CN106492798B - The catalyst and preparation method thereof of Direct Epoxidation production propylene oxide - Google Patents
The catalyst and preparation method thereof of Direct Epoxidation production propylene oxide Download PDFInfo
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Abstract
The invention discloses a kind of catalyst containing Ag and preparation method thereof of Direct Epoxidation production propylene oxide.Belong to metal catalyst technology field.Catalyst activity metal component of the present invention is silver, and carrier is that surface modification has tin or/and rhenium auxiliary agent and the γ-Al of BaO2O3.The weight percent of catalyst forms are as follows: Ag 2% ~ 10%, auxiliary agent 0.1% ~ 5%, BaO1.0% ~ 20%, surplus are γ-Al2O3.For using molecular oxygen as the propylene gas-phase one-step epoxidation propylene oxide process of oxidant.Under conditions of there is no inhibitor in relatively mild reaction condition and unstripped gas, there is higher propylene oxide selectivity, can achieve 80% or more, up to 91.6%.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method thereof of Direct Epoxidation production propylene oxide, especially with propylene
Gas-phase epoxidation prepares catalyst of propylene oxide and preparation method thereof, belongs to metal catalyst technology field.
Background technique
Propylene oxide (PO) is a kind of important Organic Chemicals, mainly for the production of the polyether polyol of polyurethane
And propylene glycol, it is the third-largest Organic chemical products that yield is only second to polypropylene and acrylonitrile in acryloyl derivative.Industry at present
The method of upper production PO mainly has chlorohydrination and conjugated oxidation.Both methods accounts for 99% or more of world's total productive capacity,
Middle conjugated oxidation accounts for 60% or so.
Traditional chlorohydrination process is shorter, technical maturity, and operation composite elastic is big, not high to raw material propylene purity requirement, builds
If small investment.The disadvantage is that having corrosion to equipment, and a large amount of inorganic bisulfate waste liquor and the by-product containing chlorine can be generated in production process
Object, problem of environmental pollution are serious.Conjugated oxidation is since nineteen sixty realizes industrialization, using iso-butane and ethylbenzene as the total oxygen of raw material
Change method achieves rapid development, and becomes one of the main chemical industry method of production PO at present.The method overcome chlorohydrinations
The disadvantages of environmental pollution and equipment are corroded, but the process flow of this method is long, and investment cost is high, and connect product object amount is big, economic benefit
Seriously restricted by factors such as the situations of market distich product demand.
Some new epoxy reaction synthetic routes are reported successively, such as M.G.Clerici (J.Catal.129
(1991) 159-167) and Z.W.Xi etc. (Science 292 (2001) 1139-1141) proposed respectively with H2O2For oxidant
TS-1 molecular sieve and heteropoly acid catalysis epoxidation of propylene system.Under the effect of the catalyst, propylene can also make oxygen with molecular oxygen
Agent generates PO.Due to the process have many advantages, such as it is low in cost, it is environmentally friendly, therefore all the time by domestic and international many
The concern of researcher, but the rate constant of propylene complete oxidation is 25 times of its partial oxidation, and therefore, epoxidation of propylene is no matter
From dynamics or thermodynamically more difficult generation.(the J.Catal such as N.W.Cant.52 (1978) 81-94) refer to it is a kind of with
Oxygen is catalyst, the epoxidation of propylene technical solution carried out with Ag catalyst, obtains the selectivity of PO less than 6%, and by-product
Object CO2And H2O has comparative advantage.The application for a patent for invention of publication number 1260787A discloses a kind of containing using oxygen as oxidant
The epoxidation of propylene method that the silver catalyst of chloride carries out, which needs 250 DEG C, and the selectivity of PO is lower than 60%.
Although people have done many effort for the modification and optimization of silver catalyst system, from industrialization, still there is a big difference, especially
It still needs further improvement for the PO selectivity of the system.
