CN106311228B - Silver catalyst, preparation method and application - Google Patents
Silver catalyst, preparation method and application Download PDFInfo
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- CN106311228B CN106311228B CN201510382523.1A CN201510382523A CN106311228B CN 106311228 B CN106311228 B CN 106311228B CN 201510382523 A CN201510382523 A CN 201510382523A CN 106311228 B CN106311228 B CN 106311228B
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Abstract
The present invention relates to a kind of loading type silver catalysts comprising metallic silver and alumina support, the content of the metallic silver are 5-60wt%, and the specific surface area of the loading type silver catalyst is 2.0-6.0m2/ g, preferably 2.0-4.0m2/ g, the loading type silver catalyst average pore size are 0.62-3.0 μm, preferably 0.62-1.8 μm.The invention further relates to the preparation method and applications of the silver catalyst.
Description
Technical field
The present invention relates to a kind of silver catalyst more particularly to a kind of loading type silver catalysts.The invention further relates to the silver to urge
The preparation method and application of agent.
Background technique
The ethylene selectivity epoxidation reaction production ethylene oxide of silver catalyst catalysis is that an important petrochemical industry is raw
Production process.For a long time, which uses always load type metal silver catalyst, and used carrier is alpha-alumina supports.
Since epoxidation of ethylene is strong exothermal reaction, usually require that silver catalyst has lower surface area and larger
Duct, be rapidly diffused into air-flow, avoid from catalyst duct in order to react purpose product ethylene oxide (EO)
The selectivity of purpose product is reduced because of further complete oxidation.For this purpose, numerous patents and document, such as United States Patent (USP) US
6184175, US 5705661 and Chinese invention patent CN1361105A etc. thinks alpha-alumina supports used in silver catalyst
Specific surface area should be 1m2/ g or so is not higher than 2.0m more2/g。
The specific surface area of the silver catalyst prepared by low specific surface area carrier is relatively low, will lead to catalytically active surface compared with
Small, which has limited the raisings of silver-colored catalytic activity and catalyst service life.But when using the alumina support of high-specific surface area,
The selectivity of epoxidation of ethylene is again significant lower, does not have practical value.Therefore, it is more excellent to need a kind of performance for this field
The silver catalyst of good (there is preferably activity, stability and/or selectivity).
Summary of the invention
In order to solve the problems in the existing technology, the present inventor unexpectedly sends out by numerous studies
It is existing, by being carefully controlled carrier physical property and using catalyst preparation appropriate and application method, specific surface can be used completely
The higher (> 2.0m of product2/ g) alumina support the silver catalyst that catalytic performance significantly improves, the ratio of gained catalyst is prepared
Also higher (the 2.0-6.0m of surface area2/ g), which has preferably activity, selectivity and/or stability.For example, this is urged
Agent has considerably higher catalytic activity and/or service life while keeping more highly selective.
Therefore, the present invention provides a kind of loading type silver catalysts comprising metallic silver and alumina support, the gold
The content for belonging to silver is 5-60wt%, and the specific surface area of the loading type silver catalyst is 2.0-6.0m2/ g, the supported silver are urged
The average pore size of agent is 0.62-3.00 μm.In a preferred embodiment of the invention, the loading type silver catalyst
Specific surface area be 2.0-4.0m2/ g, preferably 2.1-3.5m2/g.It is described in a preferred embodiment of the invention
Loading type silver catalyst average pore size is 0.62-1.80 μm, preferably 0.62-1.3 μm.In of the invention one preferred implementation
In mode, the content of the metallic silver is 10-50wt%, preferably 12-45wt%.
In a preferred embodiment of the invention, the loading type silver catalyst further comprises alkali metal promoter
And/or base earth metal promoter.In a preferred embodiment of the invention, the alkali metal promoter is included but are not limited to
One of lithium, sodium, potassium, rubidium and caesium are a variety of, and content is based on overall catalyst weight and is calculated as 10-2000ppmw with metallic element.
In a preferred embodiment of the invention, the base earth metal promoter includes but are not limited to beryllium, magnesium, calcium, strontium and barium
One of or it is a variety of, content is based on overall catalyst weight and with metallic element is calculated as 600-3000ppmw.
