CN1452511A - Catalyst for producing lower aliphatic carboxylic acid esters - Google Patents
Catalyst for producing lower aliphatic carboxylic acid esters Download PDFInfo
- Publication number
- CN1452511A CN1452511A CN 01815333 CN01815333A CN1452511A CN 1452511 A CN1452511 A CN 1452511A CN 01815333 CN01815333 CN 01815333 CN 01815333 A CN01815333 A CN 01815333A CN 1452511 A CN1452511 A CN 1452511A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- acid
- catalyzer
- gas
- alphatic carboxylic
- 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.)
- Pending
Links
Classifications
-
- 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
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A catalyst for use in producing a lower aliphatic carboxylic acid ester, which can exhibit high initial activity and high space time yield, ensure a sufficiently long catalyst life in the industrial practice, and reduce the production of by-products; a process for producing the catalyst; and a process for producing a lower aliphatic carboxylic acid ester using the catalyst. The catalyst is produced by a process comprising a step of contacting the catalyst with a gas containing at least one member selected from water, a lower aliphatic carboxylic acid and a lower aliphatic alcohol.
Description
The cross reference of related application
The application is the application of submitting according to 35U.S.C. § 111 (a), require provisional application 60/238 according to 35U.S.C. § 119 (e) (1), the rights and interests of 431 the applying date, provisional application 60/238,431st, the application of submitting on October 10th, 2000 according to 35 § 111 (b).
Technical field
The present invention relates to a kind of catalyzer, the method for preparing the method for this catalyzer and use this Catalyst Production lower aliphatic carboxylic acid ester by light alkene and lower alphatic carboxylic acid production lower aliphatic carboxylic acid ester.
Or rather, the present invention relates to a kind of catalyzer that contains special heteropolyacid, is used for preparing the method for lower aliphatic carboxylic acid ester with light alkene esterification lower alphatic carboxylic acid, wherein catalyzer before reaction with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact; The method for preparing this catalyzer; And the method for using this Catalyst Production lower aliphatic carboxylic acid ester.
Background technology
As everyone knows, can generate corresponding ester by lower alphatic carboxylic acid and alkene.And the known catalyzer that comprises heteropolyacid and/or heteropolyacid salt plays useful effect in this reaction.The specific examples of this catalyzer is included in
Kogyo Kagaku Zasshi (technical chemistry magazine)Those that describe among the 72nd volume the 9th phase (1969) and Japanese unexamined patent open 4-139148 (JP-A-4-139148), 5-65248 (JP-A-5-65248), 5-294894 (JP-A-5-294894) and the 9-118647 (JP-A-9-118647).
In these specific exampless,
Kogyo Kagaku Zasshi (technical chemistry magazine)The 72nd volume the 9th phase (1969) discloses and has a kind ofly carried tungstosilicic acid or silicon-dioxide with silicon-dioxide to carry tungstophosphoric acid be the method for catalyzer by ethene and acetate synthesizing ethyl acetate.According to this method, show high initial catalytic activity but active descend very soon that only active rate of descent just reaches 10% in 3 hours.There is the low problem of target product selection rate in the disclosed catalyzer that contains tungstosilicic acid, molybdophosphate or tungstophosphoric acid in JP-A-9-118647, though and initial activity higher, when reaction active decline when carrying out for a long time.
In order to address these problems, at JP-A-4-139148 and JP-A-5-65248 and do not examine the catalyzer that disclosed method use among the open 4-139149 (JP-A-4-139149) of Japanese Patent contains the salt of at least a cesium salt, rubidium salt, thallium salt, ammonium salt and the sylvite that is selected from tungstophosphoric acid, tungstosilicic acid, molybdophosphate and molybdenum silicic acid, wherein can obtain high initial activity and higher space-time yield, and the selection rate of target product can be improved.But their application on technical scale still exist problem to be solved: the active and space-time yield decline along with the carrying out of reaction.
In order to address this problem, not examine the open 5-170698 (JP-A-5-170698) of Japanese Patent and advised a kind of method that above-mentioned catalyzer and water and organic carboxyl acid or organic carboxylic ester are contacted in gas phase.In the production method of using the catalyzer that contacts processing according to aforesaid method in advance, show, almost do not descend with using initial activity height and the activity of not comparing catalyzer through the conventional production methods of contact position reason catalyzer.
On the other hand, JP-A-5-294894 discloses and a kind ofly has been stated from the catalyzer that obtains on the carrier by the heteropolyacid with at least a lithium that is selected from heteropolyacid, copper, magnesium, gallium salt, although do not use the disclosed method that catalyzer and water and organic carboxyl acid or organic carboxylic ester are contacted of JP-A-5-170698 in gas phase, the initial activity that catalyzer shows is identical or higher and can keep active.
Disclosure of the Invention
The purpose of this invention is to provide a kind of catalyzer that is used for preparing lower aliphatic carboxylic acid ester by light alkene and lower alphatic carboxylic acid, this catalyzer shows high initial activity and high space-time yield, guarantees to be enough to adapt to the long catalyst life of industrial practice and to reduce to generate by product; A kind of method for preparing catalyzer; And the method for using this Catalyst Production lower aliphatic carboxylic acid ester.
The inventor is for showing not only in gas-phase reaction prepares the reaction of lower aliphatic carboxylic acid ester that at light alkene and lower alphatic carboxylic acid the catalyzer that high initial activity and sufficiently long catalyst life but also minimizing generate by product has carried out extensive studies.Found that, although the neutralized salt of heteropolyacid not as catalyzer, provides particular step in the preparation process of heteropolyacid catalyst after, can prevent active decline.The present invention is based on that this discovery finishes.In addition, in practice of the present invention, find, to the deleterious by product of catalyzer for example the generation of butylene and aldehyde can be greatly reduced.The present invention is based on also that this discovery finishes.
Or rather, the present invention (I) is a kind of catalyzer that is used to produce lower aliphatic carboxylic acid ester, this catalyzer uses in gas-phase reaction production lower aliphatic carboxylic acid ester at light alkene and lower alphatic carboxylic acid, and the method that wherein prepares catalyzer comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid; With
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
The present invention (II) is the method that a kind of preparation is used to produce the catalyzer of lower aliphatic carboxylic acid ester, this catalyzer uses in gas-phase reaction production lower aliphatic carboxylic acid ester at light alkene and lower alphatic carboxylic acid, and the method that wherein prepares catalyzer comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid;
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
The present invention (III) is a kind of method of producing lower aliphatic carboxylic acid ester, is included in catalyzer that the present invention (I) is used to produce lower aliphatic carboxylic acid ester and makes light alkene and lower alphatic carboxylic acid in gas-phase reaction under existing.
