JPS5839811B2 - Production method of acetic anhydride - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing acetic anhydride by reacting methyl acetate or dimethyl ether with carbon monoxide.

More specifically, a method for producing acetic anhydride by reacting methyl acetate or dimethyl ether with carbon monoxide in the presence of nickel or a nickel compound component, a bromide or iodide halide, and an organic nitrogen group compound containing phosphorus or nitrogen. I of the periodic table as a cocatalyst in
Acetic anhydride characterized by using one or more metals of Group VB or a compound thereof and one or more metals selected from the group consisting of Groups IA and IIA or a compound of the metals. Concerning the manufacturing method.

Conventionally, methods for producing carboxylic acid anhydrides by the reaction of carboxylic acid esters, ethers, and carbon monoxide include (a) using Group II noble metals, mainly rhodium, halides, and other third components as catalysts; Method (Japanese Patent Publication No. 52-3926, Japanese Patent Application Publication No. 5165709, Japanese Patent Application Publication No. 1983
1-115403, etc.) (0) A method using nickel (or cobalt), a halide, and other third components as a catalyst (Japanese Patent Laid-Open No. 54-59214 filed by the present inventors)
JP-A-52-78814, JP-A-52-78815, US Pat. No. 2,729,651, etc.) are known.

However, rhodium used as a catalyst in the former method (a) is an extremely expensive substance (for example, Hy
drocarbon pro-cossing 54
, June 83 (1975)), and in industrial implementation, preventing the rhodium complex from being reduced to metal in a reducing atmosphere (Chemistry and Industry, 29(5), 376 Mitsugu (1975)) or distilling the product. Prevent it from volatilizing and dissipating from the reaction system due to separation operations, etc. (
Special measures such as Japanese Patent Application Laid-Open No. 53-90204) are required.

In contrast to the method using this expensive noble metal, the present inventors previously disclosed a method using a catalyst system using nickel in JP-A-54-59214.

That is, JP-A-54-59214 or the latter (Fanghukou, typified by U.S. Pat. No. 2,729,651) is an excellent method in that it uses a particularly inexpensive catalyst, but the present inventors have Continuing intensive research with the aim of further increasing the reaction rate, we found that one or more types of group IVB of the periodic table were added as cocatalysts to a catalyst consisting of nickel, halides, and organic nitrogen group compounds containing phosphorus or nitrogen. The present invention has been completed by discovering a catalyst system using a metal or a compound of the metal and one or more metals selected from the group consisting of Groups IA and IIA or a compound of the metal.

That is, the present invention provides (al) nickel or a nickel compound component, (a2) a halide that is a bromide or iodide, and (a3)! A type of group (b 1 ) IVB of the periodic table as a cocatalyst in a method for producing acetic anhydride by reacting methyl acetate or dimethyl ether with carbon monoxide in the presence of an organic nitrogen group compound containing nitrogen or nitrogen. or two or more metals or a compound of the metals,
(b2) 1 selected from the group consisting of groups IA and IIA;
This is a method for producing acetic anhydride characterized by using one or more metals or compounds of the metals.

The periodic table of the present invention is based on [New Experimental Chemistry Course, Volume 12, 4
~5p, Nihon Kagaku Zenhen (1976)) is used.

As the (al)nickel or nickel compound component used as the main catalyst metal in the present invention, organic or inorganic nickel compounds can be used.

For example, nickel compounds such as nickel powder, nickel acetate, nickel iodide, nickel acetylacetone, nickel tetracarbonyl, nickel dicarbonyl, nickel dicarbonylbistriphenylphosphine, and tetramethylammonium nickel iodide components are used.

Preferred (a2) halides for use with the nickel or nickel compound component are bromides or iodides or mixtures thereof.

Usually, the halides are mostly used in the form of alkyl halides such as methyl iodide, acid halides such as acetyl iodide, hydrogen halides such as hydrogen iodide, or any mixture thereof, and are reacted directly. can be introduced into the liquid.

Furthermore, a method of introducing a substance into the reaction solution in which any one or more of these halides, ie, alkyl halides, acid halides, or hydrogen halides, is produced in the reaction solution is also a right-handed method.

Substances that react with other components in the reaction solution to produce alkyl halides, acid halides, or hydrogen halides include inorganic halides, such as alkali metal halides such as lithium, sodium, and potassium, and magnesium; Alkaline earth metal halides such as calcium or metal halides such as aluminium, zinc, copper, lanthanum or cerium, and bromine or iodine, in the case of metal halides of Groups 1A, IA and IVB, as described below. Also used as a promoter.

Among the halides mentioned above, it is a particularly preferred embodiment to use methyl halides such as methyl iodide from the viewpoint of the contact resistance of the reactor or the separation and purification of the reaction products.

In the present invention, (a3) an organic nitrogen group compound containing phosphorus or nitrogen is used together with the above nickel component and halide.

Non-limiting examples of effective organic nitrogen group compounds are classified into groups.

(I) Trivalent organic nitrogen group compound 1 (4) General formula M〈Organic nitrogen group 3 represented by R2 Compound (where M represents N or P.

) (a) R1, R2, R3 are hydrogen or have 1 carbon number
~10 saturated alkyl, cycloalkyl, or aryl groups, each of which may be the same or different from each other M2N Monomethylamine, dintylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, dimethylethylamine, trin- Propylamine, tri-iso-propylamine, tri-n-butylamine, tri-tert-butylamine, aniline,
Amines such as dimethylaniline, diethylaniline, dimethylbenzylamine, toluidine, triphenylamine, and cyclohexylamine;

-probylphosphine, tri-n-butylphosphine,
to! Phosphines (b) such as Jtert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, etc. R1 represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R2 and R3 have 1 to 10 carbon atoms. Compounds linked with 5 polymethylene groups Pyrrolidine, N-methylpyrrolidine, piperidine, N-
Cyclic compound (C) such as phenylpiperidine R1 and R2 represent hydrogen, a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and may be the same or different from each other.

R3 is a compound representing a saturated aliphatic amyl group having 1 to 10 carbon atoms, and R1 is hydrogen or a saturated alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms;
Lactam compounds in which R3 is linked with a carboxypolymethylene group Carboxylic acid amides such as acetamide, N,N-dimethylacetamide, acetanilide, N~methyl-N-phenylacetamide, and lactams such as N-methyl-pyrodinone (d) At least one of R1, R2, and R3 is a carboxymethyl group, and the remainder represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, which may be the same or different Compounds N, N- Carboxylic acid derivatives (B) such as dimethylglycine, N,N-di-ethylglycine, iminodiacetic acid, N-methyldiiminoacetic acid, nitrilotriacetic acid, etc. General formula: N3C-R, where R has 1 to 10 carbon atoms Compounds that are alkyl groups, cycloalkyl groups, or aryl groups Nitriles such as acetonitrile, propionitrile, benzonitrile (C) Organic nitrogen group compounds represented by the general formula R'>M1R5M2<, 2 (However, M12M2 is N.

P, and may be the same or different.

)(a) Rlt R2t R3s R4 represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R3 has 1 to 10 carbon atoms.
Compounds representing 10 polymethylene groups, phenylene groups, or carbonyl groups M1, M22N, P ethylenebis(diphenylphosphine), phenylenebis(dimethylphosphine), N,N',N'-tetramethylethylenediamine.

N, N, N', N'-tetraethylethylenediamine, N, N, N', N/-tetra-n-propylethylenediamine, N, N, N', N/-tetramethylmethylenediamine, N, N, N Compounds such as ',N'-tetramethylurea, N-methyl-2-pyrodinone, triethylenediamine, etc. (b) R,,R3 is hydrogen, a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. , R2, R4 are connected by a polymethylene group having 1 to 5 carbon atoms, and R5 is a polyalkylmethylene group having 1 to 5 carbon atoms; piperazine, N-methyl-piperazine, N-ethyl-piperazine, 2-methyl-N , N'-dimethylpiperazine and other cyclic compounds (c) Other compounds 2.5-dicarboxypiperazine, cyclohexane-1
, 2-diamine-N, N, N', N'-tetraacetic acid and salts and tetramethyl ester, ethylenediaminetetraacetic acid and salts and tetramethyl ester, 1,4-azabicyclo[2,2,2]octane, methyl substituted 1,4-diazacyclo(2,2,2)octane,
Compounds such as adiponitrile and N-methylpholine (l[) Heterocyclic compounds pyridine and alkylpyridines: pyridine, α-picoline, β-picoline, γ~rubicoline 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2 −
Propylpyridine, 4-propylpyridine, 4-butylpyridine, 4-isobutylpyridine, 4-t-butylpyridine, 2,6-lutidine, 2,4-lutidine, 2゜5-
Lutidine, 3,4-lutidine, 3,5-lutidine, 2,
4.6-collidine, 2-methyl-4-ethylpyridine,
2-methyl-5-ethylpyridine, 3-methyl-4-ethylpyridine, 3-ethyl-4-methylpyridine, 3,
4-diethylpyridine, 3,5-diethylpyridine, 2
-Methyl-5-butylpyridine, 4-pentylpyridine, 4-(5-)triyl)-pyridine, 2,6-di-ethylglycine lysine rubiridine; Pyridines containing functional groups: 2-cyanopyridine, 3 -cyanopyridine, 4-cyanopyridine, 2,6-dicyanopyridine, 3,5-dicyanopyridine, 2-cyano-6
-Methyl-pyridine, 3-cyano-5-methyl-pyridine, picolinic acid amide, nicotinic acid amide, isonicotinic acid amide, picolinic acid, nicotinic acid, isonicotinic acid, cyhicholic acid, dinicotinic acid, cinchometronic acid, 5 --Methyl-picolinic acid, nicotinic acid alkyl ester, 2-amino-pyridine, 3-aminopyridine, 4
-aminopyridine, 2,3-diaminopyridine, 2,5
-diaminopyridine, 2,6-diaminopyridine, 2,
3゜6-triaminopyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino/-6-methylpyridine, 2-amino-4 -ethylpyridine, 2-amino-
4-propylpyridine, 2-amino-4-(5-nonyl)-pyridine, 2-amino-4,6-cintylpyridine, 2,6-diami2-4-methylpyridine, 2,2'-
Dipyridylamine, 4-(N,N-dimethylamino)pyridine, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,6-cyhydroxypyridine, 3-hydroxy-6-methylpyridine, 2-
Chloropyridine, 2,6-dichloropyridine, 4-chloropyridine, 2-amino-5-chloropyridine, 2-amino-3,5-dichloropyridine, 2-methyl-3,5
-dichloro-6-methylpyridine, 2-amino-5-chloro-3-methylpyridine, 2-amino-3,5-dichloro-4-methylpyridine, 2-amino-3,5-dichloro-4,6- Syntylpyridine, 4-amino-3,5
-dichloropyridine, pyridine-N-oxide, α-picoline-N-oxide, β-picoline-N-oxide,
γ-picoline-N-oxide, 2,6-lunasin-N-
oxide, 3,5-lutidine-N-oxide, 4-phenylpropylpyridine-N-oxide, 1゜3-di(
4-pyridyl)-propane di-N-oxide, 4-(5
-nonyl)-pyridine-N-oxide, 2-chloropyridine-N-oxide, 4-cyanopyridine-N-oxide, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2,6-pyridinemethanol, 2-pyridineethanol, 4-pyridineethanol, 3-picolylamine, 4-picolylamine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, 4-piperidinoethylpyridine, 4-(4-pipecolinoethyl)- Pyridine, 4-morpholinoethylpyridine; Pyridines containing cyclic compounds = 2-phenylpyridine, 4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4-phenylpropylpyridine, 4,4'-dipyridyl, 4.4'-dimethyl-2,
2'-dipyridyl, 1゜3-di(4-pyridyl)propane, ■, 2di(4-pyridyl)-ethane, ■, 2-
Di(4-pyridyl)-ethylene, 1,2,3-tri(
4-pyridyl)propane, 2,4,6-tri(4-pyridyl)-S-triazine, 2゜4-di(4-pyridyl)-6-methyl-S-triazine, 2,5-di(4-pyridyl) -8-Tetrazine; Alkenylpyridine and high molecular weight pyridines: 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methyl-pyridine, 2-vinyl-5ethylpyridine, 4-butenylpyridine, 4-vinylpyridine homo polymer, 2
-vinylpyridine homopolymer, 2-vinylpyridine copolymer, 4-vinylpyridine-acrylonitrile copolymer, 4-vinylpyridine-styrene copolymer, 4-vinylpyridine-divinylbenzene copolymer, 2-vinylpyridine-divinylbenzene copolymer rimmer,
4-vinylpyridine homopolymer-N-oxide; Pyrroles: Pyrrolines: Pyrimidines: Pyrazines:
Pyrazole: Pyrazoline: Pyridazine: Imidazole: 1,10-phenanthroline and its derivatives:
1,10-phenanthroline, 4-chloro-1,10-
Phenanthroline, 5-(thiapentyl)-1,10-
Phenanthroline: Quinoline and its derivatives: Quinoline, 2-(dimethylamino)-6-medoxyquinoline, 8
Among the compounds including -hydroxyquinoline and 2-carboxyquinoline, compounds containing trivalent phosphorus or nitrogen are particularly preferred.

More preferred organic nitrogen group compounds are phosphine compounds containing trivalent phosphorus, camponamides, or heterocyclic compounds typified by pyridine.