Wherein, ppmw refers to the millionth unit indicated by mass.
In a preferred embodiment of the invention, the loading type silver catalyst further comprise the VIth B and/or
The compound of VIIth B race element.In a preferred embodiment of the invention, the group VIB element includes but not only
It is limited to one of chromium, molybdenum and tungsten or a variety of, the group VIB element is 10-2000ppmw with elemental metal content.At this
In one preferred embodiment of invention, the VIIth B race element includes but are not limited to one of manganese, technetium and rhenium or more
Kind, the VIIth B race element is 10-2000ppmw with elemental metal content.
In a preferred embodiment of the invention, the loading type silver catalyst further include boron, nitrogen, sulphur, chlorine and
One of silicon compound is a variety of, and content is calculated as 100-2000ppmw, preferably 200- with corresponding nonmetalloid
2000ppmw。
It include barium and silicon in the loading type silver catalyst in an especially preferred embodiment of the invention.
It is a further object of the invention to provide a kind of preparation methods of loading type silver catalyst comprising such as
Lower step:
A) the argentiferous organic amine complex solution that silver content is 1-28wt% is prepared；
B) with a) gained argentiferous organic amine complex solution oxide impregnation alumina supporter, the specific surface of the alumina support
Product is 2.0-6.0m2/ g, preferably 2.0-4.0m2/g；
C) after redundant solution is gone in leaching, in the thermal decomposition air-flow that temperature is 150-400 DEG C, preferably 170-300 DEG C, heat
1-60min is decomposed, preferably thermal decomposition 1-30min.
Wherein, step a)-c) sequentially carry out.
It is silver-colored in argentiferous organic amine complex solution in step a) to come in a preferred embodiment of the invention
Source can be selected from the compound of any silver soluble, include but are not limited to silver oxide, silver nitrate, silver acetate, silver oxalate etc., excellent
It is selected as silver oxide and the organic amine aqueous solution of silver oxalate.In a preferred embodiment of the invention, the organic amine is carbon
Atomicity is not more than 4 water-soluble organic amine, and preferably carbon atom is not higher than 3 organic amine, more preferably methylamine, ethamine, second
One of diamines, ethanol amine and propylamine are a variety of, especially preferably ethylenediamine.
In above-mentioned method for preparing catalyst in step b) shape of alumina support used can be spherical shape, Rasching ring,
Cylindrical, porous honeycomb shape or other arbitrary shapes and size；Preferred vector is specific surface area 2.1-4.0m2/ g, average Kong Zhi
0.6-3.0 μm of diameter of alpha-alumina supports.
In a preferred embodiment of the invention, the specific surface area of the alumina support is 2.1-5.0m2/ g,
Average pore diameter is 0.5-3.0 μm, especially preferably 0.6-3.0 μm.It is described in a preferred embodiment of the invention
The specific surface area of alumina support is 2.1-4.0m2/ g, average pore diameter are 0.62-3.0 μm.It is preferred at of the invention one
In embodiment, the preferred 2.1-4.0m of the specific surface area of the alumina support2/ g, 0.62-1.8 μm of average pore diameter.At this
In one more preferred embodiment of invention, the preferred 2.1-3.5m of the specific surface area of the alumina support2/ g, average hole
0.62-1.3 μm of diameter.
Also containing content in a preferred embodiment of the invention, in the alumina support is 0.01-
The silicon and/or content of 0.2wt% is the alkaline-earth metal of 600-2000ppmw.
In a preferred embodiment of the invention, the preparation method further includes step d): repeating step b)-c)
It is one or many, until reaching required silver and auxiliary agent content.The step d) is in step a)-c) after.
In a preferred embodiment of the invention, the thermal decomposition air-flow is one in air, nitrogen and hydrogen
Kind is a variety of, preferably air and/or nitrogen.
There is silver granuel size appropriate distribution and silver-colored dispersion degree by silver catalyst prepared by the present invention, be conducive to raising silver and urge
The performance of agent.For example, improving the service life of catalytic activity and catalyst while keeping more highly selective.
In a preferred embodiment of the invention, the argentiferous organic amine complex solution also contains alkali metal
And/or alkaline-earth metal, content are calculated as 10-2000ppmw with metallic element.
In a preferred embodiment of the invention, the argentiferous organic amine complex solution also contains the VIth B
And/or the VIIth B compounds of group, content are calculated as 10-2000ppmw with metallic element.
In a preferred embodiment of the invention, the argentiferous organic amine complex solution also contains nonmetallic
Element boron, nitrogen, sulphur and chlorine one of compound or a variety of, content is calculated as 10-2000ppmw with nonmetalloid.
It is excellent including barium and silicon in carrier described in step b) in an especially preferred embodiment of the invention
Choosing, the content of the barium is 0.08-0.18wt%, and preferably 0.10-0.15wt%, the content of the silicon is 0.05-
0.15wt%, preferably 0.08-0.12wt%.
It is made yet another object of the invention is that providing a kind of above-mentioned loading type silver catalyst or above-mentioned preparation method
Application of the silver catalyst in epoxidation of ethylene.It will be made from above-mentioned loading type silver catalyst or above-mentioned preparation method
Silver catalyst is applied to be applied in epoxidation of ethylene, can have a more preferably combined reaction performance, such as catalytic activity and is made
It is more excellent with the service life.
In the present invention, the specific surface area (A) of carrier and catalyst is according to international test standards ISO-9277 using nitrogen
The measurement of gas physical absorption BET method.Catalyst and pore volume (V) and average pore diameter (Dav=4V/A) are using pressure mercury
Method measurement.Silver content using plasma mass spectrum (ICP-MS) measurement, catalyst and carrier composition use atomic emission spectrometry
(ICP-AES) it determines.
The catalytic perfomance of sample is respectively adopted the measurement of three kinds of conditions, respectively " reactivity worth determination condition one ", " anti-
Answer performance measurement condition two " and " reactivity worth determination condition three ", the content being specifically shown in specific embodiment.
The beneficial effects of the present invention are the catalytic performance of silver catalyst of the invention is more preferable, which has more preferable
Activity and/or stability and/or selectivity (for example, the catalyst keep it is more highly selective while, have it is considerably higher
Catalytic activity and/or service life), be particularly suited for epoxidation of ethylene.And catalyst of the invention is suitable for a variety of
Epoxidation of ethylene condition is especially adapted for use in the reaction close to the industrial production real reaction condition of epoxidation of ethylene
Condition.
Detailed description of the invention
Fig. 1 is the broken line for indicating the long reaction performance of silver catalyst of the embodiment of the present invention 2 and 3 and comparative example 4
Figure.
Specific embodiment
Below with reference to non-limiting specific embodiment, the invention will be further described, but protection scope of the present invention is simultaneously
It is not limited to following embodiments.
Comparative example 1
32.5g ethylenediamine, 11.9g ethanol amine and 56.0g deionized water are added in the glass flask with stirring, is stirring
While 70.3g silver oxalate (silver content 62.6%) is slowly added in glass flask, keep solution temperature at 0-15 DEG C, make
Silver oxalate all dissolves.And deionized water is added, so that solution gross mass is reached 200g.
Take 100g porosity Alpha-alumina carrying agent (specific surface area 1.0m2/ g, pore volume 0.50ml/g, average pore diameter 2.0
μ nm) in flask, above-mentioned acquired solution submergence carrier is poured into, (be evacuated to pressure and be lower than 10mmHg) leaching under vacuumized conditions
Stain 30min, leaching remove redundant solution, later 250 DEG C of thermal decomposition 5min in air, and obtaining silver content is bearing for 15.8wt%
Carry silver catalyst comparative example 1.Gained catalyst specific surface 1.08m2/ g, 1.77 μm of average pore size.
