CN109225197A - A kind of preparation method of propylene oxygen gas-phase epoxidation catalyst - Google Patents
A kind of preparation method of propylene oxygen gas-phase epoxidation catalyst Download PDFInfo
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- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
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Abstract
The invention discloses a kind of preparation method of the propylene oxygen gas-phase epoxidation catalyst of high activity, the catalyst, in preparing epoxypropane with propylene gas-phase epoxidation reaction that molecular oxygen is oxidant, catalytic activity with higher.Catalyst of the invention is with (the Bi containing bismuth silicate2SiO5) SiO2Mesoporous material Bi2SiO5/SiO2For carrier, soluble cobalt adulterates reagent, MoO as carrier3For active component, it is 0.05 ~ 1 that wherein Si/Bi molar ratio, which is 30 ~ 60, Co/Bi molar ratio, in carrier.This catalyst is synthesized using traditional excessive infusion process, and prepared catalyst performance stabilised, catalytic activity is greatly improved.
Description
Technical field
The invention belongs to petrochemical catalyst method of modifying fields, more specifically to a kind of propylene of high activity
The preparation method of oxygen gas-phase epoxidation catalyst, especially with the catalyst of preparing epoxypropane with propylene gas-phase epoxidation and its preparation
Method.
Background technique
Propylene oxide is a kind of Organic Chemicals of high added value, is only second to the third-largest propylene of polypropylene and acrylonitrile
Derivative, while being also one of maximum 50 kinds of chemicals of global yield.Traditional propylene oxide synthesis technology is broadly divided into four
Kind: chlorohydrination, HPPO method, liquid phase oxidation and vapour phase oxidation process.Chlorohydrination is due to that can generate a large amount of chlorine in production process, sternly
Heavy corrosion equipment, and waste water and dregs amount is big；Although HPPO method process is simple, environmental-friendly, H has been used in reactant2O2,
H2O2The problem of there is storage and transport difficult, at high cost, explosive；The selectivity and propylene conversion of PO in liquid phase oxidation
It is all higher, but reaction process has used organic solvent, and organic solvent is not only easy pollution environment, but also the harm of some pairs of human bodies
It is also very big；Then the principle of environment friendly and economy is grasped, researchers develop propylene gas-phase epoxidation
Method, this method and process is simple, does not need to add any solvent, product is easily separated.But under current catalyst system, use
Propylene gas-phase epoxidation method, the selectivity and yield of PO be not high, therefore finds a kind of catalyst of economical and efficient or to existing
Some catalyst, which are modified, becomes present research hotspot.
Active component, carrier and co-catalyst are three common units of catalyst, wherein active component is most important
It is an indispensable component part, therefore the research emphasis of each System Catalyst all concentrates in active component.From work
Property component set out, addition auxiliary agent, the optimal carrier of selection or to change preparation method be all relatively common raising catalyst
Active method.In gas-phase propene epoxidation systems, either Au, Ag, Cu base catalyst or other metallic catalysts,
Reaching the high dispersive of active component by above-mentioned three kinds of methods to improve catalytic activity is still mainstream.And in the screening of carrier
On, possess really preferably selecting for the conventional molecular sieve of large aperture or high-specific surface area, but faces the activity of huge number
The limitation of component, application just embodies.Therefore it is contemplated that being modified for certain carrier, thus acquisition compared with
Excellent surface nature makes it be more conducive to the dispersion of different activities component, this method enhances between carrier and different activities component
Matching degree, it is applied widely, be a kind of more promising method.Compared to traditional oxidation catalyst of cyclopropene, Mo-Bi
Catalyst shows preferably catalytic activity and higher stability.Y. J. Pang etc. (ChemCatChem, 2014,6
(3): 876-884) the MoO synthesized with simple infusion process3-Bi2SiO5/SiO2It is active with good propylene gas-phase epoxidation,
But catalyst Mo content is higher, with MoO3It is calculated as 18.1wt%, molybdenum is easy to reunite in carrier surface, and dispersion is uneven, and PO is caused to select
Selecting property is lower, and activity needs to be further increased.By the load of active component by common dipping in publication number CN104128176A
Method transforms ultrasonic assistant soakage method into, and introduces Butyl Phthalate as Ti modifying agent presoma.This new process changes to a certain extent
It has been apt to the phenomenon that the dispersion of Mo species is uneven on catalyst, but catalyst surface acid distribution is uneven, so that the oxygen tool after activation
There are biggish nucleophilicity, easily attack allylic hydrogen, causes PO isomerization, form methacrylaldehyde, reduce the selectivity of target product.This
Invention passes through a large number of experiments, and doping cobalt element can improve surface nature in discovery carrier preparation, reduces acidity, is formed simultaneously crystal
Defect is more advantageous to the dispersion of active component, substantially increases activity.
Summary of the invention
The present invention is intended to provide one kind, using silicon bismuth molecular sieve as carrier, Co is carrier doped chemical, molybdenum trioxide is activity
Component reduces surface acidity, forms more crystal defects to improve the dispersibility of molybdenum, and forms Mo-Co-Bi collaboration and urge
Change, makes it with O2In the propylene gas-phase epoxidation of oxygen source, to obtain high PO selectivity and propylene conversion, while improving and urging
The stability of agent.
A kind of preparation method of propylene oxygen gas-phase epoxidation catalyst, which is characterized in that 1) silicon bismuth of the preparation containing cobalt carries
Body；2) pickling is carried out to carrier using weak acid；3) molybdenum presoma is loaded in certain proportion in pickling carrier, wherein silicon
(with SiO2Meter) with bismuth (bismuth atom) molar ratio be 30 ~ 60, cobalt (cobalt atom) and bismuth molar ratio are 0.05-1, molybdenum (molybdenum atom) with
The molar ratio of bismuth is 0.01 ~ 6.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that propylene gas-phase epoxidation
Reaction pressure is 0.1 ~ 0.5 MPa, and reaction temperature is 300 ~ 500 DEG C.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, it is characterised in that the following steps are included:
1) it takes template cetyl trimethylammonium bromide and ethyl orthosilicate to mix in aqueous solution, stirs, obtain under ice-water bath
To solution A；It takes a certain amount of bismuth presoma to be dissolved in 20% ~ 70% glycerine water solution of volume fraction and obtains solution B；By solution B by
It is added dropwise in solution A and obtains solution C, continue to stir；It takes cobalt precursor to be dissolved in ethyl alcohol and obtains solution D；Solution D is added dropwise
Solution E is obtained into solution C；It is transferred in the autoclave with polytetrafluoroethyllining lining afterwards, the crystallization 18- at 80-120 DEG C
24h.It is down to room temperature to temperature of reaction kettle, centrifuge washing is dry, and grinding roasts 5 ~ 10 under the K of 573 K ~ 873 in air atmosphere
H can obtain Bi2SiO5/SiO2Mix Co carrier.Wherein a mole composition for each component is ethyl orthosilicate: bismuth presoma in solution D:
Cobalt precursor: cetyl trimethylammonium bromide: glycerol: water: ethyl alcohol=1:0.005 ~ 0.03:0 ~ 0.03:0.01 ~ 0.05:0.5 ~
2:20~100:1~5。
2) appropriate above process resulting vehicle is weighed, is added in certain volume and the weak acid solution of concentration, in certain temperature
The lower stirring of degree, is centrifuged water washing, keeps its pH neutral, dry.
It weighs appropriate step 2 support dispersion and is put into ice-water bath stirring in ethyl alcohol；Take a certain amount of molybdenum presoma solid molten
It in distilled water, is added drop-wise in the ethanol solution of above-mentioned support powder, stirs dropwise；It is dry then in ice-water bath ultrasound, it grinds
Mill roasts 5 ~ 10 h in air atmosphere at the K of 573 K ~ 873 and carries molybdenum catalyst to get to Co doped silicon bismuth.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that molybdenum presoma can be inclined
One of ammonium molybdate, molybdic acid or two kinds.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that weak acid is acetic acid and lemon
One or both of acid.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that the concentration of weak acid is
0.001-0.01mol/L。
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that bismuth presoma be bismuth nitrate,
One of bismuth subcarbonate and bismuth subnitrate are a variety of.
The preparation method of the propylene oxygen gas-phase epoxidation catalyst, which is characterized in that cobalt precursor can be second
One or more of sour cobalt, cobaltous sulfate, acetylacetone cobalt, cobalt chloride.
Propylene catalytic epoxidation activity rating carries out, reaction temperature 300 ~ 500 in fixed bed gas-solid reaction device
DEG C, 0.1 ~ 0.5 MPa of reaction pressure (gauge pressure), catalyst is that reaction gas group becomes volume ratio C3H6/O2/N2=(1~3)/(2~
5)/(15 ~ 20), air inlet total volumetric flow rate are 20 ~ 30 mL/min, and reaction end gas is tested and analyzed by gas-chromatography TCD.
Specific embodiment
Below by specific example to the preparation method of the propylene gas-phase epoxidation catalyst of high activity of the present invention
It is described further, but content not thereby limiting the invention.
Embodiment 1: the cetyl trimethylammonium bromide for weighing about 0.25 g is added in the deionized water of 30 mL in ice water
The lower stirring of bath；After CTAB dissolution, the tetraethyl orthosilicate of 5.2 g is slowly added dropwise into its solution, stirs, obtains solution A；It presses
A certain amount of five nitric hydrates bismuth is dissolved in 50% glycerine water solution for 50 and obtains solution B by silicon bismuth molar ratio；By solution B
It is slowly dropped in solution A, stirs, Co/Bi=0.1 takes cobalt acetate to be dissolved in 5mL ethyl alcohol and obtains solution D in molar ratio；By solution
D is added dropwise in solution C obtain solution E after be transferred in the autoclave with polytetrafluoroethylene (PTFE), in 110 DEG C of 12 h of crystallization；
It is cooled to room temperature under field conditions (factors) to reaction kettle, takes out gel centrifugal washing three times, be dried overnight under 383 K；It will obtain
Solid particle grind into powder, 8 h are roasted in air atmosphere under 823 K, can must mix the Bi of Co2SiO5/SiO2Carrier.
Appropriate obtained carrier will be weighed, is added in the acetic acid of 0.005 mol/L of 20 mL, is stirred at 293 K
1 h is mixed, is washed twice with water after centrifugation, its pH 7, dry 12 h are made.
The about 1 processed support powder of g is weighed, 10 mL dehydrated alcohols are added thereto, ice-water bath stirs 1 h；Then
A certain amount of ammonium molybdate solid is weighed for 3 by molybdenum bismuth molar ratio to be dissolved in 5 mL distilled water, then ammonium molybdate aqueous solution is dripped dropwise
It is added in the ethanol solution of above-mentioned support powder, 1 h of stir about；Then 1 h of ultrasound in the Ultrasound Instrument for filling ice-water bath, then at
It is dried overnight under 383 K；By obtained solid abrasive at fine powder to no granular sensation, 8 h are roasted in air atmosphere at 823 K,
Obtain final catalyst.
Propylene catalytic epoxidation activity rating carries out in fixed bed gas-solid reaction device, and 400 DEG C of reaction temperature,
0.15 MPa of reaction pressure, catalyst 0.1g, reaction gas group is as volume ratio C3H6/O2/N2=2/4/19, air inlet total volume stream
Amount is 25 mL/min, and reaction end gas is tested and analyzed by gas-chromatography TCD.
Embodiment 2: such as the catalyst system of embodiment 1, during synthetic vectors, Co/Bi=0.2 takes acetic acid in molar ratio
Cobalt, which is dissolved in 5mL ethyl alcohol, obtains solution D；Solution D is added dropwise in solution C and obtains solution E, after be transferred to band polytetrafluoroethylene (PTFE)
Autoclave in, in 120 DEG C of 12 h of crystallization；Other conditions and embodiment 1 are consistent, and activity rating condition such as embodiment 1 is urged
Change reaction result and is shown in Table 1.
Embodiment 3: such as the catalyst system of embodiment 1, molybdenum presoma used is molybdic acid, and bismuth presoma is time carbonic acid
Bismuth is 30 by silicon bismuth molar ratio, and the amount of the substance of presoma used is same as Example 1, massages during synthetic vectors
You take cobalt acetate to be dissolved in 7mL ethyl alcohol and obtain solution D than Co/Bi=0.1；Solution D is added dropwise in solution C and obtains solution
E, after be transferred in the autoclave with polytetrafluoroethylene (PTFE), in 90 DEG C of 15 h of crystallization；Weak acid is the 0.01 mol/L lemon of 25ml
Acid, other conditions and embodiment 1 are consistent, activity rating condition such as embodiment 1, and catalysis reaction result is shown in Table 1.
Embodiment 4: such as the catalyst system of embodiment 1, bismuth presoma used is bismuth subnitrate, presoma used
The amount of substance is same as Example 1, and during synthetic vectors, Co/Bi=0.3 takes cobalt acetate to be dissolved in 5mL ethyl alcohol in molar ratio
Obtain solution D；Solution D is added dropwise in solution C and obtains solution E, after be transferred in the autoclave with polytetrafluoroethylene (PTFE),
In 80 DEG C of 24 h of crystallization；Weak acid be 20ml 0.005 mol/L citric acid and 0.005 mol/L acetic acid mixed acid, other
Part and embodiment 1 are consistent, activity rating condition such as embodiment 1, and catalysis reaction result is shown in Table 1.
Embodiment 5: being 60 by silicon bismuth molar ratio such as the catalyst system of embodiment 1, during synthetic vectors, by mole
It takes cobalt acetate to be dissolved in 7mL ethyl alcohol than Co/Bi=0.5 and obtains solution D；Solution D is added dropwise in solution C and obtains solution E,
It is transferred in the autoclave with polytetrafluoroethylene (PTFE) afterwards, in 100 DEG C of 18 h of crystallization；Weak acid is the 0.008 mol/L lemon of 20ml
Acid, other conditions and embodiment 1 are consistent, activity rating condition such as embodiment 1, and catalysis reaction result is shown in Table 1.
Embodiment 6: such as the catalyst system of embodiment 1, cobalt precursor used is cobaltous sulfate, during synthetic vectors,
Co/Bi=0.6 takes cobaltous sulfate to be dissolved in 7mL ethyl alcohol and obtains solution D in molar ratio；Solution D is added dropwise in solution C and is obtained
Solution E, after be transferred in the autoclave with polytetrafluoroethylene (PTFE), in 110 DEG C of 12 h of crystallization；Weak acid is 0.008 mol/ of 20ml
L acetic acid, other conditions and embodiment 1 are consistent, activity rating condition such as embodiment 1, and catalysis reaction result is shown in Table 1.
Embodiment 7: such as the catalyst system of embodiment 1, cobalt precursor used is acetylacetone cobalt, synthetic vectors process
In, Co/Bi=0.6 takes acetylacetone cobalt to be dissolved in 7mL ethyl alcohol and obtains solution D in molar ratio；Solution D is added dropwise to solution C
In obtain solution E, after be transferred in the autoclave with polytetrafluoroethylene (PTFE), in 95 DEG C of 12 h of crystallization；Other conditions and embodiment 1
Unanimously, activity rating condition such as embodiment 1, catalysis reaction result are shown in Table 1.
Embodiment 8: being 40 by silicon bismuth molar ratio such as the catalyst system of embodiment 1, cobalt precursor used is chlorination
Cobalt, during synthetic vectors, Co/Bi=0.6 takes cobalt chloride to be dissolved in 7mL ethyl alcohol and obtains solution D in molar ratio；Dropwise by solution D
Be added in solution C and obtain solution E, after be transferred in the autoclave with polytetrafluoroethylene (PTFE), in 115 DEG C of 12 h of crystallization；Weak acid
For the 0.01 mol/L citric acid of 20ml, other conditions and embodiment 1 are consistent, activity rating condition such as embodiment 1, catalysis reaction
It the results are shown in Table 1.
