GB2056970A - Process for separating an alkanol from an ether - Google Patents
Process for separating an alkanol from an ether Download PDFInfo
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- GB2056970A GB2056970A GB8020528A GB8020528A GB2056970A GB 2056970 A GB2056970 A GB 2056970A GB 8020528 A GB8020528 A GB 8020528A GB 8020528 A GB8020528 A GB 8020528A GB 2056970 A GB2056970 A GB 2056970A
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- Prior art keywords
- alkanol
- calcium chloride
- ether
- mixture
- methanol
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 82
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 66
- 239000001110 calcium chloride Substances 0.000 claims abstract description 64
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 36
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 13
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 235000011148 calcium chloride Nutrition 0.000 abstract 3
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000004584 weight gain Effects 0.000 description 5
- 235000019786 weight gain Nutrition 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- QSLUWZMIMXNLJV-UHFFFAOYSA-L calcium methanol dichloride Chemical compound [Cl-].[Cl-].[Ca+2].OC QSLUWZMIMXNLJV-UHFFFAOYSA-L 0.000 description 4
- 230000000536 complexating effect Effects 0.000 description 4
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
- C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- 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
- C07C41/44—Separation; Purification; Stabilisation; Use of additives by treatments giving rise to a chemical modification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A C1-C3 alkanol is separated from an ether corresponding to the formula R-O-R', wherein R is an alkyl group containing 1-3 carbon atoms and R' is a t-butyl or t-amyl group, by intimately mixing the alkanol-ether mixture with at least 0.25 mol of calcium chloride per mol of alkanol. The calcium chloride is preferably used as an aqueous solution. The intimate admixture leads to the formation of a calcium chloride-alkanol complex corresponding to the formula CaCl2. ROH which is easily separated from the ether. The invention is particularly useful for extracting methanol from the crude reaction product obtained by reacting an excess of methanol with isobutylene or a C4 hydrocarbon stream containing isobutylene to form methyl t-butyl ether.
Description
SPECIFICATION
Process for separating an alkanol from an ether
This invention relates to a process for separating alkyl tert-alkyl ethers from alkanols.
As shown in U.S. patent 4,148,695 (Lee et al.),
John C. Davis et al., "MTBE bandwagon", CHEMI
CAL ENGINEERING, May 1979, pp.91-93, and
Stephen C. Stinson, "New plants, processes set for octane booster", CHEMICAL & ENGINEERING
NEWS, June 1979, pp.35 and 36, it is known that alkyl t-alkyl ethers can be prepared by reacting an isoolefin with an alkanol in the presence of an ionexchange resin. Such reactions have general interest, although the greatest current interest is in the reaction of isobutylen with methanol to form methyl t-butyl ether. Methyl t-butyl ether has utility as an additive for improving the octane rating of petrol.
In the reactions of isoolefins with alkanols, it is preferred to use an excess of alkanol in order to minimize the formation of by-products. However, the use of an excess of alkanol results in contamination of the ether product with an impurity which is removable with difficulty. The alkanol forms an azeotrope with the ether and therefore cannot be separated therefrom by simple atmospheric distillation.
It is frequently desirable to separate the alkanol from the ether. It is also desirable to separate the alkanol from any unreacted hydrocarbons in the crude reaction product, since the unreacted hydrocarbons could not otherwise be used in alkylation units. (Any alkanol contaminating the hydrocarbons would react with the alkylation catalyst). Thus, since atmospheric distillation cannot be used, it is conventional to remove the alkanol by pressure distillation.
This method of removing the alkanol is costly in terms of energy requirements and capital investment.
It would be desirable to find a more economical method of separating alkanols from alkyl t-alkyl ethers.
However, to be economical and efficient, this method would have to be one which would remove the alkanol without removing any substantial amount of the ether.
As disclosed in Frank C. Whitmore, "Organic
Chemistry", D. Van Nostrand Company, Inc. (New York), 1941, p.106, and in A. B. Kuchkarovetal.,
CHEMICAL ABSTRACTS, Vol. 13514b (1954), it is known that many metal salts form complexes with alcohols. French patent 1,505,547 (Matasa et al.) shows that this complexing ability of the salts makes them useful in separating alcohols from esters.
However, it has not previously been suggested that any of the salts that are known to form complexes with alcohols might be capable of efficiently separating alkanols from alkyl t-alkyl ethers.
An object of this invention is to provide a process for separating C1-C3 alkanols from ethers of the formula R-O-R', wherein R is an alkyl group containing 1-3 carbon atoms and R' is a t-butyl ort-amyl group which is economical in apparatus and process terms and does not involve substantial loss of the ether.
In the invention (1) a mixture comprising a C,-C3 alkanol and an ether corresponding to the formula
R-O-R', wherein R is an alkyl group containing 1-3 carbon atoms and R' is a t-butyl ort-amyl group is intimately mixed with (2) at least 0.25 mol of calcium chloride per mol of alkanol to form a calcium chloride-alkanol complex.
The alkanol-ether mixture that is treated in accordance with the invention may be any mixture comprising an alkanol containing 1-3 carbon atoms and an alkyl t-alkyl ether wherein the alkyl group contains 1-3 carbon atoms and the t-alkyl group is t-butyl ort-amyl. Thus, the alkanol may be methanol, ethanol, propanol, or isopropanol; the alkyl group of the ether may be methyl, ethyl, or propyl; the proportionation of the components is not critical and the mixture may consist only of the alkanol and ether our it may have other components.
The invention is particularly useful, however, in treating the crude reaction product, i.e., the total reaction mixture, resulting from the reaction of an excess of a C,-C3 alkanol with isobutylene or isoamylene to form an alkyl t-alkyl ether. Such reactions are well known and include processes wherein the alkanol is reacted with pure isoolefin as well as processes wherein the alkanol is reacted with a steam-cracker or catalytic-cracker C4 or C5 hydrocarbon stream containing the isoolefin and other hydrocarbons primarily having the same number of carbon atoms.Atypical process utilizes a C4 hydrocarbon stream containing 25-55% by weight of isobutylene, a methanol/isobutylene mol ratio of 1.7, an ion exchange resin as a catalyst, a reaction temperature of about 90-100"C., and a pressure of about 280 psig, although other reactants and otherconditions are also utilizable when desired.
As is also well known, the crude reaction products resulting from such processes are generally mixtures of desired ether, unreacted alkanol, unreacted hydrocarbon, and small amounts of by-product, formation is minimized by the use of an excess of the alkanol. For example, in the typical process mentioned above, the crude reaction product typically contains methyl t-butyl ether, methanol, isobutylene, n-butane, isobutane, cis-butene-2, trans-butene-2, butene-1, and small amounts of t-butyl alcohol and diisobutylene. On the other hand, when pure isoolefin is used as a starting material, isoolefin is the only reacted hydrocarbon in the crude reaction product.
The calcium chloride that is used in the practice of the invention may be solid calcium chloride but is preferably an aqueous solution. The aqueous solutions are generally more efficient than solid calcium chloride and are particularly suitable for use in processes wherein the alkanol is to be recovered and recycled to a reactor. When an aqueous solution of calcium chloride is employed, the concentration is generally at least 30%, preferably about 35-45%, most preferably about 40-44% by weight.
The calcium chloride is used in an amount such as to provide at least 0.25 mol of calcium chloride per mol of alkanol in the alkanol-ether mixture, and it is preferably used in larger amounts. The use of smaller amounts would not permit complete complexing of the alkanol and would be conducive to the loss of substantial amounts of ether. The use of larger amounts insures the presence of enough calcium chloride to permit substantially complete complex
ing of the alkanol and minimizes the chances that any substantial amount of ether might be lost.
