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United States Patent [191 [11] Patent Number: 4,978,778

Isshiki et al. [45] Date of Patent: Dec. 18, 1990

[54] PROCESS FOR PRODUCING VINYL 4,189,441 2/1980 Braca et a1. ....................... .. 560/232
ACETATE 4,221,918 9/1980 Suzuki . .. ... . . . . . . .. 560/263

4,337,351 6/1982 Larkins, Jr. ....................... .. 560/263


[75] Inventors: Tomiya Isshiki, Tokyo; Yasuhiko
Kijima, Chiba; Akiro Ito, Chiba; Yuh FOREIGN PATENT DOCUMENTS
Miyauchi, Chiba; Takao Konko, 1112555 5/1968 United Kingdom.
Tokyo; Takayuki Watanabe, Chiba, 1538782 1/1979 United Kingdom .
all of Japan
OTHER PUBLICATIONS
[73] Assignee: Mitsubishi Gas Chemical Company, Hydrocarbon Processing, vol. 44, No. 11, Nov. 1965, p.
Inc., Tokyo, Japan 287.
[21] Appl. No.: 560,279 Pittman, Jr. et al., “Polymer-bound Catalysts and Rea
[22] Filed: Dec. 13, 1983 gents”, Chemtech, Sep. 1973, pp. 560-566.
Michalska et al., “Supported Homogenous Catalysts”,
Related U.S. Application Data Chemtech, Feb. 1975, pp. 117-122.
Patent Abstracts of Japan, vol. 5, No. 75, May 19, 1981,
[63] Continuation of Ser. No. 301,409, Sep. 11, 1981, aban p. 55. .
doned.
Chemical Abstracts, 2726-2727, vol. 10, (1961).
[30] Foreign Application Priority Data Berichte, vol. 49, (1916), 1063-1071.
Sep. 16, 1980 [JP] Japan .............................. .. 55-128404 Primary Examiner—-Vivian Garner
Oct. 3, 1980 [JP] Japan .............................. .. 55-138411 Attorney, Agent, or Firm-—-Fleit, Jacobson, Cohn, Price,
Holman & Stern
[51] Int. Cl.5 ..................... .. C07C 67/00; C07C 69/15
[52] U.S. Cl. ................ .. 560/261; 560/248; [57] ABSTRACT
560/263; 560/265; 562/607; 562/608; 568/484; A process for producing vinyl acetate which comprises
1 568/492
reacting acetic anhydride with hydrogen in the pres
[58] Field of Search .............................. .. 560/261, 263
ence of a catalyst comprising
[56] References Cited (a) a metal belonging to Group VIII of the Periodic
U.S. PATENT DOCUMENTS Table or a compound of the metal, and
(b) (i) an acidic substance, or (ii) a halide ,
2,021,698 11/1935 Perkins .............................. .. 260/106
2,425,389 8/1947 Oxley et al. is disclosed.
2,860,159 11/1958 Sharp et 211.
3,579,566 5/1971 Fenton .............................. .. 560/263 16 Claims, 2 Drawing Sheets
US. Patent Dec. 18,1990 Sheet 1 of2 4,978,778

Fig. /
US. Patent Dec. 18, 1990 Sheet 2 of2 4,978,778

Fig. 3
4,978,778
1 2
odic Table, compounds of the metals and mixtures
PROCESS FOR PRODUCING VINYL ACETATE thereof and
(b) (i) at least one acidic substance selected from the
This application is a continuation of application Ser. group consisting of protic acids, Lewis acids, solid acids
No. 301,409 ?led Sept. 11, 1981, now abandoned. and mixtures thereof or
(ii) at least one halide selected from the group consist
BACKGROUND OF THE INVENTION ing of chlorides, bromides, iodides and mixtures thereof
This invention relates to a process for producing is used.
vinyl acetate which comprises reacting acetic anhy The metals belonging to Group VIII of the Periodic
dride with hydrogen. 10 Table can be used in any form of zero valence to higher
Vinyl acetate has been produced from acetylene in valence state. For example, they can be used as metal
the past. Recently vinyl acetate has also been produced itself or Raney metals, or ?nely divided particles of the
from ethylene. In case of producing vinyl acetate from metals, or as metal compounds, such as carbonates,
ethylene, palladium chloride or mixture of palladium oxides, peroxides, hydroxides, nitrates, sulfates, phos
chloride and sodium acetate has been used as a catalyst. phates, halides, cyanides, thiocyanides, sulfonates,
In addition, process for producing vinyl acetate C1-C5 alkoxides, such as methoxides and ethoxides,
which comprises producing ethylidene diacetate (1,1 phenoxide, carboxylates derived from C1-C20 alkanoic
diacetoxy ethane) from acetaldehyde and acetic anhy acids, oxyhalides, hydrides, carbonyls, nitrites, sul?tes,
dride and causing thermal decomposition of the ethyli phosphites, acetylacetonates and sul?des of metals or
dene diacetate to form vinyl acetate, and process for 20 metal compounds coordinated with ammonia, cyanide,
producing vinyl acetate and acetic acid from acetalde amines or amino acids. _
hyde and acetic anhydride directly have been proposed The components (a) include, for example, metallic
(refer to Hydrocarbon Process, 44 (11) 287 (1965), Brit Pd, PdXg, PdX2.2I-I2O, PdX2.2NI-I3, Pd(CN)2, PdzH,
ish Patent No. 1,112,555 and U.S. Pat. Nos. 2,021,698, Pd(OH)2, Pd(OI-I)2.2NH3, Pd(NO3)2, PdZO, PdO,
2,425,389 and 2,860,159). 25
Pd02, PdSO4.2H2O, PdzS, [Pd(PPh3)z]Cl2, PdS, PdSg,
SUMMARY OF THE INVENTION Pd3(PO4)2, Na2PdX4, Pd[(n-C4H9)3P](CO)CI2,
K2PdX4, Li2PdX4, Pd(OAc)2, Pd(AcAc)2,
The present inventors carried out research to fmd a PdX2(PhCN)2, Pd(SCN)2, Pd(NC)2, palladium benzene
process for effectively synthesizing vinyl acetate from sulfonate, metallic Rh, RhX3, RhX3.3H2O, Rh(OH)3,
aceticanhydride. As a result, we found a process for Rh(NO3)3.2H20, Rho, R1102, Rh03, Rh2(SO4)3.6I-I20,
producing vinyl acetate by one stage by reacting acetic R115, [Rh(A°O)2]2, R112(C0)3, Rh6(co)1e,
anhydride with hydrogen. RhC1(PPhs)3, [RhX(C0)2]2, Rh(ACA<>)s, Rh(SCN)s,
This invention relates to a process for producing Rh(PPh3)2(CO)Cl2, Rh(OPh)3, metallic Ir, IrZ3, IrX33
vinyl acetate which comprises reacting acetic anhy H2O, 11'02, IrO2.2H2O, I1'2O3.3H2O, IrS, II‘2(CO)3, me
dride with hydrogen in the presence of a catalyst com 35 tallic Pt, H2PtX6, PtXz, PtX4.Pt(OH)2, Pt(0H)4, PtOg,
prising PtO, Pt(PPh3)2(SnCl3)2, Pt304, Pt(CO)X2, PtS, Pt2S3,
(a) at least one material selected from the group con Pt(CN)1, metallic Ru, RuXz, R11X3, RuX4, Ru(OH)3,
sisting of metals belonging to Group VIII of the Peri R1102, Rl1203, R11(NO3)36H20, Ru(CO)2I2, Ru(CO)12,
odic Table, compounds of the metals and mixtures metallic Os, OsXg, OsX3, Os(CO)4X2, Os3(CO)12, Os(
thereof [sometimes hereinunder referred to as compo CO)5, metallic Fe, FeSZ, FeX2, Fe(NO3)2.6H2O, Fe
nent (a)] and SO4_5H2O, Fe(H2PO2)3, F6503, FeS2O3.5H2O, Fe(
(b) (i) at least one acidic substance selected from the NO2)2, metallic Ni, NiXg, NiX23H2O, NiO, Ni2O3,
group consisting of protic acids, Lewis acids, solid acids Ni(CO)4, NiCO3, NiSO4, NiS, Ni(CN)2, metallic Co,
and mixtures thereof [sometimes hereinunder referred C0304, CoX3, Co(OAc)2.4H2O, CoCO3, Co2(SO4)3,
45
to as component (b)(i)] or C0504, wherein X is F, Cl, Br or I; Ph is phenyl group;
(ii) at least one halide selected from the group consist A00 is acetoxy group and AcAc is acetylacetonate
ing of chlorides, bromides, iodides and mixtures thereof group.