With Au catalyst, the propylene gas-phase epoxidation PO of in-situ hydrogen peroxide is people in hydrogen and oxygen atmosphere
Another approach attempting.Using deposition-precipitation by gold be highly dispersed in it is various containing titanium carrier (such as titanium dioxide, titanium silicon,
TS-1, Ti-MCM41/48 and three-dimensional meso-hole oxide material etc.) surface, in hydrogen and oxygen atmosphere and relatively mild reaction item
Under part, the PO selectivity of generation is 90% or more.For example, (the J.Catal such as M.Hanruta.209 (2002) 331-340) description
Ti-MCM-48 carries the propylene gas-phase epoxidation catalytic performance of Au catalyst, and under the conditions of reaction temperature is 150 DEG C, propylene turns
The best result of rate and PO selectivity is respectively 5.6% and 92%；(the J.Catal such as W.N.Delgass.226(2004)156-
170) the propylene gas-phase epoxidation catalyst system for referring to Au/TS-1 can get 2.5-6.5% under 170 DEG C of reaction temperatures
Propylene conversion and 60-85% PO selectivity；M.Harura etc. (J.Phys.Chem.B 109 (2005) 3956-3965)
A kind of load Au catalyst of three-dimensional meso-hole titanium silicalite material through silanization treatment is referred to, using the catalyst, propylene is at 150 DEG C
The selectivity that the conversion ratio of reaction 30 minutes can achieve 7.0% or so, PO is greater than 90%, and effective percentage reaches 40%.In order to change
The catalytic performance of kind catalyst, people also use many methods and are modified to catalyst, such as add alkali metal salt, alkaline earth gold
Belong to salt and silanization treatment etc., and achieves some preferable progress, such as M.Haruta (Angew Chem116 (2004)
It 1572-1574)) uses barium nitrate for auxiliary agent and the load Au catalyst that is handled with silylating reagent, propylene can be made to convert
Rate reaches 9.8%, PO and is selectively greater than 90%.Nonetheless, it is still necessary to develop new load Au catalyst, further to mention
The utilization rate of high propylene conversion and PO selectivity and hydrogen, to meet the requirement of industrial application.
Chinese patent CN446626A discloses a kind of Ag-MO3/ZrO2Catalyst, the weight percent composition of the catalyst
Are as follows: 10~50%Ag, 9.0% oxygen, under conditions of 68.3% nitrogen, propylene conversion 1.6%, the selectivity of propylene oxide
It is 60.3%.
Chinese patent CN1347760A discloses a kind of non-loading type Ag-CuCl catalyst, the weight percent of the catalyst
Than composition are as follows: 70~75%Ag, 25~30%CuCl.It is 350 DEG C in reaction temperature, gas space velocity 18000h-1, unstripped gas group
At 10% propylene, 20% oxygen, under conditions of 70% nitrogen, the conversion ratio of propylene is 1.63%, and propylene oxide is selectively
30.5%.
United States Patent (USP) US5625084 and US5686380 disclose a kind of alkaline earth metal carbonate carried silver catalyst, this is urged
The weight percent of agent forms are as follows: 25~60%Ag, 0.5~2.5%Mo, 34.5~74.45%CaCO3.In reaction temperature
It is 245 DEG C, gas space velocity 1200h-1, unstrpped gas composition: 10% propylene, 5% oxygen, 200PPM vinyl chloride, 10% dioxy
Change carbon, under conditions of 75% nitrogen, the conversion ratio of propylene is 2.8%, and propylene oxide is selectively 58%.
United States Patent (USP) US5703254 discloses a kind of alkaline earth metal carbonate load Yin-gold bimetallic catalyst, the catalysis
The weight percent of agent forms are as follows: 5~50%Ag, 1~10%Au, 40~94%CaCO3.It is 250 DEG C in reaction temperature, gas
Air speed is 1200h-1, unstrpped gas composition: 10% propylene, 5% oxygen, under conditions of 85% nitrogen, the conversion ratio of propylene is
2%, propylene oxide is selectively 40%.
United States Patent (USP) US5770746 discloses a kind of alkaline earth metal carbonate carried silver catalyst, the weight of the catalyst
Percentage composition are as follows: 10~60%Ag, 0.2~2.2%Mo, 37.8~89.8%CaCO3.It is small using vinyl chloride pretreatment 18
When, it is 250 DEG C in reaction temperature, gas space velocity 1200h-1, unstrpped gas composition: 8.15% propylene, 6.35% oxygen,
14.8% carbon dioxide, under conditions of 70.7% nitrogen, the conversion ratio of propylene is 6.5%, and propylene oxide is selectively 52%.
