CN1089933A - The method for preparing pentenoic acid with acidity or basic catalyst isomerization of lactones - Google Patents
The method for preparing pentenoic acid with acidity or basic catalyst isomerization of lactones Download PDFInfo
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- CN1089933A CN1089933A CN93118204A CN93118204A CN1089933A CN 1089933 A CN1089933 A CN 1089933A CN 93118204 A CN93118204 A CN 93118204A CN 93118204 A CN93118204 A CN 93118204A CN 1089933 A CN1089933 A CN 1089933A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
Abstract
The present invention relates to isomerization of lactones, be specifically related to the method that the various valerolactones of isomerization and isomer thereof prepare pentenoic acid.
This method mainly comprises makes a kind of lactone isomery that contains 5 carbon atoms turn to the process of pentenoic acid at least, it is characterized in that the described lactone that is gas phase is arranged to contact with tart solid catalyst (being selected from acidic molecular sieve, clay, bridging clay (or post clay), soild oxide and superphosphate), or contact with the solid catalyst (being selected from basic metal phosphoric acid salt, alkaline metal oxide, metal carbonate and alkaline molecular sieve) of alkalescence.
Description
The present invention relates to isomerization of lactones, be specifically related to the method that the various valerolactones of isomerization and isomer thereof prepare pentenoic acid.
Hydroxy carbonyl 3-pentenoic acid prepares hexanodioic acid and usually causes generating the γ-Wu Neizhi byproduct.
Therefore, adopting hydroxy carbonyl 3-pentenoic acid to prepare in the course of industrialization of hexanodioic acid, γ-Wu Neizhi (or 4-methyl butyrolactone) being converted into value product, is that a major issue needs to solve.
One of the method that γ-Wu Neizhi is converted into valuable product that can look forward to is to attempt the carbonylation γ-Wu Neizhi.Patent EP-A-0 for example, 395,038 have narrated this carbonylation method: be greater than or equal to 190 ℃ in temperature, carry out in the presence of rhodium/hydrogen iodide or rhodium/hydrogen bromide.
This method is more selective to hexanodioic acid, but generates valeric acid simultaneously; And although the content height of rhodium, the productive rate of hexanodioic acid is lower.
Thereby, explore γ-Wu Neizhi is converted into valuable compounds therefrom, improve the problem of 3-pentenoic acid hydroxy carbonyl process productive rate, do not find satisfied solution so far.
Purpose of the present invention can make γ-Wu Neizhi or its isomer isomerization generate pentenoic acid just in order to address this problem, and the latter can generate hexanodioic acid through hydroxy carbonyl again.
This method comprises makes a kind of lactone isomery that contains 5 carbon atoms turn to the process of pentenoic acid at least, it is characterized in that the above-mentioned lactone that is gas phase is arranged to contact with the solid catalyst of tart or alkalescence.
In this manual, acidic solid catalyst is meant some solid chemical compound (in most of the cases being metal oxide or metal-salt), and these compounds can make the methylbutynol dehydration be methyl butene alkynes (" methylbutynol " test) by following reaction:
Alkali solid catalyst is meant some solid chemical compound (in most of the cases being metal oxide or metal-salt), and these compounds can make methylbutynol be degraded to acetylene and acetone (" methylbutynol " test) by following reaction:
The details of relevant this test can with reference to " Applied Catalysis, 78(1991), the p.213-225 " paper in.
The lactone that can adopt in the method for the present invention mainly is γ-Wu Neizhi (or 4-methyl butyrolactone), δ-Wu Neizhi, 2-methyl butyrolactone, 3-ethyl propiolactone, 2-ethyl propiolactone and 2,3-dimethyl propiolactone.
In above-mentioned lactone, γ-Wu Neizhi is best a kind of, because it generates hexanodioic acid in the hydroxy carbonyl process of 3-pentenoic acid.
In an acidic catalyst, what can mention is acidic molecular sieve, acid clay, bridging clay (or post clay), soild oxide and superphosphate.
Acidic molecular sieve mainly is the zeolite of pentasil structure, for example the zeolite of the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, ferrierite structure, mordenite structure and faujusite structure, for example X zeolite or zeolite Y.
The zeolite of pentasil structure or mordenite structure mainly is the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48 and mordenite type, and they have with the logical formula I of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal,
-X represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-m represents to be equal to or greater than 10 number,
-p represents from 0 to 40 number.
The zeolite of faujusite type mainly has with the logical formula II of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal, M at least a portion is a hydrogen atom
-Z represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-d represents to be equal to or greater than 2 number,
-x represents from 5 to 100 number.
The acid zeolite of Cai Yonging mainly is that to be used in its general formula with silicon-dioxide bonded oxide compound be those zeolites of trivalent metal oxide within the scope of the invention.
Usually preferred zeolite is that M is selected from hydrogen, NH in its logical formula I or (II)
4, basic metal Na, K, Li, Rb or Cs, alkaline-earth metal Be, Mg, Ca, Sr or Ba, rare earth metal La or Ce and transition metal Fe for example for example for example for example.
But the detailed introduction referenced patent FR-A-2 of relevant acid clay, 622,575(incorporates this paper into as the reference data).
In the method for the invention, preferably adopt terre verte for example montmorillonite, beidellite, nontronite, hectorite, high magnesium montmorillonite and talcum powder.
Can be between its thallus, to have introduced the bridge at maintenance base portion interval or the clay of post in the method for the invention as the bridging clay of catalyzer.This base portion is the thickness sum at interval between clay thallus and the thallus at interval.
The preparation of above-mentioned bridging clay is at patent FR-A-2, is described specially in 563,446 and patent FR-A-2,618,143.
Beidellite is preferably raw clay usually.
The bridging of clay especially can realize by the oxyhydroxide of aluminium, vanadium, molybdenum, zirconium, iron, niobium, tantalum, chromium, lanthanum, cerium, titanium or gallium or by the mixed hydroxides of above-mentioned some metal.
Above-mentioned bridging clay can be modified, particularly by dihalo, ammonium halide or certain acid for example the effect of sulfuric acid or haloid acid carry out modification.Can select preferred chlorine of halogen or the fluorine introduced.
Clay, particularly the beidellite by the aluminium hydroxide bridging preferably adopts in the method for the invention.
Soild oxide is the mixture of metal oxide, metal oxide or the metal oxide of modification, particularly by dihalo, ammonium halide or certain acid metal oxide of the effect modification of sulfuric acid or haloid acid for example.Can select preferred chlorine of halogen or the fluorine introduced.
As unrestriced example, the mixture that can mention is SiO
2/ Al
2O
3, SiO
2/ Ga
2O
3, SiO
2/ Fe
2O
3And SiO
2/ B
2O
3, halogenated alumina for example chlorating alumina and fluorizated alumina, sulfonated zirconium white, niobium oxides or Tungsten oxide 99.999.
In the method for the invention the superphosphate that can adopt as an example mainly be that the phosphoric acid salt of boron (is introduced separately into or by different H
3BO
3/ H
3PO
4Mol ratio and alumina or silicon-dioxide mix the back to be introduced in building-up process), the phosphoric acid salt of lanthanum orthophosphate, aluminium (is equivalent to different Al
2O
3/ H
3PO
4Mol ratio is introduced in building-up process), Vanadium Pentoxide in FLAKES/-mixture (being commonly referred to the UOP catalyzer) of silicon-dioxide, have zeolite structured aluminate or phosphate (AlPO) and have zeolite structured aluminosilicophosphate (SAPO).
The alkali solid catalyst that can adopt mainly is basic metal phosphoric acid salt, alkaline metal oxide, metal carbonate and alkaline molecular sieve in the method for the invention.
Basic metal phosphoric acid salt mainly is phosphoric acid salt, hydrophosphate and the dihydrogen phosphate of logical formula III:
In the formula:
-A represents that an atoms metal, one group of atoms metal or a part are hydrogen atoms;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents alkaline impregnation compound, and its contained metal (be used for oppositely negatively charged ion chemical combination to guarantee electric neutrality) is selected from alkaline-earth metal, basic metal and composition thereof;
-coefficient z represents soaker and macerate (A
yPO
4) weight ratio, its value is for 0%-20%, preferred 2%-10%.
The compound of the alkaline phosphate preferred formula (III) that can adopt in the method for the invention, in the formula:
-A represents that calcium, zirconium, lanthanum, cerium, samarium, aluminium, boron, iron and a part are hydrogen;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents oppositely negatively charged ion of basic metal or alkali-metal mixture and alkalescence;
The value of-coefficient z is 2%-10%.
As unrestriced example, the alkaline phosphate that can mention is the combination of lanthanum orthophosphate and caesium, rubidium or potassium compound, the combination of Cerium monophosphate and caesium, rubidium or potassium compound, the combination of samaric orthophosphate and caesium, rubidium or potassium compound, the combination of calcium phosphate and caesium, rubidium or potassium compound, the combination of the combination of secondary calcium phosphate and caesium, rubidium or potassium compound or phosphoric acid hydrogen zirconium and caesium, rubidium or potassium compound.
The alkaline phosphate of logical formula III can be with the Imp suspension in a kind of solution or the volatile solvent, preferably water for example, and dipping leads to formula IV (A
' yPO
4) compound be prepared, in the general formula, A' is identical with the implication of A.
If Imp can dissolve and A
' yPO
4Be just to prepare, then the gained result is better.
Therefore, the logical phosphatic best method of formula III of preparation comprises:
A) synthetic compound A
' yPO
4; Preferably from reaction mixture, do not separate A
' yPO
4,
B) soaker Imp is introduced in the reaction mixture,
C) raffinate in the separating reaction solid,
D) dry and calcining in case of necessity.
If with reference to the phosphatic current techique of preparation (as p.821-823 and " Gmelins Handbuch der anorganischen Chemie " the 8th edition at " P.Pascal Nouveau trait é de chimie min é rale " X volume (1956), 16 volumes (C) are p.202-206(1965) described in), can understand two kinds and main utilize phosphatic technological line.A kind of is to precipitate soluble metallic salt (muriate, nitrate) and use the ammoniacal liquor aftertreatment with ammonium hydrogen phosphate, neutralizes in case of necessity subsequently.Another kind of route is with phosphoric acid and reactive metal oxide, then, to do aftertreatment with alkali metal hydroxide in case of necessity under heating.
The alkaline metal oxide that can adopt is the oxide compound of alkalescence or by for example can become the oxide compound of alkalescence after the hydroxide treatment of basic metal or alkaline-earth metal with alkali in the method for the invention.
The alkaline metal oxide that can mention (not containing any restrictive sense) is the oxide compound that III a family alkali-metal, alkaline-earth metal, the period of element table sort is metal, transition metal or rare earth metal, pass through or do not handle through alkali metal hydroxide.
What can mention as an example, mainly is alumina, zinc oxide and the calcium oxide of crossing with sodium-hydroxide treatment.
The alkaline molecular sieve that can adopt mainly is the zeolite of pentasil structure in the method for the invention, the zeolite of for example ZSM-5, ZSM-11, ZSM-22, ZSM-23 or ZSM-48, mordenite structure, the ferrierite structure or faujusite structure, for example zeolite of X zeolite or zeolite Y, the general formula (V) represented with oxide compound:
In 0:
-E represents basic metal or alkaline-earth metal, and whole or small portion is a hydrogen,
-T represents to be selected from the trivalent metal of Al, Ga, Fe and B,
-a represents from 1 to 2 number,
-b represents to be equal to or greater than 2 number,
-r represents from 0 to 100 number.
In general formula (V), the meaning of " small portion hydrogen " that symbol E expresses is meant that the proton that can exist in the molecular sieve must not cause molecular sieve to have acid-reaction in above-mentioned test.
In the alkaline molecular sieve of general formula (V), what preferably adopt is that those E represent alkali-metal molecular sieve.
As unrestriced example, the alkaline molecular sieve that can mention is zeolite NaZSM-5, zeolite NaMOR, zeolite 13XCs, zeolite NaY, zeolite KY and zeolite CsY.
This method adopts operate continuously.
Used catalyzer can maybe can be operated by fluidized-bed by fixed bed.In order to increase contact area, this catalyzer can mix use with inert solid.
Isomerization process is to carry out under 200 ℃-500 ℃ in temperature normally, preferred 250 ℃-400 ℃.
Be defined as the ratio of catalyst volume and total gas flow rate (lactone+suitable carrier gas) duration of contact, under chosen temperature, between 0.1-50sec, change usually, and in most cases be 1-10sec.
Pressure is not crucial.Usually being in normal atmosphere clings to 10MPa(100) between, preferably cling to from normal atmosphere to 1.5MPa(15).
Lactone can enter in the reactor that catalyzer is housed individually.
Lactone also can be introduced reactor together with inert carrier gas; The mode of associating introducing can be taked the form of mixture or two kinds of gases are introduced respectively simultaneously.
Inert carrier gas can be made up of the mixture of a kind of gas or some gases, and they are inert under reaction conditions, for example nitrogen, argon gas, air, water vapor and be the carboxylic acid of gas under the temperature of operation.
The content of lactone is the 10%-100%(weight of the gas gross weight of introducing reactor), preferred 40%-100%.
Method of the present invention can produce the mixture of 2-pentenoic acid, 3-pentenoic acid and 4-pentenoic acid usually.
3-pentenoic acid and 4-pentenoic acid can be by turning to hexanodioic acid with carbon monoxide and water reaction hydroxycarbonyl group.
The 2-pentenoic acid can turn to the 3-pentenoic acid and the 4-pentenoic acid that can directly effectively utilize by isomery.
According to the present invention, because isomerization reaction is the reaction of difficulty on the thermodynamics, therefore, the transforming degree of lactone generally is limited in actually operating less than 80%, and in most cases less than 60%, but, this method can easily make unconverted lactone recycle.
Following examples will further be illustrated the present invention.
Except as otherwise noted, following working method will adopt in an embodiment.
Vertically arranged reactor (silica tube, length=15cm, the diameter=2cm) 2cm that packs into continuously
3Quartz, 2cm
3Catalyzer and 10cm
3Quartzy mixture closely refills 5cm then
3Quartz.Granulated glass sphere (diameter: 2-3mm) as the last filler of reactor.
In that (300 ℃, unless otherwise indicated) down logical nitrogen two hours (under normal pressure and temperature condition per hour 2 liters) is regulated catalyzer for the selected temperature of reaction.
Then, with syringe lactone is injected.
In each embodiment, will the rate of injection of lactone be explained: with the cm of the lactone of liquid state
3Expression.
After about 15 minutes, promptly set up steady state, test continues 1 hour usually.The product that leaves reactor is collected in 10cm is housed
3In the collector of acetonitrile.
With vapor-phase chromatography (GC) analytical reaction product and unreacted lactone.
And the following is calculated in each test:
-hour weight yield (HWE): with respect to the weight of catalyzer with per hour (with h
-1Expression) the lactone weight of introducing;
The transforming degree of-lactone (DC); Interior ester conversion rate % with respect to the lactone of introducing;
The productive rate of-various pentenoic acids (RY): with respect to the mole % of each pentenoic acid that lactone generated of introducing.
Embodiment 1-7(Substrate: γ-Wu Neizhi)
The test of the different zeolites of the ZSM-5 type of logical formula I, this zeolite have different Si/Al mol ratios also more or less by acidifying:
-zeolite 1:Si/Al=30
75% element M is a hydrogen in the logical formula I,
-zeolite 2:Si/Al=52
75% element M is a hydrogen in the logical formula I,
-zeolite 3:Si/Al=120
75% element M is a hydrogen in the logical formula I,
-zeolite 4:Si/Al=30
That the M representative mainly is NH in the logical formula I
4, minority is a hydrogen,
-zeolite 5:Si/Al=50
That the M representative mainly is NH in the logical formula I
4, minority is a hydrogen,
-zeolite 6:Si/Al=120
That the M representative mainly is NH in the logical formula I
4, minority is a hydrogen,
-zeolite 7:Si/Al=50
The whole of M representative are hydrogen in the logical formula I.
What provide in operational condition and the above-mentioned total working method is identical.
The duration of contact of each embodiment, (tc) was about 1.4sec.
Gained is the result be organized in the following table 1.
Abbreviation P2, the P3 and the P4 that adopt have following meaning:
The P2=2-pentenoic acid
The P3=3-pentenoic acid
The P4=4-pentenoic acid
Embodiment 8-15(Substrate: γ-Wu Neizhi)
The test of different an acidic catalysts:
-SiO
2/ Al
2O
3(Degussa sale)
Contain 16%(weight) SiO
2,
-SiO
2/ Al
2O
3Than the zeolite Y (Toyo Soda sale) that is 5,
-BPO
4(B/P is than=1),
- LaPO
4，
-montmorillonite Volclay clay (Montmo),
The zeolite of the ZSM-5 type of-Tong formula I, X represents Fe,
SiO
2/ Fe
2O
3Than=120(ZSM-5/Fe),
-chlorating Al
2O
3,
-niobium oxides.
Operational condition as mentioned above.Be 1 hour reaction time, and except the embodiment 14 of chlorination alumina, be 0.5 hour its reaction time, and temperature may be different from 300 ℃, and the flow of nitrogen may be different from 2L/h, and the introducing speed of γ-Wu Neizhi may be different from 3.2mL liquid/h.
Table 2 has been listed the test-results of some different parameter values and gained.
Table 2
| Embodiment | Catalyzer | Temperature | N 2Flow L/h | Lactone flow mL/h | DC% | RY% | tc (s) | HWE (h -1) | ||
| P4 | P3 | P2 | ||||||||
| Embodiment 8 | SiO 2/Al 2O 3 | 300 | 2 | 3.2 | 9 | 2 | 6 | 3 | 1.4 | 4.1 |
| Embodiment 9 | Zeolite Y | 300 | 2 | 3.2 | 8 | 2 | 5 | 2 | 1.4 | 4.6 |
| Embodiment 10 | BPO 4 | 300 | 2 | 3.2 | 5 | 2 | 5 | 2 | 1.4 | 2.1 |
| Embodiment 11 | LaPO 4 | 300 | 2 | 3.2 | 38 | 2 | 9 | 6 | 1.4 | 1.9 |
| Embodiment 12 | Montmorillonite | 275 | 2 | 3.2 | 4.5 | 1 | 3.5 | 0 | 1.4 | 1.9 |
| Embodiment 13 | ZSM-5／Fe | 300 | 2 | 6.4 | 10.5 | 2 | 6 | 2.5 | 1.0 | 6.1 |
| Embodiment 14 | Chlorination Al 2O 3 | 380 | 0.45 | 9.6 | 11.5 | 4 | 4.5 | 2.5 | 1.1 | 10.6 |
| Embodiment 15 | Niobium oxides | 380 | 2 | 3.2 | 39 | 5 | 9 | 5 | 1.1 | 2.0 |
Embodiment 16(Substrate: γ-Wu Neizhi)
Test (SiO with Fe exchanging zeolite Y
2/ Al
2O
3Than=5, M=Fe).
Operational condition is existing narration in above-mentioned total working method, and difference is as follows:
-temperature of reaction: 370 ℃
-catalyst volume 1.5cm
3
-N
2Flow 3L/h
-lactone flow 3.2mL/h.
The gained result is as follows:
The DC 10% of lactone
P
2RY： 4.3%
0%
P
4RY： 1.3%
Tc：??0.8s
HWE： 7.3h
-1。
Embodiment 17-20(Substrate: γ-Wu Neizhi)
The test of different alkali solid catalysts:
The Cerium monophosphate of-3% phosphoric acid hydrogen the caesium that mixes
-secondary calcium phosphate (hydroxylapatite)
-zeolite 13XCs
The alumina of-usefulness sodium-hydroxide treatment (10% sodium hydroxide is in the heavy weight of per unit alumina) (4cm
3, rather than 2cm
3Value).
Operational condition is existing narration in above-mentioned total working method.
Gained result and the parameter value that parameter in total working method has been done to change put in order in table 3.
Embodiment 21-24(Substrate: γ-Wu Neizhi)
Be used for test (per-cent of soaker and lanthanum orthophosphate is represented with w/w) with the lanthanum orthophosphate of various soaker combination.
Operational condition is existing narration in above-mentioned total working method.
The rate of injection of gained result and temperature of reaction and lactone is put in order in table 4.
Claims (27)
1, makes a kind of lactone isomery that contains 5 carbon atoms turn to the method for pentenoic acid at least, it is characterized in that the above-mentioned lactone that is gas phase is arranged to contact with the solid catalyst of tart or alkalescence.
2,, it is characterized in that lactone is selected from γ-Wu Neizhi (or 4-methyl butyrolactone), δ-Wu Neizhi, 2-methyl butyrolactone, 3-ethyl propiolactone, 2-ethyl propiolactone and 2,3-dimethyl propiolactone according to the method for claim 1.
3,, it is characterized in that this catalyzer is the acidic solid catalyst that is selected from acidic molecular sieve, acid clay, bridging clay (or post clay), soild oxide and superphosphate according to the arbitrary method in claim 1 and 2.
4, according to the method for claim 3, it is characterized in that acidic molecular sieve is the zeolite of pentasil structure, the for example zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48 ferrierite, mordenite and faujusite structure, for example X zeolite or zeolite Y.
5, according to the arbitrary method in claim 3 and 4, the acid zeolite that it is characterized in that pentasil structure or mordenite structure is the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48 or the zeolite of mordenite type, and they have with the logical formula I of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal,
-X represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-m represents to be equal to or greater than 10 number,
-p represents from 0 to 40 number.
6, according to the method for claim 3, it is characterized in that this acidic molecular sieve is the zeolite of the faujusite structure of X zeolite or zeolite Y type, they have with the logical formula II of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal, M to small part be hydrogen atom,
-Z represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-d represents to be equal to or greater than 2 number,
-x represents from 5 to 100 number.
7, according to each method among the claim 3-6, it is characterized in that this acidic molecular sieve is an acid zeolite, in its general formula, be used for silicon-dioxide bonded oxide compound be the oxide compound of trivalent metal.
8,, it is characterized in that the clay that adopts is for example montmorillonite, beidellite, nontronite, hectorite, rich magnesium montmorillonite and a talcum powder of terre verte according to the method for claim 3.
9, according to the method for claim 3, it is characterized in that the bridging clay that adopts is to have introduced the bridge at maintenance base portion interval or the clay of post between its thallus, the bridging of clay especially can be by the oxyhydroxide of aluminium, vanadium, molybdenum, zirconium, iron, niobium, tantalum, chromium, lanthanum, cerium, titanium or gallium or by the mixed hydroxides of above-mentioned some metal, preferably by the beidellite of aluminium hydroxide bridging.
10,, it is characterized in that the bridging clay that adopts is by for example effect modification of sulfuric acid or haloid acid of dihalo, ammonium halide or certain acid, can select preferred chlorine of halogen or the fluorine introduced according to the arbitrary method in claim 3 and 9.
11, according to the method for claim 3, it is characterized in that the soild oxide that is adopted is the mixture of metal oxide, metal oxide or by dihalo, ammonium halide or certain acid metal oxide of the effect modification of sulfuric acid or haloid acid for example, can select preferred chlorine of halogen or the fluorine introduced.
12,, it is characterized in that the soild oxide that is adopted is to be selected from mixture SiO according to the arbitrary method in claim 3 and 11
2/ Al
2O
3, SiO
2/ Ga
2O
3, SiO
2/ Fe
2O
3, SiO
2/ B
2O
3, halogenated alumina for example chlorating alumina and fluorizated alumina, sulfonated zirconium white, niobium oxides or Tungsten oxide 99.999.
13,, it is characterized in that this superphosphate is selected from the phosphoric acid salt of boron and (is introduced separately into or by different H according to the method for claim 3
3BO
3/ H
3PO
4Mol ratio and alumina or silicon-dioxide mix the back to be introduced in building-up process), the phosphoric acid salt of lanthanum orthophosphate, aluminium (is equivalent to different Al
2O
3/ H
3PO
4Mol ratio is introduced in building-up process), Vanadium Pentoxide in FLAKES/-mixture (being commonly referred to the UOP catalyzer) of silicon-dioxide, have zeolite structured aluminate or phosphate (AlPO) and have zeolite structured aluminosilicophosphate (SAPO).
14,, it is characterized in that this catalyzer is the alkali solid catalyst that is selected from basic metal phosphoric acid salt, alkaline metal oxide, metal carbonate and alkaline molecular sieve according to the arbitrary method in claim 1 and 2.
15,, it is characterized in that this basic metal phosphoric acid salt mainly is the various phosphoric acid salt of logical formula III according to the method for claim 14:
In the formula:
-A represents that a kind of atoms metal, one group of atoms metal or a part are hydrogen atoms;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents alkaline impregnation compound, and its contained metal (be used for oppositely negatively charged ion chemical combination to guarantee electric neutrality) is selected from alkaline-earth metal, basic metal and composition thereof;
-coefficient z represents soaker and macerate (A
yPO
4) weight ratio, its value is for 0%-20%, preferred 2%-10%.