[sometimes hereinunder referred to as component The metal-polymer complexes in which a metal be
(b)(ii)l longing to Group VIII of the Periodic Table is bonded
BRIEF EXPLANATION OF THE DRAWINGS to for example, silica, polyvinyl chloride, or polysty
rene-divinylbenzene substrate crosslinked by phos
FIGS. 1-3 show flow sheets of the apparatus for phine, silyl, an amine, pyridine or sul?do bond can be
carrying out this invention. used-as component (a).
, DETAILED EXPLANATION OF THE 55 The metal-polymer complexes are disclosed in
INVENTION CHEMTECH, 1973 Pages 560-566 and CHEMTECH,
1975 pages 117-122.
The mechanism of the reaction of acetic anhydride Of these metals and metal compounds, palladium
with hydrogen in this invention is not perfectly clear. rhodium, platinum, ruthenium, osmium, cobalt and
However, it is believed that the reaction is expressed by
60 nickel and compounds of the metals are suitable; palla
the following equation: dium, rhodium, platinum, ruthenium, cobalt and nickel
and compounds of the metals are preferable; and palla
dium, rhodium, platinum and ruthenium and com
pounds of the metals are more preferable. Palladium or
The above reaction proceeds in a good state when a 65 a palladium compound is most preferable. Of course,
catalyst comprising mixtures of metals belonging to Group VIII of the Peri
(a) at least one material selected from the group con odic Table or compounds of the metals can also be used
sisting of metals belonging to Group VIII of the Peri as component (a).
4,978,778 4
3
Component (a) constituting the catalyst may be solu In general, strong organic or inorganic protic acids as
ble in a reaction solution. In this case a catalytic reac mentioned above or mixtures thereof can be used as an
tion is effected in a homogeneous system. The compo acidic substance. However, materials from which
nent (a) may also be insoluble in the reaction solution or strong protic acids are formed in the reaction solution
partially soluble in the solution. In this case the reaction can also be used as an acidic substance.
is effected in a heterogeneous system. The heteroge (II) Lewis acids
neous system catalysts include, for example, a metal (A) Halides of metals belonging to Group IIa, IIIa,
itself, compounds of the metals or a metal supported on IVa, Va, VIa, IIIb, IVb, Vb, VIb, VIIb and VIII such
a carrier. as BeXz, MgXg, BX3, B2X4, AlX3, GaX2, GaXg, InX,
A metal can be supported on a carrier by coprecipita InXz, InX3, TlX, T1X3, T1X4, SiX4, Si2X6, Si3X3,
tion, impregnation, blending, adsorption, and ion ex Si4X10, Si5X12, GCX, GBXZ, GCX4, SnX2, SI1X4, PX3,
change and the like. PX5, P2X4, ASX3, ASX5, SbX3, SbX5, BiX, BiXz, BiX3,
One of the processes for supporting a metal on a TiXg, TiX3, TiX4, ZI‘X2, Z1‘X3, ZrX4, VX2, VX3, VX4,
carrier is as follows: A carrier is impregnated with a CrXz, C1'X3, MOXz, MOX3, MOX4, MOX5, WX2, WX4,
solution of a metal belonging to Group VIII of the WX5, WX5, MnXz, MnX3, MnX4, ReX3, ReX4, ReX5,
Periodic Table or a compound of the metal. The metal ReXg, FeX2, FeX3, COXZ, COX3, COX4, NiXz, RuX,
or the metal compound on the carrier is reduced with RuXz, RuX3, RUX4, CuX, CuXz, AuX, AuXz, AuX3,
formalin, hydrogen, sodium formate, carbon monoxide, ZnXg, CdXZ, Hg2X2, HgX2, wherein X is F, Cl, Br or I.
sodium borohydride, lithium aluminum hydride, or Of these Lewis acids, MgClg, MgBrg, MgIZ, BF3, BC13,
hydrazine, and then dried. Of course, the component (a) BBI'3, B13, A1013, AlBr3, A113, SiCl4, GeCl4, SnCl4,
may be supported on a carrier by other methods. SnBr4, SnI4, SbF5, SbCl5, SbBI‘3, SbCl3, TiCl4, TiBr4,
Examples of the carriers include carbon, graphite, TiI4, C1‘C13, CrBr3, M0015, W016, FeCl3, FeBr3, F613,
bone black, alumina, silica, silica alumina, barium sul
C0012, COBI‘2, NiClz, NiBrz, NiIz, CuCl, CuBr, CuCl2,
fate, natural or synthetic zeolite, spinel, magnesia ad CuI, ZIlClz, ZnBrz and 2:11;.
(B) Lewis type acids, such as $03, SO; and B(CH3)3.
hered alumina, thoria, titanium oxide, zirconium oxide, (III) Solid acids
thorium oxide, lanthanum oxide, cerium oxide, zinc (A) compounds, such as ZnO, A1203, T1102, Ti02,
oxide, tantalum, clay, diatomaceous earth, Celite (trade Zr02, Ce02, AS203, V203, Bi203, Si02, C1203, M002,
name of product being commercially available from ZnS, CaS, CaSO4, M11504, NiS04, CuS04, C0504,
Johns-Manville Co.), asbestos, pumice stone, bauxite, CdSO4, SrSO4, ZnSO4, MgSO4, FeSO4, BaSO4,
terra abla, natural and treated terra abla, such as Super K2504, A12(S04)3, Fe2(S04)3, CI2(SO4)3, Ca(N03)2,
Filtrol, silicon carbide, molecular sieves, ceramic hon Bi(N03)2, Fe(NO3)3, BP04, F6P04, CrPO4, Ti3(P04)4,
eycomb, boria, cements, alundum, corundum, brick, Z1'3(PO4)4, CH3(PO4)2, Ni3(PO4)2, A1PQ4, ZI13(PO4)2
talc, gypsum and the like. Carbon, graphite, bone black, and Mg(PO4)2.
alumina, silica, silica alumina, barium sulfate, zeolite, (B) compound oxides, such as Si02-Al203, B203
spinel and magnesia adhered alumina are preferred. The Al203, Cr2O3-Al2O3, M002-Al203, M003-Si02, Zr02
carriers may be in the form of particles having uniform Si02, Ga2O3-SiO2, BeO-SiOz, MgO-SiOz, Ca0-Si02,
or ununiform size. The carriers may be in the form of S1'0-Si02, Y203-Si02,La203-Si02, Sn0-Si02, PbO
molded articles, extruded articles, ceramic bars, balls, Si02, MoO3-Fe2(MoO4)3, Mg0-B203, TiOz-ZnO, Ti
fragments, tiles and the like. 02-Zr02, TiOz-SiOz, Ti02-Sn02, Ti02-W03, Ti
Heterogeneous system catalysts are preferable to 02—-M003, Ti02-Sb203, TiO2-Fe2O3, Ti02-Cr203,
homogeneous system catalysts, because separation and Ti02-V203, Ti02-Mn203, Ti02-C0304, TiOz-NiO, Ti
puri?cation of the product, or separation or recovery of 02-Cl10, Ti02-Al203, Ti02-Bi203, Ti02-Cd0, Z110
the catalyst are easy in a heterogeneous system. Bi203, ZnO-As2O3, Zn0-Al203, Zn0-Si02, Zn0
Component (b)(i) or component (b)(ii) is necessary 45 Zr02, ZnO-Fe2O3, Zr02-Th02, A1203-Ni0, A1203
together with component (a). CO304, A1203-Cd0, Al2O3-Fe1O3, Al203-Bi203, Al
Components (b)(i) mean materials serving as an acid 2O3-ZrO2-CdO and TiOz-MgO.
in the reaction system. Components (b)(i) include protic (C) cation exchange resin or solidi?ed acids in which
acids, Lewis acids, or solid acids. Of acidic substances, p-toluene sulfonic acid, sulfuric acid, phosphoric acid,
materials acting as strong acid, such as, for example, or boric acid is adhered to activated carbon, silica,
strong protic acids or strong Lewis acids are preferable. quartz sand, alumina or diatomaceous earth.
Components (b)(i) have PKa below 5 and more suitably Of acidic substances, acids (I) are preferable, and partic
components (b)(i) have PKa below 3. ularly, phosphoric acid, sulfuric acid, acid phosphates,
Examples of the acidic substances are shown in the acid sulfates methane sulfonic acid and aromatic sul
following: 55 fonic acids, such as benzene sulfonic acid, toluene sul
(I) Protic acid fonic acid, xylene sulfonic acid and naphthalene sul
(A) inorganic acids and acid inorganic salts, such as fonic acid are more preferable; acid phosphates, acid
HI, HBr, HCl, HF, H2804, H3PO4, H3BO3, HClO3, sulfates and aromatic sulfonic acids, such as benzene
HBI'03, polyphosphoric acid, FSO3H, ClSO3H, LiH sulfonic acid, toluene sulfonic acid and xylene sulfonic
S04, NaHSO4, KHS04, PbHS04, C5HS04, LiH2P04, 60 acid are most preferable. Halides, such as iodides, chlo
KH2P04, K2HP04, RbH2P04, Rb2HP04, CSH2PO4 rides and/or bromides may be added to the reaction
and CS2HP04 medium in the form of an alkyl halide, such as methyl
(B) organic acids, such as iodide, an acid halogenide, such as acetyl iodide or
(a) methane sulfonic acid, tri?uoromethane sulfonic hydrogen halide, such as hydrogen iodide as component
acid, trichloroacetic acid, and trifluoroacetic acid, (b)(ii). Materials which can convert to an alkyl halide,
(b) aromatic sulfonic acids, such as benzene sulfonic an acid halogenide or hydrogen halide can be used as a
acid, toluene sulfonic acid, xylene sulfonic acid and halide. Examples of the materials which can convert to
naphthalene sulfonic acid. an alkyl halide, an acid halogenide or a hydrogen halide
5
4,978,778 6
by reacting with components in the reaction medium fates, sul?tes nitrates, nitn'tes, phosphates, phosphites,
include inorganic halides, such as alkali metal halides, chromates, molybdates, aliphatic, alicyclic and aro
such as lithium halides, sodium halides, or potassium matic carboxylates, such as acetates, butyrates, deca
halides; alkaline earth metal halides, such as calcium nates, laurates, stearates, succinates, adipates, benzoates
halides or magnesium halides; metal halides, such as and phthalates of the metals. Halide, such as chlorides,
aluminum halides, zinc halides, copper halides, lantha fluorides, bromides and iodides, sulfates, phosphates
num halides, or cerium halides; halogens, such as chlo and carboxylates, such as acetates of the metals are
rine, bromine or iodine; phosphrous halides, such as more preferable. The promoter may be used alone or in
phosphorus trichloride, or phosphorus pentachloride form of mixture.
and carbonyl halides, such as phosgene. l0 Use of the promoters is not critical. In general,
Of halides methyl chloride, methyl bromide and amount of the promoter employed is in the range of
methyl iodide are more preferable from the viewpoint from 1X 10-5 to 25% by weight, preferably 1X l0-4to
of corrosion resistance of reactor and separation of the 20 % by weight, more preferably 1X 10-3 to 15% by
reaction product from the reaction mixture and puri? weight and most preferably 2.5>< 10-3 to 10% by
cation of the reaction product. 15 weight on the basis of weight of a reaction solution.
Amount of the component (a) employed depends on In case of practicing this invention, the reaction tem
type of the catalyst employed, such as homogeneous perature is not critical. In general, the reaction tempera
system or heterogeneous system, and type of the reac ture may be in the range of 20° C.—500° C.
tion whether being effected in a ?xed bed or ?uidized When component (b)(i) is used, the reaction tempera
bed. However, in general, the amount of the component 20 ture of 50°—250° C. is preferable, the reaction tempera
(a) employed may be in the range of from IX 10''‘ to 25 ture of 80°—200° C. is more preferable, and the reaction
wt %, preferably in the range of from 5 X 10314 to 20 wt temperature of 100°—180° C. is most preferable.
% more preferably from 1X 10-3 to 15 wt % and most When component (b)(ii) is used, the reaction tem
preferably from 2.5><10-3 to 10 wt. % on the basis of poral of 30°-350° C. is preferable; the reaction tempera
weight of a reaction solution in terms of metal. 25 ture of 4-0°-250° C. is more preferable; and the reaction
Amount of the acidic substance employed is not criti temperature of 80°~220° C. is most preferable.
cal. In general, amount of the acidic substance em The reaction pressure is kept high enough to keep the
ployed is in the range of IX 10-2 to 20 wt %, preferably raw material(s), the solvent and the product in a liquid
1X 10-1 to 15 wt%, more preferably 2.5 X10-1to 10 wt phase and to maintain appropriately partial pressure of
% and most preferably 5 X10"1 to 5 wt % on the basis hydrogen. The partial pressure of hydrogen may be in
of weight of a reaction solution. the range of 005-300 atm. preferably 0.1-200 atm. and
Amount of halides employed as components (b) (ii) more preferably 0.2-100 atm. However, partial pressure
may be in the range of from 10-3 to 15 mol, preferably of hydrogen may be in the range of 001-500 atm.
10-2—5 mol and more preferably 10-1—3 mol per 1 Hydrogen used as a starting material need not neces
liter of a reaction solution in terms of halogen atom. 35 sarily have high purity. The hydrogen may contain
The reaction of acetic anhydride with hydrogen of carbon monoxide, carbon dioxide, methane, nitrogen,
this invention sufficiently proceeds in the presence of rare gases and the like. Synthesis gas mixture of hydro
the above mentioned catalyst. When halides (b) (ii) are gen and carbon monoxide may be used as a raw mate
used as component (b) constituting the catalyst, promot rial. Carbon monoxide contained in the hydrogen tends
ers may be used with the catalyst in order to increase 40 to make the catalyst stable and to restrain side reactions
the reaction rate and to enhance selectivity to the object and consequently assists to allow the reaction to pro
product. ceed effectively. In general, hydrogen containing more
Examples of suitable promoters include metals hav -_ than 0.1 mol % of carbon monoxide may be used; hy
ing atomic weight of at least 6and belonging to Groups drogen containing more than 1 mol % of carbon mon
Ia, IIa, IIIa, IVa, Va, Ib, IIb, Vb, VIb and VIIb of the 45 oxide is preferable; and hydrogen containing more than
Periodic Table and compounds of these metals. Prefera 2 mol % of carbon monoxide is most preferable.
ble promoters include, for example metals having Acetic anhydride employed in the practice of this
atomic weight of 210 or less and belonging to said invention may be prepared via ketene (so-called
Groups and compounds of the metals. Wacker process) from acetic acid which may be pre
Metals which can be used as promoters include lith 50 pared by reaction of methanol and carbon monoxide.
ium, sodium, potassium, rubidium, cesium, beryllium, Alternatively acetic anhydride may be prepared from
magnesium, calcium, strontium, barium, aluminum, methyl acetate and carbon monoxide. For example,
indium, tin, lead, antimony, bismuth, copper, silver, productions of acetic anhydride are disclosed in Japa
zinc, cadmium, vanadium, chromium and manganese. nese Patent Publication (Kokoku) No. 3926/1977, Japa
Preferable metals include lithium, sodium, potassium, nese Patent Publication (Kokai) No. 65709/1976, and
rubidium, cesium, magnesium, calcium, strontium, bar Japanese Patent Publication (Kokai) No. 59214/1979.
ium, aluminum, tin and antimony. More preferable met As mentioned above, acetic acid, methyl acetate and
als include lithium, potassium rubidium, cesium, cal acetaldehyde may be incorporated in acetic anhydride
cium, strontium, barium, tin and antimony. Most prefer employed as a raw material. However, incorporation of
able metals include lithium, potassium, barium and anti these compounds in acetic anhydride is permitted, as
mony. long as an overall balance of the process is obtained.
The promoters may be used in form of element, for When acetic anhydride prepared by carbonylation
example, finely divided particles of the metals. How reaction of methyl acetate is used as a starting material,
ever, preferably, the promoters may be used in form of the remainder of synthesis gas used in the carbonylation
compound of the metals. Typical compounds of the 65 reaction may be used in the present invention.
metals include, for example, oxides, hydroxides, sul Alternatively, the remainder of synthesis gas used in
?des, halides, such as chlorides, ?uorides, bromides or hydrogenation of the present invention may be used in
iodides, oxyhalides, hydrides, carbonyl, alkoxides, sul the carbonylation reaction of methyl acetate.
4,978,778
7 8
A halide, such as methyl iodide is used as a co hols, such as l-pentanol, 3-methyl-l-butanol, 3-methyl
catalyst in the above carbonylation reaction. The re 2-propanol, l-hexanol, l-octanol, cyclohexanol, phenol
mainder of the halide used in the carbonylation reaction " and benzyl alcohol; halogenated hydrocarbons, such as
may be used as component (b)(ii) of this invention. In methyl iodide, dichloro methane, chloroform, carbon
addition, the remainder of the halide as component tetrachloride, chlorobenzene dichlorobenzenes and
(b)(ii) of this invention may be used as a co-catalyst in ' iodobenzene. Mixtures of the above solvents may also
the carbonylation reaction. be used.
In general, water may be incorporated into the reac Amount of the solvent employed is not critical. In
tion system. However, since commercially available general, amount of the solvent employed is in the range
hydrogen and acetic anhydride contains small amount of 0 to 95 wt %, preferably 2 to 90 wt %, preferably 5
of water, hydrogen and acetic anhydride containing to 90 wt % and most preferably 5 to 80 wt % on the
water of such low concentration are permitted in this basis of weight of a reaction solution. It is preferable to
invention. The presence of water of more than 10 mol select kind and amount of the solvent so that dielectric
% on the basis of weight of a reaction solution is not constant of the reaction solution amounts to less than
preferable in this process, because such a large amount 19, preferably less than 18 and more preferably less than
of water causes decomposition of the starting materials 17 at 25° C.
and the products. The present process may be carried out by batch,
In general, water content less than 5 mol % is prefera semicontinuous or continuous method. When a hetero
ble, and water content less than 3 mol % is more prefer geneous system catalyst is used, the reaction can be
able. When raw materials contain large amount‘of wa 20 effected in a ?uidized bed or a ?xed bed.
ter, they should be dried before introducing them into In the present invention, the reaction solution com
the reaction system. prises acetic anhydride (starting material), a metal com
Since acetic anhydride acts as a solvent for the reac ponent, an acid substance or a halide, intermediates for
tion, another solvent is not necessarily used. As occa reaction, ethylidene diacetate, vinyl acetate (object
sion demands, other solvents may be used. Use of 25 product) and acetic acid (by-product).
proper solvent increases selectivity to vinyl acetate In order to increase amount of vinyl acetate formed,
which is an object product. withdrawal of the resulting vinyl acetate from the reac
Solvents which are usable for such purpose have tion system is suitable. So, it is preferable to maintain
electric constants of not more than 18 at room tempera concentration of vinyl acetate in the reaction system at
ture. Organic solvents having dielectric constants of not 30 less than 25 wt % by continuously withdrawing (for
more than 15 at 25° C. are preferable; organic solvents example distilling) the resulting vinyl acetate from the
having dielectric constants of not more than 10 at 25° C. reaction system; it is more preferable to maintain the
are more preferable; and organic solvents having dielec concentration at less than 15 wt %; and it is more pref
tric constants of not more than 8 at 25° C. are most erable to maintain the concentration at less than 10 wt
preferable. 35 %; and it is most preferable to maintain the concentra
In general, the organic solvents include aliphatic tion at not more than 5 wt %.
hydrocarbons having 5-20 carbon atoms, aromatic hy It should be avoided that acetic acid, which is formed
drocarbons having 6-20 carbon atoms, organic acid as a by-product, in large quantity remains in the reac
esters having 3-20 carbon atoms, ethers having 4-20 tion system. The reason is that acetic acid tends to pre
carbon atoms, ketones having 3-20 carbon atoms, alco 40 vent formation of the object product. So, in general, the
hols having 4-20 carbon atoms and halogenated hydro concentration of acetic acid in the reaction system is
carbons having l-20 carbon atoms. Of these solvents, maintained at less than 50 wt %, preferably less than 40
saturated aliphatic hydrocarbons, aromatic hydrocar wt %, more preferably less than 30 wt % and most
bons and organic acid esters are preferable. preferably less than 20 wt %.
Examples of the organic solvents include aliphatic 45 Withdrawal of vinyl acetate and acetic acid from the
hydrocarbons, such as pentane, hexane, heptane, oc reaction system is carried out, for example, by distilla
tane, nonane, decane, undecane, dodecane, tridecane, tion.
tetradecane, pentadecane, hexadecane, cyclopentane, According to this invention, vinyl acetate is directly
cyclohexane, and their alkylated derivatives; aromatic produced from acetic anhydride and hydrogen. So, this
hydrocarbons, such as benzene, toluene, o-, p- and m 50 invention does not need complicated process which"
xylenes, trimethyl benzenes, ethyl benzene, propyl ben comprises producing ethylidene diacetate from acetic
zene, naphthalene, biphenyl, diphenyl methane, and anhydride and hydrogen, followed by forming vinyl
their alkylated derivatives; organic acid esters, such as acetate from the resulting ethylidene diacetate. In other
methyl acetate, ethyl acetate, propyl acetate, butyl ace words, this invention is more simple than the prior pro
tate, amyl acetate, hexyl acetate, cyclohexyl acetate, cess; and according to this invention, separation of vinyl
octyl acetate, phenyl acetate, tolyl acetate, benzyl ace acetate is easier than that according to the prior process.
tate, butyl formate, amyl formate, methyl propionate, For better understanding of this invention, preferred
ethyl propionate, methyl butyrate, ethyl butyrate, embodiments of the invention are described hereunder
methyl benzoate, ethyl benzoate, methyl toluylate, di by reference to the non-limiting accompanying draw
methyl adipate, ethylene glycol diacetate, ethylidene 60 ll'lgS.