The (al) nickel or nickel compound component and (a
2) Halogen compounds that are bromides or iodides and (
a3) Catalysts made of nitrogen or organic nitrogen group compounds containing nitrogen are effective on their own, but their activity is low, and one or more of the group (BL) IVB of the periodic table may be used as a co-catalyst. a metal or a compound of the metal; (b2)
When one or more metals selected from the group consisting of Groups IA and IIA or their metal compounds are used, extremely high catalytic activity can be exhibited and a fast reaction rate can be obtained.

Promoter metals are based on the use of (bl) metals of group IVB and (b2) metals of groups IA and IIA, but (bl) IVB: silicon, germanium, tin (b2
) IA group: lithium, sodium, potassium, rubidium, cesium 11A group: beryllium, magnesium, calcium, strontium, barium are preferred, and more preferably (bl) IVB group: silicon, germanium, tin (b2)
Group IA: lithium, rubidium, cesium II Group A: magnesium, calcium, strontium, barium, particularly (bl) Group IVB: tin (b2)' Group IA: lithium II Group A: calcium, strontium are preferred.

(b) The cocatalyst is based on the use of metals of the Thl B and IA and IIA groups or compounds of these metals, but can be utilized in any and all forms.

For example, the metal itself or in finely divided form;
Raney metal forms or carbonates, oxides, hydroxides,
nitrates, sulfates, phosphates, halides, cyanides,
Thiocyanides, sulfonates, C1-C5 lower alkoxides such as methoxides or ethoxides, phenoxides, metal carboxylates in which the carboxy ion is derived from alkanoic acids of 1 to 20 carbon atoms, oxyhalides, hydrides, nitrites. , sulfites, phosphites,
Examples include acetylacetone salts, sulfides, compounds coordinated with ammonia, cyanide, amines, amine acids, etc., and organometallic compounds to which phenyl groups and alkyl groups are bonded.

Some examples are H25t03 t H4S t
04, S I HBr 3, S t HCA
3.

SiHF3, 5iHI3, Si, 5i2Br
6, SiBr4.

5iBrH3, 5iBrC73, 5iBr2CJl! 2
.

5iBr3Cl, 5i2C16, 5iC14, 5iCl
H3゜5ip4, 5iH4, 5i2H6, Si3H8,
5i4) 11o.

SiI2, Si2I6, SiI4.5iIC13
, 5i02.

XH2O,5i02,5i20CI6. Sin, 5in
2. Ge.

GeBr4, GeC12, G5C145GeHc13
, GeF4.

3H20, GeH4, Ge■4. Ge09GeO2,G
e0C12°GeS, Ge52, Sn, SnBr4.
5nC14, 5nF4.

SnI4, 5n02, 5nOC12, 2Sn02
"P205"10H20, SnP, Sn (SO4)
2・2H20,5nS2゜SnBr2,5nC12,S
nF2. Sn(OH)2, SnI2゜5nC204,
SnO, S no-8nCl 2 .3H20.

SnSO4, SnS, 5n(CaH,), Sn(CH3
)4゜5n(CH3)2. Sn(C2H5)4. (C3
H7) 2SnH2゜(CH3) 2SnI2s
Sn (C2H5) 2 S (C4Hg)25nC1
2.

(C2H5)2 SnI2. (CHa)asncl,
(C4H9)25lIH2t(C3H7)2 Sn I
2, (CH3)3(CH2I)Sn.

(C4H9)3SnC1, (C4H9)2SnI2.

(C2I(5) s 5nCJ? * (C4Ho)
s S n) (, (C2H5) ssnkl 5 (C6
H5CH2) s SnCl , Sn (C2)1a
02)2-8n(C2H602)4tPTH(S
nC13)(CO)(P ph3)2, Lt, L
t C2H502・2H20゜LiAlO2, LiNH
2, LiBO2, Li2 B4075H20, LiBr
, LiBr・2H20, Li2CO3°L 1Hco3
．． Lic 103. LiClO3・0.5H20
.

L i Cl, L i 3 C6H507・4H2
0, Li2S206・2H20-L t F -L t
□(StFe)・2H20, LiHCO2・H20, L
iH, LiOH, Li0H-H20, LiI, LiI・
3H20* L s NO3, L t NO3・3H2
0, LiNO2・H20-L t 2 C204, L
t HC204・H20°Li20. Lt ClO4
, LiCl4 ・3H20, LtMr104°LiH2
PO4, Li3 PO4, Li3 PO4・12H20
゜Li2SiO3, Li4SiO4, Li2SO4・L
i 2SO4・H20, LiH8O4, Li2S, L
12SO3,Rb.

RbB r 03 v RbB r , RbB r
3, Rb2CO3tRbHC(J, RbCJ
! 03. RbC7, RbF, SukeH, RbOH.

RbIO3, RbI, Rbl3. RbNO3, Rb2
O, Rb202°Rb203. Rb204. RbClO
4, Rbl04.

RbMn()4 t Rb25e04 t Rb2SO
4, Rb25.

Rb2 S ・4H20, Rb2 S s , Rb(
C2Ha 02 ).

Cs, CsBrO3, CsBr, CsBr3, Cs2
CO3.

CsHCO3, CsC7, C5CH, CsF, CsH,
CsOH.

Cs IO3, Cs I, C5I3, CsNO
3, CsNO2Cs2O5Cs202, Cs203
tC3204, CsClO4゜C5IO4, CsMnO
4, Cs8SiW, 2042C5SOC3H8O4,C
52S・4H20, C82S2゜2 49 Cs2S2・H20, C52S3. C52Ss, C
5HC4H406.

C3(C2H302) 2MgtMg(C2Hs02)
2.

Mg (C2H302) 2 ・4H205MgO94
H2O5°MgCIJ2. NH4Cl・6H20,Mg
NH4PO4・6H20゜MgSO4・(NH4) 2
804・6H20, Mg (BO2) 28H20, M
g (B PO3) 2 ・6H20, MgB r2M
g B r 2 ・6H209Mg CO3t Mg
CO3, 3H20y3MgC03・Mg(OH)2・3
H202Mg (C1l O3) 26H202MgC
122MgC12・6H206H2O2゜Mg (S
i F6 )・6H20t Mg (OH) 22Mg
(H2PO2)2.6H202Mg (I O3)
2.4H20t Mg I 2 pMg(NO3)2.
6H202Mg3N22MgC26H2O20, MgO
, Mg (C,ill!04) 2.6H20°Mg
(MnO4) 2 ・6H202Mg s (PO4
) 2 ・4H20.

Mga (PO4)2・8H202M8H2O2・3H
20゜MgHPO, 7H202Mg2P2072Mg
7H2O2,3H20゜MgHPO3・3H20,Mg
Cl2・KCl・6H20゜MgSO4・K2SO4・
6H2026H2O2・NaC4-H20°MgSO4
, MgSO4・7H202MgS27H2O2・6H2
0゜Mg (C4H406) ・5 H202Mg 8
20g 6H20, Ca.

Ca(C2H302)2・H20, Ca(NO2)2.
Ca0-M2Q・2S i02, CaNH4As0
4 ・6H20, CaNH4PO47H20, Ca s
(A SO4) 2 , Ca (BO2)2 ・2
H20, caB6゜Ca (B PO3)2-H2o
? CaBr2 + CaBr2 ・6H201CaC
2, Ca COs, Ca (CA'03) 2
・2H20, Ca C4.

CaCl2・H20, CaCl2・6H20゜Ca3(
C6H307)2 ・4H20,Ca(CN)2゜Ca
CN2, Ca 8206 ・4H20, CaF2
, Ca (S t F6).

Ca (S 1F6) ・2H20, Ca (HCO2)
2, CaH2.

Ca(SH)2-6H20,Ca(OH)2tca
(CA!0)2・4H20,Ca(IO3)2. CaI
2. CaI2・6H20°Ca(C3H503)2・5
H20, CaO-MgO・2co2゜Ca()Mg()
28i02. CaMoO4, Ca(NO3)2Ca (
NO3) 2 ・4H20, Ca3N2 , Ca (N
O2) 2 ・H20, CaC2O4, CaO2Ca(
MnO4)2・4H20°Ca02 + 8 H20,
CaHP 04 ・2H20, Ca 2P 206 ・
2H20, Ca(PO3)2. Ca(H2PO4)2・
H20゜Ca2P2O7, Ca2P, 207・5H20
.

Ca3(PO4)2,2CaHPO3・3H20゜Ca
(H2PO2) 2 , CaX2 (SO4) 2
・H20, Ca5iOs.

CaSi CaSO4・2Na2SO4・2H20,
CaSO4゜2゜Ca50 ・2HOsCash4+0-5H20t C
aS.

2 CaSO3・2H20,CaC4H406+4H,0,
CaC83゜Ca (SCN) 2 ・3H20, C
a S 203 ・6 H20, CaWO4.

Sr, 5r(C2H302)2, 5rB407-4H
20.

Sr (BrC)3)2・H20,5rBr2,5r
Br2・6H20.

5rC03,5r(C103)2,5r((J'03)
2,8H20.

5rC12, 5r(CN)2・4H20, 5rS206
・4 H20t S r F 2 , S r (S r
F2) ・2 H20.

5r(HCO2)2, 5r(HCO2)2・2H20,
5r(SH)2゜S r (OH)2 , S r (
OH)2 ・8H20, Sr(IOa)2.

SrI2. SrI2・6H20, Sr(NO3)2. S
r(NO3)2・4H20,5r(NO2)2. Sr.
(NO2)2 ・H20.

SrCO-HOSrO,5r02,5r02 j 8H
20゜24 2 2 Sr (MnO+)2・3H20t S rHP O4
tSrSiOs.

S rsO4, S r (HS 04 )2, S r
s, S rS4 ・6H20゜5rSO3t S
r (CNS)2 ・3H20+ S rs203・
5H20tBatBa(C2H4-)2,
B a (C2H502) 2 ”H20,Ba(NH
a) 2, Ba3 (As04) 2゜Ba5203・H2
0tBa (N3) 2tBa (N3) 2”H20+Ba
(Br03)2・H20, BaBr2, BaBr2
, 2H20? Ba(PtBr6)・10H20,Ba
C2,BaCO3゜Ba (C103)2. Ba (C
l0s) 2 ・H20, BaCl2.

BaCl2・2H20, Ba(CN)2. Ba5206
・2H20゜BaF2; Ba(SiF6), Ba(H
CO2)2. BaH2゜Ba(SH)2・4H20,B
a(OH)2. Ba(OH)28H20,Ba(C4O
)2. BaPO3, Ba(H2PO2)2H20, Ba
(IO3)2. Ba(IO3)2・H20, BaI2・
2HOBaI ・6H'OBaMnO4, BaMoO
4゜2g 2 2 9 Ba (N03)2. Ba(NO2)2yBa(NO2)
2'H20゜BaC2O4, Bad, B'a((J'
04)2, Ba (C104)23H20t B
a (Mn04) 2 t B a02 g B a
02 ・8H20tBaS208-4H20,BaH
PO4,Ba(H2PO,)2゜Ba2P2O7,Ba
3 (PO4)2. BaSiO3, BaS 103-6H
20, Ba 804, BaS, Ba 84,
2H20, BaS3, BaSO3.

These include Ba(CNS)2.2H20, Ba5203.H20, etc.

When considering that the catalyst is a halide of bromide or iodide, and the desired product is an organic acid anhydride, a promoter metal compound in the form of a halide of bromide, iodide, or an organic acid salt such as acetic acid is used. is a preferred embodiment.

The amount of nickel or nickel compound used in the present invention is 1/11 based on the total volume of the reaction solution.
0-6 to 5 mol, preferably 10-4 to 4 mol, more preferably 10-3 to 2 mol, most preferably 5
The range from 10-3 to 1.0 mole is generally selected.

The amount of the halogen compound to be used is 10-3 to 15 mol, preferably 10-2 to 10 mol, more preferably 10-1 based on the total volume of the reaction solution based on the halogen atom.
It is used in a range of 8 mol.

The amount of organic nitrogen group compound containing phosphorus or nitrogen is related to the amount of nickel or nickel compound component used, but it is usually 10/11 based on the total volume of the reaction solution.
-6 to 10 mol, preferably 10-4 to 5 mol, more preferably 10-3 to 2.5 mol.

Similarly, the cocatalysts IVB group metals, IA group metals, and IA group metals or compounds of these metals each have a concentration of 0.01 to 100 (Ni: IVB group metal: I
A and/or HA group metal-1: (0,01-100
): (0,01-100)), preferably 0.03-3
0 (Ni: IVB group metal: IA and/or IIA group metal-1: (0,03-30): (0,03-30)]
, more preferably o, i~20 (Ni: IVB group metal: IA and/or HA group metal = 1: (0,1~20
): (0,1 to 20)], but the amount used is usually based on the total volume of the reaction solution (10-6 to 30 mol per type, preferably 10- 4～
A range of 20 mol, more preferably 10-3 to 10 mol, is selected.

In the above range t, the metal of groups IA and IIA or the compound of the metal has a ratio of 10-3 to 103, preferably 1
It is used in the range of 0-2 to 102, preferably 0.1 to 50.

The reaction temperature for carrying out the method of the present invention is, for example, 20 to 350°C, preferably 80 to 300°C, and more preferably 100 to 250°C.

The total reaction pressure may be sufficient to maintain the volatile reaction liquid in a liquid phase and to maintain -carbon oxide at an appropriate partial pressure.