As far as accomplishing the desired complexing is concerned, there is no maximum to the amount of calcium chloride that may be employed in the practice of the invention. However, since there is no advantage to using excessively large amounts of calcium chloride, and it would be uneconomical to do so, it is generally preferred to employ the calcium chloride in amounts such as to provide about 0.25-10 mols, most preferably about 0.5-5 mols, of calcium chloride per mol ofalkanol.
When planning to remove alkanol from several successive batches of alkanol-ether mixture being produced in a reactor, it is frequently desirable to prepare an aqueous solution containing sufficient calcium chloride to complex with all of the alkanol expected to be present in a few batches rather than to prepare separate aqueous solutions for each mixture to be resolved. For example, good results are obtained by treating three successive batches of alkanol-ether mixture with an aqueous solution orig inaliy containing about 5 mols of calcium chloride per mol of alkanol in each batch.
In continuous processes, particularly good results are obtained when using an amount of aqueous solution such as to provide about 2.5 mols of calcium chloride per mol of alkanol to be removed.
The particular manner in which the calcium chloride is mixed with the alkanol-ether mixture is not critical, as long as the method permits intimate admixture of the materials. However, the preferred methods of achieving the admixture generally depend on the nature of the materials being admixed. For example, when solid calcium chloride is used as the complexing agent, it is convenient to pack a column with calcium chloride, pour the alkanol-ether mixture through the column to allow the alkanol to contact and complex with the calcium chloride, and recover ether that is substantially free of alkanol from the bottom of the column.
When aqueous calcium chloride is used as the complexing agent, it is convenient to charge the aqueous solution and the alkanol-ether mixture to an agitated vessel, agitate the contents of the vessel to
achieve intimate admixture, allow the mixture to
separate into an upper phase comprising the ether
and any unreacted hydrocarbon and by-products
and a lower phase comprising a calcium chloride
alkanol complex in water, and withdraw the complex
from the bottom ofthe vessel.
When aqueous calcium is used to separate the
alkanol from the crude reaction product of an
isoolefin-alkanol reaction, it is convenient to (1)
charge the crude reaction product to a separator, (2)
intimately mix the crude reaction product in the separator with the aqueous calcium chloride to form
a calcium chloride-alkano complex, (3) withdraw the
ether and any unreacted hydrocarbon and by
products from the separator as overhead, (4) with
draw the calcium chloride-alkanol complex from the separator as bottoms, (5) separate the alkanol from the calcium chloride, (6) recycle the separated alkanol to the reactor, and (7) recycle the separated calcium chloride to the separator.
In the latter procedure, particularly good results are achieved when (1) the separator is a vessel equipped with mixing baffles and agitators, (2) the alkanol-ether mixture is introduced through the bottom of the vessel, (3) the aqueous calcium chloride is introduced through a port in the upper side of the vessel so as to provide countercurrent mixing, (4) the contents of the separator are maintained at about 20-45"C, and (5) the alkanol is stripped from the calcium chlodde-alkanot complex at about 100 C.
Once the alkanol has been separated from the ether, and simultaneously also from any unreacted hydrocarbons, any desired further purifications can be accomplished by conventional techniques. For example, as indicated above, the aqueous calcium chloride-alkanol complex can be separated into reusable components by stripping the alkanol at about 100"C. (Actually, this stripping operation ordinarily does not completely free the aqueous calcium chloride ofalkanol, but the minor amount ofalkanol left in the solution is not enough to make the solution ineffective in subsequent alkanol extractions).
Also, once they are separated from the alkanol, the ether and any unreacted hydrocarbons may be recovered by simple atmospheric distillation, if desired, and it is especially convenient to recover the ether by the use of a glycol condenser.
The invention is particularly advantageous in that it provides an economical, efficient way of separating alkanols from alkyl t-alkyl ethers, that it simultaneously accomplishes separation of the alkanols from any hydrocarbons in the alkanol-ether mixture, and that it achieves these separations without bringing about any substantial loss of ether. Thus, both the ethers and the hydrocarbons are rendered capable of being purified to produce ethers that are at least substantially free of alkanols and hydrocarbons that are suitable for use in alkylation units.
The ability of calcium chloride to remove the alkanols without also extracting substantial amounts of ether is particularly surprising when aqueous calcium chloride is employed. Aqueous solutions of other complexing agents are not as selective in removing alkanols and, when used, extract substantial amounts of ether as well as alkanol.
The following examples are given to illustrate the
invention and are not a limitation thereof. Unless
otherwise specified, quantities mentioned in the examples are quantities by weight.
EXAMPLE 1
Charge a solution of40 parts of calcium chloride in
50 parts of water to a suitable vessel. Add a mixture
of 20 parts of 99% methyl t-butyl ether and 20 parts of methanol, and shake the vessel on a mechanical shakerforfive minutes. Then allow the mixture to
stand for five minutes and separate into two phases, the lower of which is an aqueous calcium chloride
methanol complex. Drain out the lower phase and
measure the refractive index of the upper layer. The
upper layer has a refractive index of 1.3680, which is
comparable with the refractive index ofthe 99% methyl t-butyl ether starting material. The process results in the recovering of 100% of the original charge of methyl t-butyl ether.
EXAMPLE 11-CONTROL Repeat Example I except for replacing the calcium chloride with calcium bromide. Only 90% of the original charge of methyl t-butyl ether is recovered.
EXAMPLE -CONTROL Repeat Example I except for replacing the calcium chloride with sodium chloride. Only 94% of the original charge of methyl t-butyl ether is recovered.
EXAMPLE 111-CONTROL Repeat Example I except for replacing the calcium chloride with zinc chloride. Also, since good phase separation is not achieved in five minutes, allow the mixture to stand overnight after being shaken for five minutes. Some zinc chloride precipitates out, and only 93.5% of the original charge of methyl t-butyl ether is recovered.
EXAMPLE I CONTROL
Repeat Example I except for eliminating calcium chloride so as to use water as the extracting medium. Only 74% of the original charge of methyl t-butyl ether is recovered.
EXAMPLE V
PartA
Charge a solution of 40 parts of calcium chloride in 50 parts of water a suitable vessel. Add a mixture of 20 parts of 99% methyl t-butyl ether and 20 parts of methanol to form a total mixture containing 0.58 mol of calcium chloride per mol of methanol. Shake the vessel on a mechanical shaker for five minutes.
Then allow the mixture to stand for five minutes and separate into a methyl t-butyl ether layer and an aqueous layer containing calcium chloride and a calcium chloride-methanol complex. Drain out the lower aqueous layer. Measure the weight of the methyl t-butyl ether layer to determine how much of the ether has been recovered. Measure the aqueous layer to determine how much weight has been added by the extraction of methanol. The weight of the methyl t-butyl ether layer is 20.13 parts; the weight gain in the aqueous layer is 19.87 parts.
PartB Repeat Part A except for using as the starting aqueous calcium chloride a recycle of the aqueous calcium chloride/calcium chloride-methanol complex layer obtained in Part A to form a total mixture estimated to contain 0.33 mol of calcium chloride per mol of methanol. The weight of the methyl t-butyl ether layer is 20.07 parts, and the weight gain in the aqueous layer is 19.93 parts.
Part C- Control Repeat Part A except for using as the starting aqueous calcium chloride a recycle of the aqueous calcium chloride/calcium chloride-methanol complex layer obtained in Part B to form a total mixture estimated to contain 0.08 mol of calcium chloride per mol of methanol. The weight of the methyl t-butyl ether layer is only 18.13 parts, indicating that about 9.4% of the methyl t-butyl ether has been lost. The weight gain in the aqueous layer is 21.87 parts.
EXAMPLE Vl Repeat Example V, Part A, except for replacing the calcium chloride solution with a solution of 40 parts of calcium chloride in 30 parts of water. The weight of the methyl t-butyl ether layer is 19.89 parts, and the weight gain in the aqueous layer is 20.11 parts.
EXAMPLE VII
Repeat Example V, Part A, except for replacing the calcium chloride solution with a solution of 40 parts of calcium chloride in 40 parts of water. The weight of the methyl t-butyl ether layer is 19.42 parts, and the weight gain in the aqueous layer is 20.58 parts.
EXAMPLE Vffl Charge a mixture of 221 parts of methanol and 450 parts of a C4 hydrocarbon stream containing 50.8% isobutylene to a tubular reactor packed with an acidic ion exchange resin. React the ingredients at 100 C. and pass the reactor effluent through two stirred vessels connected in series and equipped with a condenser, each of the vessels containing 450 parts of 44% aqueous calcium chloride. Isolate crude methyl t-butyl ether and trap unreacted C4,s in a flask kept at dry ice/alcohol temperature. The crude methyl t-butyl ether has a methanol content of only 0.5% and the C4,s contain only 0.2% methanol.
Charge the aqueous calcium chloride/calcium chloride-methanol complex remaining in the separator to a distillation flask equipped with a 20-inch pack Vigreux column. Heat the mixture to a pot temperature of 102"C., and take the methanol overhead at a head temperature of 65"C. The distillation results in the recovery of 97% of the methanol that was extracted by the calcium chloride.
EXAMPLE IX
Charge a mixture of 221 parts of methanol and 450 parts of C4 hydrocarbon stream containing 50.8% isobutylene to a tubular reactor packed with an acidic ion exchange resin. React the ingredients at 100"C. to form a reaction mixture comprising methyl t-butyl ether, excess methanol, and unreacted hydrocarbons. Withdraw this reaction mixture from the bottom of the reactor and charge it to a separator equipped with mixing baffles and agitators and having (1) a bottom entry port for introduction of the reactor effluent, (2) an entry port in the upper side, (3) a top exit port, and (4) a bottom exit port.
While operating the agitators, charge 900 parts of 44% aqueous calcium chloride through the upper entry port to provide countercurrent admixture of the reactor effluent and aqueous solution at 35"C.
and formation of a CaCI2.4 CH3OH complex. Withdraw the ether and unreacted hydrocarbons through the top exit port and separate them. Drain an aqueous calcium chloride/calcium chloride-methanol complex mixture through the bottom exit port.
Charge the aqueous mixture withdrawn from the bottom of the separator to a suitable distillation flask, and heat into 100 C. to strip the methanol from the calcium chloride-methanol complex at a head temperature of 65 C. Recycle the recovered methanol to the tubular reactor, and recycle the separated aqueous calcium chloride to the separator.
The process leads to the isolation of methyl t-butyl ether and C4 hydrocarbons that are substantially free of methanol, and it separates most of the methanol from the calcium chloride-methanol complex to provide methanol and aqueous calcium chloride
streams suitable for use in subsequent reactions.
Similar results are observed when the examples
are repeated except that the ingredients are replaced
with ingredients taught to be their equivalents in the
specification.
Claims (11)
1. A process for separating a C-C3 alkano I from a
mixture including at least such an alkanol and an ether corresponding to the formula R-O-R', wherein
R is an alkyl group containing 1-3 carbon atoms and
R' is a t-butyl ort-amyl group, which process comprises intimately mixing the alkanol-ether mixture with at least 0.25 mol of calcium chloride per mol of alkanol to form a calcium chloride-alkanol complex
2. A process according to claim 1 wherein the alkanolis methanol and the ether is methyl t-butyl ether.
3. A process according to claim 1 or claim 2 wherein the mol ratio of calcium chloride to alkanol is about 0.25:1 to 110:1.
4. A process according to claim 3 wherein the mol ratio of calcium chloride to alkanol is about 0.5:1 to 5:1.
5. A process according to any one of preceding claims wherein the calcium chloride is mixed with the alkanol-ether mixture in the form of an aqueous solution of calcium chloride.
6. A process according to claim 5 wherein the concentration of calcium chloride in the aqueous solution is about 40-44% by weight.
7. A process according to any one of preceding claims wherein the mixture is the total reaction mixture resulting from the reaction of an excess of the alkanol with an isoolefin containing 4 or 5 carbon atoms.
8. A process according to claim 7 wherein the mixture is the total reaction mixture resulting from the reaction of an excess of methanol with a C4 hydrocarbon stream containing isobutylene.
9. A process for separating an ether prepared by reacting an excess of a C,-C3 alkanol with an isoolefin containing 4 or 5 carbon atoms to form a crude reaction product including a mixture of (1) an ethercorresponding to the formula R-O-R', wherein R is an alkyl group containing 1-3 carbon atoms and R' is a t-butyl ort-amyl group (2), unreacted alkanol, and (3) unreacted hydrocarbon, which includes the steps of::
(A) charging the crude reaction product to a separator,
(B) intimately mixing the crude reaction product in the separator with an aqueous solution containing at least 0.25 mol of calcium chloride per mol of unreacted alkanol to form a calcium chloride-alkanol complex,
(C) withdrawing the ether and unreacted hydrocarbon from the separator as overhead,
(D) withdrawing the calcium chloride-alkanol complex from the separator as bottoms,
(E) separating the alkanol from the calcium chloride,
(F) recycling the separated alkanol to the reactor,
and
(G) recycling the separated calcium chloride to the
separator.
10. A process according to claim 9 wherein the crude reaction product is the product obtained by reacting an excess of methanol with a C4 hydrocarbon stream containing isobutylene.
11. A process for separating an ether from an alkanol by the use of calcium chloride substantially as herein disclosed and exemplified.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US6921079A | 1979-08-23 | 1979-08-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB2056970A true GB2056970A (en) | 1981-03-25 |
Family
ID=22087445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8020528A Withdrawn GB2056970A (en) | 1979-08-23 | 1980-06-23 | Process for separating an alkanol from an ether |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS5630934A (en) |
| DE (1) | DE3026506A1 (en) |
| GB (1) | GB2056970A (en) |
| IT (1) | IT1151087B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0143639A2 (en) * | 1983-11-28 | 1985-06-05 | Ciba Specialty Chemicals Water Treatments Limited | Separation of Methanol from mixtures containing it |
| US5013444A (en) * | 1989-08-31 | 1991-05-07 | Hoechst Aktiengesellschaft | Process for separating off enol ethers from reaction mixtures containing alcohols |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2843341B2 (en) * | 1988-11-16 | 1999-01-06 | 宇部日東化成株式会社 | Fiber reinforced synthetic resin pile tension wire for optical fiber cable |
-
1980
- 1980-06-11 IT IT22721/80A patent/IT1151087B/en active
- 1980-06-23 GB GB8020528A patent/GB2056970A/en not_active Withdrawn
- 1980-07-12 DE DE19803026506 patent/DE3026506A1/en not_active Ceased
- 1980-08-20 JP JP11355780A patent/JPS5630934A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0143639A2 (en) * | 1983-11-28 | 1985-06-05 | Ciba Specialty Chemicals Water Treatments Limited | Separation of Methanol from mixtures containing it |
| EP0143639A3 (en) * | 1983-11-28 | 1986-06-04 | Allied Colloids Limited | Separation of methanol from mixtures containing it |
| US5013444A (en) * | 1989-08-31 | 1991-05-07 | Hoechst Aktiengesellschaft | Process for separating off enol ethers from reaction mixtures containing alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5630934A (en) | 1981-03-28 |
| IT8022721A0 (en) | 1980-06-11 |
| IT1151087B (en) | 1986-12-17 |
| DE3026506A1 (en) | 1981-03-26 |
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| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |