CN1759089A - Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols - Google Patents
Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols Download PDFInfo
- Publication number
- CN1759089A CN1759089A CN 200480006238 CN200480006238A CN1759089A CN 1759089 A CN1759089 A CN 1759089A CN 200480006238 CN200480006238 CN 200480006238 CN 200480006238 A CN200480006238 A CN 200480006238A CN 1759089 A CN1759089 A CN 1759089A
- Authority
- CN
- China
- Prior art keywords
- carboxylic acid
- alphatic carboxylic
- production method
- lower alphatic
- earth metal
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for producing a lower aliphatic carboxylic acid alkenyl, comprising reacting a lower olefin, a lower aliphatic carboxylic acid and oxygen in a gas phase in the presence of a catalyst comprising a support having supported thereon a catalyst component containing a compound containing alkali metal and/or alkaline earth metal, an element belonging to Group 11 of the Periodic Table or a compound containing at least one of these elements, and palladium, wherein the conversion of the lower aliphatic carboxylic acid is 80% or less or the concentration of the lower aliphatic carboxylic acid at the reactor outlet is 0.5 mol% or more.
Description
The cross reference of related application
The application is the application of submitting to according to 35U.S.C. § 111 (a), and according to 35U.S.C. § 111 (e) (1), requirement is according to the right of the applying date of the provisional application of submitting to the 19 days March in 2003 of 35U.S.C. § 111 (b) 60/455,588.
Technical field
The present invention relates to produce the method for lower alphatic carboxylic acid alkenyl esters and enol; And the lower alphatic carboxylic acid alkenyl esters and the enol that obtain by this production method.More specifically, the present invention relates to a kind of method from light alkene, lower alphatic carboxylic acid and oxygen production lower alphatic carboxylic acid alkenyl esters; The lower alphatic carboxylic acid alkenyl esters that obtains by this production method; A kind of method of producing enol by the above-mentioned lower alphatic carboxylic acid alkenyl esters of hydrolysis; And the enol that obtains by this production method.
Background technology
In the production method of lower alphatic carboxylic acid alkenyl esters, wherein the lower alphatic carboxylic acid alkenyl esters is obtained by the gas-phase reaction that starts from light alkene, lower alphatic carboxylic acid and oxygen, be extensive use of the catalyzer comprise carrier, support on the carrier as the palladium of main catalyst component with as the basic metal and/or the alkaline earth metal component of promotor.For example, the open 2-91045 (JP-A-2-91045) of Japanese unexamined patent publication No. discloses and has a kind ofly comprised the method for the Catalyst Production allyl acetate of carrier by use, has supported platinum/Potassium ethanoate/copper on the described carrier.
Producing with this catalyst system in the method for allyl acetate, see a kind of phenomenon: as the alkali metal containing and/or the alkaline earth metal compounds of a kind of component of catalyzer or be derived from this compound a kind of component (below, they are referred to as " basic component ") desorption and flow out during reaction from catalyzer, this is counted as a reason that causes catalyst deactivation.The mechanism of desorption is unclear especially, but it is believed that the reason that desorption takes place is that lower alphatic carboxylic acid in the raw material closes with basic component and reacts, generate a kind of new compound (hereinafter referred to as " lower alphatic carboxylic acid compound "), compare with the basic component in being present in catalyzer, this lower alphatic carboxylic acid compound is easier to from the catalyzer desorption.
For overcoming the purpose of this problem, among the JP-A-2-91045, when in the presence of the catalyzer that comprises palladium/Potassium ethanoate/copper, producing allyl acetate, Potassium ethanoate is added to supply gas and sneaks in this system, with the amount of compensation from the Potassium ethanoate of catalyzer desorption.And, in the open 61-238759 (JP-A-61-238759) of Japanese unexamined patent publication No., when in the presence of palladium/Potassium ethanoate catalyzer, producing allyl acetate, the 20ppm Potassium ethanoate is added in the raw acetic acid.
From prevent catalyzer owing to basic metal close/or alkaline earth metal compound flow out and to reduce active position, these technology have certain effect, particularly for the Potassium ethanoate of producing in the allyl acetate.Yet described in these patent disclosures, the high-level efficiency sometimes and the output of stabilization of industry only can not keep for a long time with the Potassium ethanoate amount that control is added in the raw material.More specifically, the Potassium ethanoate that is added partly is trapped in the reactor, and the result is reflected at the interior part of part catalyst layer and carries out, and has reduced total reaction output or has made the catalyst member deterioration and the lost of life.In addition, the Potassium ethanoate that flows out from catalyzer partly is detained, and blocks reaction tubes or increases resistance to flow, is difficult to sometimes produce steadily in the long term.
Summary of the invention
An object of the present invention is to provide a kind of method, this method can long-term stability and more efficient ground production lower alphatic carboxylic acid alkenyl esters.
Another object of the present invention provides a kind of method, and this method can be produced enol by the lower alphatic carboxylic acid alkenyl esters of aforesaid method production effectively by hydrolysis.
As for realizing the result of the intensive research that these purposes are carried out, the inventor has been found that not only by adding to effusive basic component in the raw material and compensating this component, and add this component by the discharge of contained basic component in the control catalyst and with the amount that compensates this discharge, activity of such catalysts and life-span can be kept and operation steady in a long-term can be carried out.The present invention is based on this discovery is achieved.
Particularly, the present invention (I) is a kind of method of producing the lower alphatic carboxylic acid alkenyl esters, this method comprises makes light alkene, lower aliphatic acid and oxygen gas-phase reaction in the presence of catalyzer, this catalyzer comprises the carrier that is loaded with catalyst component on it, described catalyst component comprises (a) and contains basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or comprise the compound of at least a these elements, and (c) palladium; Wherein the transformation efficiency by the lower alphatic carboxylic acid of formula (I) representative is 80% or lower:
Transformation efficiency (%)={ amount (mol) of (amount (mol) of the amount of reactor inlet lower alphatic carboxylic acid (mol)-reactor outlet lower alphatic carboxylic acid)/reactor inlet lower alphatic carboxylic acid } * 100 (1)
The present invention (II) is a kind of lower alphatic carboxylic acid alkenyl esters of being produced by the present invention's (I) method.
The present invention (III) a kind ofly produces the method for enol and comprises the enol that a kind of production method is thus produced, described method comprise make the present invention (II) the lower alphatic carboxylic acid alkenyl esters in the presence of an acidic catalyst hydrolysis to obtain enol.
The present invention with structure like this for example comprises following key element:
[1] a kind of method of producing the lower alphatic carboxylic acid alkenyl esters, this method comprises makes light alkene, lower aliphatic acid and oxygen gas-phase reaction in the presence of catalyzer, this catalyzer comprises the carrier that is loaded with catalyst component on it, described catalyst component comprises (a) and contains basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or comprise the compound of at least a these elements, and (c) palladium; Wherein the transformation efficiency by the lower alphatic carboxylic acid of formula (I) representative is 80% or lower: transformation efficiency (%)={ amount (mol) of (amount (mol) of the amount of reactor inlet lower alphatic carboxylic acid (mol)-reactor outlet lower alphatic carboxylic acid)/reactor inlet lower alphatic carboxylic acid } * 100 (1)
[2] a kind of method of producing the lower alphatic carboxylic acid alkenyl esters, this method comprises makes light alkene, lower aliphatic acid and oxygen gas-phase reaction in the presence of catalyzer, this catalyzer comprises the carrier that is loaded with catalyst component on it, described catalyst component comprises (a) and contains basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or comprise the compound of at least a these elements, and (c) palladium; Wherein the concentration of reactor exit lower alphatic carboxylic acid is 0.5mol% or higher.
[3] production method described in above [1] or [2], the per hour rate of outflow of being represented by formula (2) that contains basic metal and/or alkaline earth metal compounds is 1.0 * 10
-5-0.01%/h: the quality (kg) of basic metal or alkaline-earth metal in the total catalyst of the basic metal that rate of outflow (%) h={ records or the quality (kg/h) of alkaline-earth metal/filling } * 100 (2)
[4] as each described production method in above [1]-[3], wherein (a) contains basic metal and/or alkaline earth metal compounds is to comprise at least a compound that is selected from lithium, sodium, potassium, caesium, magnesium, calcium and the barium.
[5] as each described production method in above [1]-[4], wherein (a) contains basic metal and/or alkaline earth metal compounds is a lower alphatic carboxylic acid salt.
[6] production method described in above [5], wherein lower alphatic carboxylic acid salt is selected from least a in lithium, sodium, potassium, caesium, magnesium, calcium and the barium salt of formic acid, acetate, propionic acid, acrylic or methacrylic acid.
[7] as each described production method in above [1]-[6], wherein (b) compound of belonging to the element of periodictable the 11st family or comprising at least a these elements is copper or gold element, or contains in copper and the gold one or more compound.
[8] as each described production method in above [1]-[7], wherein light alkene, lower aliphatic acid and oxygen react in the presence of water.
[9] a kind of lower alphatic carboxylic acid alkenyl esters of producing by each described production method in above [1]-[8].
[10] as each described production method in above [1]-[8], wherein lower aliphatic acid is acetate, and light alkene is an ethene, and the lower alphatic carboxylic acid alkenyl esters of gained is a vinyl acetate.
[11] vinyl acetate of producing by the production method described in above [10].
[12] as each described production method in above [1]-[8], wherein lower aliphatic acid is acetate, and light alkene is a propylene, and the lower alphatic carboxylic acid alkenyl esters of gained is an allyl acetate.
[13] allyl acetate of producing by the production method described in above [12].
[14] a kind of method of producing enol, this method comprise makes the hydrolysis in the presence of an acidic catalyst of the lower alphatic carboxylic acid alkenyl esters described in above [9] obtain enol.
[15] production method described in above [14], wherein an acidic catalyst is an ion exchange resin.
[16] production method described in above [14] or [15], wherein the lower alphatic carboxylic acid alkenyl esters is an allyl acetate, the enol of gained is a vinyl carbinol.
[17] enol of producing by each described production method in above [14]-[16].
[18] vinyl carbinol of producing by the production method described in above [16].
Implement best mode of the present invention
Below describe preferred implementation of the present invention in detail.
Be used in the catalyzer of the present invention (I) contain basic metal and/or alkaline earth metal compounds (a) is not subjected to particular restriction, the example comprises and contains at least a element that belongs to according to the 1st and 2 families in the periodictable of IUPAC inorganic chemistry nomenclature mo 1989.This compound preferably comprises the compound that is selected from least a element in lithium, sodium, potassium, caesium, magnesium, calcium and the barium, more preferably lower alphatic carboxylic acid salt, further be preferably selected from least a salt in lithium, sodium, potassium, caesium, magnesium, calcium and the barium salt of formic acid, acetate, propionic acid, acrylic or methacrylic acid, preferred especially acetate, most preferably Potassium ethanoate.
Be used for comprising the element of the 11st family and nitrate, carbonate, vitriol, organic acid salt and the halogenide of the 11st family's element belonging in the catalyzer of the present invention (I) according to the element of the 11st family in the periodictable of IUPAC inorganic chemistry nomenclature mo 1989 or the example that contains the compound (b) of at least a these elements.This component is preferably one or more element or its compound, most preferably independent copper and/or independent gold of being selected from copper and gold.
The palladium (c) that is used in the catalyzer of the present invention (I) can be any valence mumber, but is preferably palladium metal.The palladium of used " palladium metal " expression 0 valency in the literary composition.This palladium usually can be by obtaining divalence and/or the reduction of tervalent palladium ion as reductive agent with hydrazine, hydrogen or ethene.At this moment, palladium needn't be entirely metallic state.(c) raw material of palladium is not subjected to particular restriction, can use the palladium salt or the palladium metal that can be converted into palladium metal.The example that can be converted into the palladium salt of palladium metal includes but not limited to Palladous chloride, chlorine palladium acid sodium, Palladous nitrate and palladous sulfate.
Be used for the carrier in the catalyzer of the present invention (I) if the porous material that adopts just is enough to satisfy the demand usually.Its preferred embodiment comprises silicon-dioxide, aluminum oxide, silica-alumina, diatomite, polynite, titanium dioxide and zirconium white, more preferably silicon-dioxide.Silicon-dioxide used in the literary composition is not limited to SiO
2, the silicon-dioxide that contains impurity also can use.The shape of carrier is not subjected to particular restriction, and the example comprises powder, sphere or particle, although preferred ball type carrier.
The size of carrier is not subjected to particular restriction yet, and the optimum size of carrier depends on that shape and reaction type change.For example, when carrier is sphere, be not subjected to the particle diameter of particular restriction to be preferably 1-10mm, more preferably 3-8mm.In by the situation that catalyst loading is reacted in tubular reactor, if particle diameter less than 1mm, gas by the time produce the big pressure-losses, can not effectively carry out gas circulation; And if particle diameter surpasses 10mm, reactant gases can not be diffused into the inside of catalyzer, can not effectively carry out catalyzed reaction.
As for the pore structure of carrier, the preferred 0.1-1 of mean pore size, 000nm, more preferably 0.2-500nm, most preferably 0.5-200nm.If mean pore size is lower than 0.1nm, gas is difficult to diffusion; And if mean pore size surpasses 1,000nm, then the surface-area of carrier becomes too small and catalytic activity can reduce.
By quality ratio, carrier and (c) ratio between the palladium be preferably carrier: (c) palladium=10-1,000: 1, more preferably carrier: (c) palladium=30-500: 1.If based on the quality of carrier, the ratio of carrier and (c) palladium is less than carrier: (c) palladium=10: 1, and it is excessive that the amount of palladium becomes for carrier, causes palladium dispersion state difference and reaction yield to reduce; And if based on the quality of carrier, the ratio of carrier and (c) palladium is greater than carrier: (c) palladium=1,000: 1, the quality of carrier becomes excessive, and this is impracticable.
By quality ratio, (a) contain basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or contain the compound of at least a these elements and (c) ratio between the palladium be preferably (a) and contain basic metal and/or alkaline earth metal compounds: (b) belong to the element of periodictable the 11st family or contain the compound of at least a these elements: (c) palladium=0.1-100: 0.001-10: 1, more preferably (a) contains basic metal and/or alkaline earth metal compounds: (b) belong to the element of periodictable the 11st family or contain the compound of at least a these elements: (c) palladium=1-50: 0.05-5: 1.
Can by (a) contained basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or contain the compound of at least a these elements and (c) palladium be loaded into the catalyzer that obtains to be used for the present invention (I) on the carrier.In this case, loading component (a) and (b) and method (c) are not subjected to particular restriction, but the example comprises the method for implementing following steps (1)-(6) with such order:
Step (1):
Obtain the step of catalyst precursor A with the solution impregnating carrier that contains palladium salt and (b) belong to the element of periodictable the 11st family or contain the compound of at least a these elements;
Step (2):
With the catalyst precursor A that obtains in the step (1) not drying contact the step that obtains catalyst precursor B with the aqueous solution of an alkali metal salt;
Step (3):
The catalyst precursor B that obtains in the step (2) is contacted the step that obtains catalyst precursor C with reductive agent such as hydrazine or formalin;
Step (4):
The step of the catalyst precursor C that obtains in the water-washing step (3);
Step (5):
The catalyst precursor C that obtains in the step (4) is contained basic metal with (a) and/or alkaline earth metal compounds contacts the step that obtains catalyzer; And
Step (6):
The step of the catalyzer that obtains in the drying step (5).
The for example preferably a kind of specific surface area by this method preparation of catalyzer that is used among the present invention (I) is 10-250m
2/ g and pore volume are the catalyzer of 01.-1.5ml/g.
The light alkene that is used among the present invention (I) is not subjected to particular restriction, but preferably has the unsaturated hydrocarbons of 2-4 carbon atom, more preferably ethene or propylene.Ethene and propylene are not subjected to particular restriction and rudimentary stable hydrocarbon such as ethane, methane and propane or rudimentary unsaturated hydrocarbons such as divinyl can be sneaked in these hydrocarbon.Preferred this hydrocarbon is highly purified unsaturated hydrocarbons.
The lower alphatic carboxylic acid that is used among the present invention (I) is not subjected to particular restriction, but preferably has the lower alphatic carboxylic acid of 1-4 carbon atom, more preferably formic acid, acetate or propionic acid, more preferred acetate.Can use the common lower alphatic carboxylic acid that can on market, obtain.
The oxygen that is used among the present invention (I) is not subjected to particular restriction, can be with by the form supply of rare gas element such as nitrogen or carbon dioxide gas dilution, and for example with the form of air, but the preferred purity of using is 99% or higher oxygen.
With molar ratio computing, the ratio that is used between lower alphatic carboxylic acid, light alkene and the oxygen among the present invention (I) is preferably lower alphatic carboxylic acid: light alkene: oxygen=1: 0.08-16: 0.01-4.At light alkene is in the situation of ethene, and this ratio is preferably lower alphatic carboxylic acid: ethene: oxygen=1: 0.2-9: 0.07-2; At light alkene is in the situation of propylene, and this ratio is preferably lower alphatic carboxylic acid: propylene: oxygen=1: 1-12: 0.5-2.
The reactor feed gas that is used for the present invention (I) comprises light alkene, lower alphatic carboxylic acid and oxygen, and if desired, for example nitrogen, carbonic acid gas or rare gas can be used as thinner.When light alkene, lower alphatic carboxylic acid and oxygen were called reaction raw materials, in mole, reaction raw materials was preferably reaction raw materials with the ratio of thinner: thinner=1: 0.05-9, more preferably reaction raw materials: thinner=1: 0.1-3.
Preferably be used in reactor feed gas among the present invention (I) with 10-15 under standard state, 000hr
-1Air speed pass catalyzer, more preferably 300-8,000hr
-1If air speed is lower than 10hr
-1, can be difficult to remove reaction heat; And if air speed surpasses 15,000hr
-1, required device such as compressor variable are too much, and this is impracticable.
In the reactor feed gas that is used for the present invention (I), can add the water of 0.5-20mol%.The preferred water that adds 1-18mol%.Although do not know clearly reason, because the existence of water in the system (a) contains the discharge minimizing from catalyzer of basic metal and/or alkaline earth metal compounds.Even add water with the amount that surpasses 20mol%, this effect can not strengthen yet, but can carry out the hydrolysis of acetic acid alkenyl esters.Thereby, a large amount of water preferably is not provided.
In the production method of the present invention (I), so long as in gas phase, the reaction in the presence of catalyzer of light alkene, lower alphatic carboxylic acid and oxygen can be carried out with the form known to any routine, and still preferred this reacts and be the fixed bed flowing reactive.
The building material that is used to implement the reactor of the present invention (I) production method is not subjected to particular restriction, but preferably by the reactor of the material structure with corrosion stability.
During implementing the present invention (I) production method, temperature of reaction is 100-300 ℃, preferred 120-250 ℃.If temperature of reaction is lower than 100 ℃, this will make reaction carry out with low excessively speed unfriendly; And if temperature of reaction surpasses 300 ℃, then can not shift out reaction heat, this does not expect.
During implementing the present invention (I) production method, reaction pressure is 0-3MPaG, preferred 0.1-1.5MPaG.If reaction pressure is lower than 0MPaG, this will make speed of response reduce unfriendly; And if reaction pressure surpasses 3MPaG, it is expensive that required device such as reaction tubes become, and this is impracticable.
In the present invention (I), the transformation efficiency of lower alphatic carboxylic acid is 80% or lower.The concentration of lower alphatic carboxylic acid and be trapped between the amount that (a) of outlet in the peripheral region contain basic metal and/or alkaline earth metal compounds and have mutual relationship, when the concentration of lower alphatic carboxylic acid reduced, the amount that (a) of delay contains basic metal and/or alkaline earth metal compounds increased.If the transformation efficiency of lower alphatic carboxylic acid surpasses 80%, the concentration of the lower alphatic carboxylic acid in the reactor outlet peripheral region reduces, and causes (a) to contain basic metal and/or alkaline earth metal compounds delay, and this can induce reaction and stop up or the catalytic performance reduction.
In addition, in the production method of the present invention (I), the concentration of reactor exit lower alphatic carboxylic acid is 0.5mol% or higher.The concentration of lower alphatic carboxylic acid and be trapped between the amount that (a) of outlet in the peripheral region contain basic metal and/or alkaline earth metal compounds and have mutual relationship, when the concentration of lower alphatic carboxylic acid reduced, the amount that (a) of delay contains basic metal and/or alkaline earth metal compounds increased.If the concentration of lower alphatic carboxylic acid is lower than 0.5mol%, can cause (a) to contain basic metal and/or alkaline earth metal compounds delay, this can induce reaction and suppress or the catalytic performance reduction.
By the specified rate of outflow of formula (2), promptly be used for basic metal in the catalyzer of the present invention (I) and/or alkaline-earth metal from the ratio that catalyzer flows out, be preferably 1.0 * 10
-5-0.01%/h.If this rate of outflow is lower than 1.0 * 10
-5%/h, may be blocked or containing basic metal and/or alkaline earth metal compounds can be trapped on the catalyzer in the hole of catalyzer, causes reaction tubes to block, and the result produces can be unstable.On the other hand, if rate of outflow surpasses 0.01%/h, owing to contain the big discharge of basic metal and/or alkaline earth metal compounds, catalytic performance can reduce at a high speed unfriendly.In this case, contain basic metal and/or alkaline earth metal compounds, can keep active, although this is nonprofit by infeeding with the big amount that must be enough to compensate the discharge that contains basic metal and/or alkaline earth metal compounds from reaction inlet.
In the formula (2), the quality of effusive basic metal and/or alkaline-earth metal is the quality of institute's alkali metal containing and/or alkaline-earth metal in the reactor exit gas.Alkali metal used herein and alkali earth metal are meant as catalyst component and are contained in alkali metal or alkali earth metal in the catalyzer.The quality (kg) of basic metal or alkaline-earth metal in the total catalyst of rate of outflow (%)/basic metal that h={ records or the quality of alkaline-earth metal (kg/h)/filling } * 100 (2)
For example, in the production method of allyl acetate, usually Potassium ethanoate is used as promotor, even during reaction also suitably Potassium ethanoate is added in the reactor, because this promotor was included in the gas of reactor exit from the reaction tubes outflow and as potassium or potassium compound between the reaction period.
" catalyzer of filling " used herein is meant and is seated in the reactor and the catalyzer of institute's maintaining condition before reactor feed gas passes through.In a device (method), exist in the situation of reactor of two or more serial or parallel connections, then refer to be seated in the total amount of the catalyzer in all reactors.
Alkali metal and/or alkali earth metal in the gas of available any method detection reaction device exit.The example is included in and separates and detect method as the element of condensation product during the purification reactor exit gas, with by making reaction mixture contact the method for absorption element with ion exchange resin or analogue.Its specific examples comprises this method: reactor outlet gas is cooled to the degree that makes its condensation, by the concentration of potassium in the analytical procedure detection gained condensation product, for example inductively coupled plasma emmission spectrometric analysis of described analytical procedure (hereinafter referred to as the ICP spectroscopic analysis) or atomic absorption method.Adopt the detection method of ICP spectroscopic analysis not to be subjected to particular restriction, but for example can use absolute calibration curve method.
In the present invention (I) in the used rate of outflow, the basic metal in the total catalyst of filling and/or the quality of alkaline-earth metal are meant the quality of basic metal in the whole catalyzer that are seated in the reactor and/or alkaline-earth metal, particularly, be meant the catalyzer basic metal of filling before catalyzer is used for reacting and/or the quality of alkaline-earth metal.Because the outflow or the delay of the component that infeeds, the quality change of basic metal and/or alkaline-earth metal between the reaction period, but the calculated of the quality of used basic metal and/or alkaline-earth metal before in the literary composition based on reaction.
Can control rate of outflow (%/h), for example temperature of reaction, reaction pressure and feed composition by the control reaction conditions; And set reaction conditions to obtain the rate of outflow in the expected range.Control method is not subjected to particular restriction, for example can or increase the ratio of lower alphatic carboxylic acid in feed composition by the rising temperature of reaction and improve rate of outflow.
Between the reaction period, must infeed (a) with the big amount that must be enough to compensate the quality of effusive basic metal and/or alkaline-earth metal from Reactor inlet and contain basic metal and/or alkaline earth metal compounds.Preferably, based on the quality of effusive basic metal and/or alkaline-earth metal, add basic metal and/or the alkaline-earth metal that contains basic metal and/or alkaline earth metal compounds as (a) with the amount of 0.01-200 quality %.More preferably, add (a) with the amount of the quality that is equal to or greater than effusive basic metal and/or alkaline-earth metal and contain basic metal and/or alkaline earth metal compounds.Although do not know clearly reason, when with the amount that equates or when more volume is added (a) and contained basic metal and/or alkaline earth metal compounds, reaction yield reduces less.
Can add with any method and contain basic metal and/or alkaline earth metal compounds (a), but preferably add by it is sneaked in the reactor feed gas.
The present invention (II) is below described.The present invention (II) is a kind of lower alphatic carboxylic acid alkenyl esters of being produced by the production method of the present invention (I) lower alphatic carboxylic acid alkenyl esters.Owing to do not add halogen in the reaction system, with compare by the lower alphatic carboxylic acid alkenyl esters of liquid phase Wacker process production, the present invention's (II) lower alphatic carboxylic acid alkenyl esters is not mixed with halogen, and owing to there is not halogen to sneak into, when this ester is used as raw material, the less generation of the problem such as equipment corrosion.In addition, when this lower alphatic carboxylic acid alkenyl esters is used as raw material, can advantageously save the step of removing halogen.
The present invention (III) is below described.The present invention (III) a kind ofly produces the method for enol and comprises the enol that a kind of production method is thus produced, described method comprise make the present invention (II) the lower alphatic carboxylic acid alkenyl esters in the presence of an acidic catalyst hydrolysis to obtain enol.
The lower alphatic carboxylic acid alkenyl esters that is used for the present invention (III) is not subjected to particular restriction, as long as it is the lower alphatic carboxylic acid alkenyl esters that the production method by the present invention (I) obtains, and can contain impurity.This lower alphatic carboxylic acid alkenyl esters is preferably allyl acetate.
Pressure in the hydrolysis reaction is not subjected to particular restriction, still, for example can react under 0.0-1.0MPaG.
Temperature of reaction in the hydrolysis reaction is not subjected to particular restriction, but preferred 20-300 ℃, more preferably 50-250 ℃.
The hydrolysis reaction that can be used for the present invention (III), for example gas-phase reaction, liquid phase reaction and solid-liquid reaction with any reaction system.
Preferably carry out this hydrolysis reaction, thereby improve the transformation efficiency of lower alphatic carboxylic acid alkenyl esters in the hydrolysis reaction by in the lower alphatic carboxylic acid alkenyl esters, adding water.The water yield of adding is preferably 1.0-60 quality %, more preferably 5-40 quality %.
And, preferably when shifting out reaction system, the enol that will generate carries out this hydrolysis reaction.The method that is used for enol is shifted out reaction system is not subjected to particular restriction, but can use for example such method: add between the reaction period and can form the material of azeotropic mixture and shift out enol simultaneously implementing distillatory with enol.
An acidic catalyst that is used for this lower alphatic carboxylic acid alkenyl esters hydrolysis reaction comprises organic acid, mineral acid, solid acid and salt thereof.Its object lesson comprises formic acid, acetate, propionic acid, tartrate, oxalic acid, butyric acid, terephthalic acid, fumaric acid, heteropolyacid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Hydrogen bromide, hydrofluoric acid, silica alumina, silicon oxide titanium oxide, silicon oxide magnesium oxide, acidic cation-exchange resin, and sodium salt, sylvite, magnesium salts and aluminium salt.Wherein, be easy to separate enol or acidity after considering reaction, the most preferred solid acid Zeo-karb.This resin more preference as so a kind of ion exchange resin: be bonded on the SDVB resin matrix such as sulfonic acid active function groups in this resin.
The device that enforcement is used for the present invention's (III) hydrolysis reaction is not subjected to particular restriction, but preferred fixed bed flow-type reactor.When two or more reactor units are used in parallel connection, can obtain the enol of constant basis continuously, be preferred therefore.
In the present invention (III), be not subjected to particular restriction by acidic cation-exchange resin is produced alcohol as hydrolyst in fixed-bed type reactor method, but preferred such method: it facilitates upwards mobile to be transported in the reactor assembly with the reaction soln that will contain lower alphatic carboxylic acid alkenyl esters and the water bottom from reactor.In this case, can suppress the drift with reaction raw materials of solidifying of ion exchange resin, this can take place reaction soln is walked the situation of bottom from the top.
The enol of the present invention (III) is below described.Since not halogen-containing as the lower alphatic carboxylic acid alkenyl esters of raw material, so this enol advantageously is not mixed with halogen.Thereby, when this alcohol is used as raw material, can save the step of removing the halogen that causes equipment corrosion, and can advantageously this method be simplified.
Followingly the present invention is described in more detail with reference to embodiment.Yet the present invention is not limited to this.
In order to following method analysis reactor exit gas.
1. propylene
Adopt absolute calibration curve method to analyze, wherein with the 50ml eluting gas as sample, all the gases of amount flow into 1-ml gas sampler and the analysis under the following conditions that is connected with gas chromatograph.
Gas chromatographic analysis: gas chromatograph (Shimadzu Corporation make GC-7B), have gas sampler (MGS-4, buret: 1ml), be used for the Shimadzu gas chromatographic analysis:
Post: packed column Unibeads IS, length: 3m
Carrier gas: helium (flow velocity: 35ml/min)
Temperature condition: detector temperature is 100 ℃, and the vaporizer temperature is 140 ℃, and column temperature is constant to be 140 ℃.
(He presses detector: TCD: 125kPaG, electric current: 125mA)
2. oxygen
Adopt absolute calibration curve method to analyze, wherein with the 50ml eluting gas as sample, all the gases of amount flow into 1-ml gas sampler and the analysis under the following conditions that is connected with gas chromatograph.
Gas chromatographic analysis: gas chromatograph (Shimadzu Corporation make GC-14B), have gas sampler (MGS-4, quantity tube: 1ml), be used for the Shimadzu gas chromatographic analysis:
Post: MS-5A IS, 60/80 order (3mm φ * 3m)
Carrier gas: helium (flow velocity: 20ml/min)
Temperature condition: the temperature of detector and vaporizer is 110 ℃, and column temperature is constant to be 70 ℃.
(He presses detector: TCD: 70kPaG, electric current: 100mA)
3. acetate
Adopt marker method to analyze, wherein with 1ml 1, the 4-dioxane adds in the 10ml reaction soln as internal standard substance, injects 0.2 μ l income analysis solution and analysis under the following conditions.
Gas chromatographic analysis: the GC-14B that Shimadzu Corporation makes
Post: packed column Thermon 3000 (length: 3m, internal diameter: 0.3mm)
Carrier gas: nitrogen (flow velocity: 20ml/min)
Temperature condition: the temperature of detector and vaporizer is 180 ℃, analyzes to begin column temperature was kept 6 minutes at 50 ℃, rises to 150 ℃ and kept 10 minutes at 150 ℃ with the heat-up rate of 10 ℃/min then.
Detector: FID (H
2Press: 40kPaG, air pressure: 100kPaG)
4. allyl acetate
Adopt marker method to analyze, wherein the 1g amyl acetate-n is added in the 25g reaction soln as internal standard substance, inject 0.3 μ l income analysis solution and analysis under the following conditions.
Gas chromatographic analysis:
The GC-9A that Shimadzu Corporation makes
Post: capillary column TC-WAX (length: 30m, internal diameter: 0.25mm, thickness: 0.5 μ m)
Carrier gas: nitrogen (flow velocity: 30ml/min)
Temperature condition: the temperature of detector and vaporizer is 200 ℃, analysis begins column temperature was kept 2 minutes at 45 ℃, heat-up rate with 4 ℃/min rises to 130 ℃ then, keeps 15 minutes at 130 ℃, rises to 200 ℃ and kept 10 minutes at 200 ℃ with the heat-up rate of 25 ℃/min again.
Detector: FID (H
2Press: 60kPaG, air pressure: 100kPaG)
5. vinyl carbinol
Adopt marker method to analyze, wherein the positive amine of 200 μ l acetate is added in the 10ml reaction soln as internal standard substance, inject 0.1 μ l income analysis solution and analysis under the following conditions.
Gas chromatographic analysis: the GC-14B that Shimadzu Corporation makes
Post: packed column Thermon 3000 (length: 3m, internal diameter: 0.3mm)
Carrier gas: nitrogen (flow velocity: 2.0ml/min)
Temperature condition: the temperature of detector and vaporizer is 180 ℃, analyzes to begin column temperature was kept 5 minutes at 45 ℃, rises to 130 ℃ and kept 13 minutes at 130 ℃ with the heat-up rate of 7 ℃/min then.
Detector: FID (H
2Press: 98kPaG, air pressure: 98kPaG)
6. vinyl acetate
Adopt marker method to analyze, wherein the 1g n-propyl acetate is added in the 6g reaction soln as internal standard substance, inject 0.3 μ l income analysis solution and analysis under the following conditions.
Gas chromatographic analysis:
The GC-9A that Shimadzu Corporation makes
Post: capillary column TC-WAX (length: 30m, internal diameter: 0.25mm, thickness: 0.5 μ m)
Carrier gas: nitrogen (flow velocity: 30ml/min)
Temperature condition: the temperature of detector and vaporizer is 200 ℃, analysis begins column temperature was kept 2 minutes at 45 ℃, heat-up rate with 4 ℃/min rises to 130 ℃ then, keeps 15 minutes at 130 ℃, rises to 200 ℃ and kept 10 minutes at 200 ℃ with the heat-up rate of 25 ℃/min again.
Detector: FID (H
2Press: 60kPaG, air pressure: 100kPaG)
Embodiment 1
The catalyst A preparation
Chlorine palladium acid sodium crystal (56.4mmol), 8.50mmol Copper dichloride dihydrate are closed the 18.4mmol zinc chloride and be dissolved in the pure water, and the gained solution amount is 97% carrier water regain.
The aqueous metal salt of above gained evenly is impregnated in the silica supports (KA-160 that Sud-chemi AG produces), and this carrier is dry 4 hours down prior to 100 ℃ in advance.
Subsequently, anhydrous sodium metasilicate is dissolved in the pure water, and the amount of solution is adjusted into two times of the carrier water regain.Add gained solution to flooded carrier and also at room temperature left standstill 20 hours, obtain catalyzer.
In this solution, add 720mmol one hydrazine hydrate again, stir under the room temperature after 4 hours, catalyzer with the pure water washing and in hot air dryer in 110 ℃ dry 4 hours down.
After this, the 509mmol Potassium ethanoate is dissolved in the pure water, the gained solution amount is about 97% catalyzer water regain.This solution evenly is loaded on the catalyzer,, obtains catalyst A and be used for reaction then in 110 ℃ times dry 4 hours.
Reaction:
The catalyzer (20ml) of gained is loaded in the stainless steel reaction pipe that internal diameter is 21.4mm, contain the mixture of 30mol% propylene, 7.0mol% oxygen, 5.5mol% acetate, 14.0mol% hydration 43.5mol% nitrogen by supply, under the pressure of 135 ℃ of temperature of reaction and 0.8MPaG, react.The results are shown in the table 2.With every kind of component concentrations in the gas chromatographicanalyzer assaying reaction solution.The weight of potassium and the weight of using potassium in the procatalyst from the condensation product that the gas by cooling reaction tubes exit gets are calculated the transformation efficiency of acetate and are calculated rate of outflow (%/h) according to formula (2) according to formula (1).
The analysis of potassium
1. use the analysis of procatalyst
Catalyzer fine grinding in agate mortar before will using, then in 110 ℃ down dry 2 hours with the preparation powdered sample.In the powdered sample of 1g, add the 100ml pure water and add 10ml35% hydrochloric acid again.After this, this sample was seethed with excitement 2 hours in sand-bath, make it then to cool off and to the pure water that wherein adds the 500ml amount.After the filtration, the SPS1700HUR that makes with Seiko Instruments Inc. carries out the ICP spectroscopic analysis to filtrate under the following conditions, and calculates the amount of potassium.
Measuring method: absolute calibration curve method
Photometer height: 15nm
High frequency output: 1.3kw
Nebulizer gas pressure: 0.22MPa
Plasma body flow velocity: 16L/min
Photomultiplier cell voltage: H
Auxiliary agent flow velocity: 0.5L/min
2. the analysis of the potassium that detects after the reactor outlet
Under the condition identical, the condensation product that obtains by recovery reactant gases under normal temperature and normal atmosphere is carried out the ICP spectroscopic analysis, and calculate the amount of potassium with " 1. using the analysis of procatalyst ".
The results are shown in the table 2.
Embodiment 2
With with embodiment 1 in identical mode react, except change reaction conditions as shown in table 1 to obtain 78% acetate transformation efficiency.The results are shown in the table 2.
Embodiment 3
With with embodiment 1 in identical mode react, but the amount that during reaction comes from the rate of outflow (%/h) of reaction tubes with correspondence infeeds Potassium ethanoate.The results are shown in the table 2.
Embodiment 4
The preparation of catalyst B
The aqueous solution and the 10.2mol four hydration hydrochloro-auric acids that will comprise 47.0mmol chlorine palladium acid sodium are dissolved in the pure water, and the gained solution amount is 90% carrier water regain.
The aqueous metal salt of above gained evenly is impregnated in the silica supports (KA-160), and this carrier is dry 4 hours down prior to 100 ℃ in advance.
Subsequently, the 135mmol anhydrous sodium metasilicate is dissolved in the pure water, and the amount of solution is adjusted into two times of the carrier water regain.Add gained solution to flooded carrier and also at room temperature left standstill 20 hours, obtain catalyzer.
In this solution, add 538mmol one hydrazine hydrate again, stir under the room temperature after 4 hours, catalyzer with the pure water washing and in hot air dryer in 110 ℃ dry 4 hours down.
After this, the 33g Potassium ethanoate is dissolved in the pure water, the gained solution amount is about 90% catalyzer water regain.This solution evenly is loaded on the catalyzer,, obtains catalyst B and be used for reaction then in 110 ℃ times dry 4 hours.
Then, with embodiment 1 in identical mode react, except change reaction conditions as shown in table 1.And, with embodiment 1 in identical mode analyze.
Comparative example 1
Raw material with density of propylene 25mol%, acetic acid concentration 2.5mol%, water concentration 25mol% and nitrogen gas concn 39.5mol% reacts under 165 ℃ temperature of reaction.The results are shown in the table 2.After the reaction, take out catalyzer, found that Potassium ethanoate is present in the peripheral region of reaction tubes outlet.The decreasing ratio of STY is big.
Table 1
| Catalyzer | SV | Temperature of reaction | Reaction pressure | Reactant gases | |||||
| Alkene | Oxygen | Acetate | Water | Nitrogen | |||||
| h -1 | ℃ | MPaG | mol％ | ||||||
| Embodiment 1 | A | 1600 | 135 | 0.8 | Propylene 30 | 7 | 5.5 | 14 | 43.5 |
| Embodiment 2 | A | 1600 | 145 | 0.8 | Propylene 30 | 6.5 | 5 | 14 | 44.5 |
| Embodiment 3 | A | 1600 | 135 | 0.8 | Propylene 30 | 7 | 5.5 | 14 | 43.5 |
| Embodiment 4 | B | 2700 | 150 | 0.8 | Ethene 60 | 6.5 | 17 | 1.3 | 15.2 |
| Comparative example 1 | A | 1600 | 165 | 0.8 | Propylene 25 | 8 | 2.5 | 25 | 39.5 |
Table 2
| The acetic acid alkenyl esters, STY | The acetic acid alkenyl esters, Sel | The acetate transformation efficiency | The concentration of exit acetate | Rate of outflow | |||
| Behind the 5h | Behind the 2400h | Behind the 5h | Behind the 2400h | Behind the 5h | After 5h hour | Rate of outflow | |
| The g/L catalyzer | ％ | ％ | mol％ | ％/h | |||
| Embodiment 1 | 355.7 | 291.7 | 92 | 91 | 70.3 | 2.34 | 6.5×10 -4 |
| Embodiment 2 | 366.6 | 300.6 | 94 | 90 | 78 | 1.61 | 0.008 |
| Embodiment 3 | 355.7 | 320.1 | 92 | 91 | 70.3 | 2.34 | 6.5×10 -4 |
| Embodiment 4 | 349.7 | 301.4 | 92 | 90 | 26 | 16.3 | 2.2×10 -4 |
| Comparative example 1 | 213.9 | 160.4 | 93 | 42 | 92 | 0.43 | 8×10 -5 |
Industrial applicability
According to the present invention, from the process of lower alphatic carboxylic acid, light alkene and oxygen production lower alphatic carboxylic acid alkenyl esters, the compound that contains alkali metal and/or alkaline-earth metal as catalytic component can be during reaction controlled in its outflow process, thereby can produce steadily in the long term and do not damage the activity of catalyst.
Claims (18)
1. method of producing the lower alphatic carboxylic acid alkenyl esters, this method comprises makes light alkene, lower alphatic carboxylic acid and oxygen gas-phase reaction in the presence of catalyzer, this catalyzer comprises the carrier that is loaded with catalyst component on it, described catalyst component comprises (a) and contains basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or comprise the compound of at least a these elements, and (c) palladium; Wherein the transformation efficiency by the lower alphatic carboxylic acid of formula (I) representative is 80% or lower: transformation efficiency (%)=(amount (mol) of amount (the mol)/reactor inlet lower alphatic carboxylic acid of the amount of reactor inlet lower alphatic carboxylic acid (mol)-reactor outlet lower alphatic carboxylic acid } * 100 (1)
2. method of producing the lower alphatic carboxylic acid alkenyl esters, this method comprises makes light alkene, lower aliphatic acid and oxygen gas-phase reaction in the presence of catalyzer, this catalyzer comprises the carrier that is loaded with catalyst component on it, described catalyst component comprises (a) and contains basic metal and/or alkaline earth metal compounds, (b) belong to the element of periodictable the 11st family or comprise the compound of at least a these elements, and (c) palladium; Wherein the concentration of reactor exit lower alphatic carboxylic acid is 0.5mol% or higher.
3. the production method described in claim 1 or 2, the per hour rate of outflow that is contained basic metal and/or alkaline earth metal compounds by (a) of formula (2) representative is 1.0 * 10
-5-0.01%/h: the quality (kg) of basic metal or alkaline-earth metal in the total catalyst of rate of outflow (%)/basic metal that h={ records or the quality of alkaline-earth metal (kg/h)/filling } * 100 (2)
4. as each described production method among the claim 1-3, wherein (a) contains basic metal and/or alkaline earth metal compounds is to comprise at least a compound that is selected from lithium, sodium, potassium, caesium, magnesium, calcium and the barium.
5. as each described production method among the claim 1-4, wherein (a) contains basic metal and/or alkaline earth metal compounds is a lower alphatic carboxylic acid salt.
6. the production method described in claim 5, wherein lower alphatic carboxylic acid salt is selected from least a in lithium, sodium, potassium, caesium, magnesium, calcium and the barium salt of formic acid, acetate, propionic acid, acrylic or methacrylic acid.
7. as each described production method among the claim 1-6, wherein (b) compound of belonging to the element of periodictable the 11st family or comprising at least a these elements is copper or gold element, or contains in copper and the gold one or more compound.
8. as each described production method among the claim 1-7, wherein light alkene, lower aliphatic acid and oxygen react in the presence of water.
9. lower alphatic carboxylic acid alkenyl esters of producing by each described production method among the claim 1-8.
10. as each described production method among the claim 1-8, wherein lower aliphatic acid is acetate, and light alkene is an ethene, and the lower alphatic carboxylic acid alkenyl esters of gained is a vinyl acetate.
11. vinyl acetate by the production of the production method described in the claim 10.
12. as each described production method among the claim 1-8, wherein lower aliphatic acid is acetate, light alkene is a propylene, and the lower alphatic carboxylic acid alkenyl esters of gained is an allyl acetate.
13. allyl acetate by the production of the production method described in the claim 12.
14. a method of producing enol, this method comprise that the lower alphatic carboxylic acid alkenyl esters hydrolysis in the presence of an acidic catalyst that makes described in the claim 9 obtains enol.
15. the production method described in claim 14, wherein an acidic catalyst is an ion exchange resin.
16. the production method described in claim 14 or 15, wherein the lower alphatic carboxylic acid alkenyl esters is an allyl acetate, and the enol of gained is a vinyl carbinol.
17. enol by each described production method production among the claim 14-16.
18. vinyl carbinol by the production of the production method described in the claim 16.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003061528 | 2003-03-07 | ||
| JP061528/2003 | 2003-03-07 | ||
| US60/455,588 | 2003-03-19 | ||
| JP119758/2003 | 2003-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1759089A true CN1759089A (en) | 2006-04-12 |
Family
ID=36703985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480006238 Pending CN1759089A (en) | 2003-03-07 | 2004-02-25 | Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1759089A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596886A (en) * | 2009-10-30 | 2012-07-18 | 莱昂德尔化学技术公司 | Process for producing allyl acetate |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103121954A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103121955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103120961A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Propenyl ethanoate catalyst and preparation method thereof |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103351279A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Method for continuous preparation of allyl alcohol from propylene |
| CN103878022A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing allyl acetate |
| CN111995494A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Preparation method of 2-methallyl alcohol |
| CN111992248A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN112299990A (en) * | 2020-11-11 | 2021-02-02 | 北京水木滨华科技有限公司 | Method and reaction system for preparing methyl allyl alcohol acetate through isobutene oxoacetylation |
| CN112341314A (en) * | 2020-11-11 | 2021-02-09 | 北京水木滨华科技有限公司 | Method for preparing 2-methyl-1, 3-propylene glycol from isobutene |
| CN116550383A (en) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
-
2004
- 2004-02-25 CN CN 200480006238 patent/CN1759089A/en active Pending
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102596886A (en) * | 2009-10-30 | 2012-07-18 | 莱昂德尔化学技术公司 | Process for producing allyl acetate |
| CN102596886B (en) * | 2009-10-30 | 2015-11-25 | 莱昂德尔化学技术公司 | For the production of the method for allyl acetate |
| CN103121952B (en) * | 2011-11-18 | 2015-02-11 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103120961B (en) * | 2011-11-18 | 2015-07-08 | 中国石油化工股份有限公司 | Propenyl ethanoate catalyst and preparation method thereof |
| CN103120961A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Propenyl ethanoate catalyst and preparation method thereof |
| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103121952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate preparation method |
| CN103121955A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103121954B (en) * | 2011-11-18 | 2014-08-13 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103120958B (en) * | 2011-11-18 | 2015-02-11 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
| CN103121954A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing allyl acetate |
| CN103878022A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method of catalyst for synthesizing allyl acetate |
| CN103878022B (en) * | 2012-12-19 | 2016-05-18 | 中国石油化工股份有限公司 | The preparation method of acetic acid synthesized allyl ester catalyst |
| CN103351279A (en) * | 2013-07-01 | 2013-10-16 | 太仓市恒益医药化工原料厂 | Method for continuous preparation of allyl alcohol from propylene |
| CN111995494A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Preparation method of 2-methallyl alcohol |
| CN111992248A (en) * | 2019-11-15 | 2020-11-27 | 北京水木滨华科技有限公司 | Catalyst for oxidation esterification of isobutene, preparation method and application thereof |
| CN111995494B (en) * | 2019-11-15 | 2021-11-16 | 北京水木滨华科技有限公司 | Preparation method of 2-methallyl alcohol |
| CN112299990A (en) * | 2020-11-11 | 2021-02-02 | 北京水木滨华科技有限公司 | Method and reaction system for preparing methyl allyl alcohol acetate through isobutene oxoacetylation |
| CN112341314A (en) * | 2020-11-11 | 2021-02-09 | 北京水木滨华科技有限公司 | Method for preparing 2-methyl-1, 3-propylene glycol from isobutene |
| CN112341314B (en) * | 2020-11-11 | 2021-11-02 | 北京水木滨华科技有限公司 | Method for preparing 2-methyl-1, 3-propylene glycol from isobutene |
| CN116550383A (en) * | 2023-07-12 | 2023-08-08 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
| CN116550383B (en) * | 2023-07-12 | 2023-10-31 | 中国天辰工程有限公司 | Preparation method of unsaturated acetate and catalyst thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1308074C (en) | Oxide catalyst composition | |
| CN1301947C (en) | Process for producing perfluorocarbons and use thereof | |
| CN1759089A (en) | Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols | |
| CN1126195A (en) | Process for producing high purity acetic acid | |
| CN1678552A (en) | Process for obtaining a purified hydrofluoroalkane | |
| CN1029679C (en) | Method for producing ibuprofen | |
| CN1113853C (en) | Process for producing alkyl nitrite | |
| CN1639092A (en) | Alkene separation process | |
| CN1025182C (en) | Process for preparing propylene | |
| CN1759090A (en) | Production processes of lower aliphatic carboxylic acid alkenyl esters and alkenyl alcohol obtained therewith | |
| CN1185201C (en) | Method for purifying acrylic acid obtained by oxidation of propylene and/or acrolein | |
| CN1281322C (en) | Process for preparing group VIII-metal contg. catalyst, use thereof for preparing alkenyl carboxylate | |
| CN1299990C (en) | Refining process of ammonia | |
| CN1662302A (en) | Metallic copper catalyst for polyfluoroalkylethyl iodide production and process for producing polyfluoroalkylethyl iodide | |
| US20060247462A1 (en) | Production processes of lower aliphatic carboxylic acid alkenyl and alkenyl alcohol | |
| CN1488421A (en) | Method for removing fluorine-contained anions surfactant | |
| CN1039710C (en) | Hydroxycarbonylation of butadiene | |
| US20060167307A1 (en) | Processes for the production of alkenyl esters of lower carboxylic acids and process for the production of alkenyl alcohols | |
| CN1516621A (en) | Regeneration of catalyst for use in production of lower aliphatic carboxylic acid ester and production of lower aliphatic carboxylic acid ester | |
| JP2004339195A (en) | Method for producing lower aliphatic alkenyl carboxylate and alkenyl alcohol and lower aliphatic alkenyl carboxylate and alkenyl alcohol produced by the same | |
| CN1929915A (en) | Production and use of supported catalysts | |
| CN1759091A (en) | Production process of allyl alcohol, and allyl alcohol obtained by the production processes | |
| CN1039243A (en) | Make tetrahydrofuran (THF) and 1, the method for 4-butyleneglycol with pd/Re hydrogenation catalyst | |
| CN1832908A (en) | Process for activation of aif3 based catalysts and isomerization methods for chlorofluorocarbons | |
| CN1147457C (en) | Method for producing dichloro-acetoxy-propane and derivative thereof |
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 |