The present invention (IV) is a kind of method of producing lower aliphatic carboxylic acid ester, comprises making light alkene and lower alphatic carboxylic acid in gas-phase reaction, and wherein this production method comprises following first to fourth step:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid;
Second step
The catalyzer of the carried heteropoly acid that first step is obtained is inserted and is used for the step that light alkene and lower alphatic carboxylic acid carry out the reactor of gas-phase reaction;
Third step
Make and contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts with the catalyzer of the carried heteropoly acid of inserting reactor; With
The 4th step
Make the mixed gas that contains light alkene and lower alphatic carboxylic acid catalyzer, to obtain the step of lower aliphatic carboxylic acid ester by the carried heteropoly acid handled through third step.
Implement best mode of the present invention
The present invention (I) is a kind of catalyzer that is used to produce lower aliphatic carboxylic acid ester, and this catalyzer uses in gas-phase reaction production lower aliphatic carboxylic acid ester at light alkene and lower alphatic carboxylic acid, and the method that wherein prepares catalyzer comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid; With
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
Or rather, the catalyzer that the present invention (I) is used for producing lower aliphatic carboxylic acid ester is a kind ofly to comprise the catalyzer that the production method of above-mentioned first and second steps obtains by production stage.
First step is described below.Be used for producing the catalyzer of lower aliphatic carboxylic acid ester in the present invention (I), the heteropolyacid that uses at first step comprises 1 central element and one and the peripheral element of oxygen bonded.Central element generally is silicon or phosphorus, but also can comprise the arbitrary element of selecting from the various atoms of periodic table of elements I-XVII family.
The specific examples of central element comprises cupric ion, divalence beryllium, zinc, cobalt and nickel ion, trivalent boron, aluminium, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, chromium and rhodium ion, tetravalence silicon, germanium, tin, titanium, zirconium, vanadium, sulphur, tellurium, manganese, nickel, platinum, thorium, hafnium, cerium ion and other rare earth element ion, pentavalent phosphorus, arsenic, vanadium and antimony ion, sexavalence tellurium ion and septivalency iodide ion, but the present invention is not limited to this.The specific examples of peripheral element comprises tungsten, molybdenum, vanadium, niobium and tantalum, but the present invention is not limited to this.
These heteropolyacids also are called " polyoxy negatively charged ion ", " polyoxy metal-salt " or " metal oxide cluster ".Some famous anionic structure is with researchist's name in this field, for example Keggin, Wells-Dawson or Anderson-Evans-Perloff structure.These are by Nippon KagakuKai (1993) editor's
Poly-San no Kagaku, Kikan Kagaku Sosetsu (Chemistry of Polyacids, The comprehensive quarterly of looking at of chemistry)The 20th phase had a detailed description.Heteropolyacid generally has high molecular, and for example molecular weight is 700-8, and 500, not only comprise monomer but also comprise its dimerization title complex.
The heteropolyacid specific examples that can be used as the heteropolyacid raw material at the catalyzer that the present invention (I) is used for producing lower aliphatic carboxylic acid ester comprises:
Tungstosilicic acid H
4[SiW
12O
40] xH
2O
Tungstophosphoric acid H
3[PW
12O
40] xH
2O
Molybdophosphate H
3[PMo
12O
40] xH
2O
Molybdenum silicic acid H
4[SiMo
12O
40] xH
2O
Vanadium tungstosilicic acid H
4+n[SiV
nW
12-nO
40] xH
2O
Vanadium tungstophosphoric acid H
3+n[PV
nW
12-nO
40] xH
2O
Vanadium molybdophosphate H
3+n[PV
nMo
12-nO
40] xH
2O
Vanadium molybdenum silicic acid H
4+n[SiV
nMo
12-nO
40] xH
2O
Molybdenum tungstosilicic acid H
4[SiMo
nW
12-nO
40] xH
2O
Molybdenum tungstophosphoric acid H
3[PMo
nW
12-nO
40] xH
2O wherein n is the integer of 1-11, and x is 1 or bigger integer.But the present invention is not limited to this.In these acid, preferred tungstosilicic acid, tungstophosphoric acid, molybdophosphate, molybdenum silicic acid, vanadium tungstosilicic acid and vanadium tungstophosphoric acid, more preferably tungstosilicic acid, tungstophosphoric acid, vanadium tungstosilicic acid and vanadium tungstophosphoric acid.
Synthetic method to these heteropolyacids is not specifically limited, and can use any method.For example, heteropolyacid can contain the acidic aqueous solution (pH: about 1-2) obtain of molybdic acid or tungstate and heteroatomic simple oxygen acid or its salt by heating.For heteropoly compound is separated, can use the method for crystallization and separating metal salt form compound from the heteropolyacid aqueous solution.Specific examples is included in that NipponKagaku Kai edits, Maruzen publishes (on August 20th, 1984)
Shin Jikken Kagaku Synthetic (III))Those of the 3rd edition the 1413rd page of description, but the present invention is not limited to this.The Keggin structure of synthetic heteropolyacid can be measured by chemical analysis or X-ray diffraction or UV or IR and determine.
Heteropolyacid for example has higher solubleness in water and other oxo solvent at polar solvent, and can be by suitably selecting counter ion control solubleness.
Be used for producing the catalyzer of lower aliphatic carboxylic acid ester in the present invention (I), be stated from the carrier as the heteropolyacid of catalytic active component.Can be not specifically limited as the material of carrier, can use the porous mass that is used as carrier usually.Specific examples comprises that those comprise silicon-dioxide, diatomite, montmorillonite, titanium dioxide, gac, aluminum oxide and oxidation sial, the material of preferred silicon-dioxide and titanium dioxide.
The shape of carrier can be powder, sphere, ball shape or other arbitrary shape also without limits.Shape is preferably sphere or ball shape.In addition, granularity also is not specifically limited, and under the situation of fixed-bed reactor, granularity is preferably 2-10mm, more preferably 3-7mm; Under the fluidized-bed reactor situation, granularity is preferably powder to 5mm, and more preferably powder is to 2mm, but depends on reactor and change.
Carrier most preferably is sphere or ball shape siliceous supports.The source of the element that comprises in advance in the carrier and amount can be passed through chemical analysis for example inductively coupled plasma emmission spectrum (hereinafter to be referred as " ICP "), x-ray fluorescence spectrometry or Atomic Absorption Spectrometry.
Be used for producing the first step of the catalyzer of lower aliphatic carboxylic acid ester in the present invention (I), the method that heteropolyacid solution or suspension are stated from the carrier is not specifically limited, and can use known method.Particularly, for example can make solution infiltrate the preparing carriers catalyzer then by heteropolyacid being dissolved in the distilled water suitable with used carrier liquid-absorbent amount.Can also use excessive water solution, make solution infiltrate carrier, remove by filter excess acid then and prepare catalyzer by suitable mobile vehicle in heteropolyacid solution.Solution used herein or suspension vol change with used carrier or carrying method.
Thus obtained moist catalysis is suitably dry by place several hours in process furnace.Drying means is not specifically limited, and can use any method for example to leave standstill or endless belt conveyor.After the drying, catalyzer preferably arrives envrionment temperature so that nonhygroscopic at the moisture eliminator internal cooling.
The heteropolyacid amount that is stated from the catalyzer of carried heteropoly acid can be calculated from the weight that the dried weight of prepared catalyzer deduct used carrier simply.Charge capacity also can be passed through chemical analysis, and for example ICP, x-ray fluorescence spectrometry or atomic absorption spectrum are determined exactly.
Based on all wts of carrier, the charge capacity of heteropolyacid is preferably 10-150 quality %, more preferably 30-100 quality %.
If the content of heteropolyacid is lower than 10 quality %, active component content is low excessively in the catalyzer, and the unit weight activity of such catalysts can descend unfriendly.If the content of heteropolyacid surpasses 200 quality %, the active porosity volume descends, and the result may be difficult to manifest because of the effect that charge capacity improves, and is tending towards occurring coking unfriendly seriously to shorten catalyst life simultaneously.
Second step is described below.Second step that the present invention (I) is used to produce the catalyzer of lower aliphatic carboxylic acid ester is the catalyzer that makes the carried heteropoly acid that obtains at first step and contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts.
The catalyzer that term used herein " contact " means the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact.Contact method is not specifically limited, and for example following method can be used:
(a) catalyzer of the carried heteropoly acid that will obtain at first step places the method for the atmosphere of the gas that contains at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol;
(b) make the gas that contains at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol method by the catalyzer of the carried heteropoly acid that obtains at first step; With
(c) make catalyzer at the carried heteropoly acid that first step obtains contain the method for passing through in the atmosphere of gas of at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol.
Specifically, carry out the method that the method for second step can use the supported catalyst that for example first step is obtained to insert container and contact with gas, or the supported catalyst that first step obtains is not inserted container and inserted in the reactor that carries out the lower aliphatic carboxylic acid ester production technique subsequently and the method that contacts with gas before sending into reaction raw materials.
The type of relevant used container or reactor without any concrete restriction, can be used vertical or horizontal.
Have in mind from the time or the container cost that recharge the catalyzer cost, the preferred embodiment of second step comprises that the supported catalyst that first step is obtained is inserted light alkene and lower alphatic carboxylic acid generates in the reactor of lower aliphatic carboxylic acid ester in gas-phase reaction therein, made it then and contain the method that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts before sending into reaction raw materials.At this moment, the reaction circulating system or the current system that can seal carries out.
Second step is preferably carried out under than the high condition of the dew point of the gas that contains at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol.If condition is lower than the dew point of this gas, portion gas will become liquid.In this case, be stated from the heteropolyacid on the catalyzer or other catalyst component of load when needing may stripping changes the composition of catalyzer in first step, catalyzer may inactivation under the worst case.As long as catalyzer does not affect adversely, the condition of carrying out second step is not specifically limited.
The preferred embodiment that is higher than the condition of gas dew point can change in the enforcement of this step according to gas composition or pressure etc., but contacting temperature is preferably 80-300 ℃, more preferably 100-260 ℃.
Contact pressure is not specifically limited, and can be that normal pressure maybe can be exerted pressure.Contact pressure is preferably 0MPaG (gauge pressure)-3MPaG (gauge pressure), more preferably 0MPaG (gauge pressure)-2MPaG (gauge pressure).
Lower alphatic carboxylic acid in the gas of at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol of second step containing of using is preferably the lower alphatic carboxylic acid that contains 1-6 carbon atom.Specific examples comprises formic acid, acetate, propionic acid, butanic acid and isopropylformic acid.Wherein preferred acetate and propionic acid.
Rudimentary aliphatic alcohol in the gas of at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol of second step containing of using is preferably the rudimentary aliphatic alcohol that contains 1-6 carbon atom.Specific examples comprises methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols and 2-butanols.Wherein particular methanol, ethanol and n-propyl alcohol.
At least a gas composition of using in second step that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol that contains is not specifically limited, and water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol can mix by arbitrary proportion.Its composition is preferably water: lower alphatic carboxylic acid: the mol ratio of rudimentary aliphatic alcohol=1.0: (0.1-10.0): (0.1-5.0).
The composition of gas can be in contact beginning to finishing to keep constant or according to changing duration of contact or contact phase.
The gas of at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol more preferably only is the mixed gas of water or water and acetate in second step containing of using; The mixed gas of further preferably water and acetate, this is because can tell at short notice.
Under the situation of the mixed gas that makes water and acetate as gas, composition is not specifically limited, but the mol ratio of water and acetate is preferably 1.0: (0.1-10.0), and more preferably 1.0: (0.5-5.0).
The gas hourly space velocity of gas (hereinafter to be referred as " GHSV "), promptly make with contain second step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts in the speed of sending into of gas be not specifically limited.GHSV is preferably 100-7,000hr
-1, 300-3 more preferably, 000hr
-1
If GHSV is too high, the gas usage quantity improves, and considers not preferred from the cost angle.Based on this viewpoint, the gas that contact also can be by sending into constant and it is enclosed in the container carries out.
Be not specifically limited duration of contact, but preferred 0.5-200 hour, more preferably 0.5-100 hour, most preferably 0.5-50 hour.Best Times with gas composition and concentration, contact temperature and pressure and catalyst component changes.
Usually, if be lower than 0.5 hour duration of contact, the effect of second step can not manifest fully; Otherwise if prolong duration of contact, effect is tending towards improving, even but extending to duration of contact above 200 hours, effect will no longer improve; In addition, gas with flow state contact situation under the gas usage quantity improve, have in mind for not preferred from yield.
Be used for producing the catalyzer of lower aliphatic carboxylic acid ester in the present invention (I), the first step and second step can independently be carried out continuously or fully.More particularly, for example be used to produce in the range of catalysts of lower aliphatic carboxylic acid ester by buying through the heteropolyacid of first step and making its catalyzer of producing lower aliphatic carboxylic acid ester by second step process being used to of obtaining be included in the present invention (I) certainly subsequently.
The present invention (II) is described below.The present invention (II) is a kind of Preparation of catalysts method that is used to produce lower aliphatic carboxylic acid ester, and this catalyzer is used for light alkene and lower alphatic carboxylic acid is produced lower aliphatic carboxylic acid ester in gas-phase reaction, and wherein production method comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid; With
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
At heteropolyacid that first step uses and carrier, heteropolyacid is stated from method on the carrier at first step, the preferred negative carrying capacity of heteropolyacid is identical with the present invention (I) on the method for measuring the loaded by heteropoly acid amount and the carrier.
In addition, make catalyzer and contain the method that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts what second step was carried out, such as conditions such as temperature, pressure, GHSV and times, lower alphatic carboxylic acid that uses in the gas and rudimentary aliphatic alcohol, and also identical to the ratio of components of the gas that wherein adds water in addition with the present invention (I).
Be used for producing the Preparation of catalysts method of lower aliphatic carboxylic acid ester in the present invention (II), as long as comprise following first and second steps, if desired, can be before these steps, afterwards or add other step in the process.
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid.
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
The step example that provides as required comprises that loading the 3rd composition is so that improve the step of catalytic activity more.In this case, if possible, loading operation can carry out simultaneously with the operation that first step loads heteropolyacid.
After making catalyzer and containing second step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts, catalyzer can further contact with other gas.
The present invention (III) is described below.The present invention (III) is a kind of method of producing lower aliphatic carboxylic acid ester, is included in catalyzer that the present invention (I) is used to produce lower aliphatic carboxylic acid ester and makes light alkene and lower alphatic carboxylic acid in gas-phase reaction under existing.
In the method for implementing the present invention (III) production lower aliphatic carboxylic acid ester, the reaction formation of gas-phase reaction does not have particular restriction, can use any form such as fixed bed or fluidized-bed to react.According to the reaction formation that adopts, the support shapes of decision catalyst shape or size can be selected to being of a size of in several millimeters the briquetting scope from powder.
Can comprise ethene, propylene, n-butene, iso-butylene at the example that the present invention (III) produces the light alkene that use in the method for lower aliphatic carboxylic acid ester and two or more mixture in them.
It is the aliphatic carboxylic acid that contains 1-4 carbon atom that lower alphatic carboxylic acid is fit to, and specific examples comprises formic acid, acetate, propionic acid, butyric acid, vinylformic acid, methacrylic acid and two or more mixture in them.Wherein preferred acetate, propionic acid and vinylformic acid, more preferably acetate.
Preferably the specific examples of light alkene that uses in the method (III) of producing lower aliphatic carboxylic acid ester and lower alphatic carboxylic acid combination comprises ethene and acetate, ethene and propionic acid, propylene and acetate and propylene and propionic acid.Wherein most preferred combination is ethene and acetate.
Be not specifically limited as the light alkene of raw material and the ratio of lower alphatic carboxylic acid.Consider from the angle that light alkene transforms, light alkene preferably with mole or excessive use such as lower alphatic carboxylic acid.Specifically, the mol ratio of light alkene and lower alphatic carboxylic acid is preferably light alkene: lower alphatic carboxylic acid=1: 1-30: 1, more preferably 3: 1-20: 1, further more preferably 5: 1-15: 1.
Interpolation to water in the raw material is not specifically limited, and can add or can not add.Have in mind from the angle of keeping catalytic activity, preferably add less water.But if the addition of water is excessive, the amount of by product such as pure and mild ether will improve unfriendly.
In the production method of the present invention (III) lower aliphatic carboxylic acid ester, preferred reaction conditions such as temperature and pressure change with light alkene and the lower alphatic carboxylic acid as raw material.Reaction conditions such as temperature and pressure preferably combination are so that every kind of raw material can keep gaseous state and reaction to carry out satisfactorily.
Usually, temperature is preferably 120 ℃-300 ℃, more preferably 140 ℃-250 ℃.Pressure is preferably barometric point-3MPaG (gauge pressure), more preferably barometric point-2MPaG (gauge pressure).
Every kind of raw material is not specifically limited on GHSV.If GHSV is too high, gas passes through before reaction satisfaction is carried out, if instead GHSV is low excessively, may produce the problem that productivity descends.GHSV is preferably 100hr
-1-7,000hr
-1, more preferably 300hr
-1-3,000hr
-1
By-product alcohol that produces in unreacted light alkene and the reaction and ether can recirculation and former state uses.
The present invention (IV) is described below.The present invention (IV) is a kind of method of producing lower aliphatic carboxylic acid ester, comprises light alkene and lower alphatic carboxylic acid in gas-phase reaction, and wherein this production method comprises following first to fourth step:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid;
Second step
The catalyzer of the carried heteropoly acid that first step is obtained is inserted and is used for the step that light alkene and lower alphatic carboxylic acid carry out the reactor of gas-phase reaction;
Third step
Make and contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts with the catalyzer of the carried heteropoly acid of inserting reactor; With
The 4th step
Make the mixed gas that contains light alkene and lower alphatic carboxylic acid catalyzer, to obtain the step of lower aliphatic carboxylic acid ester by the carried heteropoly acid handled through third step.
First step is described below.First step in the production method of the present invention (IV) lower aliphatic carboxylic acid ester is that one or more heteropolyacids are stated from the step that obtains the catalyzer of carried heteropoly acid on the carrier.
Heteropolyacid that first step uses and carrier, the method that heteropolyacid is stated from carrier that first step carries out, measure the loaded by heteropoly acid amount method and carrier on the preferred negative carrying capacity of heteropolyacid identical with the present invention (I).
Second step is described below.Second step in the production method of the present invention (IV) lower aliphatic carboxylic acid ester is that the catalyzer of carried heteropoly acid that first step is obtained is inserted and is used for light alkene and lower alphatic carboxylic acid in the step of the reactor of gas-phase reaction.
Second step is the catalyzer of carried heteropoly acid to be inserted the step of the reactor that is used for light alkene and lower alphatic carboxylic acid reaction, so the present invention (I) is used to produce second step of the catalyzer of lower aliphatic carboxylic acid ester, or the present invention (II) is used to produce second step of the Preparation of catalysts method of lower aliphatic carboxylic acid ester, though the catalyzer that first step obtains carried heteropoly acid with contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts and can not use other container in this reactor, to carry out.
The reactor that uses in second step is not specifically limited.Fixed Bed Gas Phase contact-type reactor is preferred, and the reactor with multitube system and/or multilayer system form is for more preferably.Usually, it is more outstanding at the aspects such as easiness of reaction result, thermo-efficiency, control to have a reactor of multitube system and/or multilayer system form.Certainly, the present invention is not limited to this.
In the present invention, term " is inserted reactor with catalyzer " meaning is put into the predetermined position of reactor with catalyzer.The method of position and placement and use the variation of the method for stagnant catalyst under the fixed bed system situation according to reactor at reactor, and be not specifically limited.The specific examples of reactor be included in by Kagagu Kogyo Kyokai edit, Maruzen publishes (on February 20th, 1980)
Kagaku Sochi Binran (chemical apparatus handbook)Second edition is augmented the figure C443 " methyl alcohol contact Gas-phase reactor " in the described column of 905-906 page or leaf " 4) stagnant catalyst Gas-phase reactor " for the third time.
Third step is described below.Third step in the production method of the present invention (IV) lower aliphatic carboxylic acid ester is to make to contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts with the catalyzer of the carried heteropoly acid of inserting reactor.
Making of carrying out in the third step contains the method that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts with the catalyzer of the carried heteropoly acid of inserting reactor, condition such as temperature, pressure, GHSV and time, lower alphatic carboxylic acid and rudimentary aliphatic alcohol that gas uses, and identical to the ratio of components of the gas that wherein adds water in addition with the present invention's (I) second step.
The condition that contacts in reactor is not specifically limited, and preferred condition is considered to change according to form, shape, size or the building material of the reactor that is used to contact.Usually, contact can be carried out under the condition of above-mentioned the present invention (I) second step.
