JPS5839808B2 - Production method of carboxylic acid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carboxylic acid by reacting a hydrocarbon alcohol with carbon monoxide.

A method for producing a carboxylic acid by a carbonylation reaction of alcohol is particularly known as a method for producing acetic acid from methanol and carbon monoxide.

That is, (a) A method using a Group I noble metal mainly containing rhodium, a halide, and other third components as a catalyst (Japanese Patent Publication No. 47-3331-3337, etc.) (0) Nickel (or cobalt), a halide, and Other third commandment-catalyzed methods (e.g., U.S. Pat. No. 2,729,651;
2,727,902, German patent 921,938.93
3,148.947.469 and JP-A-54-59211.54-63002.54- filed by the present inventors.
66614 etc.) are known.

However, rhodium used as a catalyst in the former method (a) is an extremely expensive substance (for example, Hy
drocarbon processing54, J
une 83 (1975)), and in industrial implementation to prevent the rhodium complex from being reduced to metal in a reducing atmosphere (Chemistry and Industry, 29(5), p. 376 (1975).
)) or to prevent the product from volatilizing and dissipating from the reaction system by distillation and separation operations (Japanese Patent Laid-Open No. 53
-90204), etc., special measures are required.

In contrast to this method using expensive precious metals, a method using a catalytic system using nickel was proposed in JP-A-54-59211.54-
No. 63002, 54-66614, etc., which the present inventors previously disclosed.

That is, the latter method (D) is an excellent method in that it uses a particularly inexpensive catalyst, but the present inventors continued intensive research with the aim of relaxing the reaction conditions and further increasing the reaction rate, and found that nickel or one or more metals selected from silicon, germanium, and tin or compounds of the metals are used as a cocatalyst in a catalyst consisting of cobalt, a halide, and an organic nitrogen group compound containing phosphorus or nitrogen, or The present invention was completed by discovering a catalyst system using a cocatalyst system in which these cocatalysts are combined with one or more metals of lithium, rubidium, cesium, magnesium, calcium, strontium, and barium, or compounds of the metal group.

That is, the present invention provides a method for reacting hydrocarbons in the presence of a catalyst containing (a 9s or cobalt), (R2) a halide which is a bromide or iodide, and (a3) an organic nitrogen group compound containing nitrogen or nitrogen. In the method of producing carboxylic acid by reacting alcohol and carbon monoxide, silicon, germanium,
Use of one or more metals of tin or compounds of the metals, or these cocatalysts and (b2) one metal selected from the group consisting of lithium, rubidium, cesium, magnesium, calcium, strontium, and barium. Alternatively, it is a method for producing a carboxylic acid characterized by using two or more metals or compounds of the metals in combination.

In the present invention, organic and inorganic nickel and cobalt compounds can be used as the (al)nickel or nickel compound component and the cobalt or cobalt compound component used as the main catalyst.

For example, nickel compounds such as nickel powder, nickel acetate, nickel iodide, nickel acetylacetone, nickel tetracarbonyl, nickel dicarbonyl, nickel dicarbonyl bistriphenylphosphine, tetramethylammonium nickel iodide powder, as well as cobalt powder, cobalt hydroxide, Cobalt carbonate, cobalt acetylacetone, cobalt iodide, cobalt acetate, octacarbonyl nicobalt, dodecacarbonyltetracobalt, hydridetetracarbonylcobalt, hexacarbonylbis(
Various cobalt compounds are used, such as nicobalt (tri-n-butylphosphine).

The nickel compound or cobalt compound is effective as a main catalyst even when used alone, but both metals or metal compounds can also be used in combination.

As mentioned above, the metal catalyst is based on the use of nickel or cobalt, and catalysts containing nickel as a metal component are particularly effective.

Suitable (
R2>\Rogenide is bromide or iodide or a mixture 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, it is also effective to introduce into the reaction solution a substance that generates any one or more of these halides, ie, alkyl halides, acid halides, and hydrogen halides.

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, lithium, rubidium, cesium,
In the case of metal halides such as magnesium, calcium, strontium, barium, silicon, germanium, and tin, they are also used as co-catalysts, which will be described later.

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, (R3) an organic nitrogen group compound containing phosphorus or nitrogen is used together with the above nickel or cobalt component and halide.

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

(I) Trivalent organic nitrogen group compound Compound (where M represents N or P.

) (a) R1, R2, R3 are hydrogen or have 1 to 1 carbon atoms
0 saturated alkyl group, cycloalkyl group or aryl group, each of which may be the same or different from each other M=N Monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, dimethylethylamine, tri- Amines such as propylamine, tri-1so-propylamine, tri-n-butylamine, tri-tert-butylamine, aniline, dimethylaniline, diethylaniline, dimethylbenzylamine, toluidine, triphenylamine, cyclohexylamine M=P tri-propyl Phosphine, T'J-is.

Phosphines (b) such as propylphosphine, tri0-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, triphenylphosphine, etc. R1 is hydrogen, or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group. Cyclic compounds such as pyrrolidine, N-methylpyrrolidine, piperidine, and N-phenylpiperidine (c) Bl and B2 are hydrogen or carbon atoms 1 to 1;
0 saturated alkyl group, cycloalkyl group, or aryl group, each of which may be the same or different from each other.

R3 is a compound representing a saturated aliphatic acyl 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, and R2t
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 rest are hydrogen or have 1 to 1 carbon atoms
Carboxylic acids such as N, N-dimethylglycine, N,N-diethylglycine, iminodiacetic acid, N-methyldiiminoacetic acid, nitrilotriacetic acid, etc. Derivatives (Bl Compounds represented by the general formula N3C-Ft, in which R is a saturated alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms; organic compounds including nitriles such as acetonitrile, propionitrile, and benzonitrile) Nitrogen group compound (However, M12M2 is N.

P, and may be the same or different.

) (a) R,, R2, Ft3. Ft represents hydrogen or a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, and R6 represents a saturated alkyl group having 1 to 10 carbon atoms;
Compounds representing 10 polymethylene groups, phenylene groups, or carbonyl groups Ml, N2=N, PM ethylenebis(diphenylphosphine), phenylenebis(dimethylphosphine), N,N,N',N'-tetramethylethylenediamine, N , N', N',
N'-tetraethylethylenediamine, N, N, N',
N'-tetra-n-7'lopylethylenediamine, N
,N.

N,N-tetramethylmethylenediamine, N,N,N'
, N'-tetramethylurea, N nonal-2-pyrodinone, triethylenediamine, etc. (b) R1t ``a is hydrogen, a saturated alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or an aryl group, chicken, R4 piperazine, N-methyl-piperazine, N-ethyl-piperazine, 2-methyl-N.

Cyclic compounds such as N'-dimethylpiperazine (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
) Compounds such as octane, methyl-substituted 1,4-diazacyclo[2,2,2]octane, adiponitrile N-methylmorpholine (n) Heterocyclic compounds pyridine and alkylpyridines: pyridine α-picoline, β-picoline, γ- Picoline, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2-
Propylpyridine, 4-propylpyridine, 4-butylpyridine, 4-inbutylpyridine, 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-nonyl)-pyridine, 2,6-dipropylpyridine, 2-methyl-3-ethyl-6-propylpyridine, 2,6 diethylpyridine , 2,6-dipropylpyridine, 2,6-sibutylpyridine, 2,6-di-t
-Butylpyridine; 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, dipicolinic acid, dipicolinic acid, cinchometronic acid, 5 -butyl-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-ethyl Pyridine, 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-dipyridine Hydroxypyridine, 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-cinthi Lupyridine, 4-amino-3,5-
Dichloropyridine, pyridine N-oxide, α-picoline-N-oxide, β-picoline-N-oxide, γ-
Picoline N-oxide, 2,6-lunasine-N-oxide, 3,5-lutidine-N-oxide, 4-phenylpropylpyridine-N-oxide, ■.

3-di(4-pyridyl)-propane di-N oxide,
4-(5-nonyl)-pyridine-N-oxide, 2-chloropyridine-N-oxide, 4-cyanopyridine-N-
oxide, 2-pyridine methanol, 3-pyridine methanol.

4-pyridine methanol, 2,6-pyridine methanol, 2-pyridine ethanol, 4-pyridine ethanol,
3-picolylamine, 4-picolylamine, 2-methylaminoethylpyridine, 4-alkylaminoethylpyridine, 4piperidinoethylpyridine, 4-(4-pipecolinoethyl)-pyridine, 4-morpholinoethylpyridine; cyclic compound Containing pyridines: 2-phenylpyridine,
4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 4-7enylpropylpyridine, 4,
4'-dipyridyl 4-4'-dimethyl-2,2/-dipyridyl 1゜3-di(4-pyridyl)propane, 1,
2-di(4-pyridyl)-ethane, 1,2-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-8-triazine, 2,5-di(4-pyridyl)S-tetrazine; Alkenylpyridine and high molecular weight pyridines: 2-vinylpyridine, 4-vinylpyridine, 2-vinyl-6-methyl-pyridine, 2 -vinyl-5ethylpyridine, 4-butenylpyridine, 4-vinylpyridine homopolymer, 2
-vinylpyridine homopolymer, 2-vinylpyridine copolymer, 4-vinylpyridine-acrylonitrile-copolymer, 4-vinylpyridine-styrene-copolymer, 4-vinylpyridine-divinylbenzene-copolymer, 2-vinylpyridine-divinylbenzene copolymer,
4-vinylpyridine homopolymer-N-oxide; Pyrroles: Pyrrolines: Pyrimidines: Pyrazines:
Pyrazole: Pyrazoline: Pyridazine: Imidazole: 1,10-7 enanthroline and its derivatives:
1.10-7 enanthroline, 4-chloro-1,10
-phenanthroline, 5-(thiapentyl)-1,10
7 Enanthroline: 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 compounds are phosphine compounds containing trivalent phosphorus, carboxylic acid amides, or heterocyclic compounds typified by pyridine.

The (al) nickel or cobalt component and (I2
) halides and (I3) phosphorus or nitrogen-containing organic nitrogen group compounds. Catalysts are effective by themselves, but their activity is low, and as co-catalysts (bl) one or two of silicon, germanium, or tin. When more than one metal or metal compound is used, extremely high catalytic activity is exhibited and a fast reaction rate can be obtained.

(bl) Silicon, germanium, and tin are used as the promoter metal, and tin is particularly preferred.

Cocatalyst forms are available in any type.

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-C6 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 , phosphites, acetylacetone salts, sulfides, and compounds coordinated with ammonia, cyanide, amines, amino acids, etc., or organometallic compounds to which phenyl groups and alkyl groups are bonded.

To give some examples, H2SiO3゜H45i04
, 5iHBr3.5iHe, //l, SiHF3,
5iHI3゜Sr, St (OCH3)425t2
Br6 t 5tBr4j 5tBrH3゜5tBrC
, /, , 5tBr2Ct2.5IBrsC1, 51
2C4゜S iC74t S s CAH3j 5IF
4? S tF4 t 5tI(4t 5i2N(6
tSi3H3,5i4H1o, SiI2.5i2I6
, SiI4,5iIC4゜SiO2・)G(20,
5i02, 5i20C41, SiS, SiS2
.

Ge, GeBr, , GeCl2. GeCl4
．． GeHC/,,GeF,・3H20,GeH,,G
eI2, GeI, , GeO, Gem2゜(3e
OC/-,,GeS,Ge52. Sn, 5n
Br, , 5nC4.

SnF, , 5nI4.5no2.5nOC4, 2S
n02'P2O5''10H20, SnP, Sn(S
O4)2”2H20,5nS2゜5nBr2y 5nC
4s snF'2j Sn(OH)2, SnI2
゜5nC204, SnO, 5nO-8nC4・3H20
,5nS04゜SnS,Sn(CH3)4,5n(CH
3)2. Sn(C2H5)4゜5n(CaH5)4,
(C3H7)2snH2, (CH3)2SnI2.

(CH3)25nC4, Sn (C2H5)2, (
C4H9)2SnC4.

(C2H5)2SnI2, (CH3)3SnC7, (
C4H9)2SnH2゜(C3H7)2 S n I2
, (CHs)s (CH2I)Sn, (C4Hg
)3SnC4(C4HQ)2SnI2, (C2)L
s)3SnC,/, (C,H,)3SnH.

(C2H5)3SnHt (C6H5CH2)3Sn
C1s 5n (C2H302)2 pSn (C2H5
02) 4j PtH (SnC, /, χC0) (Pph
3) 2,5rIHPO4°, etc.

Considering that the catalyst is a halide of bromide or iodide and the desired product is a carboxylic acid, it is a preferred practice to use a cocatalyst metal compound in the form of a halide of bromide or iodide or a carboxylic acid salt such as acetic acid. It is a mode.

As mentioned above, the use of metal components of silicon, germanium, and tin is effective, but in addition, as a cocatalyst (bi) one or more metals of silicon, germanium, and tin in the periodic table or compounds of these metals. and (b2) lithium, rubidium, cesium, magnesium, calcium in the periodic table,
When one or more metals selected from the group consisting of strontium and barium or compounds of these metals are used in combination, the reaction rate is further increased than when the metal components of silicon, germanium, and tin are used alone.

That is, (bl) silicon, germanium, tin and (b
2) IJ When two or more metals such as thium, rubidium, cesium, magnesium, calcium, strontium, and barium or compounds of these metals are used together, a synergistic effect is obtained.

The effective co-catalyst (b2) used in combination is one or more metals or metal compounds selected from the group consisting of rhium, rubidium, cesium, magnesium, calcium, strontium, and barium.

Among these, lithium, calcium, and strontium are particularly preferred.

The co-catalysts used are based on the use of lithium, rubidium, cesium, magnesium, calcium, strontium, barium metals or compounds of these metals, but they can be used in any arbitrary form.

For example, the metal itself or in finely divided form;
Raney metal forms or carbonates, acids arsenides, hydroxides, nitrates, phosphates, halides, cyanides, thiocyanides, sulfonates, C1 to C6 lower alkoxides such as methoxides or ethoxides, phenoxides, carboxy Metal carboxylates, oxyhalides, hydrides, nitrites, sulfites, phosphites, acetylacetone salts, sulfides, and ammonia, cyanide, amines whose ions are derived from alkanoic acids with 1 to 20 carbon atoms. There are compounds coordinated with amino acids, etc.

Examples of ~ part are Lo, LiC2H502・2H
20, LiAlO2, LiNH2゜L' BO2, Li
2B4O7" 5H20, LiBr, LiBr"
2H20゜Li2SO3, LiHCO3, LiCto3
．． LiCto3・0.5H20゜L' C1, L 1
3C6H, 07・4H20, Li2S206・2H20
゜LiF, Li2 [5iFal・2H20, LiHC
O2・H20, Li2C2O4, Li0H-H20, L
iI, LiI・3H20, L t NO3・L +
N03・3H20, LiNO2・H20, Li2C2O
4, LiH et al. O4・H20, Li2O, LiCto,
, LiCto, ・3H20, LiMnO4゜i, 1
3po, , Li3PO4・12H20t Li2S
206, Lt4St04゜Li2SO4, Li2SO
4.H20, LiH8O4, Li2S.

Li2SO3, Rh, RbBrO3, BbBr,
BbBrs, Bb2CO3.

RbHCO3, Rb2SO4, RbCt, RbF, Rb
H2RbOH2 rib■03. Rb■, Rb■3. RbNO
3, Rb2O, Rb202°Rb203, Rb20
4, Rbcto4. Rbl0+, RbMn0
．． .

Rb25e04, Rb2SO4, Rb25, R
b25 ・4H20, Rb25s.

Rb(C2H302), Cs, CsBr03j
CsBr, CsBr3tCs2CO3, Cs
HCO3, CsC, /, ,' CsCN, CsF
, CsH.

CsOH, CsIO3, CsI, C5I3. Cs
NO3, CsNO2゜Cs2O, Cs202, Cs
203, Cs204, C2Ct04. Cs IO
4゜CsMnO4, Cs5SiW12042, Cs
2SO4, CsH804°C52S ” 4H20, C
52S2, Cs282”H20, C52S3Cs
2Ss, C5HC4H406, C3(C2H302
), Mg.

Mg (C2H502)2t Mg(C2H502)
2・4H24H2O2・A403. MgC4・NH,C
t・6H,0,MgNH,PO,・6H20t Mg
S04・(NH4), SO4・6J(20,Mg
(BO2)2・8H202Mg(BrOs)2'6H2
0, MgBr2. MgBr26H202MMgBr
26H2O2・3H20,3MgCO3・Mg(OH)
2.3H205H2O2?)2.6H20゜Mg C
42M g C4t Mg C4・6H206H2O2
.

Mg[l5tF6)・6H20s Mg(OH)2. H2PO□2・6H26H2O2■03)2・4H
20, Mg I2, Mg (NO3)2・6 H2
02Mg 3N2 t Mg ”204・2H202H
2O2 pigeon Cω4)2・6H20y Mg (MnO,)
2” 6H20, Mg5(P 04)2 ・4H20
.

Mg5(PO4)2・8H20, MgHPO,・3H2
0, MgHPO, 7H202Mg2P2072Mg7
H2O2・3H202M5H2O2・3H20, MgC
4・KC7・6H2026H2O2・K2SO4・6H
20, MgC4-NaC7-H20, Mg5O,, Mg
S04-7H2MgSO4-7H202・6H20s
Mg (C4H406)・5 H202Mg 8203
” 6H20, Ca, Ca (C2H2O2)2
H20, Ca(nω2)2. CaO-At203・2S
i02゜CaNH, As 04 ・6H20, CaNH
, P 04 ・7 H205Ca3(As04 )2
, Ca(BO2)2''2H20, CaB6.

Ca(BrO3)2 ・H20, CaBr2,
CaBr2.6 H20゜CaC2, CaCO3, Ca
(CtO3)2・2H20, CaCl2゜CaCl2
"H20, CaCl2" 6H20, Ca3 (C6
H507)2"4H20, Ca (CN)2.C
aCN2, Ca5206"4H20, CaF2.

Ca(SiF6'J, CaC3iF6)-2H2o
, Ca(HCO2)2yCaH2, Ca(SH)2・
6H20, Ca(OH)2. Ca(CtO)2・4H2
0, Ca(I03)2. CaI2. CaI2・6H20
゜Ca(C3H603)2・5H20, CaO-MgO
・2CO2, CaO・MgO・2 S I02. Ca
MoO4, Ca(NO3)2. CaeJOs ) 2”4
H20p Ca3N2 j Ca (NO2)2 ・H
20p CaC2O4, CaOsCa(Mn04)2-
4H20, CaO2-8H20, CaHPO4-2H2
0, Ca2P2Q, ・Another, 0. Ca(PO3)2. C
a(H2PO4)2”H20.

Ca2P2O7, Ca2P2O7°5H20, Ca3
(PO4)2-2CaHPo3” 3H20, Ca
(H4F 02 )2 , CaX2 (804)2'H
20, CaSiO3, CaSi2. Ca5O,,2N
a25o4-2 H20, CaSO4, CaSO4"
2H20, CaSO4” 0.5H20°CaS,
CaSO3”2H20, CaC4H406”4H2
0, CaC83°Ca(SCN)2-3H20, Ca5
203-6H20, CaWO4, Sr.

5r(C2H2C2)2,5rB40□・4H20,5
r(BrO3)2・H20, 5rBr2.5rBr2-
6H20, SrCO3,5r(C,m3)2.

5r(CtO3)2・8H20,5rC1,2,5r(
CN)2・4H20゜5rS206-4H20,SrF
2. Sr[l5iFol) -2H20゜5r(HC
O2)2,5r(HCO2)2・2H20,5r(SH
)2゜Sr(OH)2, Sr(OH)2”
8H20, Sr(IO3)2 y SrI2.

SrI2 ・6H20, Sr(NO3)2, Sr(
NO3)2 ・4H20゜5r(NO2)2 ,5r(
NO2)2-n2o, 5rC204”H20tSrO
,5r02. 5r02 * 8 H20, Sr(M
nO+)2 ・3H20.

5rI(PO4,5rSi03.5rS04.Sr
(H8O4)2. SrS.

5rS4-6H20, 5rSO3, 5r(CNS)2-
3H20.

5rS203 ・5 H20j Bat Ba((<
H30z)2, Ba(C2H302)2・H20, B
a(NH3)p, Ba3(As04)2, Ba520
3”H20゜Ba(N3)2.Ba(Na)2・H2
0, Ba(BrOa)2”H20.

BaBr2. BaBr2,2H20,Ba[PtBr6
]・10H20,BaC2゜BaC0a, Ba (
CtOs)2, Ba(Cto3)2”H2
0, BaC'2.

BaC, /, H2H20, BaCH2, Ba5206
#2H20t BaF2.

Ba [IS iF6 ), Ba (HCO2)2
t BaH2, Ba (5H)2 ”4 H20, B
a (OH)2. Ba (OH)2-8 H20,B
a(C,ω)2゜BaPOa, Ba (H2PO2
)2 ” H20, B=<l03)2.Ba(IO3)
2'H20, Ba % -2H20t Ba I2 ・
6H20, BaMn 04 .

BaMo0. , Ba(NOa)2. Ba(NO2
)2. Ba(NO2)2'H20, BaC2O4
, BaO, Ba(ClO2)2, Ba(CI, o
,),,”3H20,Ba(Mn04)2.BaO2
, BaO2-8H, 20°Ba 52o8” 4H20
1BaHPo4j Ba (H2PO4)2 *Ba
2P207 , I3a 3 (PO4)2 , Ba S
103. BaS l 03”6H20.

BaSO4, BaS, Ba54 + 2 H20,
Ba5s, BaSO3.

I3a (CNS)2-2H20, Ba5203-
H20 etc.

Considering that a halide of bromide or iodide is used as a catalyst and that the desired product is a carboxylic acid, a co-catalyst is used in combination with a halide of bromide or iodide or a carboxylic acid salt such as acetic acid. This is a preferred practice.

The amount of the nickel or cobalt metal or compound of the metal used in the present invention is 10-6 to 5 mol, preferably 10-5 mol per 1 based on the total volume of the reaction solution.
A range of 4 to 4 mol, more preferably 10-3 to 2 mol, most preferably 5 x 10-3 to 1.0 mol 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 on a halogen atom basis.
It is used in a range of 8 mol.

The amount of the organic nitrogen group compound containing phosphorus or nitrogen is related to the amount of the nickel or cobalt metal component used, but it is usually 10-1/1 based on the total volume of the reaction solution.
The range is selected from 6 to 10 mol, preferably from 10-4 mol, more preferably from 10-3 to 2.5 mol.

The amount of silicon, germanium, tin metal or a compound of the metal used as a co-catalyst is 0.01 to 100, preferably 0.03 to 30. More preferably, it is used in the range of 0.1 to 20, but the amount used is usually 10-6 to 30 mol, preferably 10-4 to 20 mol, based on the total volume of the reaction solution.
More preferably, the range of 10-3 to 10 mol is selected.

The amount of the co-catalyst lithium, rubidium, cesium, magnesium, calcium, strontium, barium or a compound of these metals is 0.01 to 100, preferably 0, based on the metal atom based on the group (I) metal component. .03-30°, more preferably 0.1-20
The amount used is usually 10-6 to 30 mol, preferably 10-4 to 20 mol, more preferably 10-3 to 20 mol, based on the total volume of the reaction solution.
A range of 10 moles is chosen.

In the above range, lithium, rubidium, cesium, magnesium, calcium, strontium, barium metals or compounds of these metals include silicon, germanium,
1 on a metal atom basis for tin metal or its compounds
It is used in the range of 0-3 to 10, preferably 10-2 to 102, more preferably o, i 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 more optimal partial pressure is 3 to 150 atm.
Although it is atmospheric pressure, a wider partial pressure range of 0.05 to 5000 atmospheres may also be used.

In the present invention, the alcohol used as a raw material is a hydrocarbon alcohol having 1 to 11 carbon atoms.

These alcohols include methanol, ethanol,
Examples include propatool, butanol, pentanol, hexanol, decanol, benzyl, alcohol, etc.

The above alcohol is CO+ ROH-+RCOOH (1) (R is an alkyl group having 1 to 10 carbon atoms, an aryl group, a phenyl group, or a benzyl group).

), the corresponding carboxylic acid is produced.

For example, methanol produces acetic acid, and ethanol produces propionic acid.

Further, in the present invention, it is possible to use carboxylic acid esters and ethers corresponding to the alcohols as raw materials, and the use of these raw materials is included in the present invention.

When these carboxylic acid esters and ethers are used as raw materials, the chemical reaction formula (1) is slightly different and becomes as follows.

For example, when methyl acetate or dimethyl ether is used as a raw material, acetic acid is produced.

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 be contained in nitrogen, rare gas, etc.

Among these, hydrogen in the reaction gas has a tendency to stabilize the catalyst, and in many cases has a favorable influence on the progress of the reaction.

However, extremely low purity carbon monoxide is undesirable because it increases the pressure in the reaction system.

In the method of the present invention, the raw material alcohol such as methanol or the product carboxylic acid such as acetic acid itself serves as the reaction solvent, so it is not necessary to use a solvent, but it is compatible with the raw materials and products in the reaction environment. It is.

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, methanol, methyl acetate, water and acetic acid, acetic anhydride.

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

Diluents that can generally be used include organic acids such as propionic acid, butyric acid, octanoic acid, phthalic acid, and benbroic acid, methyl acetate, ethyl acetate, ethylene glycol diacetate, and propylene glycol diacetate. Carbonization of organic acid esters such as dimethyl adipate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, dioctyl heptathalate, phenyl acetate, tolyl acetate, dodecane, hexadecane, benzene, naphthalene, biphenyl, etc. Hydrogens, inorganic acid esters such as triphenyl phosphate, tricresyl phosphate, dibutylphenyl phosphate, tetramethyl orthosilicate, tetrabutyl silicate, aromatic ethers such as diphenyl ether, acetone, methyl ethyl ketone, dibutyl ketone, methyl isobutyl ketone,
Examples include ketones such as acetophenone and benzophenone.

In the present invention, it is possible to maintain the reaction system in a substantially anhydrous state and simultaneously produce the corresponding acetic acid and acetic anhydride using, for example, methanol and methyl acetate or dimethyl ether as raw materials.

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

The method of the present invention, which has been explained in detail above, produces carboxylic acid by reacting hydrocarbon alcohol and carbon monoxide while maintaining a high activity of an inexpensive catalyst, and has extremely high industrial significance. be.

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

Example 1 Methanol 25.6f, acetic acid 24. Of, nickel powder 0.415S', 2,4-lutidine 1.52y, methyl iodide 14? , filled with 4.43P of stannous iodide in a pressure-resistant reactor, and heated at 80 kVC at a reaction temperature of 180°C.
, total pressure of G (-carbon oxide 55 kVC4, hydrogen 10
/cd).

During the reaction, the pressure decreased, so -carbon oxide was introduced to keep the reaction pressure constant.

When analyzed after 2 hours, acetic acid was determined to be 96.5% of the raw methanol.

Examples 2 to 14 The results of almost the same operations as in Example 1 are summarized in a table.

Reference example 1 As a system using a 0-dium catalyst, Japanese Patent Publication No. 47-3334
Example 2 is also listed as Reference Example 1.

Claims (1)

[Claims] 1. Hydrocarbon alcohol and carbon monoxide are reacted in the presence of a catalyst containing nickel or cobalt, a halide such as bromide or iodide, and an organic nitrogen group compound containing phosphorus or nitrogen. 1. A method for producing a carboxylic acid, which comprises using one or more metals of silicon, germanium, and tin, or a compound of these metals as a cocatalyst. 2. Claim 1 further uses, as a promoter, one or more metals selected from the group consisting of lithium, rubidium, cellulum, magnesium, calcium, strontium, and barium, or compounds of these metals. Manufacturing method described.