Sieve takes 10-32 mesh catalyst sample 0.20g when evaluation, is packed into microreactor, reaction gas is passed through, in " reactivity worth
Reactivity worth measurement: reacting system pressure 0.16MPa, reaction gas total flow 100ml/min (mark is carried out under determination condition one "
Quasi- state), gas composition " ethylene 13%- oxygen 7%- Balance Air nitrogen "；Using equipped with PLOT-Q capillary column and Thermal Conductivity
The Japanese Dao Jin company GC2014 gas chromatograph of device carries out quantitative analysis.Selectivity (SEO) calculated using following formula: selectivity
(SEO) calculated using following formula:
Reactivity is indicated with the content (EO (outlet)) of purpose product EO in tail gas.It is 180 DEG C of initial temperature, warm herein
Degree is lower to react 10h or more, and 190 DEG C, 200 DEG C are successively warming up to after stable reaction, are stablized 3 hours or more, response data is measured.
Response data is shown in Table 1.
Comparative example 2
Using the identical preparation method of same comparative example 1,32.5g ethylenediamine, 11.9g are added in the glass flask with stirring
70.3g silver oxalate (silver content 62.6%) is slowly added to glass while agitating and burnt by ethanol amine and 56.0g deionized water
It in bottle, keeps solution temperature at 0-15 DEG C, dissolves silver oxalate all.And deionized water is added, reach solution gross mass
200g。
Take 100g porosity Alpha-alumina carrying agent (specific surface area 2.12m2/ g, pore volume 0.345ml/g, average pore diameter
0.65 μm) it immerses in above-mentioned acquired solution, 30min is impregnated under vacuumized conditions, leaching removes redundant solution, later in air
250 DEG C of thermal decomposition 5min obtain the carried silver catalyst comparative example 2 that silver content is 11.0wt%.Gained catalyst specific surface
2.19m2/ g, 0.60 μm of average pore size.
Catalytic performance is measured using the reaction condition of same comparative example 1, the results are shown in Table 1.
Comparative example 3
200g argentamine liquid is prepared using the identical preparation method of same comparative example 1.
Take 100g porosity κ-alumina support (specific surface area 49m2/ g, pore volume 0.36ml/g, average pore diameter
0.029 μm) it immerses in above-mentioned acquired solution, 30min is impregnated under vacuumized conditions, leaching removes redundant solution, later in air
In 250 DEG C of thermal decomposition 5min, obtain silver content be 12.0wt% loading type silver catalyst comparative example 3.Gained catalyst compares table
Face 50m2/ g, 0.028 μm of average pore size.
Catalytic performance is measured using the reaction condition of same comparative example 1, the results are shown in Table 1.
Embodiment 1
Using the identical preparation method of same comparative example 1,32.5g ethylenediamine, 11.9g are added in the glass flask with stirring
70.2g silver oxalate (silver content 62.6%) is slowly added to glass while agitating and burnt by ethanol amine and 56.0g deionized water
It in bottle, keeps solution temperature at 0-15 DEG C, dissolves silver oxalate all.And deionized water is added, reach solution gross mass
200g。
Take 100g porosity Alpha-alumina carrying agent (specific surface area 2.44m2/ g, pore volume 0.52ml/g, average pore diameter
0.85 μm, barium content 0.15wt%, silicone content 0.10wt% in carrier) it immerses in above-mentioned acquired solution, it is soaked under vacuumized conditions
Stain 30min, leaching remove redundant solution, later 250 DEG C of thermal decomposition 5min in air, and obtaining silver content is bearing for 16.4wt%
Carry silver catalyst embodiment 1.Gained catalyst specific surface 2.65m2/ g calculates 0.75 μm of averaging of income aperture.
Catalytic performance is measured using the reaction condition of same comparative example 1, the results are shown in Table 1.In table statistics indicate that, this hair
Bright embodiment 1 is relative to comparative example 1-3, and the content of purpose product EO is more under same reaction temperature, in reactor outlet tail gas
Height shows considerably higher epoxidation of ethylene activity.Meanwhile under appropriate reaction conditions, identical ethylene oxide produces
When rate (outlet EO volume content is close, i.e. EO% is close), the selectivity of the embodiment of the present invention 1 is obvious compared with comparative example 1~3 more
It is high.It can be seen that the specific surface area of loading type silver catalyst is excessive or too small or loading type silver catalyst average pore size is too small
Or it is excessive, the performance that will lead to silver catalyst is poorer than silver catalyst of the invention.
Table 1
Note: 1. " EO% " refers to EO volume content in reactor tail gas, S in tableEO% refers to selectivity；
2. "-" refers to as determination data；" 3. * " institute's indicating value be 0 statistics indicate that, ethylene occur complete oxidation.
Comparative example 4
Silver catalyst is prepared using method identical with comparative example 1, unlike, thermal decomposition process is in air
10min is completed at 210 DEG C.
Reactivity worth measurement carries out under the conditions of " reactivity worth determination condition two ":
Catalyst loading: the catalyst sample 0.20g of 10-32 mesh；
Reaction pressure 1.6MPa
Reaction gas flow speed 100ml/min (standard state),
Reaction gas composition:
When evaluation, 30h or more is reacted at this temperature, target is successively warming up to after stable reaction by 190 DEG C of initial temperature
Temperature is stablized 3 hours or more, measures response data.The composition of reaction gas use the continuous analysis detection of on-line mass spectroscopy instrument, and according to
To calculate selectivity.The performance data of initial reaction stage catalyst is shown in Table 2, and long reaction data (reaction temperature is 220 DEG C) are shown in attached
Fig. 1.
Comparative example 5
Ag-containing solution is prepared using method identical with comparative example 1.
Take 100g porosity Alpha-alumina carrying agent (specific surface area 1.5m2/ g, pore volume 0.55ml/g, average pore diameter
1.47 μm, barium content 0.06wt% in carrier) it immerses in above-mentioned acquired solution, 30min is impregnated under vacuumized conditions, leaching removes
Redundant solution, 250 DEG C of thermal decomposition 5min in air, obtain the carried silver catalyst comparative example 5 that silver content is 18wt% later.
Gained catalyst specific surface 1.60m2/ g, 1.31 μm of average pore size.
Catalytic performance is measured using the reaction condition of same comparative example 4, the performance data of initial reaction stage catalyst is shown in
Table 2.
Embodiment 2
Catalyst is prepared using method same as Example 1, the difference is that thermally decomposing 7min in air, at 230 DEG C
The activation process of completion.Gained silver content is the carried silver catalyst embodiment 2 of 16.4wt%.Gained catalyst specific surface
2.65m2/ g, 0.75 μm of average pore size.
Catalytic performance is measured using the reaction condition of same comparative example 4, the performance data of initial reaction stage catalyst is shown in
Table 2, long reaction data (reaction temperature is 205 DEG C) are shown in attached drawing 1.
Embodiment 3
200g argentamine liquid is prepared using the identical preparation method of same comparative example 1.
Take 100g porosity Alpha-alumina carrying agent (specific surface area 3.1m2/ g, pore volume 0.54ml/g, average pore diameter
0.70 μm, barium content 0.12wt%, silicone content 0.12wt% in carrier) it immerses in above-mentioned acquired solution, it is soaked under vacuumized conditions
Stain 30min, leaching remove redundant solution, later 230 DEG C of thermal decomposition 7min in air, and obtaining silver content is bearing for 16.4wt%
Carry silver catalyst embodiment 3.Gained catalyst specific surface 3.2m2/ g, 0.64 μm of average pore size.
Catalytic performance is measured using the reaction condition of same comparative example 4, the performance data of initial reaction stage catalyst is shown in
Table 2.
The catalytic activity of embodiment 2 and embodiment 3 is apparently higher than comparative example 4 and comparative example 5 as can be seen from Table 2；In phase
Under same or close EO production conditions, reaction temperature is lower than comparative example (activity is higher), and selectivity is also above comparative example.Silver is urged
Agent industry in actual use, usually requires that in the case where meeting certain EO production conditions, reaction temperature it is lower better, be selectively cured
It is high better.This shows that catalyst performance of the present invention is more excellent, is more advantageous to industrial production.
Table 2
Note: 1. " EO% " refers to EO volume content in reactor tail gas in table；②SEO% refers to selectivity.
Catalysis for the service life for further investigating the catalyst, at 205 DEG C of reaction temperature, to the embodiment of the present invention 2 and 3
The long reaction performance (reaction temperature is 205 DEG C) of agent is determined, while at 220 DEG C of reaction temperature, right to the present invention
The long reaction performance (reaction temperature is 220 DEG C) of the catalyst of ratio 4 is determined, and data are shown in attached drawing 1.In general,
For the silver catalyst of same performance, reaction temperature is higher, then EO% value should be higher, but the EO% of comparative example 4 is anti-
And the EO% of always below embodiment 2 and 3.Since the EO% of comparative example 4 is always below embodiment 2 and 3, therefore only measure about
20 days, it is not necessary that continue to measure it.Therefore, by data in attached drawing 1, it is apparent that catalysis prepared in accordance with the present invention
The not only activity of agent embodiment 2 and embodiment 3 is higher, and service life is also considerably longer.
Embodiment 4
35.6g ethylenediamine, 13.0g ethanol amine and 61.0g deionized water are added in the glass flask of belt stirrer, obtains
To mixed liquor.Powdery silver oxalate 76.0g (silver content 62.6%) obtained in comparative example 1 is slowly added to mix while stirring
It closes in liquid, keeps solution temperature at 0-15 DEG C, dissolve silver oxalate all.0.230g cesium sulfate, 0.25g acetic acid are added later
Strontium, 0.17g ammonium perrhenate, 0.050g lithium sulfate and appropriate amount of deionized water, make solution gross mass reach 200g, acquired solution are mixed
It closes uniformly, obtains argentiferous maceration extract, for use.
Take 100g porosity Alpha-alumina carrying agent (specific surface area 3.1m2/ g, pore volume 0.54ml/g, average pore diameter
0.70μm；Barium content 0.12wt%, silicone content 0.12wt% in carrier) it immerses in above-mentioned acquired solution, it is soaked under vacuumized conditions
Stain 30min, leaching remove redundant solution, later 250 DEG C of thermal decomposition 5min in air, obtain silver content as the reality of 18.0wt%
Apply example 4.Gained catalyst specific surface 3.2m2/ g, 0.65 μm of average pore size.
After catalyst breakage, sieve takes the sample of 0.70g 10-32 mesh, loads microreactor, using following " reactivity worth survey
The reactivity worth of the measurement catalyst of fixed condition three ":
Reaction pressure 1.6MPa
Reaction gas flow speed 100mL/min (standard state)
Reaction gas composition:
Evaluation initial stage, reaction temperature are fixed as 185 DEG C, stablize 48h in reaction atmosphere at this temperature, put into later just
Often temperature automatically controlled (by constantly regulating and controlling reaction temperature, making reactor outlet EO content weighing apparatus is 2.5vol%).The group of reaction gas
At using the continuous analysis detection of on-line mass spectroscopy instrument, and accordingly, calculating is selective.10 groups of effective reactivity worth data are chosen daily
It is averaged the performance data as the same day.The reactivity worth data of catalyst are shown in Table 3.
Embodiment 5
Preparation process is with embodiment 4, the difference is that gained catalyst uses 200g and embodiment 4 again after first time activates
In identical maceration extract double-steeping, 250 DEG C of thermal decomposition activation 5min after leaching.5 silver content of gained CATALYST EXAMPLE
30.1wt%, specific surface area 3.3m2/ g, 0.62 μm of average pore size.
Reactivity worth is evaluated with embodiment 4 (reactivity worth determination condition three), the results are shown in Table 3.
Embodiment 6
36.0g ethylenediamine, 12.0g ethanol amine and 62.0g deionized water are added in the glass flask of belt stirrer, obtains
To mixed liquor.Powdery silver oxalate 76.0g (silver content 62.6%) obtained in comparative example 1 is slowly added to mix while stirring
It closes in liquid, keeps solution temperature at 0-15 DEG C, dissolve silver oxalate all.0.320g cesium sulfate, 0.32g acetic acid are added later
Strontium, 0.25g ammonium perrhenate, 0.052g ammonium molybdate ((NH4)6Mo7O24·4H2O) and appropriate amount of deionized water, reach solution gross mass
To 200g, acquired solution is uniformly mixed, obtains argentiferous maceration extract, for use.
Take 30g porosity Alpha-alumina carrying agent (specific surface area 3.3m2/ g, pore volume 0.60ml/g, average pore diameter 0.73
μm；Barium content 0.10wt%, silicone content 0.09wt% in carrier), it is impregnated under vacuum-pumping conditions using the above-mentioned solution of 60g
30min, leaching remove redundant solution, later 250 DEG C of thermal decomposition 5min in air.After first time activates, gained catalyst
Again with the identical maceration extract double-steeping of 60g, 250 DEG C of thermal decomposition activation 5min after leaching, repeatedly twice.Final gained catalyst
The silver content 40.3wt% of embodiment 6, specific surface area 3.5m2/ g, 0.62 μm of average pore size.
Reactivity worth is evaluated with embodiment 4 (reactivity worth determination condition three), the results are shown in Table 3.
Comparative example 6
Preparation process is with embodiment 5, except that being 4.6m in used carrier specific surface area2/ g (pore volume 0.51ml/
G, 0.44 μm of average pore diameter；Barium content 0.07wt%, silicone content 0.20wt% in carrier).Silver content is in gained comparative example 6
29.2wt%, specific surface 4.8m2/ g calculates 0.39 μm of averaging of income aperture.
Reactivity worth is evaluated with embodiment 4 (reactivity worth determination condition three), the results are shown in Table 3.
Table 3
Note: SEO% refers to selectivity.
3 data of table further demonstrate that CATALYST EXAMPLE 4,5 and 6 prepared in accordance with the present invention has considerably higher choosing
The performance of selecting property, catalyst is more preferable, is more suitable for industrial production.
By in different reactivity worth determination conditions one, reactivity worth determination condition two and reactivity worth determination condition
Three, it is found that catalyst of the invention is more applicable for the industrial reaction condition of a plurality of types of epoxidation of ethylene, especially
It is more applicable for being more nearly the reaction condition of actual industrial reaction condition, there is better catalyst performance, for example, catalyst
Activity, stability and/or selectivity.
Claims (28)
1. a kind of loading type silver catalyst comprising metallic silver and alumina support, the content of the metallic silver are 5-
60wt%, the specific surface area of the loading type silver catalyst are 2.0-6.0 m2/ g, the average pore size of the loading type silver catalyst
It is 0.62-1.3 μm；
In the alumina support also containing content be 0.01-0.2wt% silicon and content be 600-2000ppmw alkaline earth gold
Belong to.
2. loading type silver catalyst according to claim 1, which is characterized in that the content of the metallic silver is 10-
50wt%, the specific surface area of the loading type silver catalyst are 2.0-4.0 m2/g。
3. loading type silver catalyst according to claim 2, which is characterized in that the content of the metallic silver is 12-
45wt%, the specific surface area of the loading type silver catalyst are 2.1-3.5 m2/g。
4. loading type silver catalyst according to claim 1, which is characterized in that the loading type silver catalyst further wraps
Include alkali metal promoter and/or base earth metal promoter.
5. loading type silver catalyst according to claim 4, which is characterized in that the alkali metal promoter be lithium, sodium, potassium,
One of rubidium and caesium are a variety of, and content is based on overall catalyst weight and is calculated as 10-2000ppmw, the alkaline earth gold with metallic element
Category auxiliary agent is one of beryllium, magnesium, calcium, strontium and barium or a variety of, and content is based on overall catalyst weight and is calculated as 600- with metallic element
3000ppmw。
6. loading type silver catalyst according to any one of claims 1-5, which is characterized in that the supported silver catalysis
Agent further comprises the compound of the VIth B and/or the VIIth B race element.
7. loading type silver catalyst according to claim 6, which is characterized in that the group VIB element is chromium, molybdenum and tungsten
One of or it is a variety of, the group VIB element is 10-2000ppmw with elemental metal content, and the VIIth B race element is
One of manganese, technetium and rhenium are a variety of, and the VIIth B race element is 10-2000ppmw with elemental metal content.