The 4th step is described below.The present invention's (IV) the 4th step is to make the mixed gas that contains light alkene and the lower alphatic carboxylic acid catalyzer by the carried heteropoly acid handled through third step, to obtain the step of lower aliphatic carboxylic acid ester.
Aspect specific examples, the light alkene that the 4th step is used and the preferably combination and the amount ratio of lower alphatic carboxylic acid amount, the implementation condition in the 4th step such as interpolation, temperature, pressure and the GHSV of water, and the main recirculation operation of unreacted light alkene, can use the present invention (III) to produce in the method for lower aliphatic carboxylic acid ester those.
The present invention's (IV) third step and the 4th step can have maybe and can significantly not distinguish.Have between two steps in the example of embodiment of obvious differentiation and comprise this situation: after the contact of judging third step is finished, stop to feed the gas stream that contains at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol immediately or further reduce temperature and pass through with the unstripped gas that stops third step, make then containing light alkene and lower alphatic carboxylic acid reactant gases as the 4th step.
Do not have between two steps to comprise this situation in the example of the embodiment obviously distinguished: after the contact of judging third step is finished, when not stopping to feed the gas stream that contains at least a composition that is selected from water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol immediately or by adjusting temperature to being fit in the temperature range that the preparation of the 4th step begins to react the unstripped gas that contains light alkene and lower alphatic carboxylic acid to be passed through as the 4th step reaction gas.
For example, when the lower alphatic carboxylic acid that wherein is used for contacting at third step is that reaction can be carried out according to the embodiment that not have obviously differentiation between third and fourth step when producing the corresponding lower alphatic carboxylic acid of target ester of method of lower aliphatic carboxylic acid ester with the present invention (IV).On the other hand, when the lower aliphatic carboxylic carboxylic that wherein is used to contact at third step is not during with the corresponding lower alphatic carboxylic acid of target ester, reaction is preferably carried out with the embodiment that obvious differentiation is arranged between third and fourth step.
Usually, the contact of third step preferably uses the corresponding lower alphatic carboxylic acid of producing in the method for lower aliphatic carboxylic acid ester with the present invention (IV) of target ester to carry out.For example, using the present invention (IV) to produce under the situation of method production ethyl acetate as lower aliphatic carboxylic acid ester of lower aliphatic carboxylic acid ester, one of them embodiment preferred is to use the mixed gas of water and acetate to contact the constant time under controlled condition to carry out the contact of third step, change the interior various conditions of reactor such as temperature, pressure and GHSV then to be fit to the production method of lower aliphatic carboxylic acid ester, then ethene is added and introduced in the gas of reactor.Certainly, the present invention (IV) is not limited in this.
Below with reference to embodiment and Comparative Examples the present invention is elaborated, but the present invention should not be limited.The analysis condition of metal in the carrier
Use x-ray fluorescence analysis instrument (PW2404 is made by PHILIPS) that the metal in the carrier is analyzed.Measuring condition is: atmosphere is helium, and effective diameter is 25.0mm, and matrix is 2SiO
2The analysis condition of uncondensed gas
Use absolute calibration curve method to analyze.Analysis is carried out under following condition: the eluting gas of getting 50ml all feeds it in 1ml gas sampler that is installed on the gas chromatographicanalyzer then as sample.1. ether, carboxylicesters, pure and mild trace by product gas chromatographicanalyzer: have the gas sampler (MGS-4 that is used for the Shimadzu gas chromatographic analysis, measuring tube: gas chromatographicanalyzer (GC-14B 1ml), make by Shimadzu Seisakusho Co.) post: packed column SPAN 80, (length: 5m) carrier gas: nitrogen (flow velocity: 25ml/ minute) temperature condition: the temperature of detector and vaporizing chamber is 120 ℃ to 60-80 purpose Shinchrom A 15%, and the temperature of post is 65 ℃ and keeps constant.Detector: FID (H
2Pressure: 60kPa, air pressure: 100kPa) 2. butylene gas chromatographicanalyzers: have the gas sampler (MGS-4 that is used for the Shimadzu gas chromatographic analysis, measuring tube: gas chromatographicanalyzer (GC-14B 1ml), make by Shimadzu Seisakusho Co.) post: 80/100 purpose Unicarbon A-400 packed column, length: 2m carrier gas: helium (flow velocity: 23ml/ minute) temperature condition: the temperature of detector and vaporizing chamber is 130 ℃, and the temperature of post is elevated to 95 ℃ with 40 ℃/minute temperature rise rate by 40 ℃.Detector: FID (H
2Pressure: 70kPa, air pressure: 100kPa) 3. ethene gas chromatographicanalyzers: have the gas sampler (MGS-4 that is used for the Shimadzu gas chromatographic analysis, measuring tube: gas chromatographicanalyzer 1ml) (GC-14B, Shimadzu Seisakusho Co. makes).Post: Unibeads IS packed column, length: 3m.Carrier gas: helium (flow velocity: 20ml/ minute).Temperature condition: the temperature of detector and vaporizing chamber is 120 ℃, and the temperature of post is 65 ℃ and keeps constant.Detector: TCD (He pressure: 70kPa, electric current: 90mA, temperature: 120 ℃).Collect the analysis of liquid
Use marker method to analyze, wherein analytical solution is passed through 1ml1, and the 4-dioxane adds the 10ml reaction soln as interior mark and prepared, and injects 0.4 μ l analytical solution.Gas chromatographicanalyzer: gas chromatographicanalyzer (GC-14B is made by Shimadzu Seisakusho Co.).Post: capillary column TC-WAX (length: 30m, internal diameter: 0.25mm, thickness: 0.25 μ m).Carrier gas: nitrogen (splitting ratio: 20, column flow rate: 1ml/ minute).Temperature condition: the temperature of detector and vaporizing chamber is 200 ℃, and the temperature of analyzing the beginning post certainly kept 7 minutes at 40 ℃ earlier, is elevated to 230 ℃ with 10 ℃/minute temperature rise rate then, and keeps 5 minutes at 230 ℃.Detector: FID (H
2Pressure: 70kPa, air pressure: 100kPa).＜carrier〉carrier 1: synthetic silica (N-602T is made by Nikki Kagaku K.K.) (specific surface area: 132m
2/ g, pore volume: 0.7cm
3/ g).Carrier 2: synthetic silica (CARiACT Q-10 is made by Fuji Silicia Kagaku K.K.) (specific surface area: 219.8m
2/ g, pore volume: 0.660cm
3/ g).Carrier 3: silica gel (Wakogel C-200 is made by Wako Junyaku Kogyo K.K.) (specific surface area: 762m
2/ g, pore volume: 0.23cm
3/ g).
The metal analysis of every kind of carrier the results are shown in table 1.
Table 1
| ??SiO 2 | ??K 2O | ??Na 2O | ||
| ????1 | ????N-602T | ??99.7 | ??0.0085 | ??0.3190 |
| ????2 | ????CARiACT?Q-10 | ??100.0 | ??- | ??0.0214 |
| ????3 | ????C-200 | ??100.0 | ??- | ??- |
The preparation method of unit (%)＜catalyzer 1 〉
In adjusting to 110 ℃ moisture eliminator (hot-air type) in advance with carrier 1 preliminarily dried 4 hours.Behind the preliminarily dried, use the bulk density of 1 liter of this carrier of graduated cylinder measurement of 1 liter.Take by weighing tungstosilicic acid, make its uniform dissolution to wherein adding the 15ml pure water then as the listed amount of table 1.To further adding pure water in this dipping solution so that amount of liquid shown in the volume of table 2 preparation solution.Then, take by weighing through pre-dried carrier, put into dipping solution, in well-beaten this solution impregnation of using simultaneously according to the amount shown in the table 2.To transfer in the ceramic disc through the carrier of solution impregnation, air-dry 1 hour, then at the hot-air type moisture eliminator inner drying 5 hours of adjusting to 150 ℃.After the drying, catalyzer is moved in the moisture eliminator, leave standstill cool to room temperature.Measure the weight of thus obtained catalyzer.
Table 2
HPW:H
3PW
12O
40HSiW:H
4SiW
12O
40HPVW:H
4PVW
11O
40The preparation method of＜catalyzer 2-7 〉
| The catalyzer title | Carrier | Bulk density (g/L) | Vehicle weight (g) | The kind of catalyst component | The amount of catalyst component (g) | The volume (ml) of preparation solution | Dried weight (g) |
| Catalyzer 1 | Carrier 1 | ??813 | ??81.3 | ??HSiW | ????46.51 | ??69 | ????112.2 |
| Catalyzer 2 | Carrier 1 | ??813 | ??81.3 | ??HSiW | ????40.70 | ??69 | ????116.8 |
| Catalyzer 3 | Carrier 2 | ??456 | ??45.6 | ??HSiW | ????40.70 | ??43 | ????76.1 |
| Catalyzer 4 | Carrier 1 | ??813 | ??81.3 | ??HPW | ????47.51 | ??69 | ????116.8 |
| Catalyzer 5 | Carrier 1 | ??813 | ??81.3 | ??HPW | ????53.44 | ??69 | ????121.9 |
| Catalyzer 6 | Carrier 2 | ??456 | ??45.6 | ??HPVW | ????35.90 | ??43 | ????76.3 |
| Catalyzer 7 | Carrier 3 | ??1045 | ??104.5 | ??HSiW | ????34.88 | ??31 | ????134.7 |
Prepare these catalyzer by changing kind of carrier and weight, the kind of catalyst component and weight are shown in the table 2 among catalyzer 1 preparation method.
Embodiment 1
The catalyzer that obtains among 50ml catalyzer 1 preparation method is inserted in the pressure vessel of being made by SUS316L, under the listed contact conditions of table 3, contacted then.After the contact, container recovery room temperature and the catalyzer (being designated hereinafter simply as " contact catalyst ") that will be used to contact take out from container.Afterwards, the 40ml contact catalyst inserted in the reaction tubes and be that 165 ℃, pressure are that 0.8MPaG (gauge pressure) and GHSV are 1,500hr in temperature
-1Condition under introduce ethene: acetate: steam: nitrogen (volume ratio=78.5: 8.0: 4.5: 9.0) mixed gas, and reaction.Gas by catalyst layer is collected down to schedule ice-cooled, and whole amounts are reclaimed and analyze (being designated hereinafter simply as " condensing soln ").Uncooled exit gas (being designated hereinafter simply as " uncondensed gas ") is got gaseous sample and the analysis of 50ml then according to the scheduled time measurement gas flow velocity identical with condensing soln.The results are shown in table 3.
Table 3
Embodiment 2-11
| Catalyzer | Pretreatment condition | Reaction result | ||||||||
| Handle gas composition, acetate: water: nitrogen (mol ratio) | Gas flow rate (NL/hr) | Pressure (MPaG) | Treatment temp (℃) | Treatment time (hour) | Reaction times (hour) | Ethyl acetate, STY (g/L-hr) | Butylene generation (vol ppm) | Trace by product (wt%) | ||
| Embodiment 1 | Catalyzer 1 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????245 ????234 | ????313 ????399 | ??0.0119 ??0.0138 |
| Embodiment 2 | Catalyzer 1 | ????0.0∶12.5∶87.5 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????243 ????231 | ????424 ????521 | ??0.0123 ??0.0140 |
| Embodiment 3 | Catalyzer 2 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????265 ????251 | ????419 ????515 | ??0.0132 ??0.0154 |
| Embodiment 6 | Catalyzer 3 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????254 ????243 | ????245 ????342 | ??0.0089 ??0.0111 |
| Embodiment 7 | Catalyzer 4 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????255 ????242 | ????480 ????578 | ??0.0243 ??0.0340 |
| Embodiment 8 | Catalyzer 4 | ????0.0∶12.5∶87.5 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????253 ????241 | ????491 ????582 | ??0.0251 ??0.0374 |
| Embodiment 9 | Catalyzer 5 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????267 ????253 | ????524 ????589 | ??0.0359 ??0.0462 |
| Embodiment 10 | Catalyzer 6 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????140 ????136 | ????150 ????192 | ??0.0050 ??0.0075 |
| Embodiment 11 | Catalyzer 7 | ????6.0∶6.0∶88.0 | ??60.0 | ????0.8 | ??165 | ??12 | ??5 ??50 | ????235 ????228 | ????319 ????342 | ??0.0098 ??0.0113 |
According to the mode identical, insert the catalyzer that obtains among 50ml catalyzer 1 preparation method in the pressure vessel of making by SUS316L and under the listed contact conditions of table 3, contact with embodiment 1.Then, take out catalyzer, it is inserted in the reaction tubes and react in the mode identical with embodiment 1.The results are shown in table 3.Comparative Examples 1
40ml and embodiment 1 identical catalyzer is inserted in the reaction tubes, is that 165 ℃, pressure are that 0.8MPaG (gauge pressure) and GHSV are 1 in temperature then, 500hr
-1Condition under introduce ethene: acetate: steam: nitrogen (volume ratio=78.5: 8.0: 4.5: 9.0) mixed gas and reaction.According to the gas of the method Collection and analysis identical by catalyst layer with embodiment 1.The results are shown in table 4.
Table 4
Comparative Examples 2-7
| Catalyzer | Pretreatment condition | Reaction result | ||||||||
| Handle gas composition, acetate: water: nitrogen (mol ratio) | Gas flow rate (NL/hr) | Pressure (MPaG) | Treatment temp (℃) | Treatment time (hour) | Reaction times (hour) | Ethyl acetate, STY (g/L-hr) | Butylene generation (vol ppm) | Trace by product (wt%) | ||
| Comparative Examples 1 | Catalyzer 1 | Do not have | - | - | - | - | ??5 ??50 | ????230 ????214 | ????420 ????443 | ??0.0219 ??0.0253 |
| Comparative Examples 2 | Catalyzer 2 | Do not have | - | - | - | - | ??5 ??50 | ????247 ????228 | ????453 ????589 | ??0.0255 ??0.0348 |
| Comparative Examples 3 | Catalyzer 3 | Do not have | - | - | - | - | ??5 ??50 | ????245 ????216 | ????308 ????328 | ??0.0123 ??0.0145 |
| Comparative Examples 4 | Catalyzer 4 | Do not have | - | - | - | - | ??5 ??50 | ????245 ????226 | ????521 ????604 | ??0.0352 ??0.0492 |
| Comparative Examples 5 | Catalyzer 5 | Do not have | - | - | - | - | ??5 ??50 | ????255 ????236 | ????480 ????578 | ??0.0234 ??0.0329 |
| Comparative Examples 6 | Catalyzer 6 | Do not have | - | - | - | - | ??5 ??50 | ????135 ????124 | ????200 ????243 | ??0.0129 ??0.0246 |
| Comparative Examples 7 | Catalyzer 7 | Do not have | - | - | - | - | ??5 ??50 | ????225 ????208 | ????424 ????534 | ??0.0234 ??0.0358 |
Insert reaction tubes according to the catalyzer that the method identical with Comparative Examples 1 is listed with 40ml table 2, and react according to the mode identical with Comparative Examples 1.Reaction result is listed in table 4.
Industrial usability
The result given by the front obviously can find out: can suppress activity decreased by comprise particular step in the preparation of heteropolyacid catalyst, and when in the method for being produced lower aliphatic carboxylic acid ester by light alkene and lower alphatic carboxylic acid, being used as catalyst, can show high initial activity and high space-time yield, thereby in industrial practice, guarantee sufficiently long catalyst life and reduce the generation of accessory substance.
Claims (25)
1. catalyzer that is used to produce lower aliphatic carboxylic acid ester, this catalyzer are produced in the lower aliphatic carboxylic acid ester in gas-phase reaction at light alkene and lower alphatic carboxylic acid and are used, and the method that wherein prepares described catalyzer comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid; With
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
2. catalyzer as claimed in claim 1, wherein second step is carried out in the reactor of gas-phase reaction being used for light alkene and lower alphatic carboxylic acid.
3. catalyzer as claimed in claim 1 or 2, wherein heteropolyacid is selected from tungstosilicic acid, tungstophosphoric acid, molybdophosphate, molybdenum silicic acid, vanadium tungstosilicic acid, vanadium tungstophosphoric acid, vanadium molybdophosphate, vanadium molybdenum silicic acid, molybdenum tungstosilicic acid and molybdenum tungstophosphoric acid.
4. method for preparing the catalyzer that is used to produce lower aliphatic carboxylic acid ester, described catalyzer be used for light alkene and lower alphatic carboxylic acid in gas-phase reaction to produce lower aliphatic carboxylic acid ester, wherein this method comprises following first and second steps:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid; With
Second step
The catalyzer that makes the carried heteropoly acid that obtains at first step with contain at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol and contact the step that is used to produce the catalyzer of lower aliphatic carboxylic acid ester with acquisition.
5. method as claimed in claim 4, wherein second step is carried out in the reactor of gas-phase reaction being used for light alkene and lower alphatic carboxylic acid.
6. as claim 4 or 5 described methods, wherein heteropolyacid is selected from tungstosilicic acid, tungstophosphoric acid, molybdophosphate, molybdenum silicic acid, vanadium tungstosilicic acid, vanadium tungstophosphoric acid, vanadium molybdophosphate, vanadium molybdenum silicic acid, molybdenum tungstosilicic acid and molybdenum tungstophosphoric acid.
7. as each described method among the claim 4-6, wherein second step is carried out under 80-300 ℃.
8. as each described method among the claim 4-7, wherein second step is carried out under the pressure of 0MPaG (gauge pressure)-3MPaG (gauge pressure).
9. as each described method among the claim 4-8, wherein second step is at 100-7,000hr
-1Gas hourly space velocity (GHSV) under carry out.
10. as each described method among the claim 4-9, wherein second step is used contains at least a mixed gas that is selected from the gas of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol as water and acetate.
11. a method of producing lower aliphatic carboxylic acid ester is included under the existence of the catalyzer of each requirement among the claim 1-3 and makes light alkene and lower alphatic carboxylic acid in gas-phase reaction.
12. a method of producing lower aliphatic carboxylic acid ester is included under water and the existence as the catalyzer of each requirement among the claim 1-3 and makes light alkene and lower alphatic carboxylic acid in gas-phase reaction.
13. as claim 11 or 12 described methods, wherein light alkene is selected from ethene, propylene, n-butene and iso-butylene.
14. as each described method among the claim 11-13, wherein lower alphatic carboxylic acid is selected from formic acid, acetate, propionic acid, butyric acid, vinylformic acid and methacrylic acid.
15. as each described method among the claim 11-14, wherein light alkene is an ethene, lower alphatic carboxylic acid is an acetate.
16. a method of producing lower aliphatic carboxylic acid ester in gas-phase reaction by light alkene and lower alphatic carboxylic acid, wherein this method comprises following first to fourth step:
First step
One or more heteropolyacids are stated from the carrier step with the catalyzer that obtains carried heteropoly acid;
Second step
The catalyzer of the carried heteropoly acid that first step is obtained is inserted and is used for the step that light alkene and lower alphatic carboxylic acid carry out the reactor of gas-phase reaction;
Third step
Make and contain the step that at least a gas that is selected from the composition of water, lower alphatic carboxylic acid and rudimentary aliphatic alcohol contacts with the catalyzer of the carried heteropoly acid of inserting reactor; With
The 4th step
Make the mixed gas that contains light alkene and lower alphatic carboxylic acid catalyzer, to obtain the step of lower aliphatic carboxylic acid ester by the carried heteropoly acid handled through third step.
17. method as claimed in claim 16, wherein heteropolyacid is selected from tungstosilicic acid, tungstophosphoric acid, molybdophosphate, molybdenum silicic acid, vanadium tungstosilicic acid, vanadium tungstophosphoric acid, vanadium molybdophosphate, vanadium molybdenum silicic acid, molybdenum tungstosilicic acid and molybdenum tungstophosphoric acid.
18. as claim 16 or 17 described methods, wherein third step carries out under 80-300 ℃.
19. as each described method among the claim 16-18, wherein third step carries out under the pressure of 0MpaG (gauge pressure)-3MPaG (gauge pressure).
20. as each described method among the claim 16-19, wherein third step is at 100-7,000hr
-1Gas hourly space velocity (GHSV) under carry out.
21. as each described method among the claim 16-20, wherein the lower alphatic carboxylic acid that uses at third step is identical with the lower alphatic carboxylic acid of producing the lower aliphatic carboxylic acid ester use.
