that is used to make ETBE mixture of the present invention example is shown.
Fig. 2 is the cross-sectional illustration figure that one of reaction chamber in the reactor shown in Figure 1 example is shown, and (a) be the cross-sectional illustration figure of reaction chamber, (b) divides explanatory view for (a) middle A-A cross-section.
Fig. 3 is the configuration pie graph that one of ETBE mixture manufacturing installation of the present invention example is shown.
Fig. 4 illustrates other routine configuration instruction figure of ETBE mixture manufacturing installation of the present invention.
Fig. 5 illustrates the routine configuration instruction figure of ETBE mixture manufacturing installation another other of the present invention.
Drawing reference numeral
10 reactors, 12 dividing plates
14a～14h reaction chamber 16 hot water supply paths
18 Cold water supply paths, 20 reaction tubess
22 solid catalysts, 24 strainers
30IB head tank 31IB raw material supplying path
32 heat exchangers, 34 pumps
39EtOH supply passageway 40 pumps
42 well heaters 44 take out path
46 distillation towers 48 are received path
50 product jars, 52 product paths
54,56 pumps, 58 byproduct tank
60 reactive distillation columns
Embodiment
Below, further specialize in order to make the present invention, with reference to accompanying drawing, describe the embodiment of several typical of the present invention in detail.
At first, Fig. 1 illustrates the concept map of one of the reactor that can be effective to make ETBE mixture of the present invention example.This DESIGN OF REACTOR design is as described below: the ETBE building-up reactions of above-mentioned formula (2) is the thermopositive reaction of 35kJ/mol, in addition, the TBA building-up reactions of above-mentioned formula (3) also is the thermopositive reaction of 38kJ/mol, must remove heat, and, above-mentioned reaction is reversible reaction, and temperature is low more, and the output of ETBE and TBA is many more, but, if temperature is low excessively, then speed of response itself is slack-off rapidly, so controlled temperature is very important, most preferably adopt the mode that temperature is reduced along with the carrying out of above-mentioned reaction, therefore, based on this, reactor design is become the multitube multistage fixed bed reactor.
Particularly, as shown in Figure 1, with the dividing plate 12 of horizontal direction, the tank interior of the direction up and down of reactor 10 being extended specified length is separated into independently 8 chamber 14a～14h, chamber 14a bottom is the raw material supplying chamber, and chamber 14h topmost is product taking-up chamber.Depress adding,, will be supplied to raw material supplying chamber 14a respectively from the outside as the aqueous ethanol (EtOH) and the iso-butylene (IB) of raw material by pump etc. in the theoretical ratio of the necessary chemistry amount of reaction usually; In addition, the ETBE mixture of the present invention that is generated by moisture EtOH and IB reaction is collected in the product taking-up chamber 14h, can be used as product and is taken out to the outside.
In this reactor 10, each the chamber 14b～14g of intermediary that is separated into separate space by dividing plate 12,12 up and down is respectively the reaction chamber that moisture EtOH and IB are reacted.In addition, above-mentioned independently reaction chamber 14b～14g connects hot water supply path 16 and Cold water supply path 18 respectively, independently above-mentioned reaction chamber 14b～14g is supplied with hot water or cold water respectively, so that can control the temperature of reaction of each reaction chamber.Particularly by the control Cold water supply, reaction chamber is more upward moved, its temperature of reaction is low more
In addition,, in each reaction chamber 14b～14g, many reaction tubess 20 are set at certain intervals in parallel with each other, are installed on the dividing plate 12,12 up and down, make each reaction chamber 14b～14g become hydraulic seal and pressure sealing each other as Fig. 2 (a) and (b).Thereby, make interior hot water of importing reaction chamber 14b～14g or cold water gap by above-mentioned reaction tubes 20, with after above-mentioned reaction tubes 20 heating or being cooled to specified temperature, be discharged from outdoor thus.In addition, in each reaction tubes 20, fill solid catalyst 22 granular, sheet isotactic setting shape usually, the strainer 24 of liquid permeability is installed in end thereon, prevent that solid catalyst 22 from flowing out, only make reaction solution direction (the being meant from bottom to top) circulation of forming by the mixture of moisture EtOH and IB up and down simultaneously herein.Thus, in the presence of solid catalyst 22, carry out the reaction of moisture EtOH and IB effectively, generate target product ETBE or TBA.
The dividing plate 12 of each reacting chamber space only will be in reaction tubes 20 the mobile reaction solution from below indoor above importing, chamber, for example, the chamber of reaction solution below from reaction chamber 14b～14g is imported the indoor of top, at this moment, except can be with from being configured in reaction tubes 20 effusive reaction solutions in the lower chambers directly import in the reaction tubes 20 in the upper chamber, also can suitably adopt the disposable importing of reaction solution of deriving respectively will many reaction tubess in being configured in lower chambers to be arranged on common reaction solution ensemble space in the dividing plate 12, and then the distribution reaction solution, make structures such as its inflow is configured in the many reaction tubess 20 in the upper chamber.
Therefore, use above-mentioned reactor 10, the IB (iso-butylene) of one of operable raw material when making ETBE mixture of the present invention, can use the raw material that provides by subterranean resource or biomass effectively expediently as mentioned above, in addition, even moisture EtOH (ethanol) also can effectively utilize the raw material that is obtained by biomass ferment.Only with as the biomass of renewable resources during as raw material, the raw material that is provided by ethanol fermentation or methyl alcohol fermentation is provided in special recommendation.The moisture content of moisture EtOH is preferably 30vol% usually or below the 30vol%, the azeotropic mixture of EtOH and water is used in special recommendation.
In addition, being reflected in the liquid phase of above-mentioned moisture EtOH and IB carried out, and usually in temperature moderate below 100 ℃ or 100 ℃, particularly can effectively implement under the temperature about 60～100 ℃.In addition, in order to ensure reactant at reaction unit, particularly be liquid phase in reaction tubes 20, pressure is generally 2MPa or below the 2MPa, is preferably the pressure about 1.3～2MPa especially, so that can carry out liquid phase reaction in reactor 10.
In addition, according to the present invention, the solid catalyst 22 that is filled in the reaction tubes 20 in order to make moisture EtOH and IB reaction can suitably use known various catalyzer, uses Zeo-karb usually, and wherein catalyzer can be used effectively with storng-acid cation exchange resin.As this storng-acid cation exchange resin, the preferred use imported sulfonic group (SO
3H) etc. strong acid group is as porous matter type (MR type) styrene resin of ion-exchange group.In addition, as this storng-acid cation exchange resin, can adopt any commercially available product,, " Diaion " (Mitsubishi Chemical), " Dowex " (U.S.:, " Duolite " (U.S.: title product sold such as for example, can suitably use (the U.S.: ROHM and HAAS company) DowChemical company) Diamond Shamrock company) with " Amberlyst ", " Amberlite ".The particle diameter of this storng-acid cation exchange resin is generally about 0.5～1.0mm.
By using above-mentioned reactor 10, make moisture EtOH and IB reaction, can obtain containing the ETBE of generation and TBA, and the reaction product of unreacted EtOH, in the present invention, contain the EtOH of TBA, 5～20vol% of ETBE, 5～20vol% of 60～90vol% and the moisture of 0～3vol% in this reaction product respectively, from reaction system, take out, obtain ETBE mixture of the present invention.The ETBE mixture that particularly has above-mentioned compositing range by preparation can in addition, be added on it in gasoline as octane enhancer with it effectively as the oil engine superoctane fuel, can bring into play good fuel economy.
In addition, Fig. 3 illustrates the layout diagram of one of the ETBE mixture manufacturing installation that uses above-mentioned reactor 10 example.A preference of the device when manufacturing installation shown in Figure 3 is to use IB100% as the IB raw material, the 100%IB that derives from IB head tank 30 passes through IB raw material supplying path 31, in heat exchanger 32, carry out heat exchange, after being heated, it is supplied to reactor 10 by pump 34.In addition, the moisture EtOH that takes out from EtOH head tank 36 is supplied to EtOH supply passageway 39 by surge tank 38, utilizes pump 40, it is supplied to reactor 10 under specified pressure.In well heater 42, be heated to specified temperature below 100 ℃ or 100 ℃ by the 100%IB of said pump 34 and 40 positive delivery and moisture EtOH, be imported into then in the reactor 10, carry out the formation reaction of ETBE and TBA by water vapour.
To contain the ETBE that in this reactor 10, generates of specified amount and the reacting coarse product of TBA and unreacted EtOH or residual moisture and take out, be supplied to distillation tower 46 by taking out path 44.In this distillation tower 46, adopt the distillation procedure of regulation, the reacting coarse product that distillation is supplied to, from the product of bottom taking-up, in addition, make by the distillation overhead product that isolating unreacted IB forms from reacting coarse product to be liquefied through water quench as raffinate, and take out from the top of tower of distillation tower 46, by reclaiming path 48, mix with the 100%IB raw material of supplying with from IB head tank 30, it can be used effectively.In addition, the raffinate that takes out from distillation tower 46 bottoms imports product jar 50 by product path 52, and is stored in wherein as ETBE mixture of the present invention.Import this product jar 50 raffinate heat by in heat exchanger 32, product path 52 and 31 heat exchanges of carrying out of IB raw material supplying path, can realize effective utilization.In addition, in above-mentioned distillation tower 46, also can from reacting coarse product, remove the hydrocarbon that is accumulated in the reaction system as required.
For the device of above-mentioned structure shown in Figure 3, sum up the material balance of the commercial plant when using 100%IB raw material, monthly output as 6000kL, the result is as shown in table 2 below.Establishing the 100%IB feed rate of being supplied with by IB head tank 30 this moment is 89L/min, and the moisture EtOH feed rate of being supplied with by EtOH head tank 36 of 92vol% is 64L/min, calculates.Be readily appreciated that forming of ETBE mixture of requirement according to the invention by the material balance shown in the table 2.
Table 2 unit: kg/min
| ETBE | TBA | EtOH | H 2O | IB | Add up to | |
| Reactor (10) inlet (1.6MPa) | ||||||
| From IB head tank (30) output (0.5MPa) | 52.4 | 52.4 | ||||
| From EtOH head tank (36) output (0.1MPa) | 46.5 | 5.1 | 51.6 | |||
| Cat head output (0.5MPa) from distillation tower (46) | 2.1 | 0.05 | 0.05 | Trace | 16.6 | 18.8 |
| From reactor (10) outlet to the output of distillation tower (46) inlet (60 ℃, 0.5MPa) | 73.5 | 16.6 | 14.4 | 1.1 | 16.7 | 122.3 |
| From the cat head of distillation tower (46) to the output of reactor (10) inlet (27.8 ℃, 0.5MPa) | 2.1 | 0.05 | 0.05 | Trace | 16.6 | 18.8 |
| At the bottom of the tower of distillation tower (46) to product jar (50) output (113.7 ℃, 0.5MPa) (unit: L/min (30 ℃ 0.1MPa) are converted) | 71.9 (98.5) | 16.5 (22.0) | 14.3 (18.1) | 1.1 (1.1) | 0.1 (0.1) | 103.9 (139.8) |
Fig. 4 does not use the 100%IB raw material, uses the IB class raw material layout diagram of one of the isochronous ETBE mixture of C 4 fraction manufacturing installation example for example also contain other hydrocarbon except IB.Adopt the structure that two groups of reaction members that are made of reactor shown in Figure 3 10 and distillation tower 46 are connected in series and form herein.For easy understanding, make the structure identical have identical numbering with Fig. 3 device.
In manufacturing installation shown in Figure 4, to be connected in series by the first reactor 10a and the first distillation tower 46a reaction member that constitutes and the reaction member that constitutes by the second reactor 10b and second column 46b, the IB raw material of being made up of C 4 fraction that takes out from IB head tank 30 imports the first reactor 10a through over-heat-exchanger 32.In addition, the moisture EtOH that is taken out from EtOH head tank 36 by pump 54 takes out with top of tower from the first distillation tower 46a and is coexisted after well heater 42 is heated to specified temperature with water vapour by the overhead product composition one of pump 56 positive delivery, import in the second reactor 10b, moisture EtOH and IB are further reacted.
The overhead product that takes out from the top of tower of second column 46b is the by product that contains a small amount of unreacted IB, be housed in the byproduct tank 58, in addition, in order to make the raffinate that takes out from second column 46b bottom proceed reaction, by pump 40 with it from surge tank 38 positive delivery to the first reactor 10a.In the first reactor 10a, the raffinate that is rich in moisture EtOH by these pump 40 positive delivery reacts with the IB raw material of being supplied with from IB head tank 30 by pump 34 (C 4 fraction), in the first distillation tower 46a, the reacting coarse product that obtains is thus carried out distillation procedure, the raffinate that takes out from the bottom is housed in the product jar 50 as target product ETBE mixture (product), in addition, because the overhead product that takes out from top of tower contains unreacted IB, therefore by pump 56 it is supplied in the second reactor 10b once more, makes itself and the moisture EtOH reaction of supplying with by pump 54.
Make up a plurality of reaction members that constitute by reactor 10 and distillation tower 46, make the feed(raw material)inlet of IB raw material (C 4 fraction) be the first reactor 10a as the initial reaction device, make the feed(raw material)inlet of moisture EtOH be the second reactor 10b as final reactor, supply with respectively, thereby can relax the restriction of reversible reaction effectively, ETBE mixture that can ETBE concentration is high takes out as raffinate from the first distillation tower 46a as initial distillation tower effectively as product.The by product that takes out as the overhead product of the second column 46b of last distillation tower contains considerably less IB, thereby the by product that obtains thus can be effective to other purposes.
Following table 3 illustrate use IB content as 53wt% as the raffinate 1 of C 4 fraction during with moisture EtOH reaction monthly output be the material balance of the commercial plant of 6000kL.If the feed rate of raffinate 1 is 168L/min, the moisture EtOH feed rate of 92vol% is that 68L/min calculates.Following compound represented in ellipsis in the table 3.The 1-B:1-butylene, C-2-B: suitable-2-butylene, the N-B:N-butane, T-2-B: anti--2-butylene, IBU: Trimethylmethane, 1,3-B:1, the 3-divinyl, C5+: carbonatoms is the hydrocarbon more than 5 or 5.
Table 3 unit: kg/min
| ETBE | TBA | EtOH | H 2O | IB | 1-B | C-2-B | N-B | T-2-B | IBU | 1，3-B | C5+ | Add up to | |
| First reactor (10a) inlet (1.6MPa) | |||||||||||||
| Head tank (30) output (0.5MPa) from raffinate 1 | 52.4 | 25.6 | 83 | 6.2 | 4.7 | 1.4 | 0.19 | 0.15 | 173.6 | ||||
| Export from surge tank (38) | 18.3 | 10.1 | 42.6 | 3.1 | 0.22 | 2.1 | 0.69 | 0.52 | 0.39 | 0.11 | 0.01 | 0.01 | 78.2 |
| From first reactor (10a) outlet export to first distillation tower (46a) inlet (60 ℃, 0.5MPa) | 68.2 | 17.2 | 19.6 | 1.3 | 19.4 | 25.6 | 8.3 | 6.2 | 4.7 | 1.4 | 0.18 | 0.14 | 172.2 |
| From the cat head of first distillation tower (46a) export to second reactor (10b) (44.6 ℃, 0.5MPa) | 1.9 | 0.18 | 0.41 | 9×10 -4 | 19.4 | 25.6 | 8.3 | 6.2 | 4.7 | 1.45 | 0.18 | 0.14 | 68.5 |
| At the bottom of the tower of first distillation tower (46a), export (133.1 ℃ in product jar (50) to, 0.5MPa) (unit: L/min (30 ℃ 0.1MPa) are converted) | 66.5 (91. 1) | 17.1 (21.6 ) | 19.6 (24. 8) | 1.3 (1.3) | 0.01 (0. 02) | 0.01 (0. 01) | Trace (trace) | Trace (trace) | Trace (trace) | Trace (trace) | Trace (trace) | Trace (trace) | 104.5 (13 8.8) |
| Second reactor (10b) inlet (1.6MPa) | |||||||||||||
| From moisture EtOH head tank (36) output (0.1MPa) | 49.7 | 5.5 | 55.2 | ||||||||||
| From the output of the cat head of first distillation tower (46a) (60 ℃, 0.5MPa) | 1.9 | 0.18 | 0.41 | 9×10 -4 | 19.4 | 25.6 | 8.3 | 6.2 | 4.7 | 1.45 | 0.18 | 0.14 | 68.5 |
| From second reactor (10b) outlet export to second column (46b) inlet (60 ℃, 0.5MPa) | 18.4 | 10.2 | 42.6 | 3.1 | 2.7 | 25.6 | 8.3 | 6.2 | 4.7 | 1.4 | 0.18 | 0.14 | 123.5 |
| From the cat head of second column (46b) export to byproduct tank (58) (43.8 ℃, 0.5MPa) | Trace | Trace | Trace | Trace | 2.4 | 24.6 | 7.9 | 5.9 | 4.5 | 1.3 | 0.174 | 0.13 | 46.9 |
| Export at the bottom of the tower of second column (46b) surge tank (38) (119.3 ℃, 0.5MPa) | 18.3 | 10.1 | 42.6 | 3.1 | 0.22 | 2.1 | 0.69 | 0.52 | 0.39 | 0.11 | 0.01 | 0.01 | 78.2 |
In manufacturing installation shown in Figure 4, reaction member more than 1 or 1 also can be set between reaction member that constitutes by the first reactor 10a and the first distillation tower 46a and the reaction member that constitutes by the second reactor 10b and second column 46b again, it is connected in series.At this moment, the raffinate positive delivery that will be taken out from each distillation tower bottom by suitable pumping unit makes its further reaction to the reactor of its upstream side reaction member, particularly previous reactor.
Manufacturing installation for ETBE mixture of the present invention shown in Figure 5, in order to use same C 4 fraction as raw material with device shown in Figure 4, as shown in Figure 3 in the device, use reactive distillation column 60 displaced distillation towers 46, so that the overhead product that will take out imports in the byproduct tank 58 from this reactive distillation column 60.Inside at this reactive distillation column 60, accommodate the same solid catalyst that makes aqueous ethanol and isobutene reaction 22 with reactor 10, mentioned component is reacted, simultaneously reacting coarse product is carried out distillation procedure, therefore, can make from the further reaction in reactive distillation column 60 of the reactor 10 interior reacting coarse products that take out.Thus, by using reactive distillation column 60 to replace simple distillation tower (46), can in reaction process, separate, therefore can suppress the reversed reaction in the reversible reaction effectively, thereby can make the regulation component and the poor by product of IB of ETBE mixture.
More than describe representative embodiment of the present invention in detail, but only as an example, will be understood that foregoing to the present invention without any restriction.Therefore enumerate other examples no longer one by one, based on those skilled in the art's knowledge, the present invention is carried out scheme afterwards such as various changes, modification, improvement also can implement, in addition, above-mentioned embodiment only otherwise break away from essence of the present invention just can be thought to be included in the category of the present invention.
(embodiment)
Below, in order to be described more specifically the present invention, to be used in and to implement presentation of results the present invention of obtaining in the testing installation.
At first, as testing installation, make the reactor that has order reaction chambers 6 as shown in Figure 1.The internal diameter of reactor is 15cm, and every grade of height is 30cm.The temperature control of each reaction chamber is different with structure shown in Figure 2, use hot water supply pipe and Cold water supply pipe of shape configuration in the shape of a spiral in each reaction chamber carry out temperature and control by being filled in solid catalyst (storng-acid cation exchange resin) heating cooling in each reaction chamber.In addition, employed storng-acid cation exchange resin is " Amberlyst 15 " (U.S.: ROHM and HAAS company), in addition, be 22.9L as total usage quantity of the storng-acid cation exchange resin of catalyzer, the quality of dry Zeo-karb is 4.94kg.Heat transfer area is 0.62m with the ratio of dry Zeo-karb quality
2/ kgdryresin.
In addition, the temperature in the reactor is set: carry out temperature control respectively by the feed rate of regulating hot water and cold water, reaction chamber is divided into the 1st grade to the 6th grade from the bottom to top, the 1st grade: 80 ℃, the 2nd grade: 90 ℃, 3rd level: 85 ℃, the 4th grade: 80 ℃, the 5th grade: 75 ℃, the 6th grade: 70 ℃.Making as the low indoor temperature of reaction of the 2nd order reaction thereon of the temperature of reaction in the 1st stage reactor of the subordinate of reactor is in order to prevent vigorous reaction to take place near inlet, carries out temperature easily and controls.Making the indoor temperature of the 2nd order reaction more than the 1st grade is top temperature (90 ℃), every thereafter rising first order reaction chamber, and temperature reduces by 5 ℃.
Under above-mentioned reaction conditions, make among the result that obtains of IB and moisture EtOH reaction measured value and calculated value when following table 4 comparatively illustrates and is raw material with 100%IB.Result by table 4 can confirm above-mentioned numerical value basically identical.Need to prove to calculate to be based on the testing data that obtains in the batch reactor, derivation speed of response formula is obtained by the basic formula of tube-type reactor.The simulation test of other total reactor also adopts identical method to obtain.
Table 4
| Measured value | Calculated value | |
| 100％IB(g/min) | 786 | 786 |
| Moisture EtOH (92vol%) (g/min) | 560 | 560 |
| ETBE(vol％) | 67.3 | 70.8 |
| TBA(vol％) | 16.7 | 15.8 |
| EtOH(vol％) | 15.7 | 12.8 |
| H 2O(vol％) | 0.3 | 0.6 |
Measured value and calculated value when in addition, following table 5 comparatively illustrates the raffinate 1 as the C 4 fraction that contains more IB that will obtain and uses as the IB raw material in oil factory.Need to prove that IB content is 47wt% in the raffinate 1 that uses herein.Result by this table 5 can confirm above-mentioned measured value and calculated value basically identical.
Table 5
| Measured value | Calculated value | |
| Moisture EtOH (g/min) | 280 | 280 |
| Raffinate 1 (IB47wt%) (g/min) | 840 | 840 |
| ETBE(vol％) | 68.3 | 67.9 |
| TBA(vol％) | 16.3 | 16.2 |
| EtOH(vol％) | 14.9 | 15.2 |
| H 2O(vol％) | 0.5 | 0.7 |
Result by table 4 and table 5 can confirm that all the ETBE mixture in the specific composition scope of the present invention's regulation, is applicable to combustion engine fuels such as high-octane automobile fuel.For the clear and definite above-mentioned fact, use the ETBE mixture of forming shown in the table 5, carry out running test with bike and the 125cc motorcycle of being with the 50cc engine, compare with the fuel consumption charge of regular gasoline, following table 6 illustrates the result of specific fuel consumption.As shown in Table 6, compare specific fuel consumption significantly improve (more than 2 one-tenth or 2 one-tenth) when using ETBE mixture of the present invention with regular gasoline.
Table 6
| Specific fuel consumption (km/L) | ||
| The ETBE mixture | Regular gasoline | |
| The bike of band 50cc engine | 25.5 | 21.2 |
| The 125cc motorcycle | 29.0 | 23.1 |
Claims (10)
1. an ETBE mixture is made up of the reaction product that aqueous ethanol and isobutene reaction obtain, and it is characterized by, and wherein contains the Ethyl Tertisry Butyl Ether of 60～90vol%, the trimethyl carbinol of 5～20vol%, the ethanol of 5～20vol% and the moisture of 0～3vol%.
2. ETBE mixture as claimed in claim 1 is characterized by, and the first at least in described aqueous ethanol and the described iso-butylene is that raw material is made with biomass.
3. an oil engine superoctane fuel is characterized by, and is made up of claim 1 or 2 described ETBE mixtures.
4. the manufacture method of an ETBE mixture, it is characterized by, with aqueous ethanol and iso-butylene is raw material, uses the fixed-bed reactor of having filled solid catalyst that raw material is reacted, and is contained the Ethyl Tertisry Butyl Ether and the trimethyl carbinol and unreacted alcoholic acid reaction product at least.
5. the manufacture method of ETBE mixture as claimed in claim 4 is characterized by, and along with the carrying out of reaction, with reaction system cooling, makes the temperature of reaction of last stage reaction be lower than the temperature of reaction of initial reaction stage.
6. as the manufacture method of claim 4 or 5 described ETBE mixtures, it is characterized by, described aqueous ethanol is the azeotropic mixture of ethanol and water.
7. as the manufacture method of each described ETBE mixture of claim 4 to 6, it is characterized by, described solid catalyst is a storng-acid cation exchange resin.
8. the manufacturing installation of an ETBE mixture, described device is used to make aqueous ethanol and isobutene reaction, makes to contain Ethyl Tertisry Butyl Ether and the trimethyl carbinol and unreacted alcoholic acid reaction product at least, it is characterized by, and described manufacturing installation has with the lower section:
Be used to make multitube multistage fixed bed reactor aqueous ethanol and isobutene reaction, that equipped heating-cooling device,
Distillation effusive reacting coarse product in this reactor takes out and contains the Ethyl Tertisry Butyl Ether that above-mentioned reaction generates and the distillation tower of the trimethyl carbinol and unreacted alcoholic acid raffinate.
9. the manufacturing installation of ETBE mixture as claimed in claim 8, it is characterized by, constitute manufacturing installation in the following manner, promptly, use a plurality of reaction members that constitute by described reactor and described distillation tower, configured in series, connect above-mentioned reaction member, in addition, in a plurality of reaction members of configured in series, reactor in the initial reaction unit is linked to each other with described iso-butylene feedway, and the reactor in the end reaction unit is linked to each other with described aqueous ethanol feedway, the raffinate that is taken out by the distillation tower in the specific reaction member is back in the reactor in the previous reaction member.
10. the manufacturing installation of ETBE mixture as claimed in claim 8 or 9 is characterized by, and described distillation tower is in the described reacting coarse product of distillation, makes to be present in the reactive distillation column that the unreacted reactant in this reacting coarse product reacts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP327533/2004 | 2004-11-11 | ||
| JP2004327533A JP4634777B2 (en) | 2004-11-11 | 2004-11-11 | ETBE mixture manufacturing apparatus and ETBE mixture manufacturing method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1772848A true CN1772848A (en) | 2006-05-17 |
| CN100554232C CN100554232C (en) | 2009-10-28 |
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| CNB2004101013448A Expired - Fee Related CN100554232C (en) | 2004-11-11 | 2004-12-17 | ETBE mixture, its manufacture method and the device that is used to make |
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| Country | Link |
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| JP (1) | JP4634777B2 (en) |
| KR (1) | KR100842777B1 (en) |
| CN (1) | CN100554232C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011072570A1 (en) | 2009-12-16 | 2011-06-23 | 华东理工大学 | Process and apparatus for coupling separation and purification of ethyl tert-butyl ether |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102053870B1 (en) * | 2013-01-22 | 2019-12-09 | 에스케이이노베이션 주식회사 | Method for Upgrading Biomass-derived Mixed Acids |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4334890A (en) * | 1981-02-03 | 1982-06-15 | The Halcon Sd Group, Inc. | Process for gasoline blending stocks |
| US5015783A (en) * | 1989-12-04 | 1991-05-14 | Uop | Production of ethers by the reaction of alcohols and olefins |
-
2004
- 2004-11-11 JP JP2004327533A patent/JP4634777B2/en not_active Expired - Fee Related
- 2004-12-17 CN CNB2004101013448A patent/CN100554232C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011072570A1 (en) | 2009-12-16 | 2011-06-23 | 华东理工大学 | Process and apparatus for coupling separation and purification of ethyl tert-butyl ether |
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| Publication number | Publication date |
|---|---|
| JP2006137824A (en) | 2006-06-01 |
| JP4634777B2 (en) | 2011-02-16 |
| CN100554232C (en) | 2009-10-28 |
| KR100842777B1 (en) | 2008-07-01 |
| KR20060045391A (en) | 2006-05-17 |
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