16,, it is characterized in that basic metal phosphoric acid salt mainly is the various phosphoric acid salt of logical formula III according to the arbitrary method in claim 14 and 15:
In the formula:
-A represents that calcium, zirconium, lanthanum, cerium, samarium, aluminium, boron, iron and a part are hydrogen;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents oppositely negatively charged ion of basic metal or alkali-metal mixture and alkalescence;
The value of-coefficient z is 2%-10%.
17, according to each method among the claim 14-16, it is characterized in that basic metal phosphoric acid salt mainly is the combination of lanthanum orthophosphate and caesium, rubidium or potassium compound, the combination of Cerium monophosphate and caesium, rubidium or potassium compound, the combination of samaric orthophosphate and caesium, rubidium or potassium compound, the combination of calcium phosphate and caesium, rubidium or potassium compound, the combination of the combination of secondary calcium phosphate and caesium, rubidium or potassium compound or phosphoric acid hydrogen zirconium and caesium, rubidium or potassium compound.
18,, it is characterized in that this basic metal phosphoric acid salt can be with the Imp suspension in a kind of solution or the volatile solvent, preferably water for example, the logical formula IV (A of dipping according to each method among the claim 14-17
' yPO
4) compound be prepared, in the general formula, A' is identical with the implication of A.
19, according to each method among the claim 14-18, it is characterized in that this basic metal method for production of phosphate salt comprises:
A) synthetic compound A
' yPO
4; Preferably from reaction mixture, do not separate A
' yPO
4;
B) soaker Imp is introduced in the reaction mixture;
C) raffinate in the separating reaction solid;
D) dry and calcining in case of necessity.
20,, it is characterized in that this alkaline metal oxide mainly is the oxide compound of alkalescence or by for example can become the oxide compound of alkalescence after the hydroxide treatment of basic metal or alkaline-earth metal with alkali according to the method for claim 14.
21, according to each method among the claim 14-20, it is characterized in that this alkaline metal oxide be selected from III a family alkali-metal, alkaline-earth metal, the period of element table sort metal, transition element or rare earth metal, through or the oxide compound handled through alkali metal hydroxide.
22, according to the method for claim 14, it is characterized in that this alkaline molecular sieve mainly is the zeolite of pentasil structure, the zeolite of for example ZSM-5, ZSM-11, ZSM-22, ZSM-23 or ZSM-48, mordenite structure, the ferrierite structure or faujusite structure, for example zeolite of X zeolite or zeolite Y, the general formula (V) represented with oxide compound:
In the formula:
-E represents basic metal or alkaline-earth metal, and whole or small portion is a hydrogen,
-T represents to be selected from the trivalent metal of Al, Ga, Fe and B,
-a represents from 1 to 2 number,
-b represents to be equal to or greater than 2 number,
-r represents from 0 to 100 number.
23,, it is characterized in that this alkaline molecular sieve mainly is zeolite ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48, mordenite, ferrierite, faujusite for example X zeolite or zeolite Y according to the method for claim 14.
24, according to each method among the claim 1-23, it is characterized in that the temperature that is adopted is 200 ℃-500 ℃, preferred 250 ℃-400 ℃.
25, according to each method among the claim 1-24, it is characterized in that lactone can enter in the reactor that catalyzer is housed individually.
26, according to each method among the claim 1-24, it is characterized in that lactone can introduce reactor together with inert carrier gas, this inert carrier gas is made up of the mixture of a kind of gas or some gases, they are inert under reaction conditions, for example nitrogen, argon gas, air, water vapor and be the carboxylic acid of gas under the service temperature of reaction.