diacetate, diethylene glycol diacetate, propylene glycol In FIG. 1, reaction zone 100 is composed of one or
diacetate, 'y-valerolactone, and S-caprolactone; ethers, more pressure vessels of any type. Into’ the vessel are
such as diethyl ether, dipropyl ether, methyl butyl charged a suitable catalyst system typically consisting
ether, dibutyl ether, butyl ethyl ether, diamyl ether, of a strong protic acid and a metal belonging to Group
diphenyl ether, anisole, tetrahydrofuran, 1,4-dioxane, VIII of the Periodic Table or a compound of the metal
butyl propyl ether, benzyl ethyl ether, phenetole, and and other liquid starting materials and, if necessary, a
dibenzyl e'ther; ketones, such as acetophenone, cyclo solvent. Pure hydrogen or mixture of hydrogen and
hexanone, 3-pentanone and 4-methyl-2-pentanone; alco other gases may be introduced under pressure at the
4,978,778 '
9 10
bottom of vessel 100 with recycling gas 206 through 100 through lines 203, 204 and 103 with supply gas from
line 103 and acetic anhydride is fed from line 102. The line 101. As occasion demands, part of the gas separated
reaction mixture, namely materials containing the reac in zone 200 is discharged outside from line 205. Acetal
tion products and unreacted raw materials are intro dehyde, methyl iodide, methyl acetate, vinyl acetate
duced from zone 100 through line 105 to separating and acetic acid are separated in zone 200 by stripping
zone 200 consisting of distilling units and one or more and/or by distillation. Part of acetic acid and of acetic
gas-liquid separating means. Gases containing hydrogen anhydride and most of acetaldehyde, methyl iodide and
are separated in zone, 200. Gases containing non-con methyl acetate are recycled to zone 100 with the gas
densable hydrogen are recycled through lines 204 and containing hydrogen. Materials containing vinyl acetate
206 to vessel 100 with supply gas fed from line 101. As and acetic acid separated in zone 200 are discharged
occasion demands, part of the gases is discharged out from zone 200 to separating zone 300 through line 202.
side from line 205. Vinyl acetate, acetaldehyde, acetic Low boiling point components, such as methyl acetate
acid and acetic anhydride are separated by stripping and methyl iodide are recycled from zone 300 to zone
and/or distillation in zone 200. ‘Low boiling point com 100 through line 303. High boiling point components,
ponents, such as unreacted materials, part of acetic acid 15 such as acetic anhydride and ethylidene diacetate are
and/or acetaldehyde are recycled into zone 100 recycled from zone 300 to zone 100 through line 304.
through lines 204, 206 and 103. The object product, Vinyl acetate (object product) and acetic acid (by-pro
namely vinyl acetate and acetic acid as a by-product are duct) are discharged together from lines 301 or 302, or
condensed and separated from other components in discharged separately from lines 301 and 302. As occa
zone 200 and discharged from lines 202 and 203. Acetic 20 sion demands, in order to prevent accumulation of poly
anhydride and ethylidene diacetate are recycled from mers formed as by-products during the reaction and
line 201 to zone 100. As occasion demands, in order to other high boiling point components or in order to
prevent accumulation of high boiling point compo withdraw part of the catalyst, part of the reaction solu
nents, such as by-products or in order to withdraw part tion is discharged from zone 100 through line 104.
of the catalyst part of the reaction solution is discharged 25 The following examples are given as illustrative em
from line 104. bodiment of the invention and should not be construed
In FIG. 2, reaction zone 100 is composed of one or as limiting its scope. All parts and percents are on a
more pressure vessel of any type. Into the vessel are weight basis, unless otherwise speci?ed.
charged with a suitable catalyst system typically con
sisting of methyl iodide and a metal belonging to Group 30 EXAMPLE 1
VIII of the Periodic Table or a compound of the metal This example was carried out by using the apparatus
and reaction solution. Raw material gas containing hy as shown in FIG. 1. Into zone 100 including pressure
drogen is fed into bottom of zone 100 through line 101. reactor were filled reaction solution containing 1 mil
Acetic anhydride is fed into zone 100 through line 102. - mol of palladium acetate, and 20 milli mol of para-tol
Reaction products and unreacted materials are with 35 uenesulfonic acid per 1 mol of acetic anhydride. Air in
drawn through line 103, and fed into separating zone the vessel was purged with mixed gas of hydrogen and
200 consisting of one or more distilling units, for exam carbon monoxide (7:3 by volume). The temperature
ple, ?ashing means and/or fractionating columns. Non rose to 150° C. Thereafter, the mixed gas was fed to
volatile catalyst and high boiling point components pressure of 5 kg/cmZG and gas was recycled through
separated in zone 200 are recycled to zone 100 through 40 zone 100, line 105, zone 200, lines 204, 206 and 103 at
line 201. Low boiling point components, such as acetal rate of 1.0 part of min. and at the same time acetic anhy
dehyde, methyl iodide, methyl acetate, vinyl acetate dride was continuously fed into zone 100 at rate of 0.6
and acetic acid are fed through line 202 into separating parts per hour. Hydrogen gas was continuously fed into
zone 300 consisting of one or more distilling units. Acet zone 100 from line 101 so that pressure of zone 100 was
aldehyde, methyl iodide and methyl acetate are recy 45 maintained at 5 kg/cmZG. Mixture of vinylacetate and
cled to zone 100 through line 303. Vinyl acetate and acetic anhydride were fed from zone 100 to separating
acetic acid separated in zone 300 are discharged to zone 200 including distilling units and separated in zone
gether from lines 301 or 302, or are discharged sepa 200. Vinyl acetate separated in zone was discharged at
rately from lines 301 and 302. Low boiling point compo rate of 0.522 parts per hour from line 203 with acetic
nents composed of acetaldehyde, methyl acetate and 50 acid.
methyl iodide from zone 300 are recycled into zone 100
EXAMPLE 2
through line 303; and high boiling point components
composed of acetic anhydride and ethylidene diacetate Into a pressure vessel were charged 1 mol of acetic
are recycled into zone 100 through line 304. anhydride, 1 milli mol of palladium acetate and 10 milli
In FIG. 3, reaction zone 100 is composed of one or 55 mol of sulfuric acid. Air in the vessel was purged with
more pressure vessel of any type. Into the vessel are mixed gas of hydrogen and carbon monoxide (7:3 by
charged a suitable catalyst system typically consisting volume). The mixed gas was fed to 25 Kg/cmZG. The
of methyl iodide and a metal belonging to Group VIII vessel was heated to 145° C. within a determined time.
of the Periodic Table or a compound of the metal and During heating, the mixed gas was continuously fed
reaction solution. Raw material gas is fed to bottom of 60 into the vessel so that the pressure of vessel is main
zone 100 from line 101 through line 103 with recycled tained at 25 Kg/cmZG. After the reaction completed,
gas. Acetic anhydride is fed to zonet100 from line 102. the reaction mixture was cooled and was "discharged.
The reaction products and unreacted materials are dis GC-Mass analysis showed that it contained vinyl ace
charged from zone 100 from line 105 and fed to separat tate with acetic anhydride.
ing zone 200 consisting of one or more gas-liquid sepa 65
rating means and distilling units. Vapor of materials EXAMPLE 3
containing hydrogen is separated in zone 200. Gas con The procedure of Example 2 was repeated except
taining non-condensable hydrogen is recycled to zone that potassium hydrogensulfate was used in place of
4,978,778
11 12
sulfuric acid. Similarly, formation of vinyl acetate was
EXAMPLE 8
con?rmed.
This example was carried out by using the apparatus
EXAMPLE 4 as shown in FIG. 1. Into zone 100 including pressure
In an autoclave were charged 150g of acetic anhy reactor was ?lled reaction solution containing 2.04 g of
dride, 0.45 g of palladium black, and 2.0 g of potassium palladium (5%) supported on activated carton (being
hydrogensulfate. Hydrogen was charged under pres commercially available from Nippon Engelhard) and 20
sure into the autoclave to pressure of 10 Kg/cmzG. The milli mol of para-toluenesulfonic acid per 1 mol of
temperature in the autoclave was raised to 175° C. The acetic anhydride. Air in the vessel was purged with
reaction was carried out for 30 minutes. GC analysis mixed gas of hydrogen and carbon monoxide (4:1 by
showed that the reaction mixture contained 0.421 g of volume). The temperature rose to 145° C. Thereafter,
vinyl acetate, 2.50 g of ethylidene diacetate and 1.49 g the mixed gas was fed from bottom of zone 100 to pres
of acetaldehyde with considerable amount of acetic sure of 5 Kg/cmZG, and gas was recycled through zone
acid. 100, line 105, zone 200 and lines 204, 206 and 103 at rate
of 1.0 part/minute, and at the same time acetic anhy
EXAMPLE 5 dride was continuously fed into zone 100 at rate of 0.5
The procedure of Example 2 was repeated except parts per hour. The gas was consumed and mixed solu
that aluminum chloride was used in place of sulfuric tion of vinyl acetate, acetic acid and acetic anhydride
acid. Similarly formation of vinyl acetate was con was discharged from zone 100. Hydrogen gas was con
?rmed. ' ' 20 tinuously fed into zone 100 from line 101 so that pres
sure of zone 100 was maintained at 5 Kg/cmZG. Vinyl
EXAMPLE 6 acetate and acetic acid were separated from the mixed
This example was carried out by using the apparatus solution in zone 200. Vinyl acetate was withdrawn with
as shown in FIG. 1. Into zone 100 including pressure considerable amount of acetic acid from zone 200 at rate
reactor was ?lled reaction solution containing 2 milli 25 of 0.460 parts per hour through line 203.
mol of rhodium acetate, and 20 milli mol of benzenesul EXAMPLE 9
fonic acid per 1 mol of acetic anhydride. Air in the
vessel was purged with mixed gas of hydrogen and Into an autoclave were charged 100 g of acetic anhy
carbon monoxide (4:1 by volume). The temperature dride, 35 g of methyl acetate, 15 g of methyl iodide and
rose to 145° C. Thereafter, the mixed gas was fed from 4.5 g of palladium (5%) supported on activated carbon
bottom of zone 100 to pressure of 10 Kg/cmZG, and gas (being commercially available from Nippon Engel
was recycled through zone 100, line 105, zone 200 and hard). Mixed gas of hydrogen and carbon monoxide (2:1
lines 204, 206 and 103 at rate of 1.4 part/minute, and at by volume) was charged into the autoclave to pressure
the same time acetic anhydride was continuously fed of 30 Kg/cmZG. The temperature in the autoclave was
from line 102 into zone 100 at rate of 0.35 parts per hour. raised to 175° C. At that temperature, hydrogen was fed
The gas was consumed and mixed solution of vinyl so as to maintain the pressure at 50 Kg/cm2G with
acetate, acetic acid and acetic anhydride was dis stirring for 30 minutes. After cooling the reaction mix
charged from zone 100. Hydrogen gas was continu ture, GC analysis showed that it contained 2.33 g of
ously fed into zone 100 from line 101 so that pressure of vinyl acetate, 20.6 g of ethylidene diacetate, 0.331 g of
zone 100 was maintained at 10 Kg/cmZG. Vinyl acetate 40 acetaldehyde and 0.109 g of ethyl acetate. The remain
‘and acetic acid were separated from the mixed solution der components were considerable amount of acetic
in zone 200. Vinyl acetate was withdrawn with consid acid, unreacted acetic anhydride, methyl acetate and
erable amount of acetic acid from zone 200 at rate of methyl iodide.
0.312 parts per hour through line 203. EXAMPLE l0
45
EXAMPLE 7 Into an autoclave were charged 135 g of acetic anhy
This example was carried out by using the apparatus ._ dride, 5 g of methyl iodide and 4.5 g of palladium (5 %)
as shown in FIG. 1. Into zone 100 including pressure supported on activated carbon (sold as PM Type from
reactor was ?lled reaction solution containing 1.5 milli Kawaken Finechemical Co.). The reaction was effected ’
mol or ruthenium chloride, and 20 milli mol of benzene for 30 minutes while feeding mixed gas of hydrogen and
sulfonic acid per 1 mol of acetic anhydride. Air in the carbon monoxide (2:1 by volume) into the autoclave so
vessel was purged with mixed gas of hydrogen and as to maintain the pressure at 50 Kg/cmzG. GC analysis
carbon monoxide (4:1 by volume) The temperature rose showed that the reaction mixture contained 0.778 g of
to 140° C. Thereafter, the mixed gas was fed from bot vinyl acetate, 88.0 g of ethylidene diacetate and 1.27 g
tom of zone 100 to pressure of 10 Kg/cmZG, and gas 55 of acetaldehyde.
was recycled through zone 100, line 105, zone 200 and
EXAMPLE 1 1
lines 204, 206 and 103 at rate of 0.64 part/minute, and at
the same time acetic anhydride was continuously fed
into zone 100 at rate of 0.15 parts per hours. The gas Into an autoclave were charged 135 g of acetic anhy
was consumed and mixed solution of vinyl acetic acid 60 dride, 15 g of methyl iodide, 4.5 g of palladium (5 %)
and acetic anhydride was discharged from zone 100. supported on activated carbon and 5.0 g of lithium
Hydrogen gas was continuously fed into zone 100 from acetate. The reaction was carried out at 175° C. for 30
line 101 so that pressure of zone 100 was maintained at minutes while feeding mixed gas of hydrogen and car
10 Kg/cmZG. Vinyl acetate and acetic acid were sepa bon monoxide (2:1 by volume) into the autoclave so as
rated from the mixed solution in zone 200. Vinyl acetate 65 to maintain the pressure at 50 Kg/cmzG. GC analysis
was withdrawn with considerable amount of acetic acid showed that the reaction mixture contained 1.43 g of
from zone 200 at rate of 0.125 parts per hour through vinyl acetate and 18.4 g of ethylidene diacetate with
line 203. considerable amount of acetic acid.
4,978,778
13 14
EXAMPLE 12 EXAMPLE 19
The procedure of Example 9 was repeated except The procedure of Example 17 was repeated except
that hydrogen was used in place of ?xed gas of hydro that 4.5 g of platinum (5%) supported on activated
gen and carbon monoxide. GC analysis showed that the carbon was used in place of palladium supported on
reaction mixture contained 2.58 g of vinyl acetate, 22.9 activated carbon. GC analysis showed that vinyl acetate
g of ethylidene diacetate and 0.288 g of acetaldehyde. was formed with considerable amount of acetic acid
and 8.28 g of ethylidene diacetate.
EXAMPLE l3
Into an autoclave were charged 35 g of acetic anhy EXAMPLE 20
dride, 100 g of methyl acetate, 15 g of methyl iodide and The procedure of Example 17 was repeated except
2.25 g of palladium (5%) supported activated carbon that 4.5 g of ruthenium (5%) supported on activated
(Nippon Engelhard). The reaction was effected for 50 carbon was used in place of palladium supported on
minutes in the same way as in Example 9. GC analysis activated carbon. GC analysis showed that vinyl acetate
showed that 0.861 gof vinyl acetate, 3.77 g of ethyli was formed with considerable amount of acetic acid
' dene diacetate, 2.51 g of acetaldehyde and 0.135 g of and 15.5 g of ethylidene diacetate.
ethyl acetate were formed with considerable amount of
acetic acid. EXAMPLE 21
The procedure of Example 9 was repeated except
EXAMPLE 14 20 that 10 g of methyl chloride was used in place of methyl
Into an autoclave were charged 135 g of acetic anhy iodide and the reaction was effected for 6 hours. GC
dride, 15 g of methyl iodide and 4.5 g of palladium (5%) analysis showed that 0.116 g of vinyl acetate, and 43.3 g
supported on barium sulfate (Kawaken Finechemical of ethylidene diacetate were formed with considerable
Co.). The reaction was effected for 90 minutes in the amount of acetic acid.
same way as in Example 9. GC analysis showed that
0.415 g of vinyl acetate and 14.0 g of ethylidene diace EXAMPLE 22
tate were formed with considerable amount of acetic The procedure of Example 9 was repeated except
acid. that 10 g of methyl bromide was used in place of methyl
iodide and the reaction was effected for 6 hours. GC
EXAMPLE 15 analysis showed that 0.212 g of vinyl acetate and 65.8 g
The procedure of Example 9 was repeated except of ethylidene diacetate were formed with considerable
that 0.475 g of palladium acetate was used in place of amount of acetic acid.
palladium supported on activated carbon and the reac
tion was effected for 3 hours. GC analysis showed that EXAMPLE 23
1.70 g of vinyl acetate, 35.3 g of ethylidene diacetate, The procedure of Example 9 was repeated except
0.738 g of acetaldehyde and 0.141 g of ethyl acetate that 10 g of calcium iodide was used in place of methyl
were formed with considerable amount of acetic acid. iodide and the reaction was carried out for 6 hours. GC
analysis showed that 0.083 g of vinyl acetate and 12.7 g
EXAMPLE 16 of ethylidene diacetate were formed with considerable
The procedure of Example 9 was repeated except 40 amount of acetic acid.
that 0.451 g of palladium chloride was used in place of
palladium supported on activated carbon and the reac~ EXAMPLE 24
tion was effected for 3 hours. GC analysis showed that Into an autoclave were charged 40 g of acetic anhy
1.51 g of vinyl acetate and 32.1 g of ethylidene diacetate dride, 20 g of methyl acetate, 15 g of methyl iodide, 75
were formed with considerable amount of acetic acid. 45 g of ethylidene diacetate, 4.5 g of palladium (5%) sup
ported on activated carbon (Nippon Engelhard). The
EXAMPLE 17 reaction was carried out for 4 hours at 175 ° C. and at 50
The procedure of Example 9 was repeated except Kg/cm2G by using mixed gas of carbon monoxide and
that 0.225 g of palladium black being commercially hydrogen (2:1 by volume). After cooling the reaction
available from Nippon Engelhard was used in place of mixture, GC analysis showed that it contained 7.71 g of
palladium (5%) supported on activated carbon. GC vinyl acetate, and 87.6 g of ethylidene diacetate.
analysis showed that 1.74 g of vinyl acetate, 15.8 g of
ethylidene diacetate, 0.090 g of ethyl acetate and 0.251 EXAMPLE 25
g of acetaldehyde were formed with considerable Into an autoclave were charged 135 g of acetic anhy
amount of acetic acid. 55 dride, 15 g of methyl iodide, 0.45 g of palladium black
and 2.0 g of potassium fluoride. The reaction was car
EXAMPLE 18 ried out for 30 minutes at 175° C. while maintaining the
Into an autoclave were charged 100 g of acetic anhy pressure in the autoclave at 10 Kg/cmZG by using hy
dride, 35 g of methyl acetate, 15 g of methyl iodide and drogen. After the reaction completed, GC analysis
4.5 g of rhodium (5%) supported on activated carbon. showed that the reaction mixture contained 1.14 g of
Mixed gas of hydrogen and carbon monoxide (3:1 by vinyl acetate and 4.92 g of ethylidene diacetate with
volume) was fed into the autoclave to pressure of 50 considerable amount of acetic acid.
Kg/cmZG. The temperature was raised to 175° C.
Thereafter, the reaction was effected at 50 Kg/cm2G EXAMPLE 26
and 175° C. with stirring. After cooling the reaction 65 The procedure of Example 25 was repeated except
mixture, GC analysis showed that it contained vinyl that 2.0 g of potassium chloride was used in place of
acetate with considerable amount of acetic acid and potassium fluoride. GC analysis showed that the reac
14.2 g of ethylidene diacetate. tion mixture contained 1.52 g of vinyl acetate, 4.04 g of
4,978,778
15 16
ethylidene diacetate and 0.364 g of acetaldehyde with
EXAMPLES 33-38
considerable amount of acetic acid.
The procedures of Example 32 were repeated except
EXAMPLE 27 that 35 g of each of solvents in shown in Table l was
The procedure of Example 25 was repeated except 5 used in place of benzene. The results are shown in Table
that 2.0 g of potassium bromide was used in place of 1.
TABLE 1
Ex. 38
Ex. 34 Ex. 35 Ex. 36 Ex. 37 methyl
Ex. 33 n-arnyl n-octyl phenyl benzyl isobutyl
Solvent n-heptane acetate acetate acetate acetate ketone
Product vinyl acetate 1.01 1.43 1.68 2.27 1.81 1.39
(g) ethylidene 4.44 11.3 14.1 26.4 23.4 23.5
diacetate
acetaldehyde 1.17 0.502 0.393 0.140 0.035 —

potassium ?uoride. GC anal y sis showed that the reac EXAMPLE 39


tion mixture contained 1.26 g of vinyl acetate and 3.67
g of ethylidene diacetate with considerable amount of The procedure of Example 32 was repeated except
acetic acid. 20 that 70 g of benzene was used and 65 g of acetic anhy
dride was used. After the reaction completed, 0.929 g of
EXAMPLE 28 ’
vinyl acetate, 2.14 g of ethylidene diacetate and 1.57 g
The procedure of Example 25 was repeated except of acetaldehyde were formed.
that 2.0 g of potassium iodide was used in place of potas EXAMPLE 40
sium ?uoride. GC analysis showed that the reaction 25
mixture contained 0.873 g of vinyl acetate and 2.25 g of Into an autoclave ‘were charged 90 g of acetic anhy
ethylidene diacetate with considerable amount of acetic dride 45 g of ethylidene diacetate, 15 g of methyl iodide,
acid. 0.45 g of palladium black and 2.0 g of potassium acetate.
The reaction was carried out for 30 minutes at 175° C.
EXAMPLE 29 '30 while maintaining the pressure in the autoclave at 10
The procedure of Example 25 was repeated except Kg/cm2G by using hydrogen. After the reaction com
that 2.0 g of potassium sulfate was used in place of pleted, GC analysis showed that the reaction mixture
potassium ?uoride. GC analysis showed that the reac contained 2.29 g of vinyl acetate 49.2 g of ethylidene
tion mixture contained 1.72 g of vinyl acetate, 5.69 g of diacetate and 0.094 g of acetaldehyde with considerable
ethylidene diacetate and 0.026 g of acetaldehyde with amount of acetic acid.
considerable amount of acetic acid.
EXAMPLE 41
EXAMPLE 30 vThe procedure of Example 40 was repeated except
The procedure of Example 25 was repeated except that 4.5 g of lithium iodide was used in place of potas
that 2.0 g of potassium dihydrogenphosphate was used 40 sium acetate. After the reaction completed, GC analysis
in place of potassium ?uoride. GC analysis showed that showed that 1.74 g of vinyl acetate, 45.6 g of ethylidene
the reaction‘mixture contained 2.35 g of vinyl acetate, diacetate and 0.024 g of acetaldehyde with considerable
9.14 g of ethylidene diacetate and 0.502 g of acetalde amount of acetic acid.
hyde with considerable amount of acetic acid. EXAMPLE 42
45
EXAMPLE 31 This example was carried out by using the apparatus
The procedure of Example 25 was repeated except as shown in FIG. 2. Into zone 100 was charged mixture
that 2.0 g of potassium acetate was used in place of of 35 wt % of acetic anhydride, 10 wt % of methyl
potassium ?uoride. GC analysis showed that the reac acetate, 10 wt % of methyl iodide, 42 wt % of ethyli
tion mixture contained 1.38 g of vinyl acetate and 5.63 dene diacetate and 3 wt % of palladium (5%) supported
g of ethylidene diacetate with considerable amount of on activated carbon in determined amount. Air in zone
acetic acid. 100 was purged with mixed gas of hydrogen and carbon
monoxide (2:1 by volume). The temperature in the ves
EXAMPLE 32 sel was raised to 175° C. The mixed gas was fed through
Into an autoclave were charged 100 g of acetic anhy line 101 from bottom of zone 100 under pressure to 30
dride, 35 g of benzene, 15 g of methyl iodide, and 0.45 Kg/cmzG. The mixture was stirred for 3 hours while
g of palladium black (Nippon Engelhard). Air in the maintaining the pressure at 30 Kg/cm2G by feeding
autoclave was purged with nitrogen. The temperature hydrogen into the vessel from line 101. Thereafter,
in the autoclave was raised to 175° C., and then hydro movement of the solution started so that average resi
gen was fed under pressure into the autoclave to 10 60 dence time of the solution amounted to 3 hours, and at
Kg/cmZG. The reaction was carried out for 30 minutes the same time acetic anhydride was fed into zone 100
at 175° C. with stirring while maintaining the pressure I from line 102 at rate of 13.8 g/hour, and hydrogen was
in the autoclave at 10 Kg/cmZG by feeding hydrogen continuously fed into zone 100 so as to maintain the
into the autoclave. After cooling the reaction mixture, pressure at 30 Kg/cmZG. The reaction mixture with
GC analysis showed that 2.06 g of vinyl acetate, 14.6 g 65 drawn from line 103 was fed into separating zone 200
of ethylidene diacetate and 0.360 g of acetaldehyde and ?ash-distilled there to obtain low boiling point
were formed. Other components were considerable components containing 5.22 wt % of vinyl acetate. The
‘ amount of acetic acid, low boiling point components were fed into separating
4,978,778
17 18
zone 300 including distilling units through line 202. 2. The process as de?ned in claim 1 wherein said
High boiling point components and the catalyst sepa component (a) constituting the catalyst is selected from
rated in zone 200 were recycled into zone 100 through the group consisting of palladium, rhodium, platinum,
line 201. The components charged into zone 300 were ruthenium, osmium, cobalt, nickel and compounds of
separated, the low boiling point components mainly these metals.
composed of methyl acetate and methyl iodide were 3. The process as de?ned in claim 1 wherein the
recycled into zone 100 through line 303, and high boil amount of the component (a) employed is in the range
ing point components mainly composed of acetic anhy of from 1X 10-4 to 25 wt % on the basis of weight of a
dride and ethylidene diacetate were recycled into zone reaction solution in terms of metal.
100 through line 304. Vinyl acetate (object product) 4. The process as de?ned in claim 1 wherein the reac
was discharged from zone 300 through line 302 at rate tion is carried out in the presence of a solvent, said
of 5.47 g/hour and acetic acid was discharged from solvent being organic material having a dielectric con
zone 300 through 301 at rate of 8.11 g/hour. stant of not more than 18 at 25° C.
5. The process as de?ned in claim 4 wherein the sol
EXAMPLE 43 15 vent is selected from the group consisting of aliphatic
This example was carried out by using the apparatus hydrocarbons, aromatic hydrocarbons, organic acid
as shown in FIG. 3. Mixture of 35 wt % of acetic anhy esters, ethers, ketones, alcohols, and halogenated hy
dride, 10 wt % of methyl acetate, 10 wt % of methyl drocarbons.
iodide, 42 wt % of ethylidene diacetate and 3 wt % of 6. The process as de?ned in claim 4 wherein the sol
palladium (5%) supported on activated carbon in a 20 vent is selected from the group consisting of aliphatic
determined amount was charged into zone 100. Air in hydrocarbons having 5-20 carbon atoms, aromatic hy
zone 100 was purged with mixed gas of hydrogen and drocarbons having 6-20 carbon atoms and organic acid
esters having 3-20 carbon atoms.
carbon monoxide (3:1 by volume). The temperature in 7. The process as de?ned in claim 1 wherein the hy
the zone was raised to 175° C. The mixed gas was fed
drogen gas contains carbon monoxide.
from bottom of zone 100 under pressure to 30
8. The process as de?ned in claim 7 wherein carbon
Kg/cmzG. The mixture was stirred for 3 hours while monoxide content in the hydrogen gap is between
maintaining the pressure at 30 Kg/cm2G by feeding 0.1-90 mol %.
hydrogen into zone 100 through line 101. Thereafter, 9. The process as de?ned in claim 7 wherein carbon
movement of the. solution started so that average resi monoxide content in the hydrogen gas is between 1 and
dence time of the solution amounted to 3 hours, and at 90 mol %.
the same time acetic anhydride was fed into zone 100 10. The process as de?ned in claim 1 wherein the
from line 102 at rate of 14.7 g/hour, and hydrogen was amount of the halide material employed is in the range
continuously fed into zone 100 so as to maintain the of from 10-3 to 15 mol per 1 liter of a reaction solution.
pressure at 30 Kg/cmZG, and gas was circulated 11. The process as de?ned in claim 1 wherein said
through zone 100, line 105, separating zone 200 includ reaction is carried out in the presence of said catalyst
ing distilling units, and lines 203, 204 and 103. Compo comprising said component (a) and said component (b)
nents containing 6.8 wt % of vinyl acetate condensed at and together with at least one promoter, said promoter
100° C. in zone 200 were fed into separating 300 includ being selected from the group consisting of metals hav
ing fractionating means through line 202. Low boiling 40 ing atomic weight of at least 6 and belonging to Groups
point components mainly composed of methyl acetate Ia, IIa, IIIa, IVa, Va, Ib, Hb, Vb, VIb and VIIb of the
and methyl iodide, which were separated in zone 300 Periodic Table, compounds of the metals and mixtures
were recycled into zone 100 through line 303, and high thereof.
boiling point components mainly composed of acetic 12. The process as de?ned in claim 11 wherein the
anhydride and ethylidene diacetate, which were sepa 45 amount of said promoter employed is in the range of
rated in zone 300 were recycled into zone 100 through from 10-5 to 25% by weight on the basis of weight of
line 304. Vinyl acetate (object product) was discharged a reaction solution.
charged from zone 300 through line 302 at rate of 5.76 13. The process as de?ned in claim 11 wherein said
g/hour. Acetic acid was discharged from zone 300 promoter is selected from the group consisting of fluo
through line 301 at rate of 8.61 g/hour. 50 rides, chlorides, bromides, iodides, sulfates, phosphates,
What is claimed is: organic acid salts and mixtures thereof.
1. A process for producing vinyl acetate which com 14. The process as de?ned in claim 11 wherein said
prises reacting acetic anhydride with hydrogen gas in promoter is selected from the group consisting of lith
the presence of a catalyst consisting essentially of ium, potassium, barium and antimony and compounds
(a) at least one material selected from the group con of these metals.
sisting of metals belonging to Group VIII of the 15. The process as de?ned in claim 14 wherein said
Periodic Table, compounds of the metals and mix promoter is selected from the group consisting of ?uo
tures thereof and rides, chlorides bromides, iodides, sulfates, phosphates,
(b) at least one material selected from the group con organic acid salts, and mixtures thereof‘.
sisting of alkyl chlorides, alkyl bromides, alkyl 16. The process as de?ned in any one of claims 10-12
iodides and mixtures thereof and materials convert or 1-9 wherein the reaction is carried out in a tempera
ible to an alkyl halide while removing vinyl acetate ture of range 20°—500° C.
ill * i t
from the reaction system.

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