GB1575260A - Production of esters from nitrile - Google Patents
Production of esters from nitrile Download PDFInfo
- Publication number
- GB1575260A GB1575260A GB15753/78A GB1575378A GB1575260A GB 1575260 A GB1575260 A GB 1575260A GB 15753/78 A GB15753/78 A GB 15753/78A GB 1575378 A GB1575378 A GB 1575378A GB 1575260 A GB1575260 A GB 1575260A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nitrile
- water
- hydroxyl compound
- process according
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000002825 nitriles Chemical class 0.000 title claims description 28
- 150000002148 esters Chemical class 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- -1 cyano- Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 14
- 239000007858 starting material Substances 0.000 claims description 13
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 239000007806 chemical reaction intermediate Substances 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- FUKWTMJZHKZKFA-UHFFFAOYSA-N 4-cyanobenzamide Chemical compound NC(=O)C1=CC=C(C#N)C=C1 FUKWTMJZHKZKFA-UHFFFAOYSA-N 0.000 claims description 5
- ADCUEPOHPCPMCE-UHFFFAOYSA-N 4-cyanobenzoic acid Chemical compound OC(=O)C1=CC=C(C#N)C=C1 ADCUEPOHPCPMCE-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- STQPCKPKAIRSEL-UHFFFAOYSA-N 2-cyanobenzamide Chemical compound NC(=O)C1=CC=CC=C1C#N STQPCKPKAIRSEL-UHFFFAOYSA-N 0.000 claims description 4
- DTNSDCJFTHMDAK-UHFFFAOYSA-N 2-cyanobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C#N DTNSDCJFTHMDAK-UHFFFAOYSA-N 0.000 claims description 4
- RSGBXCFAYHOKQZ-UHFFFAOYSA-N 4-(cyanomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CC#N)C=C1 RSGBXCFAYHOKQZ-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 230000002349 favourable effect Effects 0.000 claims description 4
- 238000004811 liquid chromatography Methods 0.000 claims description 4
- YJMNOKOLADGBKA-UHFFFAOYSA-N naphthalene-1-carbonitrile Chemical compound C1=CC=C2C(C#N)=CC=CC2=C1 YJMNOKOLADGBKA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011973 solid acid Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000005690 diesters Chemical group 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 claims description 3
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical group N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 3
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 3
- NWPNXBQSRGKSJB-UHFFFAOYSA-N 2-methylbenzonitrile Chemical compound CC1=CC=CC=C1C#N NWPNXBQSRGKSJB-UHFFFAOYSA-N 0.000 claims description 2
- PAQVSWFCADWSLB-UHFFFAOYSA-N 3-cyanobenzamide Chemical compound NC(=O)C1=CC=CC(C#N)=C1 PAQVSWFCADWSLB-UHFFFAOYSA-N 0.000 claims description 2
- GYLKKXHEIIFTJH-UHFFFAOYSA-N 3-cyanobenzoic acid Chemical compound OC(=O)C1=CC=CC(C#N)=C1 GYLKKXHEIIFTJH-UHFFFAOYSA-N 0.000 claims description 2
- GZPHSAQLYPIAIN-UHFFFAOYSA-N 3-pyridinecarbonitrile Chemical compound N#CC1=CC=CN=C1 GZPHSAQLYPIAIN-UHFFFAOYSA-N 0.000 claims description 2
- JMHSCWJIDIKGNZ-UHFFFAOYSA-N 4-carbamoylbenzoic acid Chemical compound NC(=O)C1=CC=C(C(O)=O)C=C1 JMHSCWJIDIKGNZ-UHFFFAOYSA-N 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical class NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 150000001916 cyano esters Chemical class 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- ZBFVJRBOKDTSMO-UHFFFAOYSA-N naphthalene-2,6-dicarbonitrile Chemical compound C1=C(C#N)C=CC2=CC(C#N)=CC=C21 ZBFVJRBOKDTSMO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
- C07C67/22—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group from nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
Description
(54) IMPROVEMENTS IN OR RELATING TO THE PRODUCTION OF ESTERS
FROM NITRILES
(71) We, THE LUMMUS COMPANY, a Corporation organised and existing under the
Laws of the State of Delaware, United States of America, of 1515 Broad Street, Bloomfield
New Jersey 07003, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
This invention relates to the production of carboxylic acid esters, and more particularly, to the production of carboxylic acid esters from nitriles.
According to this invention, there is provided a process for producing a carboxylic acid ester, comprising reacting a nitrile with at least stiochiometric proportions of water and at least stiochiometric proportions of a hydroxyl compound in the vapour phase at a temperature above the dew point of the product ester, hydroxyl compound and nitrile in the presence of a solid acid catalyst to produce the corresponding carboxylic acid ester, the mole ratio of the hydroxyl compound to nitrile being maintained at less than 500:1.
The organic nitrile which is employed for producing esters in accordance with the present invention is preferably either an aromatic or heterocyclic nitrile. The aromatic nitriles contain one or more cyano-groups, preferably one or two cyano-groups, and can be unsubstituted or substituted with other substituent groups, e.g. an alkyl, carboxyl or amide group. The aromatic nucleus is preferably benzene or naphthalene. As representative examples, there may be mentioned phthalonitrile, terephthalonitrile, isophthalonitrile, benzonitrile, tolunitrile, 1-cyanonaphthalene, and 2,6-dicyanonaphthalene, 2-, 3-, or 4- cyanobenzoic acid and 2-, 3- or 4- cyanobenzamide. Similarly, the heterocyclic nitriles can contain one or more cyano-groups, with the heterocyclic nucleus generally being pyridine. The preferred starting materials are nicotinonitrile, isophthalonitrile, terephthalonitrile and phthalonitrile.
In the case where the nitrile includes a carboxyl or amide substituent such substituent is esterified by the alcohol and the cyano-group is both hydrolysed and esterified to produce a diester. Thus, for example, reaction between methanol and 4-cyanobenzamide or 4-cyanobenzoic acid will produce dimethylterephthalate.
The hydroxyl compound can be either an alcohol or a phenol. The alcohol is preferably an alcohol of an aliphatic hydrocarbon and in particular an alkanol, preferably an alkanol of from 1 to 12 carbon atoms, most preferably 1-4 carbon atoms, with methanol being most preferred. As representative examples of suitable alcohols, there may be mentioned methanol, propanol, butanol and octanol. The alcohol is selected so that the resulting ester is in the vapour phase under the reaction conditions.
The catalyst employed for the vapour phase hydrolysis step of the invention is a solid acid catalyst. As representative catalysts, there may be mentioned silica gel, silica-alumina, supported phosphoric or boric acid or mixtures thereof, Group III metal phosphates and sulphates, e.g., phosphates and sulphates of aluminium, boron and gallium, transition metal oxides, e.g., one or more oxides of vanadium, chromium, manganese, iron, cobalt or nickel.
The catalysts are of the type employed for hydration, dehydration and esterification reactions. The preferred catalyst is supported phosphoric acid alone or in admixture with boric acid.
The nitrile, water and hydroxyl compound are reacted, in the vapour phase, at temperatures which are generally from 300"F to 900"F, and preferably of from 500"F to 7000F. The temperatures which are employed are above the dew point of both the feed and product components.
The water is employed in at least stoichiometric proportions (one mole of water per mole of cyano- ), however, an excess of water is preferably employed in that reactionXrmodynam- ics and kinetics are more favourable at higher water partial pressures. The stoichiometric excess of water can be as much as to provide a water to nitrile mole ratio of up to 500:1 with the water to nitrile mole ratio generally being from 1:1 to 50:1.
The hydroxyl compound is employed in at least stoichiometric proportions, i.e., at least one mole of hydroxyl compound per mole nitrile group. However, an excess of hydroxyl compound is preferably employed, in that reaction kinetics and thermodynamics are more favourable at higher hydroxyl compound partial pressures. For practical reasons the mole ratio of hydroxyl compound to nitrile is maintained below 500:1, with the ratio generally being from 5:1 to 50:1. If the hydroxyl compound has a high volatility, e.g., methanol, then if used in excess it also functions to maintain vapour phase conditions. However, an inert gaseous diluent, such as nitrogen, can be used for such purpose.
The total reaction pressure is generally selected to provide the desired alcohol/water partial pressure, with such total pressures generally being from 1 to 10 atm.
The catalytic vapour phase reaction may be effected by any one of a wide variety of reaction techniques, including fixed bed, fluidised bed and dilute phase transport, and the selection of a specific technique is deemed to be within the scope of those skilled in the art from the present teachings.
The gaseous reaction effluent contains, as major components, the ester reaction product, ammonia, water vapour, unreacted starting material and reaction intermediates, e.g., amides and acids, and in the case of a starting material having at least two cyano-groups, the reaction intermediates further include cyano-acids (e.g., 4-cyano benzoic acid) cyano-amides (4cyanobenzamide), amide-acids (e.g., terephthalamic acid) and cyano-esters (e.g., 4-cyanomethylbenzoate). The reaction intermediates, as well as unreacted starting material (nitrile and alcohol), can be recovered by procedures known in the art and recycled to the reaction. Ammonia present in the effluent can be recovered and employed for producing nitrile starting material. The recovered product is a diester when the starting material is a dinitrile, a cyanobenzoic acid or cyanobenzamide.
In order that the invention may be more readily understood, the invention will be further described with respect to the following Examples.
Example I
A solid phosphoric acid catalyst was prepared on diatomaceous earth according to the method outlined by F.G. Ciapetta and C.J. Plank in Catalyst Vol. 1, p.344, (Rheinhold (1954).
Fifty millilitres of the prepared catalyst was charged into a vertical reactor, made from 3/4"
O.D. tubing, and maintained at 5720F. Terephthalonitrile was introduced into the reactor, from a heated stainless steel reservoir as a vapour entrained in a stream of nitrogen. The flow of nitrogen was adjusted to pass 0.126 g. of terephthalonitrile (TPN) into the reactor per hour. Simultaneously, a solution containing 5.3 wt. % water and 94.7 wt. % methanol was introduced into the reactor by means of a syringe pump, at a rate of 3.06 ml per hour, and such mixture was immediately vaporised. The effluent was collected in a cold trap. After three hours, the contents of the cold trap were analysed by liquid chromatography and found to contain 0.16 g. of dimethylterephthalate (DMT), out of a total 0.49 g. of product.
Example II
An experiment was carried out as described in Example I, except that the reactor was charged with a catalyst prepared by impregnation of alumina spheres with 18.7 wt. % H3PO4/H3BO3 in 2/1 mole ratio. The catalyst was treated with a vaporised 10% ammonia solution for one hour and flushed with nitrogen prior to the run.
TPN was charged into the reactor at a rate of 0.82 g/hr., and a solution of 6 wt. %water and 94.0 wt. % methanol at a rate of 3.06 ml per hour. The solution was immediately vaporised.
After five hours, the cold trap was found to contain 4.40 g. of product. Analysis by liquid chromatography revealed 0.75 g. of DMT, 1.46 g. TPN and 1.84 g. of 4-cyanomethylbenzoate. Excess methanol was recovered as dimethylether.
The present invention has been found to be particularly advantageous in that it makes it possible to produce carboxylic acid esters without utilising the carboxylic acid or salt thereof as a starting material. The carboxylic acid or salt, in particular, terephthalic acid or salt, is difficult to vaporise and, therefore, complicated equipment is required for effecting such volatisation. In addition, the carboxylic acid is generally prepared from a nitrile, which requires an additional step.
In preferred methods in accordance with the present invention, hydrolysis and esterification is effected in a single reactor, under mild conditions, by proceeding in the vapour phase.
WHAT WE CLAIM IS:
1. A process for producing a carboxylic acid ester, comprising reacting a nitrile with at least stiochiometric proportions of water and at least stiochiometric proportions of a hydroxyl
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (14)
1. A process for producing a carboxylic acid ester, comprising reacting a nitrile with at least stiochiometric proportions of water and at least stiochiometric proportions of a hydroxyl
compound in the vapour phase at a temperature above the dew point of the product ester, hydroxyl compound and nitrile in the presence of a solid acid catalyst to produce the corresponding carboxylic acid ester, the mole ratio of the hydroxyl compound to nitrile being maintained at less than 500:1.
2. A process according to claim 1, wherein the nitrile is phthalonitrile, terephthalonitrile, isophthalonitrile, benzonitrile, tolunitrile, 1-cyanonaphthalene, 2, 6-dicyanoaphthalene, 2-, 3- or 4-cyanobenzoic acid, 2-, 3- or 4-cyanobenzamide, or nicotinonitrile or mixtures thereof.
3. A process according to claim 1 or claim 2, wherein the hydroxyl compound is an alkanol having from 1 to 12 carbon atoms.
4. A process according to any one of the preceding claims, wherein said reacting is effected at a temperature of from 300"F to 9000F.
5. A process according to claim 3, wherein said reacting is effected at a temperature of from 500"F to 7000F.
6. A process according to any one of the preceding claims, wherein the hydroxyl compound is methanol.
7. A process according to any one of claims 1 to 5, wherein the hydroxyl compound is an alkonol having from 1-4 carbon atoms.
8. A process according to any one of the preceding claims, wherein the nitrile is terephthalonitrile.
9. A process according to any one of the preceding claims, wherein the catalyst is supported phosphoric acid.
10. A process according to claim 9, wherein the phosphoric acid is in admixture with boric acid.
11. A process according to any one of claims 1 to 8, wherein the solid acid catalyst is silica gel; silica alumina; supported phosphoric acid or boric acid or mixtures thereof; a phosphate or sulphate of a Group III metal; or a transition metal oxide.
12. A process of producing a carboxylic acid ester, substantially as herein described in
Example I.
13. A process of producing a carboxylic acid ester, substantially as herein described in
Example II.
14. Carboxylic acid ester whenever prepared by a process according to any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79214677A | 1977-04-29 | 1977-04-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1575260A true GB1575260A (en) | 1980-09-17 |
Family
ID=25155940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB15753/78A Expired GB1575260A (en) | 1977-04-29 | 1978-04-20 | Production of esters from nitrile |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS6030302B2 (en) |
| DE (1) | DE2817508A1 (en) |
| FR (1) | FR2388787A1 (en) |
| GB (1) | GB1575260A (en) |
| IT (1) | IT7848982A0 (en) |
| NL (1) | NL7804412A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483199A (en) * | 2013-09-02 | 2014-01-01 | 浙江海昇化学有限公司 | Preparation method of tetrafluoroterephthalate |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2898356B1 (en) * | 2006-03-07 | 2008-12-05 | Rhodia Recherches & Tech | BRANCHED CARBOXYLIC ACID DIESTERS |
| FR2903983B1 (en) * | 2006-07-18 | 2010-07-30 | Rhodia Recherches & Tech | PROCESS FOR PRODUCING DIESTERS |
-
1978
- 1978-04-19 IT IT7848982A patent/IT7848982A0/en unknown
- 1978-04-20 GB GB15753/78A patent/GB1575260A/en not_active Expired
- 1978-04-20 JP JP53047151A patent/JPS6030302B2/en not_active Expired
- 1978-04-21 DE DE19782817508 patent/DE2817508A1/en not_active Ceased
- 1978-04-25 NL NL7804412A patent/NL7804412A/en not_active Application Discontinuation
- 1978-04-27 FR FR7812472A patent/FR2388787A1/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103483199A (en) * | 2013-09-02 | 2014-01-01 | 浙江海昇化学有限公司 | Preparation method of tetrafluoroterephthalate |
| CN103483199B (en) * | 2013-09-02 | 2015-06-17 | 浙江海昇化学有限公司 | Preparation method of tetrafluoroterephthalate |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2388787A1 (en) | 1978-11-24 |
| JPS53135947A (en) | 1978-11-28 |
| DE2817508A1 (en) | 1978-11-02 |
| IT7848982A0 (en) | 1978-04-19 |
| JPS6030302B2 (en) | 1985-07-16 |
| FR2388787B3 (en) | 1980-11-28 |
| NL7804412A (en) | 1978-10-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |