CN103537301A - Catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as preparation method and application of catalyst - Google Patents
Catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as preparation method and application of catalyst Download PDFInfo
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- CN103537301A CN103537301A CN201310446323.9A CN201310446323A CN103537301A CN 103537301 A CN103537301 A CN 103537301A CN 201310446323 A CN201310446323 A CN 201310446323A CN 103537301 A CN103537301 A CN 103537301A
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Abstract
The invention discloses a catalyst for coproduction of methylal and methyl formate from methanol through oxidization as well as a preparation method and application of the catalyst. The catalyst comprises the following components: vanadium, titanium, sulfur and an auxiliary element, wherein the auxiliary element is one of strontium and antimony. The preparation method of the catalyst comprises the following steps of 1) dissolving the vanadium source, the titanium source, the sulfur source and the auxiliary in water to form a solution A; 2) adding the solution A to the aqueous solution of ammonia until the pH is in the range from 7 to 11, thereby obtaining a slurry; 3) aging the slurry, and washing to obtain a solid B; 4) dissolving the solid B in water containing a surfactant, and then stirring, dehydrating and drying to obtain a solid C; and 5) roasting the solid C to obtain the catalyst. The catalyst provided by the invention is good in degree of dispersion and has good anti-sintering performance; as long as the catalyst is used for methylal and methyl formate from methanol through oxidization, the transformation rate of the methanol is 20-95% and the total selectivity of the methylal and the methyl formate is 70-95%; the single-pass service life of the catalyst is more than 8000 h.
Description
Technical field
The present invention relates to a kind of catalyst and method for making thereof and application, particularly relate to a kind of catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate and method for making and application.
Background technology
Dimethoxym ethane has another name called dimethoxymethane, is a kind of methyl alcohol downstream green chemical industry product of high added value, is widely used in cosmetics, medicine, the fields such as automobile, rubber.Dimethoxym ethane has the features such as dissolubility is strong and nontoxic as solvent, can substitute benzene,toluene,xylene, acetone equal solvent, as the additive in paint and varnish, glue and adhesive, ink and various aerosol products, especially in water-borne wood coating field, may become one of alternative optimal selection of water paint solvent.Meanwhile, dimethoxym ethane is also the important industrial chemicals of preparation high-purity formaldehyde; The particularly important is dimethoxym ethane is a kind of fuel additive that has prospect, and it can improve the diesel combustion thermal efficiency, reduces the discharge of pollutant.
The production of dimethoxym ethane at present mainly adopts traditional methyl alcohol two step synthesis route: first methanol oxidation is generated to formaldehyde, then the further condensation of formaldehyde and methyl alcohol generates target product.The technical matters of two step synthesis dimethoxym ethane is relatively ripe, but complex process, flow process are tediously long, and there is the shortcomings such as equipment corrosion, waste liquid is many, catalyst is difficult separated with reactant, cause production cost high, particularly be difficult to realize the large-scale production of high-purity methylal, greatly hindered the lifting of value of the product.Therefore,, directly by methyl alcohol oxidation step synthesizing dimethoxym ethane, can realize low-cost production and the scale application of dimethoxym ethane.The typical reporting in this field at present mainly contains US Patent No. 6403841B1, adopts SbRe
2o
6catalyst carries out methanol oxidation synthesizing dimethoxym ethane; Chinese patent CN1911503A, adopts ReO
x/ ZrO
2catalyst is prepared dimethoxym ethane; Chinese patent CN1634655 A, the V of employing sulphur modification
2o
5/ TiO
2catalyst is prepared dimethoxym ethane.From catalytic performance, still there is larger deficiency in the activity of catalyst, selective and stability aspect, wherein, in catalyst formulation described in US Patent No. 6403841 B1 and Chinese patent CN1911503A, introduce expensive rhenium element, the high oxide of rhenium is volatile, the inactivation that easily causes catalyst at high temperature, has limited the practical application of such catalyst.
Methyl formate is a kind of important organic synthesis intermediate, in the fields such as pharmacy, solvent industry, agricultural chemicals, is widely used.It can be used as the raw material of organic synthesis product, also can be used for the manufacture of acetate fiber.In agricultural, be used as pesticide, the bactericide of cereal crops, fumigant and agent for tobacco treatment etc.Current existing methyl formate industrialized preparing process mainly contains methanol dehydrogenation method, methanol esterification method, methyl alcohol liquid phase hydroxylating method, synthesis gas and directly synthesizes methyl formate etc.Wherein, methanol esterification method cost is expensive, and equipment corrosion is serious.Methanol dehydrogenation method space-time yield is low, poor selectivity, and the copper-based catalysts adopting is easily reunited and inactivation.Methyl alcohol hydroxylating method need to be used the absolute methanol that price is higher, and simultaneously working concentration is higher than 80% CO, and production cost is higher.Synthesis gas is synthetic methyl formate severe reaction conditions directly, and production capacity is low.
Chinese patent CN101327444A adopts V
2o
5/ TiO
2catalyst synthesizing dimethoxym ethane and methyl formate, but the complicated process of preparation of catalyst, produce a large amount of irritative gas in preparation process, and catalyst stable fixed time shorter.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate and method for making and application.This catalyst shows high methanol conversion ratio, high selectivity of product and high stability in methanol oxidation coproduction dimethoxym ethane and methyl formate process, and preparation method is simple, and application prospect is extensive.
For solving the problems of the technologies described above, the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate of the present invention, its component comprises: vanadium, titanium, sulphur and auxiliary element; Described auxiliary element is a kind of in strontium and antimony;
Wherein, vanadium, titanium, sulphur and auxiliary element calculate with the weight of its oxide respectively, V
2o
5and TiO
2mass ratio be 2:100～80:20; Sulphur is with the mass metrology of sulfate radical, and the percentage by weight that accounts for catalyst is 0.5～8%; The percentage by weight that the oxide of auxiliary element accounts for catalyst is 0～5%.
Preferably, V
2o
5and TiO
2the total amount percentage by weight that accounts for catalyst be 77～99.5%.
The particle diameter of described catalyst is preferably 50～200 nanometers, and the nitrogen adsorption specific surface area of catalyst is 70～400m
2/ g.
This catalyst can be prepared by following method.
The preparation method of the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate of the present invention, comprises step:
1) by ,Liu source, ,Tai source, vanadium source and the complete water-soluble certain density solution A of making of auxiliary agent; Wherein, auxiliary agent is the material containing strontium or antimony;
2) at ice-water bath with under stirring, solution A is dropwise added in ammonia spirit, until pH=7～11 obtain the slurries that contain yellowish-brown precipitation;
3) by step 2) slurries ageing, washing, obtain yellowish-brown solid B;
4) solid B is dissolved in the water containing surfactant, stirs, obtain mixed liquor, dehydration, dry, obtain solid C;
5) by solid C roasting 2～10h at 300～600 ℃, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
In described step 1), vanadium source comprises: V
2o
5, VOSO
4, NH
4vO
3in one or more; Titanium source comprises: butyl titanate, tetraethyl titanate, TiSO
4, TiOSO
4in one or more; Sulphur source comprises: H
2s, SO
2, SO
3, H
2sO
4, one or more in sulfamic acid; Auxiliary agent comprises: SbCl
3or SrCl
2;
Wherein, the strontium in vanadium, titanium, sulphur and auxiliary agent or antimony calculate with the weight of its oxide respectively, V
2o
5and TiO
2mass ratio be 2:100～80:20; Sulphur is with the mass metrology of sulfate radical, and the percentage by weight that accounts for catalyst is 0.5～8%; The percentage by weight that strontium in auxiliary agent or the oxide of antimony account for catalyst is that 0～5%[is as SbCl
3(or SrCl
2) decompose after antimony oxide (or strontium oxide strontia) weight of gained account for catalyst weight 0～5%]; The solid dissolving in solution A and the mass ratio of water are 1:10～50.
Described step 1), 3), 4) in, water is deionized water.
Preferably, described step 2), in, under ice-water bath and the mixing speed with 200～700r/min, solution A be take to the speed of 2～8ml/min and is dropwise added to mass concentration as the i.e. 5～24wt% of 5～24%() ammonia spirit in, until pH=7～11 obtain slurries.
In described step 3), the condition of ageing is: room temperature ageing 1～12h; The method of washing is: water or absolute ethanol washing, as directly washed 1～3 time with water, or wash with water after 1～3 time, then use absolute ethanol washing 1～2 time.
In described step 4), surfactant comprises: a kind of or its mixture in tween, n-butanol; The time of stirring is 1～12h; In mixed liquor, the shared percentage by weight of surfactant is 2～30%, and the shared percentage by weight of water is 40～60%, and all the other are solid B; Dry temperature is 40～120 ℃, and the dry time is 6～24h.
In addition, the invention also discloses a kind of application of the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate, as described in catalyst for the catalytic reaction of methanol oxidation coproduction dimethoxym ethane and methyl formate, wherein, the condition of catalytic reaction is:
Described catalyst filling is entered in reactor, first the speed with 50～200ml/min passes into the first gaseous mixture, at 250～600 ℃, activate 0.5～6h, then, catalytic reaction temperature is controlled to 120～180 ℃, pass into the second gaseous mixture that is preheated to 120～160 ℃, operating pressure is normal pressure, and gas space velocity is the i.e. 1000～15000ml/g.cath of every gram of catalyst 1000～15000ml(per hour);
Wherein, the first gaseous mixture is comprised of oxygen and inert gas; The volume content of oxygen is 5～50%; Inert gas comprises: one or more in argon gas, nitrogen, helium;
The second gaseous mixture is comprised of methanol steam and the first gaseous mixture; In the second gaseous mixture, the shared molar percentage of methanol gas is 0.5～72%, and the shared molar percentage of oxygen is 4～47%, and the shared molar percentage of inert gas is 14～94%.
Described reactor is fixed bed reactors.
Catalyst granules form of the present invention is nano particle, degree of scatter is good, there is good anti-sintering property, conversion ratio for methanol oxidation coproduction dimethoxym ethane and methyl formate methyl alcohol is 20～95%, the overall selectivity of dimethoxym ethane and methyl formate is 70～95%, and catalyst single pass life surpasses 8000h.
The specific embodiment
Embodiment 1
Get in the ultrasonic 400ml of the being dissolved in deionized water of 1.5g vanadic sulfate, 16.3g titanium sulfate and 5g sulfuric acid, obtain solution A.
Get 50ml ammoniacal liquor (25wt%) and add people 300ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 200r/min, the speed by solution A with 2ml/min is dropwise added in solution B, until pH=7.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 2h, with after 200ml deionized water washing 2 times, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 20ml deionized water, adds 1ml n-butanol, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 12h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 50ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 135 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
catevery gram of catalyst of h(8000ml per hour), reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 2
Get in the ultrasonic 500ml of the being dissolved in deionized water of 2.5g vanadic sulfate, 20.5g titanium sulfate, 4.5g sulfuric acid and 0.3g trichloride antimony, obtain solution A.
Get 60ml ammoniacal liquor (25wt%) and add people 600ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 250r/min, the speed by solution A with 4ml/min is dropwise added in solution B, until pH=8 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 4h, with after 300ml deionized water washing 2 times, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 15ml deionized water, adds 1ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 12h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 80ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are nitrogen), temperature rises to after 400 ℃ of activation 2h, be cooled to 145 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, nitrogen 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 3
Get in the ultrasonic 500ml of the being dissolved in deionized water of 3.5g vanadic sulfate, 19.4g titanium sulfate, 6g sulfuric acid and 0.2g strontium chloride, obtain solution A.
Get 55ml ammoniacal liquor (25wt%) and add people 450ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 300r/min, the speed by solution A with 6ml/min is dropwise added in solution B, until pH=8.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 6h, with after 150ml deionized water washing 3 times, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 15ml deionized water, adds 3ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 24h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 100ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 20%, and all the other are helium), temperature rises to after 400 ℃ of activation 2h, be cooled to 145 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, helium 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 6000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 4
Get in the ultrasonic 450ml of the being dissolved in deionized water of 4.5g vanadic sulfate, 21.5g titanium sulfate, 3g sulfamic acid and 0.2g trichloride antimony, obtain solution A.
Get 60ml ammoniacal liquor (25wt%) and add people 450ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 320r/min, the speed by solution A with 8ml/min is dropwise added in solution B, until pH=8.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 6h, with after 200ml deionized water washing 2 times, is used absolute ethanol washing 2 times, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 15ml deionized water, adds 2ml n-butanol, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 60 ℃ dry 24h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 120ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 145 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 6000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 5
Get in the ultrasonic 700ml of the being dissolved in deionized water of 5g vanadic sulfate, 19.8g titanium sulfate, 3g sulfamic acid and 0.2g strontium chloride, obtain solution A.
Get 50ml ammoniacal liquor (25wt%) and add people 300ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 340r/min, the speed by solution A with 6ml/min is dropwise added in solution B, until pH=9 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 4h, with after 200ml deionized water washing 2 times, is used absolute ethanol washing 2 times, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 20ml deionized water, adds 1ml n-butanol, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 60 ℃ dry 24h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 140ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 6000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 6
Get in the ultrasonic 350ml of the being dissolved in deionized water of 2.7g vanadic sulfate, 22.8g titanyl sulfate, 5.5g sulfuric acid and 0.2g trichloride antimony, obtain solution A.
Get 45ml ammoniacal liquor (25wt%) and add people 300ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 360r/min, the speed by solution A with 4ml/min is dropwise added in solution B, until pH=8.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 8h, with after 250ml deionized water washing 2 times, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 30ml deionized water, adds 1ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 120 ℃ dry 8h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 160ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 7
Get in the ultrasonic 800ml of the being dissolved in deionized water of 3.2g vanadic sulfate, 20.4g titanyl sulfate, 5.8g sulfuric acid and 0.3g strontium chloride, obtain solution A.
Getting 50ml ammoniacal liquor (25wt.%) adds people 450ml deionized water and is mixed with solution B.
Under the mixing speed of ice-water bath and 650r/min, the speed by solution A with 4ml/min is dropwise added in solution B, until pH=9 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 4h, with after 400ml deionized water washing 1 time, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 25ml deionized water, adds 1ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 110 ℃ dry 8h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 180ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 8
Get in the ultrasonic 250ml of the being dissolved in deionized water of 5g vanadic sulfate, 20.2g titanyl sulfate, 2.8g sulfamic acid and 0.5g trichloride antimony, obtain solution A.
Get 65ml ammoniacal liquor (25wt%) and add people 400ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 400r/min, solution A is dropwise added to solution B with the speed of 4ml/min, until pH=8.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 12h, with after 150ml deionized water washing 2 times, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 25ml deionized water, adds 2ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 100 ℃ dry 10h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 200ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 145 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 6000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 9
Get in the ultrasonic 600ml of the being dissolved in deionized water of 4.8g vanadic sulfate, 18.2g titanyl sulfate, 2g sulfamic acid and 0.3g strontium chloride, obtain solution A.
Get 45ml ammoniacal liquor (25wt%) and add people 300ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 450r/min, solution A is dropwise added to solution B with the speed of 2ml/min, until pH=7.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 10h, with after 400ml deionized water washing 1 time, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 20ml deionized water, adds 1ml n-butanol, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 24h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 60ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 10
Get in the ultrasonic 600ml of the being dissolved in deionized water of 4.5 ammonium metavanadates, 19.8g titanyl sulfate, 4.5g sulfuric acid and 0.3g trichloride antimony, obtain solution A.
Get 50ml ammoniacal liquor (25wt%) and add people 450ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 500r/min, the speed by solution A with 4ml/min is dropwise added in solution B, until pH=9 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 4h, with after 400ml deionized water washing 1 time, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 25ml deionized water, adds 1ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 110 ℃ dry 8h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 70ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 6000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 11
Get in the ultrasonic 800ml of the being dissolved in deionized water of 6.8g ammonium metavanadate, 21.2g titanium sulfate, 3.8g sulfamic acid and 0.4g strontium chloride, obtain solution A.
Get 65ml ammoniacal liquor (25wt%) and add people 400ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 550r/min, the speed by solution A with 4ml/min is dropwise added in solution B, until pH=8.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 12h, with after 150ml deionized water washing 2 times, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 25ml deionized water, adds 2ml Tween-80, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 100 ℃ dry 10h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 90ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 150 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 12
Get in the ultrasonic 800ml of the being dissolved in deionized water of 9.6g ammonium metavanadate, 21.5g titanyl sulfate, 4.8g sulfuric acid and 0.3g strontium chloride, obtain solution A.
Get 45ml ammoniacal liquor (25wt%) and add people 300ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 600r/min, the speed by solution A with 2ml/min is dropwise added in solution B, until pH=7.5 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 10h, with after 400ml deionized water washing 1 time, is used absolute ethanol washing 1 time, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 20ml deionized water, adds 1ml n-butanol, stir after 6h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 24h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 110ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 140 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector), and reactivity worth is in Table 1.
Embodiment 13
Get in the ultrasonic 3500ml of the being dissolved in deionized water of 1.8g ammonium metavanadate, 18.2g titanium sulfate and 3.5g sulfuric acid, obtain solution A.
Get 45ml ammoniacal liquor (25wt.%) and add people 350ml deionized water, be mixed with solution B.
Under the mixing speed of ice-water bath and 700r/min, the speed by solution A with 1.5ml/min is dropwise added in solution B, until pH=8 obtains the slurries that contain yellowish-brown precipitation.Then, room temperature ageing 2h, with after 200ml deionized water washing 2 times, obtains yellowish-brown solid.
Gained yellowish-brown solid is dissolved in to 20ml deionized water, adds 1ml n-butanol, stir after 12h, use Rotary Evaporators to slough moisture, and be placed at 80 ℃ dry 12h, then at 400 ℃ roasting 6h, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
Prepared catalyst porphyrize, compressing tablet, broken also sieve are got to 20～40 object particle 1ml and packed in fixed bed reactors, speed with 130ml/min passes into the first mist (wherein, the volumetric concentration of oxygen is 10%, and all the other are argon gas), temperature rises to after 400 ℃ of activation 2h, be cooled to 135 ℃, pass into the second hybrid reaction gas (the shared molar percentage of gas is: methyl alcohol 5%, oxygen 15%, argon gas 80%) that is preheated to 120 ℃, operating pressure is normal pressure, and gas space velocity is 8000ml/g.
cath, reaction end gas is through chromatography (TCD detector).
Catalyst in the present embodiment has the stable life-span, can stable operation surpass 8000h, and reaction stability is shown in Table 2.
The methanol oxidation dimethoxym ethane processed of table 1 catalyst and the performance of methyl formate
The lifetime stability of the methanol oxidation of catalyst dimethoxym ethane processed and methyl formate in table 2 embodiment 13
Embodiment 14
Roasting in embodiment 1 is made respectively into " roasting 10h at 350 ℃ ", " roasting 4h at 500 ℃ ", " roasting 2h at 550 ℃ ", other also can obtain corresponding catalyst as embodiment 1.
In addition, the particle diameter of catalyst prepared by embodiment 1-14 is in 50～200 nanometer range, and nitrogen adsorption specific surface area is at 70～400m
2within the scope of/g.
Claims (9)
1. for a catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate, it is characterized in that: the component of described catalyst comprises: vanadium, titanium, sulphur and auxiliary element; Described auxiliary element is a kind of in strontium and antimony;
Wherein, vanadium, titanium, sulphur and auxiliary element calculate with the weight of its oxide respectively, V
2o
5and TiO
2mass ratio be 2:100～80:20; Sulphur is with the mass metrology of sulfate radical, and the percentage by weight that accounts for catalyst is 0.5～8%; The percentage by weight that the oxide of auxiliary element accounts for catalyst is 0～5%.
2. catalyst as claimed in claim 1, is characterized in that: described V
2o
5and TiO
2the total amount percentage by weight that accounts for catalyst be 77～99.5%;
The particle diameter of catalyst is 50～200 nanometers;
The nitrogen adsorption specific surface area of catalyst is 70～400m
2/ g.
3. a preparation method for catalyst as claimed in claim 1, is characterized in that, comprises step:
1) by ,Liu source, ,Tai source, vanadium source and the water-soluble solution A of making of auxiliary agent; Wherein, auxiliary agent is the material containing strontium or antimony;
2) at ice-water bath with under stirring, solution A is dropwise added in ammonia spirit, until pH=7～11 obtain slurries;
3) by step 2) slurries ageing, washing, obtain solid B;
4) solid B is dissolved in the water containing surfactant, stirs, obtain mixed liquor, dehydration, dry, obtain solid C;
5) by solid C roasting 2～10h at 300～600 ℃, obtain the catalyst for methanol oxidation coproduction dimethoxym ethane and methyl formate.
4. method as claimed in claim 3, is characterized in that: in described step 1), vanadium source comprises: V
2o
5, VOSO
4, NH
4vO
3in one or more;
Titanium source comprises: butyl titanate, tetraethyl titanate, TiSO
4, TiOSO
4in one or more;
Sulphur source comprises: H
2s, SO
2, SO
3, H
2sO
4, one or more in sulfamic acid;
Auxiliary agent comprises: SbCl
3or SrCl
2;
Wherein, the strontium in vanadium, titanium, sulphur and auxiliary agent or antimony calculate with the weight of its oxide respectively, V
2o
5and TiO
2mass ratio be 2:100～80:20; Sulphur is with the mass metrology of sulfate radical, and the percentage by weight that accounts for catalyst is 0.5～8%; The percentage by weight that strontium in auxiliary agent or the oxide of antimony account for catalyst is 0～5%; The solid dissolving in solution A and the mass ratio of water are 1:10～50;
Described step 1), 3), 4) in, water is deionized water.
5. method as claimed in claim 3, it is characterized in that: described step 2), under ice-water bath and the mixing speed with 200～700r/min, solution A be take to the speed of 2～8ml/min and be dropwise added in the ammonia spirit that mass concentration is 5～24%, until pH=7～11 obtain slurries.
6. method as claimed in claim 3, is characterized in that: in described step 3), the condition of ageing is: room temperature ageing 1～12h;
The method of washing is: water or absolute ethanol washing.
7. method as claimed in claim 3, is characterized in that: in described step 4), surfactant comprises: a kind of or its mixture in tween, n-butanol;
The time of stirring is 1～12h;
In mixed liquor, the shared percentage by weight of surfactant is 2～30%, and the shared percentage by weight of water is 40～60%, and all the other are solid B;
Dry temperature is 40～120 ℃, and the dry time is 6～24h.
8. an application for catalyst as claimed in claim 1 or 2, is characterized in that: described catalyst is for the catalytic reaction of methanol oxidation coproduction dimethoxym ethane and methyl formate, and wherein, the condition of catalytic reaction is:
Described catalyst filling is entered in reactor, first the speed with 50～200ml/min passes into the first gaseous mixture, at 250～600 ℃, activate 0.5～6h, then, catalytic reaction temperature is controlled to 120～180 ℃, pass into the second gaseous mixture that is preheated to 120～160 ℃, operating pressure is normal pressure, and gas space velocity is every gram of catalyst 1000～15000ml per hour;
Wherein, the first gaseous mixture is comprised of oxygen and inert gas; The volume content of oxygen is 5～50%; Inert gas comprises: one or more in argon gas, nitrogen, helium;
The second gaseous mixture is comprised of methanol steam and the first gaseous mixture; In the second gaseous mixture, the shared molar percentage of methanol gas is 0.5～72%, and the shared molar percentage of oxygen is 4～47%, and the shared molar percentage of inert gas is 14～94%.
9. application as claimed in claim 8, is characterized in that: described reactor is fixed bed reactors.
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