United States Patent (USP) US5861519 discloses a kind of alkaline earth metal carbonate carried silver catalyst, the weight of the catalyst
Percentage composition are as follows: 10~60%Ag, 0.6~7%W, 0.5~5%K, 28~88.9%CaCO3.It is 250 in reaction temperature
DEG C, gas space velocity 1200h-1, unstrpped gas composition: 10% propylene, 5% oxygen, 200ppmNO, 50ppm vinyl chloride, 85% nitrogen
Under conditions of gas, the conversion ratio of propylene is 8.8%, and propylene oxide is selectively 53%.
United States Patent (USP) US5864047 discloses a kind of alkaline earth metal carbonate carried silver catalyst, the weight of the catalyst
Percentage composition are as follows: 10~60%Ag, 0.2~2.5%Re, 1~3%K, 34.5~88.8%CaCO3.It is in reaction temperature
250 DEG C, gas space velocity 1200h-1, unstrpped gas composition: 10% propylene, 5% oxygen, 200ppmNO, 50ppm vinyl chloride,
Under conditions of 85% nitrogen, the conversion ratio of propylene is 10%, and propylene oxide is selectively 51%.
United States Patent (USP) US6083870 discloses a kind of CaF2Carried silver catalyst, the weight percent composition of the catalyst
Are as follows: 25~60%Ag, 0.5~3%K, 37~74.5%CaF2.It is 250 DEG C in reaction temperature, gas space velocity 1200h-1, former
Expect gas composition: 10% propylene, 5% oxygen, 200ppmNO, 50ppm vinyl chloride, under conditions of 85% nitrogen, the conversion of propylene
Rate is 7%, and propylene oxide is selectively 40%.
Chinese patent CN101733137A discloses the Ag-Cu catalysis of a kind of calcium carbonate, barium carbonate or barium sulfate load
Agent, the weight percent composition of the catalyst are as follows: 0.5~10%Ag, 0.05~2.5%Cu, 87.5~99.45% barium carbonates.
It is 230 DEG C in reaction temperature, gas space velocity 5000h-1, unstrpped gas composition: 20% propylene, 10% oxygen, 70% nitrogen
Under the conditions of, the conversion ratio of propylene is 1.1%, and propylene oxide is selectively 55%.But the patent is with polyvinyl alcohol or polyethylene pyrrole
Pyrrolidone is stabilizer, and stabilizer can generate hot-spot in high-temperature roasting removal process, influences prepared Ag-Cu catalysis
The structure and homogeneity of agent, finally influence catalyst performance.
Chinese patent CN102350363A discloses a kind of using barium carbonate or rare earth modified barium carbonate is carrier, load
The catalyst of Ag-Cu, the weight percent composition of the catalyst are as follows: 0.5~10%Ag, 0.05~2.5%Cu, 87.5~
99.45% barium carbonate or rare earth modified barium carbonate.It is 200 DEG C in reaction temperature, gas space velocity 2000h-1, 20% propylene,
Under conditions of 10% oxygen and 70% nitrogen, the conversion ratio of propylene is 3.2%, and propylene oxide is selectively 87%.
It using silver is active component, calcium carbonate for carrier that US5780657, which discloses one kind, added in unstripped gas vinyl chloride,
In the case where the inhibitor such as nitrogen oxides and carbon dioxide, 60-64% propylene oxide selectivity and the propylene of 1.5-2.5% are obtained
Conversion ratio.But due to silver content height, and inhibitor causes operating cost high, and process route complexity etc. gives industrial applications band
Come difficult.Therefore under the premise of do not add any inhibitor in unstripped gas, it is low and there is high epoxy to prepare load silver content
The catalyst of propane selectivity seems and its important.
Although above-mentioned existing patented technology respectively has feature, there is also some shortcomings, for example, silver load capacity compared with
Height needs to be added the inhibitor such as chlorohydrocarbon, nitrogen oxides, carbon dioxide to improve the selectivity of propylene oxide in unstripped gas.It opens
Sending out direct oxidation method efficient, production propylene oxide is that people thirst for solving and are considered most challenging project.
Summary of the invention
It is suitable under the reaction condition relatively mitigated it is an object of the present invention to provide a kind of, is not necessarily in unstripped gas
Inhibitor is added, using molecular oxygen as oxidant, realizes the high performance catalyst by one step epoxidation propylene oxide of propylene.
The second object of the present invention is, provides that a kind of preparation process is simple, and active metallic content is low, catalytic perfomance
Method for preparing catalyst that is high, being used to prepare propylene oxide.
Purpose to realize the present invention, catalyst activity metal component of the present invention are silver, and carrier is that surface modification has tin
Or/and γ-the Al of rhenium auxiliary agent and BaO2O3.The weight percent of catalyst forms are as follows: Ag 2%~10%, auxiliary agent 0.1%~
5%, BaO1.0%~20%, surplus are γ-Al2O3。
Catalyst weight percent composition is preferred: Ag 8%~10%, auxiliary agent 0.5%~5%, BaO 5%~15% are remaining
Amount is γ-Al2O3。
The more preferable tin of auxiliary agent and rhenium.The auxiliary agent content more preferable 1.5%~5%.
The preparation method of catalyst of the present invention is achieved by the steps of:
(1) aluminum oxide dry glue powder and the solution containing barium ions are sufficiently mixed, by dry and calcination process, system
Obtain the γ-Al of barium monoxide modification2O3；
(2) by the γ-of the modification of barium monoxide made from the solution containing tin ion or/and rhenium ion auxiliary agent and step (1)
Al2O3It is sufficiently mixed, by dry and calcination process, tin or/and rhenium-barium monoxide modification γ-Al is made2O3；
(3) by tin made from step (2) or/and rhenium-barium monoxide modification γ-Al2O3Load active component Ag, through overdrying
Dry and roasting, obtains catalyst.
The active component A g and tin, rhenium, auxiliary BaO mode of loading can be existing any mode, such as it is mixed
It pinches, impregnate and sprays, the mode of preferably supersaturation dipping loads.
The precursor of the Ag is the compound containing Ag for being dissolvable in water water, preferably silver nitrate, and the precursor of Sn is to be dissolvable in water water
Compound containing Sn, preferably stannous chloride, the precursor of Re is the compound containing Re for being dissolvable in water water, preferably perrhenic acid, Ba's
Precursor is the compound containing Ba for being dissolvable in water water, preferably barium nitrate.
Drying described in step (1), step (2) and step (3) and roasting condition can be the same or different.Dried strip
Part is room temperature~300 DEG C, and drying time is 0.5 hour~24 hours；Maturing temperature is 300 DEG C~700 DEG C, and calcining time is
0.5 hour~8 hours.
Catalyst of the present invention is used for propylene and molecular oxygen Direct Epoxidation propylene oxide, the process conditions of reaction: fixed
Bed reactor, catalyst are crushed after tabletting, and 20~40 mesh particles is taken to be evaluated, and 10 milliliters of loaded catalyst, charging
Procatalyst pre-processes for 4 hours by 500 DEG C, and 210 DEG C~280 DEG C of reaction temperature, 0.1~0.5MPa of pressure, propylene 5% (v)
~20% (v), oxygen 1% (v)~10% (v), nitrogen surplus, gas space velocity 1000h-1~5000h-1.Reaction product is by gas phase
Chromatography FID and TCD are tested and analyzed, and 2 hours reaction results is taken to compare.Related calculation method is as follows:
Propylene is dense before propylene conversion %=[density of propylene (v%) after density of propylene (v%)-reaction before reacting]/reaction
It spends (v%)
The concentration (v%) of propylene oxide selectivity %=propylene oxide/[react propylene after preceding density of propylene (v%)-reaction
Concentration (v%)]
The principle of the invention is: using the γ-Al having compared with Large ratio surface and suitable cellular structure2O3It, can as carrier
Bigger reacting environment and more reaction active sites are provided for reaction, auxiliary agent tin and rhenium mainly play a part of two aspects:
One is the Acidity that aluminium surface is aoxidized for changing, and reduces the acid amount and acid strength of carrier surface, reduces the peroxidating of generation
The decomposition of object improves the selectivity of reaction；Another effect is to act on forming class alloy structure with active metal component, will be silver-colored
Particle is separated mutually with nano-form, avoids the aggregation of silver and leads to the reductions of active sites, improves the activity of catalyst.
Catalyst prepared by the present invention, due to the addition of auxiliary agent, can improve activity compared with similar silver-containing catalyst
The dispersion of metal reduces the content of active metal component, and does not have in relatively mild reaction condition and unstripped gas
Under conditions of inhibitor, propylene conversion has higher propylene oxide selectivity up to 7.5% or more, can achieve 80%
More than, up to 91.6%, it is very beneficial for actual industrial production application.
Specific embodiment
Catalyst of the present invention is further illustrated below by embodiment, but invention should not be deemed limited to below
In embodiment.
Embodiment 1 (if following indicate without special, degree is weight percentage)
The preparation step of catalyst of the present invention is as follows:
(1) by 100 grams of Al2O3Dry glue powder (Al2O3Content 80%) with 200 milliliters contain 15.4 grams of barium nitrate of aqueous solution
It is sufficiently mixed, 6 hours dry by 110 DEG C, 550 DEG C are handled for roasting 3 hours, and the γ-Al of barium monoxide modification is made2O3；
(2) 5.7 grams of stannous chloride dihydrates are dissolved in the hydrochloric acid solution of 200 milliliters of 0.5mol/L and are configured to containing solution of tin,
Then γ-the Al of barium monoxide modification step (1) obtained2O3It is added thereto, 650 DEG C roastings 24 hours dry by 130 DEG C
Tin-barium monoxide modification γ-Al is made in hour processing2O3；
(3) it takes 12.6 grams of silver nitrates to be dissolved in 200 grams of water and is configured to silver nitrate solution, with tin-oxidation made from step (2)
γ-the Al of barium modification2O3It is sufficiently mixed, 8 hours dry by 100 DEG C, 450 DEG C are handled for roasting 6 hours, and present invention catalysis is made
Agent, number E-1, composition and catalytic performance are shown in Table 1.
Embodiment 2~9
Preparation step is with embodiment 1, the difference is that catalyst composition is different with reaction condition, the present invention of preparation is urged
Agent number is respectively E-2~E-9, and composition and catalytic performance are shown in Table 1.
Comparative example 1
The preparation step of catalyst is with embodiment 1, the difference is that not stanniferous in catalyst or/and rhenium auxiliary agent and oxidation
Barium dressing agent, is made comparative catalyst of the present invention, number C-1, and composition and catalytic performance are shown in Table 1.
Comparative example 2
The weight percent of catalyst made from method according to CN101733137A embodiment 5 forms are as follows: 7.5%Ag,
Comparative catalyst of the present invention, number C-2 is made in 2.5%Cu, 90% barium carbonate.
Comparative example 3
The weight percent of catalyst made from method according to US5864047 embodiment 3 forms are as follows: 40%Ag, 2%
Re, 2%K, 56%CaCO3, comparative catalyst of the present invention, number C-3 is made.
1 each embodiment (comparative example) catalyst of table composition and reactivity worth
| Number | Ag, % | Sn, % | Re, % | BaO, % | Propylene conversion, % | Propylene oxide selectivity, % |
| E-1 | 8.0 | 3.0 | - | 9.0 | 7.6 | 92.1 |
| E-2 | 5.0 | 2.0 | - | 13.0 | 14.1 | 83.3 |
| E-3 | 3.0 | 0.5 | - | 17.0 | 15.5 | 82.9 |
| E-4 | 10.0 | 2.0 | 3.0 | 1.0 | 7.8 | 91.6 |
| E-5 | 2.0 | - | 0.1 | 20.0 | 16.0 | 80.7 |
| E-6 | 7.0 | - | 3.5 | 3.0 | 13.8 | 87.4 |
| E-7 | 9.0 | - | 4.0 | 5.0 | 11.2 | 89.0 |
| E-8 | 4.0 | - | 1.0 | 8.0 | 14.8 | 81.5 |
| E-9 | 8.0 | 1.5 | - | 15.0 | 10.3 | 90.8 |
| C-1 | 20 | - | - | - | 12.8 | 22.5 |
| C-2 | 7.5 | 2.5① | - | 90② | 3.2 | 68.3 |
| C-3 | 50.0 | - | - | 50③ | 7.3 | 51.8 |
Note: 1. copper content, 2. barium carbonate content, 3. calcium carbonate content
E-1~E-4 reaction condition: 230 DEG C of reaction temperature, pressure 0.2MPa, propylene 10% (v), oxygen 5% (v), nitrogen
Surplus, gas space velocity 2000h-1
E-5~E-8 reaction condition: 240 DEG C of reaction temperature, pressure 0.3MPa, propylene 8% (v), oxygen 6% (v), nitrogen
Surplus, gas space velocity 3000h-1
E-9, C-1~C-3 reaction condition: 250 DEG C of reaction temperature, pressure 0.4MPa, propylene 6% (v), oxygen 3% (v),
Nitrogen surplus, gas space velocity 5000h-1
From the results shown in Table 1, catalyst of the present invention is in molecular oxygen and one step propylene oxide of epoxidation of propylene
In reaction, the selectivity of propylene conversion and propylene oxide is apparently higher than comparative catalyst.
Claims (4)
1. a kind of for propylene, the catalyst of molecular oxygen Direct Epoxidation propylene oxide, which is characterized in that by the following method
It is prepared:
(1) aluminum oxide dry glue powder and the solution containing barium ions are sufficiently mixed, by dry and calcination process, oxygen is made
Change the γ-Al of barium modification2O3；
(2) by the γ-Al of the modification of barium monoxide made from the solution containing tin ion or/and rhenium ion auxiliary agent and step (1)2O3It fills
Divide mixing, by dry and calcination process, tin or/and rhenium-barium monoxide modification γ-Al is made2O3；
(3) by tin made from step (2) or/and rhenium-barium monoxide modification γ-Al2O3Load active component Ag, by dry and
Roasting, obtains catalyst；
Drying described in step (1), step (2) and step (3) and roasting condition are identical or different, and drying condition is room temperature ~ 300
℃；Maturing temperature is 300 DEG C ~ 700 DEG C；
Gained catalyst activity metal component is silver, and carrier is that surface modification has tin or/and rhenium auxiliary agent and the γ-Al of BaO2O3；It urges
The weight percent of agent forms are as follows:
Ag 8% ~ 10%, tin or/and rhenium auxiliary agent 0.5% ~ 5%, BaO 5% ~ 15%, surplus are γ-Al2O3。
2. as described in claim 1 for propylene, the catalyst of molecular oxygen Direct Epoxidation propylene oxide, feature exists
In the auxiliary agent content selects 1.5% ~ 5%.
3. the catalysis for propylene, molecular oxygen Direct Epoxidation propylene oxide as described in one of claims 1 or 2
Agent, which is characterized in that auxiliary agent selects tin and rhenium.
4. as claimed in claim 3 for propylene, the catalyst of molecular oxygen Direct Epoxidation propylene oxide, feature exists
In the mode of loading of the active component A g and auxiliary agent is supersaturation dipping.
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| CN101733137A (en) * | 2009-12-21 | 2010-06-16 | 华东理工大学 | Catalyst for preparing propylene oxide from propylene by gas-phase one-step oxidation and preparation method thereof |
| CN102133544A (en) * | 2010-01-25 | 2011-07-27 | 中国石油化工股份有限公司 | Alkaline-earth metal fluoride modified alumina supporter, preparation method thereof, and silver catalyst made from alumina supporter and application of silver catalyst in ethylene epoxide (EO) production |
| CN104321315A (en) * | 2012-05-04 | 2015-01-28 | 巴斯夫欧洲公司 | Catalyst for epoxidation of alkenes |
| CN105618048A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Olefin epoxidation catalyst preparation method, catalyst and application |
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