- The preferred partial pressure of carbon oxide is 0.5 to 300 atm, the optimal partial pressure is 1 to 200 atm, and the optimal partial pressure is 2 to 15 atm.
Although the pressure is 0 atm, a wider partial pressure range of 0.05 to 5000 atm may also be used.

Dimethyl ether, which is a raw material used in the present invention,
Methyl acetate obtained by any method can be used.

For example, dimethyl ether is supplied directly from C09H2 or by the dehydration trimerization reaction of methanol, and methyl acetate is usually supplied by the esterification reaction of methanol and acetic acid.

In this case, the basic raw material, acetic acid, is produced by the reaction of methanol and carbon monoxide (for example, JP-A-54-59
211, JP-A-54-63002, JP-A-54-666
14) Alternatively, methyl acetate, which is co-produced in the method of exchanging vinyl acetate with PVA (polyvinyl alcohol), may be used, or methyl acetate produced by the reaction of methanol and synthesis gas [for example, Japanese Patent Publication No. 48-2525, Showa 51
=149213, JP-A-52-136110, JP-A-5
2-136111 etc.] may also be used.

It is expected that impurities such as methanol, dimethyl ether, acetic acid, acetaldehyde, halides represented by iodides such as dimethyl acetal and methyl iodide will be mixed into the methyl acetate supplied by the above method. However, as long as the overall balance of the reaction is not disturbed, the above-mentioned impurities can be tolerated and the reaction can be carried out suitably.

In addition, using methyl acetate containing methanol as a raw material,
It is also possible, and sometimes advantageous, to produce acetic anhydride and acetic acid simultaneously.

Carbon monoxide used as a raw material gas does not necessarily have to be of high purity; it can be hydrogen, carbon dioxide, methane,
It may contain nitrogen, rare gas, water, etc.

Among them, hydrogen not only does not inhibit the reaction, but also tends to stabilize the catalyst.

In this respect, systems using Group 8 metals other than nickel, such as rhodium or palladium, as catalysts,
- The combined use of carbon oxide and hydrogen produces by-products such as ethylidene diacetate and acetaldehyde, which is undesirable when the intention is to produce acetic anhydride (for example, JP-A-51-1
15409 etc.).

However, in the present invention, which uses nickel or a nickel compound component as a catalyst, the above-mentioned by-products are not generated even if hydrogen is contained in the raw material gas, and this unique property is different from that of a catalyst system using rhodium or palladium. has.

However, extremely low purity carbon monoxide is not preferable as a raw material gas because it increases the pressure in the reaction system.

Although the presence of water in the reaction raw materials is a common phenomenon, the raw material gas and methyl acetate can tolerate the presence of a small amount of water, which is often present in commercially available reactants, and no problems will occur. .

However, it is generally necessary to avoid the presence of 10 moles or more of water in one or more of the reaction raw materials used in the present invention, as introducing too much water into the reaction system may lead to decomposition of the raw materials and products. easy.

In this respect, it is desirable that the water content be 5 moles or less, more preferably 3 moles or less.

Since water is not a reaction product, maintaining near-anhydrous conditions in the reaction solution is easily achieved by maintaining the necessary reactants introduced into the reaction zone as well as the reaction working fluid in a suitably dry state.

In the method of the present invention, the raw material methyl acetate and/or the reaction product acetic anhydride itself serves as the reaction solvent.
Although it is not necessary to use a solvent, it is also possible to use organic solvents and diluents that are compatible with the raw materials and products in the reaction environment.

The preferred solvent used is a catalyst, a raw material reaction intermediate, a substance that participates in the reaction as a product or a by-product,
Examples include methyl iodide, methyl acetate, acetic anhydride, and acetic acid.

In the present invention, in addition to the above-mentioned solvent, a diluent compatible with the solvent can be used in combination.

Diluents that can generally be used include ethylene glycol diacetate, propylene glycol diacetate, organic acid esters such as dimethyl adipate, methyl benzoate, and dimethyl phthalate, dodecane, hexadecane, benzene, and naphthalene.

Examples include hydrocarbons such as biphenyl, inorganic acid esters such as triphenyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, tetramethyl orthosilicate, and tetrabutyl silicate.

The method of the invention can be carried out batchwise, semi-batchwise or continuously.

When the reaction is carried out continuously, the effluent from the carbonylation reaction zone is separated by a separation operation such as distillation to separate acetic anhydride from the effluent mixture, and remove unreacted methyl acetate, halides, organic nitrogen group compounds, and metal catalyst components. Collect the
It is recycled to the carbonylation reaction zone.

This separation zone usually consists of one or more distillation units, such as a flash distillation column and/or a separation column.

Alternatively, acetic anhydride can be separated by reactive distillation in the carbonylation reaction zone.

In this case, the distillate from the carbonylation reaction zone is gaseous.

The effluent thus consists of non-condensable gases in the reaction system, such as carbon monoxide and optionally hydrogen, as well as acetic anhydride, unreacted methyl acetate, halides and optionally nickel-containing compounds.

Typically, the cocatalyst is non-volatile and therefore remains in the carbonylation reaction zone along with most of the nickel catalyst components.

The effluent is cooled, the condensed components are condensed, and the non-condensed components are recycled to the carbonylation reaction zone, leaving essentially only the non-condensed components together with freshly replenished carbon monoxide and, if necessary, hydrogen. A predetermined partial pressure in the band is maintained.

The condensed portion of the effluent is treated by distillation to separate the respective components or fractions and to recycle the unreacted methyl acetate and halide.

In the present invention, as is commonly done, a portion of the reaction gas is purged to remove impurities such as nitrogen or impurities present in the carbon monoxide or hydrogen feedstocks supplied to the reaction system, such as methane. Prevents the accumulation of impurities generated during the carbonylation reaction itself.

The method of the present invention described in detail above is for producing acetic anhydride by keeping an inexpensive catalyst highly active and reacting methyl acetate or dimethyl ether with carbon monoxide.
It has extremely high industrial significance.

Hereinafter, this will be explained in more detail with reference to Examples.

Example 1 Methyl acetate 30g, acetic acid 25g, NiO, 5g, 2
, 2 g of 4-lutidine, 14 g of methyl iodide, 1.7 g of stannous acetate (Sn(OCOCH3)2), and 2.6 g of lithium acetate (LiOAC) at 80 atoms in a pressure-resistant container.
(-carbon oxide partial pressure 55 atoms, hydrogen partial pressure approximately IQ
2iom) and reacted at 185°C.

The pressure reduced by the reaction did not compensate for the carbon monoxide, and the reaction pressure was kept constant.

After 1 hour of reaction, acetic anhydride equivalent to more than 1 part of the raw material methyl acetate was determined by analysis.

Example 14 Methyl acetate 15g, acetic acid 24. ! 9. Ni powder 0.
5g, 2,4-lutidine 2.0g, methyl iodide 14g
, SnI4 3.3g, Li0Ac 1.3. ! ? 50 atoms (-carbon oxide partial pressure of approximately 30 at
om, hydrogen partial pressure of about 10 atoms), and the reaction was carried out at 180°C.

After 2 hours of reaction time, a portion was analyzed and acetic anhydride was determined to be equivalent to 94% of the raw material methyl acetate.

Example 15 9.2 g of dimethyl ether was further pressurized into the reaction solution of Example 14 in a pressure-resistant container, and while stirring at 180°C, 45 atoms of carbon monoxide and 10 atoms of hydrogen were gradually added.
was introduced, and the reaction was carried out at a total pressure of 80 atoms.

During the reaction, the total pressure without supplementary carbon oxide was maintained at 80 atoms.

After 2 hours of reaction time, analysis revealed that acetic anhydride was present in an amount equivalent to 77% of the starting dimethyl ether.

Example 16 Methyl acetate 309, methanol 10. ! 9. Acetic acid
12. ! 9, Ni015g, 2,4-lutidine 2g, methyl iodide 14g, stannic iodide (SnI+')
4.49, lithium acetate 2.69 in a pressure container
atom (carbon oxide partial pressure: about 45 atom, hydrogen partial pressure: about 10 atnm), and the reaction was carried out at 185°C.

The pressure Gj-carbon oxide lowered by the reaction was compensated for and the reaction pressure was kept constant.

After 1.4 hours of reaction, analysis revealed that 83% of the raw material methyl acetate was
% of acetic anhydride and raw methanol approximately 100%
The amount of acetic acid corresponding to

Examples 17 to 26 Experiments were conducted in the same manner as in Example 1 using various catalysts and promoters.

Claims (1)

[Claims] 1. In a method for producing acetic anhydride by reacting methyl acetate or dimethyl ether with carbon monoxide in the presence of a nickel or nickel compound component, a bromide or iodide halide, and an organic nitrogen group compound containing phosphorus or nitrogen. , one or more metals of group IVB of the periodic table or compounds of the metals as cocatalysts, and I
One or two selected from the group consisting of Group A and Group IA
1. A method for producing acetic anhydride, characterized by using more than one metal or a compound of the metal.