8. loading type silver catalyst described in any one of -5 according to claim 1, which is characterized in that the supported silver is urged
Agent further includes one of boron, nitrogen, sulphur, chlorine and silicon compound or a variety of, and content is calculated as 100- with corresponding nonmetalloid
2000ppmw。
9. loading type silver catalyst according to claim 8, which is characterized in that the loading type silver catalyst further includes
One of boron, nitrogen, sulphur, chlorine and silicon compound are a variety of, and content is calculated as 200-2000ppmw with corresponding nonmetalloid.
10. a kind of preparation method of loading type silver catalyst described in any one of -9 according to claim 1 comprising as follows
Step:
A) the argentiferous organic amine complex solution that silver content is 1-28wt% is prepared；
B) it is with a) gained argentiferous organic amine complex solution oxide impregnation alumina supporter, the specific surface area of the alumina support
2.0-6.0 m2/g；
C) after redundant solution is gone in leaching, in the thermal decomposition air-flow that temperature is 150-400 DEG C, 1-60 min is thermally decomposed.
11. preparation method according to claim 10, which is characterized in that in step c), after redundant solution is gone in leaching,
In the thermal decomposition air-flow that temperature is 170-300 DEG C, 1-30 min is thermally decomposed.
12. preparation method described in 0 or 11 according to claim 1, which is characterized in that the organic amine is not more than for carbon atom number
4 water-soluble organic amine.
13. preparation method according to claim 12, which is characterized in that the organic amine is carbon atom having not higher than 3
Machine amine.
14. preparation method according to claim 13, which is characterized in that the organic amine be methylamine, ethamine, ethylenediamine,
One of ethanol amine and propylamine are a variety of.
15. preparation method according to claim 14, which is characterized in that the organic amine is ethylenediamine.
16. preparation method described in 0 or 11 according to claim 1, which is characterized in that the specific surface area of the alumina support is
2.1-5.0 m2/ g, average pore diameter are 0.6-3.0 μm.
17. preparation method according to claim 16, which is characterized in that the specific surface area of the alumina support is preferably
2.1-4.0 m2/ g, average pore diameter are 0.62-1.8 μm.
18. preparation method described in 0 or 11 according to claim 1, which is characterized in that also contain content in the alumina support
The alkaline-earth metal that silicon and content for 0.01-0.2wt% are 600-2000ppmw.
19. preparation method described in 0 or 11 according to claim 1, which is characterized in that the preparation method further includes step d):
Repeat step b)-c) it is one or many, until reaching required silver and auxiliary agent content.
20. preparation method described in 0 or 11 according to claim 1, which is characterized in that the thermal decomposition air-flow is air, nitrogen
With one of hydrogen or a variety of.
21. preparation method according to claim 20, which is characterized in that the thermal decomposition air-flow is air and/or nitrogen.
22. preparation method described in 0 or 11 according to claim 1, which is characterized in that the argentiferous organic amine complex solution
Also contain alkali metal and/or alkaline-earth metal, content is calculated as 10-2000ppmw with metallic element.
23. preparation method described in 0 or 11 according to claim 1, which is characterized in that the argentiferous organic amine complex solution
Also contain the VIth B and/or the VIIth B compounds of group, content is calculated as 10-2000ppmw with metallic element.
24. preparation method described in 0 or 11 according to claim 1, which is characterized in that the argentiferous organic amine complex solution
One of compound also containing nonmetalloid boron, nitrogen, sulphur and chlorine is a variety of, and content is calculated as 10- with nonmetalloid
2000ppmw。
25. preparation method described in 0 or 11 according to claim 1, which is characterized in that include barium in carrier described in step b)
And silicon.
26. preparation method according to claim 25, which is characterized in that the content of the barium is 0.08-0.18wt%, institute
The content for stating silicon is 0.05-0.15wt%.
27. preparation method according to claim 26, which is characterized in that the content of the barium is 0.10-0.15wt%, institute
The content for stating silicon is 0.08-0.12wt%.
28. according to claim 1 loading type silver catalyst described in any one of -9 or according to claim 1 in 0-27 appoint
Application of the silver catalyst in epoxidation of ethylene made from preparation method described in meaning one.
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| CN104069893A (en) * | 2013-03-27 | 2014-10-01 | 中国石油化工股份有限公司 | Carrier of silver catalyst used for ethylene oxide production, and preparing method and applications thereof |
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