Embodiment 9: 2 gained catalyst of Example measures the epoxidation activity under different condition, reaction temperature 360
DEG C, remaining reaction condition and embodiment 1 are consistent, and catalysis reaction result is shown in Table 1.
Embodiment 10: 5 gained catalyst of Example measures the epoxidation activity under different condition, using oxygen as oxygen source,
Activity rating is carried out, reaction gas group becomes volume ratio C3H6/O2/N2=2.5/2.5/7.5, air inlet total volumetric flow rate are 25mL/
Min is 380 DEG C in reaction temperature, is reacted under reaction pressure 0.2MPa that remaining reaction condition and embodiment 1 are consistent, catalysis
Reaction result is shown in Table 1.
Comparative example 1
This comparative example illustrates the propylene gas-phase epoxidation activity on the molybdenum bismuth catalyst without cobalt.
This comparative example is mentioned according to Zhichao. Dai et al. (Chemistryselect, 2016,1:2071-2078)
Method out synthesizes molybdenum bismuth binary catalyst MoO3-Bi2SiO5/SiO2。
It weighs and is stirred under ice-water bath in the deionized water of 30 mL of cetyl trimethylammonium bromide addition of about 0.25 g
It mixes；After CTAB dissolution, the tetraethyl orthosilicate of 5.2 g is slowly added dropwise into its solution, stirs, obtains solution A；By silicon bismuth ratio
A certain amount of five nitric hydrates bismuth is dissolved in 50% glycerine water solution for 50 and obtains solution B；Solution B is slowly dropped to molten
In liquid A, continue to stir, after be transferred in the autoclave with polytetrafluoroethyllining lining, in 110 DEG C of 12 h of crystallization；To reaction kettle
After natural conditions are cooled to room temperature, take out gel centrifugal washing three times, be dried overnight under 383 K；The solid that will be obtained
Grain grind into powder, 8 h are roasted under 823 K, can obtain Bi in air atmosphere2SiO5/SiO2Carrier.
The about 1 processed support powder of g is weighed, 10 mL dehydrated alcohols are added thereto, ice-water bath stirs 1 h；Then
A certain amount of ammonium molybdate solid is weighed for 3 by molybdenum bismuth ratio to be dissolved in 5 mL distilled water, then ammonium molybdate aqueous solution is added drop-wise to dropwise
In the alcoholic solution of above-mentioned support powder, continue 1 h of stir about；Then 1 h of ultrasound in the Ultrasound Instrument for filling ice-water bath, then at
It is dried overnight under 383 K；By obtained solid abrasive at fine powder to no granular sensation, 8 h are roasted in air atmosphere at 823 K,
Obtain final catalyst.
Propylene catalytic epoxidation activity rating carries out in fixed bed gas-solid reaction device, and activity rating condition is such as
Embodiment 1, catalysis reaction result are shown in Table 1.
Comparative example 2
1 gained catalyst of comparative example is taken, the epoxidation activity under different condition is measured, reaction temperature is 380 DEG C, remaining reaction item
Part and embodiment 1 are consistent, and catalysis reaction result is shown in Table 1.
Embodiment described above is only several embodiments of the invention, and description is more specific and detailed, but can not
Be interpreted as limitations on the scope of the patent of the present invention, used in chemicals be the pure above chemicals of commercially available chemistry, gas
Purity is not less than 99.9%.It should be noted that those skilled in the art, based on by present inventive concept on, can
Several improvement are made, these are all belonged to the scope of protection of the present invention, and therefore, the scope of protection of the patent of the present invention is with appended power
Subject to benefit requires.
The propylene gas-phase epoxidation Activity Results of 1 catalyst of table
In table 1:
=/×
=/×
Above-described embodiment explanation, the preparation method of the propylene oxygen gas-phase epoxidation catalyst of high activity of the invention, with
MoO3For activated centre, cobalt enters the (Bi containing bismuth silicate as doped chemical2SiO5) SiO2It is the propylene of carrier in mesoporous material
Under epoxidation catalyst, carrier surface property is improved, acidity reduces, and isomerization by-product is selectively reduced, and the gold that appraises at the current rate
The doping of category produces more crystal defects, and the dispersibility of active component molybdenum trioxide is improved, the choosing of propylene oxide
Selecting property increases, and prepared catalyst, stability has also reached promotion, is a kind of propylene oxygen with industrial prospect
Gas gas-phase epoxidation prepares the catalyst of propylene oxide.
Claims (8)
1. a kind of preparation method of propylene oxygen gas-phase epoxidation catalyst, which is characterized in that 1) prepare the silicon bismuth carrier containing cobalt；
2) pickling is carried out to carrier using weak acid；3) molybdenum presoma is loaded in certain proportion in pickling carrier, wherein silicon and bismuth
Molar ratio is 30 ~ 60, and cobalt and bismuth molar ratio are 0.05-1, and the molar ratio of molybdenum and bismuth is 0.01 ~ 6.
2. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 1, which is characterized in that propylene gas
Mutually epoxidised reaction pressure is 0.1 ~ 0.5 MPa, and reaction temperature is 300 ~ 500 DEG C.
3. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 1, it is characterised in that including with
Lower step:
1) it takes template cetyl trimethylammonium bromide and ethyl orthosilicate to mix in aqueous solution, stirs, obtain under ice-water bath
To solution A；It takes a certain amount of bismuth presoma to be dissolved in 20% ~ 70% glycerine water solution of volume fraction and obtains solution B；By solution B by
It is added dropwise in solution A and obtains solution C, continue to stir；It takes cobalt precursor to be dissolved in ethyl alcohol and obtains solution D；Solution D is added dropwise
Solution E is obtained into solution C；It is transferred in the autoclave with polytetrafluoroethyllining lining afterwards, the crystallization 18- at 80-120 DEG C
24h.It is down to room temperature to temperature of reaction kettle, centrifuge washing is dry, and grinding roasts 5 ~ 10 under the K of 573 K ~ 873 in air atmosphere
H can obtain Bi2SiO5/SiO2Mix Co carrier.Wherein a mole composition for each component is ethyl orthosilicate: bismuth presoma in solution D:
Cobalt precursor: cetyl trimethylammonium bromide: glycerol: water: ethyl alcohol=1:0.005 ~ 0.03:0 ~ 0.03:0.01 ~ 0.05:0.5 ~
2:20~100:1~5。
2) appropriate above process resulting vehicle is weighed, is added in certain volume and the weak acid solution of concentration, at a certain temperature
Stirring is centrifuged water washing, keeps its pH neutral, dry.
3) it weighs appropriate step 2 support dispersion and is put into ice-water bath stirring in ethyl alcohol；A certain amount of molybdenum presoma solid is taken to be dissolved in
It in distilled water, is added drop-wise in the ethanol solution of above-mentioned support powder, stirs dropwise；It is dry then in ice-water bath ultrasound, it grinds,
5 ~ 10 h are roasted in air atmosphere at the K of 573 K ~ 873 and carry molybdenum catalyst to get to Co doped silicon bismuth.
4. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 1, which is characterized in that molybdenum forerunner
Body can be one of metamolybdic acid ammonium, molybdic acid or two kinds.
5. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 1, which is characterized in that weak acid is
One or both of acetic acid and citric acid.
6. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 1, which is characterized in that weak acid
Concentration is 0.001-0.01mol/L.
7. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 3, which is characterized in that bismuth forerunner
Body is one of bismuth nitrate, bismuth subcarbonate and bismuth subnitrate or a variety of.
8. the preparation method of propylene oxygen gas-phase epoxidation catalyst according to claim 3, which is characterized in that cobalt precursor
Body can be one or more of cobalt acetate, cobaltous sulfate, acetylacetone cobalt, cobalt chloride.
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