CN104437624B - Vinyl acetate catalyst and preparation method thereof and vinyl acetate synthesis method - Google Patents
Vinyl acetate catalyst and preparation method thereof and vinyl acetate synthesis method Download PDFInfo
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Abstract
The present invention relates to the catalyst and preparation method thereof for ethylene process vinyl acetate synthesis, mainly solve catalyst space time yield and problem the most on the low side present in prior art.The present invention is by using the catalyst for ethylene process vinyl acetate synthesis, described catalyst includes active component, co-catalyst and carrier, described active component is Pd, Au and alloy thereof, co-catalyst is potassium acetate, in wherein said catalyst, Pd content is 1.0 12 g/L, Au content is 0.1 9.0 g/L, and described cocatalyst content is 10 ~ 50 g/L；It is characterized in that the SiO that carrier is the modification of a kind of fluorochemical of described catalyst2Technical scheme, it is characterised in that described catalyst preferably resolves this problem, can be used in the industrial production of ethylene process vinyl acetate synthesis.
Description
Technical field
The present invention relates to ethene vapor phase method vinyl acetate catalyst, the preparation method of this catalyst, and vinyl acetate
Synthetic method.
Background technology
Vinylacetate, is called for short vinyl acetate (VAM), is one of maximum Organic Chemicals of world wide production, by extensively
It is applied to produce polyvinyl acetate, polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal
A series of chemical products such as resin, its application is also in constantly extension.
The method of the industrially prepared vinyl acetate known to a kind of, refers to that ethene, acetic acid and oxygen are at Supported Pd-Catalyst
In the presence of, reacted by gas phase and realize.
A kind of preferably vinyl acetate catalyst, is at its carrier mass such as SiO2、Al2O3Or on the surface of its compound,
Load a certain amount of Pd metal and Au metal.
A kind of standard method being used for preparing the vinyl acetate catalyst containing Pd and Au disperseed on a catalyst support,
Including: (1) is with the solution impregnating carrier of a kind of water miscible Pd and Au compound；(2) catalyst carrier being through impregnation with is passed through
Can contact with the alkaline aqueous solution that water miscible Pd and Au compound reacts with a kind of, thus form the metal compound being insoluble in water
Thing, by water-fast Pd and Au compound precipitation and fixing on a catalyst support；(3) treated catalysis is washed with water
Agent, was precipitating to remove；(4) process with reducing agent, water-fast Pd and Au compound is converted in journey by
The anion discharged in Pd and the Au compound that beginning is through impregnation with, and free metallic state；Final step is non-necessary,
It usually contains (5) and impregnates the catalyst through reduction with a kind of alkali-metal alkaline solution, then is dried prepared finished catalyst；
The activity and selectivity of loading type Pd-Au catalyst, is contained by the Material Form of Pd and Au, metal in catalyst carrier
The impact of amount.Several important relevant vinyl acetate is discussed below and prepares catalyst and preparation method thereof.
Nineteen sixty-five, United States Patent (USP) US 3190912(title: Process for preparing esters) disclose use
In the preparation method of the catalyst of the unsaturated organic ester of preparation, wherein catalyst is by non-loading type or support type platinum family or palladium race gold
Belong to or its oxide or its organic salt or inorganic salts composition.Loaded catalyst is prepared by following steps: slaine is molten
Yu Shuizhong；Add carrier；Evaporate solvent.Noble metal is evenly distributed on whole carrier.
1966, Bayer company of Germany disclosed (US3275680, title: Production of organic
Acetates in presence of a noble metal catalyst and oxygen) one is supported on carrying alumina
Pd catalyst on body, when finding to use alkali metal acetate as co-catalyst, this catalyst is applicable to prepare organic acetic acid
Ester, particularly vinylacetate.In this patent, Pd catalyst with above-mentioned patent the same by uniform deposition in whole catalyst carrier
On.Except that, in catalyst preparation process, after the solution impregnating carrier of precious metal salt, adding reduction step is
Noble metal loading is on carrier.
Knapsack company (US3743607, title: Palladium-gold catalyst) disclose a kind of containing Pd and
Au bimetallic catalyst, colleague also added alkali metal acetate as co-catalyst.This method for preparing catalyst is as follows: use Pd
Salt and the solution impregnating carrier of Au salt, such as silicic acid, aluminum oxide, silicate or aluminum phosphate etc.；The mixture making generation is evaporated to
Dry.With reducing agent, Pd salt and Au salt are reverted to metallic state.Then wash catalyst with water, impregnate with SAS and do
Dry standby.
1973, Japan Patent (48-10135/1973) disclosed a kind of support type vinyl acetate preparing surface impregnation
The method of catalyst.In Vehicle element, a small amount of reducing metal (such as Au) is deposited on whole porous carrier, impregnates subsequently
The Pd catalyst of requirement, it is deposited on around prefabricated surface of metal particles.Pd catalyst deposit is superficial layer, its thickness
For particle radius about 15% or thinner.Alkali metal acetate is recommended to be used as co-catalyst.
1977, Du pont company of the U.S. disclosed (US4048096, title: Surface impregnated
Catalyst) preparation method of a kind of vinyl acetate catalyst, this catalyst selects Pd and Au bimetallic active component, alkali metal
Acetate is co-catalyst.Use the incipient impregnation precipitation method, make dissolving by being stirred by carrier machinery in a rotation container
Slaine from equal to the solution of pore volume being adsorbed onto on carrier, then in the condition of the unseasoned carrier being loaded with salt
Under, with alkali, these salt are fixed.The finished catalyst of gained belongs to " eggshell type " catalyst, and surface layer thickness is only 0.5 mm.Should
Succeeding in developing so that the performance of ethylene process vinyl acetate catalyst is remarkably enhanced of catalyst.Current industrial ethene
Catalyst formulation used in method vinyl acetate production is almost identical with above-mentioned catalyst with preparation technology.But this catalyst exists
The aspect such as catalyst activity, selectivity still has the space of lifting.
Summary of the invention
One of the technical problem to be solved is catalyst space-time yield and selectivity present in prior art
Low problem, it is provided that a kind of new vinyl acetate catalyst, this catalyst has space time yield and the highest feature.
The two of the technical problem to be solved, are to provide the corresponding catalysis of one of a kind of and above-mentioned technical problem
The preparation method of agent.
The three of the technical problem to be solved, are to provide one of the above-mentioned technical problem of a kind of employing described catalyst
The synthetic method of vinyl acetate.
For solving one of above-mentioned technical problem, the technical solution used in the present invention is as follows: close for ethylene process vinyl acetate
The catalyst become, described active component is Pd, Au and alloy thereof, and co-catalyst is potassium acetate, and in wherein said catalyst, Pd contains
Amount is 0.1-9.0 g/L for 1.0-12 g/L, Au content, and described cocatalyst content is 10 ~ 50 g/L；The load of described catalyst
Body is the SiO that a kind of fluorochemical is modified2。
Described in technique scheme, in catalyst, Oil repellent is preferably 0.5 ~ 5.0 g/L；Described fluorochemical is preferred
Mixed with what the salt of hydrofluoric acid formed at least one in hydrofluoric acid and the salt of hydrofluoric acid, fluosilicate, more preferably hydrofluoric acid
Compound；The salt of described hydrofluoric acid is preferably at least one in the alkali metal salt of the ammonium salt of hydrofluoric acid, hydrofluoric acid；Described hydrofluoric acid
Alkali metal salt be preferably at least one in NaF, KF；With the salt of hydrofluoric acid described in the molar ratio computing of fluorine element and hydrofluoric acid it
Ratio preferably 1: (0.1 ~ 10)；Described carrier B ET specific surface area is preferably 150 ~ 200 cm2/ g, pore volume is preferably 0.6 ~ 0.8
cm3/g。
For solving the two of above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation of catalyst as described above
Method, comprises the following steps:
A aequum water-soluble fluorine-containing compound is dissolved in the aqueous solution and makes maceration extract A by (), use infusion process, by institute
The carrier silica gel of requirement and maceration extract are mixed to get precursor carrier I；
B precursor carrier I is dried by (), obtain precursor carrier II；
C precursor carrier II is obtained carrier III under the conditions of air atmosphere by () after roasting；
D aequum palladium, gold compound are dissolved in solvent and make maceration extract B by (), by the desired amount of carrier III and dipping
Liquid B is mixed to get catalyst precarsor I；
E aequum alkali metal silicate solutions is mixed by () with above-mentioned catalyst precarsor I makes described palladium, gold compound convert
For sedimentation type, obtain catalyst precarsor II；
F (), by reducing agent reducing catalyst precursor II, obtains catalyst precarsor III；
G the desired amount of co-catalyst potassium acetate is dissolved in pure water and makes maceration extract C, before the desired amount of catalyst by ()
Body III mixes with maceration extract C, is dried except water obtains described catalyst.
In technique scheme, infusion process described in (a) step preferably employs equi-volume impregnating；In technique scheme,
The dry temperature of step (b) is preferably 60～120 DEG C, and the temperature of step (c) roasting is preferably 200～500 DEG C；(d) step institute
The palladium compound stated can be palladium bichloride (II), sodium chloride palladium (II), potassium chloride palladium (II), palladium nitrate (II) or palladium sulfate
(II), described gold compound can be chlorauride (III) or the alkali metal salt such as sodium salt or potassium of tetrachloro gold (III) acid
Salt；E alkali silicate described in () step can be the silicate of sodium or potassium, the K of described silicate2O/SiO2Mol ratio or
Na2O/SiO2Mol ratio is not particularly limited, and obtains alkali metal silicate solutions as long as can dissolve all can reach the present invention with water
Purpose, can be such as alkali-metal metasilicate, alkali-metal orthosilicate, it is also possible to be modulus be the potassium water glass of 1～3
Glass or sodium silicate；About (f) step, when one skilled in the art will appreciate that if catalyst precarsor III remains containing Na,
More excellent by washing the performance of the step catalyst of the present invention that precursor II I reduces wherein Na content.
For solving the three of above-mentioned technical problem, the technical solution used in the present invention is as follows: the method for vinyl acetate synthesis,
In the presence of catalyst described in one of technical problem any one technical scheme, consist of oxygen with molar ratio computing raw material: ethene: nitrogen
Gas: acetic acid=1: 5 ~ 7: 4 ~ 8: 1 ~ 2, reaction pressure is 6.0 ~ 8.0 atm, and reaction temperature is 130 ~ 200 DEG C, raw material
Volume space velocity is 1600 ~ 3000 h-1。
Reaction pressure of the present invention is gauge pressure.
Pd and Au is selected to load SiO as active component, potassium acetate as co-catalyst with prior art2Carrier prepares vinegar
Acid catalyst for ethylene is compared, and the present invention selects fluorochemical to carrier S iO2Having carried out modification, F atom part replaces silica gel table
Face-OH group, forms Si-F group, and then improves know clearly catalyst space-time yield and selectivity.Further, the present invention selects
When the salt mixture of hydrofluoric acid and hydrofluoric acid is as co-catalyst, effect in terms of the space-time yield improving catalyst and selectivity
Become apparent from, there is synergy, and this synergy is selecting NH4F and HF is to SiO2When being modified the most obvious.Experiment
Result shows, reaction pressure is 7.0 atm, reaction temperature 150 DEG C, feed gas volume air speed 2000 h-1, reacting gas consists of
Oxygen: ethene: nitrogen: acetic acid=1: when 5.25: 5: 1.2, the space time yield of catalyst of the present invention is catalyzed by prior art
638 grams per liters hour of agent bring up to 842 grams per liters hour, and selectivity improves 4.8%, achieve preferable technique effect.
Detailed description of the invention
[embodiment 1]
(1) carrier S iO2Pre-treatment
A () takes containing NH4The aqueous solution 800 ml of F is maceration extract A(F ion concentration: 3.0 g/L), impregnate 1000 ml
Preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm2/ g, pore volume is 0.7 cm3/ g) 3hr is catalyzed
Agent precursor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4The aqueous solution 800 ml be maceration extract B(palladium content: 2.75 g/L, Jin Han
Amount: 0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () in nitrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst.In catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.
The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 2]
(1) carrier S iO2Pre-treatment
A () takes containing (NH4)3SiF6The aqueous solution 800 ml be maceration extract A(F ion concentration: 3.0 g/L), dipping
Preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is 0.7 cm3/ g) 3hr obtains
To catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4 hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3 hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 3]
(1) carrier S iO2Pre-treatment
A () takes the aqueous solution 800ml containing NaF is maceration extract A(F ion concentration: 3.0g/L), impregnate 1000 ml diameters
It is preparing spherical SiO 2 carrier (BET specific surface 175 cm of 5.8 mm2/ g, pore volume is 0.7 cm3/ g) before 3hr obtains catalyst
Body I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 4]
(1) carrier S iO2Pre-treatment
A () takes the aqueous solution 800ml containing KF is maceration extract A(F ion concentration: 3.0g/L), impregnate 1000 ml a diameter of
Preparing spherical SiO 2 carrier (BET specific surface 175 cm of 5.8 mm2/ g, pore volume is 0.7 cm3/ g) 3hr obtains catalyst precarsor
I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 5]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:0.5) 800ml is that maceration extract A(F ion is dense
Degree: 3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume
It is 0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 6]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:1) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 7]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:2) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 8]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 9]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:4) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 10]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:5) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4 hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 11]
(1) carrier S iO2Pre-treatment
A () takes containing (NH4)3SiF6With HF mixed aqueous solution (nF((NH4)3SiF6):nF(HF)=1:3) 800 ml are maceration extract A
(F ion concentration: 3.0 g/L), impregnates preparing spherical SiO 2 carrier (the BET specific surface 175 of a diameter of 5.8 mm of 1000 ml
cm2/ g, pore volume is 0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 12]
(1) carrier S iO2Pre-treatment
A () takes containing NaF Yu HF mixed aqueous solution (nF(NaF):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 13]
(1) carrier S iO2Pre-treatment
A () takes containing KF Yu HF mixed aqueous solution (nF(KF):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration: 3.0
G/L), preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml is impregnated2/ g, pore volume is 0.7
cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 14]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration:
3.0g/L), preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8mm of 1000ml is impregnated2/ g, pore volume is 0.7
cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5:4:1；
Raw material volume air speed: 1600 hr-1；
Reaction pressure: 6.0 atm；
Reaction temperature: 130oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 15]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F) : nF(HF)=1: 3) 800 ml are maceration extract A(F
Ion concentration: 3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/
G, pore volume is 0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4 hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3 hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5:4:1；
Raw material volume air speed: 2400 hr-1；
Reaction pressure: 6.5 atm；
Reaction temperature: 165oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 16]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75 g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100 ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing the KOAc aqueous solution 450 ml is maceration extract (KOAc:0.1 g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:7:8:2；
Raw material volume air speed: 2700 hr-1；
Reaction pressure: 7.5 atm；
Reaction temperature: 180oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[embodiment 17]
(1) carrier S iO2Pre-treatment
A () takes containing NH4F Yu HF mixed aqueous solution (nF(NH4F):nF(HF)=1:3) 800ml is maceration extract A(F ion concentration:
3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume is
0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:7:8:2；
Raw material volume air speed: 3000 hr-1；
Reaction pressure: 8.0 atm；
Reaction temperature: 200oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[comparative example 1]
(1) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5g Na2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, and shake is for several times
To avoid caking, under the conditions of 80 DEG C, it is dried 8 hr after standing 24 hr obtains catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2 ml/min, and temperature is 150 by catalyst precarsor IIoC) reductase 12 hr in
After be down to room temperature and obtain catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(2) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(3) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
[comparative example 2]
(1) carrier S iO2Pre-treatment
A () takes containing NaF and NH4F mixed aqueous solution (nF(NaF):nF(NH4F)=1:3) 800ml is that maceration extract A(F ion is dense
Degree: 3.0 g/L), impregnate preparing spherical SiO 2 carrier (BET specific surface 175 cm of a diameter of 5.8 mm of 1000 ml2/ g, pore volume
It is 0.7 cm3/ g) 3hr obtains catalyst precarsor I；
(b) by above-mentioned precursor carrier I in air dry oven, 105oIt is dried 4hr under the conditions of C and obtains precursor carrier II；
C precursor carrier II is placed in Muffle furnace by (), in air atmosphere 400oUnder the conditions of C, roasting 3hr obtains carrier III；
(2) prepared by catalyst
A () takes containing H2PdCl4And HAuCl4Aqueous solution 800ml be maceration extract B(palladium content: 2.75g/L, gold content:
0.625 g/L), dipping 1000ml carrier III 3 hr obtains catalyst precarsor I；
B () is by 27.5gNa2SiO3·9H2O is made into the 100ml aqueous solution and is added in above-mentioned catalyst precarsor I, shake for several times with
Avoid caking, under the conditions of 80 DEG C, be dried 8hr after standing 24hr obtain catalyst precarsor II；
C () at hydrogen atmosphere, (flow velocity is 0.2ml/min, and temperature is 150 by catalyst precarsor IIoC) in after reductase 12 hr
It is down to room temperature and obtains catalyst precarsor III；
D () takes containing KOAc aqueous solution 450ml is maceration extract (KOAc:0.1g/ml), impregnated catalyst precursor II I 3
Hr, in 105oIt is dried 6 hr under the conditions of C and obtains finished catalyst；
The main preparation condition of catalyst is listed in table 1.
(3) physical property characterizes
Inductively coupled plasma spectrum generator (ICP) is used to measure Pd, Au, K content in finished catalyst, in catalyst
F constituent content passes through solid-state nuclear magnetic resonance F spectrometry.The physical property of catalyst is listed in table 2.
(4) catalyst performance evaluation
Using fixed bed reactors evaluation, actual conditions is:
Catalyst packing volume: 700 ml；
Reaction raw materials composition (in terms of mole hundred parts of ratios): oxygen: ethene: nitrogen: acetic acid=1:5.25:5:1.2；
Raw material volume air speed: 2000 hr-1；
Reaction pressure: 7.0 atm；
Reaction temperature: 150oC；
Reaction time: 500 hr；
With the content of each component in gas chromatography analytical reactions product, then calculate space time yield and the selection of catalyst
Property.
Table 2 lists space time yield and the selective data of catalyst.
Table 1 catalyst preparation conditions
| Maceration extract A Middle fluorine ion Content, g/L | In maceration extract fluoride kind and with fluorine unit The salt of the molar ratio computing hydrofluoric acid of element and hydrogen The ratio of fluoric acid | In maceration extract Palladium content, g/ L | In maceration extract Gold content, g/ L | In maceration extract Potassium content, g/ L | |
| Embodiment 1 | 3.0 | NH4F | 2.75 | 0.625 | 100 |
| Embodiment 2 | 3.0 | (NH4)3SiF6 | 2.75 | 0.625 | 100 |
| Embodiment 3 | 3.0 | NaF | 2.75 | 0.625 | 100 |
| Embodiment 4 | 3.0 | KF | 2.75 | 0.625 | 100 |
| Embodiment 5 | 3.0 | nF(NH4F) : nF(HF) = 1 : 0.5 | 2.75 | 0.625 | 100 |
| Embodiment 6 | 3.0 | nF(NH4F) : nF(HF) = 1 : 1 | 2.75 | 0.625 | 100 |
| Embodiment 7 | 3.0 | nF(NH4F) : nF(HF) = 1 : 2 | 2.75 | 0.625 | 100 |
| Embodiment 8 | 3.0 | nF(NH4F) : nF(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 9 | 3.0 | nF(NH4F) : nF(HF) = 1 : 4 | 2.75 | 0.625 | 100 |
| Embodiment 10 | 3.0 | nF(NH4F) : nF(HF) = 1 : 5 | 2.75 | 0.625 | 100 |
| Embodiment 11 | 3.0 | nF(NH4)3SiF6 : nF(HF)=1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 12 | 3.0 | nF(NaF) : nF(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 13 | 3.0 | nF(KF) : nF(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 14 | 0.5 | nF(NH4F) : nF(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 15 | 5.0 | nF(NH4F) : nF(HF) = 1 : 3 | 2.75 | 0.625 | 100 |
| Embodiment 16 | 3.0 | nF(NH4F) : nF(HF) = 1 : 3 | 0.95 | 0.5 | 100 |
| Embodiment 17 | 3.0 | nF(NH4F) : nF(HF) = 1 : 3 | 11.5 | 10.0 | 100 |
| Comparative example 1 | --- | 2.75 | 0.625 | 100 | |
| Comparative example 2 | 3.0 | nF(NaF) : nF(NH4F) = 1 : 3 | 2.75 | 0.625 | 100 |
Table 2(is continued) catalyst physical property and evaluating data
| Palladium content, g/L | Gold content, g/L | Potassium content, g/L | Oil repellent, g/L | Reaction temperature (oC) | |
| Embodiment 1 | 3.0 | 0.63 | 30 | 3.0 | 150 |
| Embodiment 2 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 3 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 4 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 5 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 6 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 7 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 8 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 9 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 10 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 11 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 12 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 13 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Embodiment 14 | 3.0 | 0.64 | 30 | 0.5 | 130 |
| Embodiment 15 | 3.0 | 0.64 | 30 | 5.0 | 165 |
| Embodiment 16 | 1.0 | 0.10 | 30 | 3.0 | 180 |
| Embodiment 17 | 12.0 | 9.0 | 30 | 3.0 | 200 |
| Comparative example 1 | 3.0 | 0.64 | 30 | 3.0 | 150 |
| Comparative example 2 | 3.0 | 0.64 | 30 | 3.0 | 150 |
Table 2(continues) catalyst physical property and evaluating data
Claims (9)
1., for the catalyst of ethylene process vinyl acetate synthesis, described catalyst includes active component, co-catalyst and carrier, institute
Stating active component is Pd, Au and alloy thereof, and co-catalyst is potassium acetate, and in wherein said catalyst, Pd content is 1.0-12g/L,
Au content is 0.1-9.0g/L, and described cocatalyst content is 10～50g/L；The carrier that it is characterized in that described catalyst is one
Plant the SiO that fluorochemical is modified2；Described fluorochemical is at least in hydrofluoric acid and the salt of hydrofluoric acid, fluosilicate
Kind.
2. catalyst as claimed in claim 1, it is characterised in that Oil repellent 0.5 5.0g/L in described catalyst.
3. catalyst as claimed in claim 1, it is characterised in that described fluorochemical is the salt group of hydrofluoric acid and hydrofluoric acid
The mixture become.
4. catalyst as claimed in claim 1, it is characterised in that the salt of described hydrofluoric acid is the ammonium salt of hydrofluoric acid, hydrofluoric acid
At least one in alkali metal salt.
5. catalyst as claimed in claim 3, it is characterised in that the alkali metal salt of described hydrofluoric acid be in NaF, KF at least
A kind of.
6. catalyst as claimed in claim 3, it is characterised in that with salt and the hydrogen of hydrofluoric acid described in the molar ratio computing of fluorine element
The ratio of fluoric acid is 1:(0.1～10).
7. catalyst as claimed in claim 1, it is characterised in that described carrier B ET specific surface area is 150-200cm2/ g, pore volume
It is 0.6～0.8cm3/g。
8. the preparation method of catalyst described in any one of claim 1～7, comprises the following steps:
A aequum water-soluble fluorine-containing compound is dissolved in the aqueous solution and makes maceration extract A by (), use infusion process, by aequum
Carrier silica gel and maceration extract be mixed to get precursor carrier I；
B (), by being dried after precursor carrier I, obtains precursor carrier II；
C precursor carrier II is obtained carrier III under the conditions of air atmosphere by () after roasting；
D aequum palladium, gold compound are dissolved in solvent and make maceration extract B by (), by the desired amount of carrier III and maceration extract B
It is mixed to get catalyst precarsor I；
E aequum alkali metal silicate solutions is mixed with above-mentioned catalyst precarsor I that to make described palladium, gold compound be converted into heavy by ()
Shallow lake type, obtains catalyst precarsor II；
F (), by reducing agent reducing catalyst precursor II, obtains catalyst precarsor III；
G the desired amount of co-catalyst potassium acetate is dissolved in pure water and makes maceration extract C, by the desired amount of catalyst precarsor by ()
III mixes with maceration extract C, is dried except water obtains described catalyst.
9. the method for vinyl acetate synthesis, in the presence of catalyst as according to any one of claim 1～7, with molar ratio computing
Raw material consists of oxygen: ethene: nitrogen: acetic acid=1:5～7:4～8:1～2, and reaction pressure is 6.0～8.0atm, reaction temperature
Degree is 130～200 DEG C, and raw material volume air speed is 1600～3000h-1。
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