27,, it is characterized in that the 10%-100%(weight of the content of lactone for the gas gross weight of introducing reactor according to the arbitrary method in claim 25 and 26), preferred 40%-100%.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9212182 | 1992-10-02 | ||
| FR9212181A FR2696448B1 (en) | 1992-10-02 | 1992-10-02 | Process for the isomerization of lactones into pentenoic acids by acid catalysis. |
| FR9212182A FR2696449B1 (en) | 1992-10-02 | 1992-10-02 | Process for the isomerization of lactones into pentenoic acids by basic catalysis. |
| FR9212181 | 1992-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1089933A true CN1089933A (en) | 1994-07-27 |
Family
ID=26229794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93118204A Pending CN1089933A (en) | 1992-10-02 | 1993-09-28 | The method for preparing pentenoic acid with acidity or basic catalyst isomerization of lactones |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0662944A1 (en) |
| JP (1) | JPH08500608A (en) |
| KR (1) | KR950703508A (en) |
| CN (1) | CN1089933A (en) |
| BR (1) | BR9307159A (en) |
| CA (1) | CA2146153A1 (en) |
| CZ (1) | CZ79795A3 (en) |
| MX (1) | MX9306070A (en) |
| PL (1) | PL308208A1 (en) |
| SG (1) | SG45321A1 (en) |
| SK (1) | SK41895A3 (en) |
| WO (1) | WO1994007835A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5948683A (en) * | 1997-10-18 | 1999-09-07 | Engelhard Corporation | Catalyst for selective oxidation of unsaturated hydrocarbons and methods of making and using the same |
| SG193629A1 (en) * | 2011-03-28 | 2013-11-29 | Agency Science Tech & Res | Synthesis of diacids |
| AU2017238018A1 (en) | 2016-03-21 | 2018-11-08 | Novomer, Inc. | Acrylic acid, and methods of producing thereof |
| US20180305286A1 (en) * | 2016-03-21 | 2018-10-25 | Novomer, Inc. | Systems and Processes for Producing Organic Acids Direct from Beta-Lactones |
| JP2018188402A (en) * | 2017-05-10 | 2018-11-29 | 宇部興産株式会社 | Method for producing pentenoic acid ester |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2382464A (en) * | 1942-01-30 | 1945-08-14 | Carbide & Carbon Chem Corp | Production of unsaturated carboxylic acids |
| US3176042A (en) * | 1959-10-20 | 1965-03-30 | Celanese Corp | Treating propiolactone with heated phosphoric acid to produce acrylic acid |
| GB1454751A (en) * | 1973-04-11 | 1976-11-03 | Laporte Industries Ltd | Production of ypsilon lactones |
| NZ209982A (en) * | 1983-11-03 | 1987-04-30 | Mobil Oil Corp | Zeolite catalyst treated with aluminium-extracting reagent to produce enhanced activity |
| FR2563446A1 (en) * | 1984-04-25 | 1985-10-31 | Raffinage Cie Francaise | NEW ZEOLITE WITH TWO-DIMENSIONAL STRUCTURE AND APPLICATION OF SAID ZEOLITE |
| US4701431A (en) * | 1984-12-24 | 1987-10-20 | Exxon Research And Engineering Company | Rare earth stabilized aluminum deficient zeolite |
-
1993
- 1993-09-23 KR KR1019950701253A patent/KR950703508A/en not_active Application Discontinuation
- 1993-09-23 CA CA002146153A patent/CA2146153A1/en not_active Abandoned
- 1993-09-23 JP JP6508767A patent/JPH08500608A/en active Pending
- 1993-09-23 SK SK418-95A patent/SK41895A3/en unknown
- 1993-09-23 SG SG1996003483A patent/SG45321A1/en unknown
- 1993-09-23 PL PL93308208A patent/PL308208A1/en unknown
- 1993-09-23 EP EP93920924A patent/EP0662944A1/en not_active Ceased
- 1993-09-23 WO PCT/FR1993/000928 patent/WO1994007835A1/en not_active Application Discontinuation
- 1993-09-23 BR BR9307159A patent/BR9307159A/en not_active Application Discontinuation
- 1993-09-23 CZ CZ95797A patent/CZ79795A3/en unknown
- 1993-09-28 CN CN93118204A patent/CN1089933A/en active Pending
- 1993-09-30 MX MX9306070A patent/MX9306070A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CZ79795A3 (en) | 1995-09-13 |
| JPH08500608A (en) | 1996-01-23 |
| EP0662944A1 (en) | 1995-07-19 |
| KR950703508A (en) | 1995-09-20 |
| BR9307159A (en) | 1999-03-30 |
| SK41895A3 (en) | 1995-09-13 |
| PL308208A1 (en) | 1995-07-24 |
| SG45321A1 (en) | 1998-01-16 |
| CA2146153A1 (en) | 1994-04-14 |
| MX9306070A (en) | 1994-05-31 |
| WO1994007835A1 (en) | 1994-04-14 |
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