22. as each described method among the claim 16-21, wherein the light alkene that uses in the 4th step is selected from ethene, propylene, n-butene and iso-butylene.
23. as each described method among the claim 16-22, wherein the lower alphatic carboxylic acid that uses in the 4th step is selected from formic acid, acetate, propionic acid, butyric acid, vinylformic acid and methacrylic acid.
24. as each described method among the claim 16-23, wherein the light alkene that uses in the 4th step is an ethene, the lower alphatic carboxylic acid that uses in the 4th step is an acetate.
25. as each described method among the claim 16-24, wherein the mixed gas that contains light alkene and lower alphatic carboxylic acid that uses in the 4th step contains water.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP271416/2000 | 2000-09-07 | ||
| JP2000271416A JP2002079089A (en) | 2000-09-07 | 2000-09-07 | Catalyst for manufacturing lower aliphatic carboxylic acid ester, method for manufacturing the same and method for manufacturing lower aliphatic carboxylic acid ester by catalyst |
| US23843100P | 2000-10-10 | 2000-10-10 | |
| US60/238,431 | 2000-10-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1452511A true CN1452511A (en) | 2003-10-29 |
Family
ID=26599436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01815333 Pending CN1452511A (en) | 2000-09-07 | 2001-09-05 | Catalyst for producing lower aliphatic carboxylic acid esters |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1353749A2 (en) |
| CN (1) | CN1452511A (en) |
| AU (1) | AU2001284440A1 (en) |
| BR (1) | BR0113736A (en) |
| WO (1) | WO2002020158A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980114A (en) * | 2014-04-14 | 2014-08-13 | 武汉强丰新特科技有限公司 | Preparation method of dicyclopentadienyl acrylate |
| CN104030919A (en) * | 2014-06-27 | 2014-09-10 | 无锡阿科力科技股份有限公司 | Process method for preparing (methyl) tert-butyl acrylate through continuous method |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070057853A (en) | 2004-09-22 | 2007-06-07 | 비피 케미칼즈 리미티드 | Silica support, heteropolyacid catalyst produced therefrom and ester synthesis using the silica supported heteropolyacid catalyst |
| EP2089156B1 (en) * | 2006-11-22 | 2022-01-05 | Technip E&C Limited | Process for producing alkenes from oxygenates by using supported heteropolyacid catalysts |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3012059B2 (en) * | 1991-11-05 | 2000-02-21 | 昭和電工株式会社 | Method for producing lower fatty acid ester |
| EP0959064B1 (en) * | 1995-08-02 | 2001-12-12 | BP Chemicals Limited | Ester synthesis |
| EP1294673B1 (en) * | 2000-06-27 | 2005-03-16 | Showa Denko K.K. | Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst |
-
2001
- 2001-09-05 BR BR0113736-0A patent/BR0113736A/en not_active IP Right Cessation
- 2001-09-05 EP EP01963448A patent/EP1353749A2/en not_active Withdrawn
- 2001-09-05 WO PCT/JP2001/007709 patent/WO2002020158A2/en not_active Application Discontinuation
- 2001-09-05 AU AU2001284440A patent/AU2001284440A1/en not_active Abandoned
- 2001-09-05 CN CN 01815333 patent/CN1452511A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980114A (en) * | 2014-04-14 | 2014-08-13 | 武汉强丰新特科技有限公司 | Preparation method of dicyclopentadienyl acrylate |
| CN103980114B (en) * | 2014-04-14 | 2016-01-20 | 武汉强丰新特科技有限公司 | A kind of preparation method of vinylformic acid DCPA |
| CN104030919A (en) * | 2014-06-27 | 2014-09-10 | 无锡阿科力科技股份有限公司 | Process method for preparing (methyl) tert-butyl acrylate through continuous method |
| CN104030919B (en) * | 2014-06-27 | 2015-11-18 | 无锡阿科力科技股份有限公司 | A kind of processing method of continuous processing preparation (methyl) tert-butyl acrylate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2002020158A3 (en) | 2002-06-20 |
| EP1353749A2 (en) | 2003-10-22 |
| AU2001284440A1 (en) | 2002-03-22 |
| WO2002020158A2 (en) | 2002-03-14 |
| BR0113736A (en) | 2003-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1154537C (en) | Prodn. of unsaturated acids or esters thereof and catalysts therefor | |
| CN1062550C (en) | Process for production of unsaturated aldehyde and unsaturated carboxylic acid | |
| CN1085197C (en) | Ester synthesis | |
| CN86102420A (en) | The method of carboxylic acid alcohols production by hydrogenation | |
| US20040152915A1 (en) | Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst, and process for producing lower aliphatic carboxylic acid ester using the catalyst | |
| CN1295550A (en) | Processes for preparing oxygenates and catalysts therefor | |
| KR20200053567A (en) | Catalysts and methods for the production of ethylenically unsaturated carboxylic acids or esters | |
| CN1635929A (en) | Heteropolyacid catalyst for producing lower aliphatic carboxylic acid ester | |
| EP1572356A1 (en) | Heteropolyacid and/or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst | |
| CN1147773A (en) | High activity catalysts | |
| CN1750878A (en) | Catalyst for methacrylic acid production and process for producing the same | |
| CN1452511A (en) | Catalyst for producing lower aliphatic carboxylic acid esters | |
| CN1129476C (en) | Catalyst for use in producing lower fatty acid ester, process for producing the catalyst, and process for producing lower fatty acid ester using the catalyst | |
| CN1516621A (en) | Regeneration of catalyst for use in production of lower aliphatic carboxylic acid ester and production of lower aliphatic carboxylic acid ester | |
| CN1226269C (en) | Process for preparation of lower aliphatic carboxylic acid esters and lower aliphatic carboxylic acid esters prepared by same | |
| CN1283613C (en) | Method for manufacturing lower diphatic carboxylic ester | |
| EP1294673B1 (en) | Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst | |
| CN1222502C (en) | Support for use in catalyst for producing lower aliphatic carboxylic acid ester, catalyst for producing lower aliphatic carboxylic acid ester using the support, process for producing catalyst | |
| US20030054945A1 (en) | Catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst, and process for producing lower aliphatic carboxylic and ester using the catalyst | |
| EP1320517B1 (en) | Process for producing lower aliphatic carboxylic acid ester | |
| CN1189443C (en) | Process for producing esters | |
| CN1681758A (en) | Method for manufacturing 4-alkylphenols | |
| CN1428327A (en) | Method for preparing catalyst of low-grade fatty acid ester | |
| US20040242918A1 (en) | Support and catalyst for use in producing lower aliphatic carboxylic acid ester, process for producing the catalyst and process for producing lower aliphatic carboxylic acid ester using the catalyst | |
| JP2002079090A (en) | Catalyst for manufacturing lower aliphatic carboxylic acid ester, method for manufacturing the same and method for manufacturing lower aliphatic carboxylic acid ester by catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |