CN109499560A - A kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method - Google Patents
A kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- 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
- C07D301/10—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 with catalysts containing silver or gold
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to catalyst field, a kind of alpha-alumina supports, ethylene epoxidizing silver catalyst and ethylene method are disclosed.The alpha-alumina supports pass through the method included the following steps and are made: S1. preparation has the solid mixture of following component: one water A1 of vacation2O3, component A, can after-flame solid lubricant, fluoride-mineralization agent and alkaline earth metal compound, the solid mixture is mixed with binder and optional water then, obtains mixture；Wherein, component A is one water A1 of vacation2O3One water A1 of product of roasting or vacation2O3Product of roasting and three water α-A12O3；S2. mixture obtained in step S1 is formed, obtains formed body；S3. formed body obtained in step S2 is dried and is roasted.Reaction of the silver catalyst made of alpha-alumina supports provided by the invention to ethylene production ethylene oxide, the active and higher advantage of selectivity.
Description
Technical field
The present invention relates to catalyst fields, and in particular to a kind of alpha-alumina supports, and the silver catalyst being made from it
And its application.More particularly, it relates to a kind of alpha-oxidation for ethylene production ethylene oxide silver catalyst
Alumina supporter and the silver catalyst as made from the carrier further relate to produce ethylene oxide using the ethylene of this catalyst
Method.
Background technique
Silver catalyst effect under ethylene mainly generate ethylene oxide, while occur side reaction generate carbon dioxide and
Water etc..Activity, selectivity and stability are the main performance index of silver catalyst.Wherein activity generally refers to ethylene oxide production
Process reaches reaction temperature required when certain reaction load, and reaction temperature is lower, and the activity of catalyst is higher；Selectivity refers to
Ethylene is converted to the ratio between the molal quantity of ethylene oxide and the overall reaction molal quantity of ethylene in reaction；And stability is then expressed as activity
With the fall off rate of selectivity, fall off rate is smaller, and the stability of catalyst is better.Silver catalyst can be mainly divided at present
Three kinds, respectively high activity, highly selective and intermediate selectivity silver catalyst.Since petroleum resources are increasingly deficient and energy-efficient want
It asks, highly selective in recent years and intermediate selectivity silver catalyst is widely used in industrial production and instead of original high work
Property silver catalyst.
The performance of silver catalyst is also used with catalyst in addition to having important relationship with the composition of catalyst and preparation method
Carrier property and preparation method have important relationship.For at present, silver catalyst generally selects Alpha-alumina to do carrier.Measure α-oxygen
The index for changing alumina supporter performance specifically includes that specific surface area, Kong Rong, water absorption rate, compression strength of carrier etc., suitable specific surface
Product provides position for the deposition of active component and auxiliary agent；Suitable Kong Rongwei ethylene provides suitable space, makes reaction heat
Amount distributes in time；Suitable water absorption rate can control the load capacity of active component, catalyst aid on carrier；And it is suitable
Crushing strength can guarantee that long-lasting catalytic bears reaction pressure.
The primary raw material for preparing alumina support in the prior art is the hydrate of aluminium oxide.Hydrated alumina is added viscous
Agent and various additives etc. are tied, through mixing and is mediated uniformly, then extrusion molding is most made more through dry and high-temperature roasting afterwards
The heat-resisting alpha-alumina supports in hole.The type and granularity of raw material have a major impact the pore structure of carrier and the performance of catalyst.
For example, CN103372466A passes through the quality of allotment gibbsite and boehmite when gibbsite
Granularity prepares the carrier that the hole that aperture is 0.5-2.5 μm accounts for 60%-90%.CN102527442A and CN102921471A is selected
Replace α-gibbsite with β-gibbsite whole/part, prepares the carrier with bigger specific surface area.
CN103769233A is used as and is carried using a variety of crystal phases and different types of activated alumina substitution or part substitution hydrated alumina
The raw material of body.CN103816940A is the primary raw material of carrier using cheap surge aluminium masonry.In the prior art to carrier
Performance and the improvement of the activity and selectivity bring of catalyst are also very limited, therefore this field still needs to carrier and its manufacture
Method improves, in favor of producing the better silver catalyst of performance.
Summary of the invention
The purpose of the invention is to overcome the deficiencies of existing technologies, a kind of alpha-alumina supports, ethylene epoxidizing are provided
With silver catalyst and ethylene method.It is being loaded silver by alpha-alumina supports of the invention and is preferably being loaded various active components
After silver catalyst is made, good activity and selectivity is shown during ethylene produces ethylene oxide.
In view of the situation of the above-mentioned prior art, the present inventor carries out in silver catalyst and its carrier preparation field
Research extensively and profoundly, as a result, it has been found that, by one water A1 of vacation2O3Product of roasting after roasting at a certain temperature replaces or part generation
For aluminium oxide hydrate as the raw material for preparing carrier, wafer size, specific surface area, the water absorption rate of adjustable finished product carrier
And Kong Rong, when the silver catalyst prepared by the carrier is for ethylene epoxy ethane, activity and selectivity are obviously changed
It is kind.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of alpha-alumina supports, wherein should
Alpha-alumina supports pass through the method included the following steps and are made:
S1. the solid mixture with following component is prepared: one water A1 of vacation2O3, component A, can after-flame solid lubricant,
Then the solid mixture is mixed with binder and optional water, is obtained by fluoride-mineralization agent and alkaline earth metal compound
Mixture；Wherein, component A is one water A1 of vacation2O3One water A1 of product of roasting or vacation2O3Product of roasting and three water α-A12O3；
S2. mixture obtained in step S1 is formed, obtains formed body；
S3. formed body obtained in step S2 is dried and is roasted, obtain the alpha-alumina supports.
The second aspect of the present invention provides a kind of ethylene epoxidizing silver catalyst, and the silver catalyst includes carrier and bears
Carry active component silver on this carrier, wherein the carrier is alpha-alumina supports provided by the invention.
The third aspect of the present invention provides a kind of ethylene method, wherein this method comprises: ethylene is mentioned in the present invention
Epoxidation of ethylene is carried out under the action of the alpha-alumina supports of confession and/or silver catalyst provided by the invention, obtains epoxy
Ethane.
According to the present invention, by one water A1 of vacation2O3Product of roasting after roasting at a certain temperature replaces or part replaces oxidation
The hydrate of aluminium is as the raw material for preparing carrier, wafer size, specific surface area, water absorption rate and the hole of adjustable finished product carrier
Hold.Compared with prior art, silver catalyst made of alpha-alumina supports provided by the invention produces epoxy second to ethylene
The reaction of alkane, the active and higher advantage of selectivity.
Other features and advantages of the present invention will then part of the detailed description can be specified.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below.Although the following describe preferred implementations of the invention
Mode, however, it is to be appreciated that may be realized in various forms the present invention without that should be limited by the embodiments set forth herein.
The present invention provides a kind of alpha-alumina supports, and the alpha-alumina supports pass through the method system included the following steps
:
S1. the solid mixture with following component is prepared: one water A1 of vacation2O3, component A, can after-flame solid lubricant,
Then the solid mixture is mixed with binder and optional water, is obtained by fluoride-mineralization agent and alkaline earth metal compound
Mixture；Wherein, component A is one water A1 of vacation2O3One water A1 of product of roasting or vacation2O3Product of roasting and three water α-A12O3；
S2. mixture obtained in step S1 is formed, obtains formed body；
S3. formed body obtained in step S2 is dried and is roasted, obtain the alpha-alumina supports.
The inventors found that: pass through three water α-A12O3, one water A1 of vacation2O3With one water A1 of vacation2O3Product of roasting
Cooperation, crystalline size, specific surface area, water absorption rate and the Kong Rong of adjustable finished product carrier；To be conducive to improve gained catalysis
The activity and selectivity of agent.
In the present invention, " optional water ", which refers to, can be added water, can also be added without water, also, water herein refers to additional add
The water entered does not include the water inherently contained in other components.
A preferred embodiment according to the present invention, the false water A12O3Product of roasting be one water A1 of vacation2O3?
The product roasted at 550-1000 DEG C.The false water A12O3Product of roasting addition, aluminium oxide in carrier can be promoted
α phase transformation so that the chip of carrier to become smaller direction grow, to influence the objects such as the specific surface area of carrier, Kong Rong and water absorption rate
Property, further influence silver catalyst performance.Under preferable case, the false water A12O3Product of roasting granularity be 10-100 μ
m。
Although as long as the false water A1 is added2O3Product of roasting can be thus achieved goal of the invention of the invention, but from
Further increasing has the reaction that silver catalyst made of the alumina support is applied to ethylene production ethylene oxide
The angle of more high activity and selectivity is set out, and on the basis of the total amount of solid component in mixture A, the dosage of the component A is
40-85 weight %, preferably 55-80 weight %.The false water A12O3The dosage of product of roasting be component A total dosage
0.1~100wt%, preferably 50~100wt%.
A preferred embodiment according to the present invention, the component A can be one water A1 of vacation2O3Product of roasting and three
Water α-A12O3, the three water α-A12O3Dehydration turns crystalline substance into α-A1 in high-temperature calcination process2O3.Under preferable case, three water
α-A12O3Granularity be 25-300 μm.
A preferred embodiment according to the present invention, on the basis of the total weight of solid mixture, a false water
A12O3Dosage is 10-55 weight %, preferably 15-45 weight %.Under preferable case, the false water A12O3Granularity be 10-
100μm.The false water A12O3It is reacted in such as sour kneading process of adding additives with acid, is converted to colloidal sol, plays binder,
Stable α-A1 is also translated into high-temperature calcination process2O3, become α-A12O3A part of carrier.According to the present invention, it is added
Binder and one water A1 of vacation2O3Aluminum sol is generated, each component is bonded together, extrudable molding paste is become.This hair
In bright, the type of the binder is known to those skilled in the art, and for example including acid, the acid is usually with the aqueous solution of acid
Form provide, preferably aqueous solution of nitric acid, the weight ratio of nitric acid and water is preferably 1:(1.25- in the aqueous solution of nitric acid
10)。
A specific embodiment according to the present invention, in order to equally play the role of binder, by mixture
Carry out it is kneaded and formed during each component is bonded together, become extrudable molding paste, the binder and vacation
One water A12O3It is all or part of to be provided in the form of Aluminum sol.
A preferred embodiment according to the present invention, can after-flame solid lubricant be added to make mediate after
Material is easy to form and is granulated, while oxidation reaction occurring in material roasting process, gas evolution is generated, when carrier is made
It does not introduce or introduces impurity as few as possible, to not influence the performance of catalyst.It is described can after-flame solid lubricant it is available
Be various this fields be used to prepare the alumina support can after-flame solid lubricant, be preferably selected from petroleum coke, carbon dust, stone
One of ink, vaseline etc. are a variety of, on the basis of the total weight of solid mixture, it is described can after-flame solid lubricant
Dosage is 0.01-10 weight %, preferably 0.01-5 weight %.
A preferred embodiment according to the present invention, the alkaline earth metal compound are oxide, the nitre of strontium and/or barium
One of hydrochlorate, acetate, oxalates and sulfate are a variety of, and its role is to improve to carrier property.
Under preferable case, on the basis of the total weight of solid mixture, the dosage of the alkaline earth metal compound is 0.01-
8 weight %, more preferably 0.05-5 weight %.
A preferred embodiment according to the present invention, the addition effect of fluoride-mineralization agent are the crystalline substance of accelerated oxidation aluminium
Type conversion, and reduce by 0.5 μm of pore below.The fluoride-mineralization agent can be hydrogen fluoride, aluminum fluoride, ammonium fluoride, fluorination
One of magnesium and ice crystal are a variety of.
Under preferable case, on the basis of the total weight of solid mixture, the dosage of the fluoride-mineralization agent is 0.05-10
Weight %, more preferably 0.5-5 weight %.
According to the present invention, in step S2, mixture obtained in step S1 is mediated to obtain a kind of paste, then
Formed body is obtained after paste extrusion molding, this method can be carried out according to the ordinary skill in the art.Wherein, the shape of formed body
Shape can be annular, spherical, cylindricality or porous column shape.
According to the present invention, in the step S3, dry and roasting method can be carried out with reference to the usual manner of this field.
Under preferable case, the formed body can dry to containing 10 weight % of free water hereinafter, drying temperature can be done for 80-120 DEG C
The dry time controls according to moisture content at 1-24 hours.Roasting makes aluminium oxide be completely converted into α-A12O3, time of roasting can be with
It is 1-20 hours, preferably 2-15 hours；Highest maturing temperature can be 1200-1500 DEG C.Roasting is totally converted aluminium oxide
For α-A12O3。
A specific embodiment according to the present invention, the Alpha-alumina of ethylene epoxidizing silver catalyst provided by the invention
The preparation method of carrier includes the following steps:
S1. it prepares with the solid mixture formed as follows:
A) on the basis of solid mixture total weight, dosage is one water of vacation that the granularity of 10-55 weight % is 10-100 μm
A12O3；
B) on the basis of solid mixture total weight, total dosage is three water that the granularity of 40-85 weight % is 25-300 μm
α-A12O3And the one water A1 of vacation that granularity is 10-100 μm2O3Product of roasting；
C) with three water α-A12O3With one water A1 of vacation2O3The total weight dosage of product of roasting be 0.1-100 weight %
The one water A1 of vacation that granularity is 10-100 μm2O3Product of roasting；
D) on the basis of solid mixture A total weight, dosage can after-flame solid lubricant for 0.01-10 weight %'s；
E) on the basis of solid mixture A total weight, dosage is the fluoride-mineralization agent of 0.05-10 weight %；
F) on the basis of solid mixture A total weight, dosage is the alkaline earth metal compound of 0.01-8 weight %；
S2. solid mixture, the binder in step S1 mixed with optional water, mediated and extrusion molding, obtained
To formed body；
The additional amount of binder is the 25-60 weight % of solid mixture total weight, and the additional amount of water is solid mixture
The 0-30 weight % of total weight；And
S3. by the formed body in step S2 be dried to containing 10 weight % of free water hereinafter, then highest roast temperature
Degree is that α-A1 is made in roasting at 1200-1500 DEG C2O3Carrier.
Alpha-alumina supports provided by the invention preferably have the feature that α-A12O3Content is 90 weight % or more, pressure
Broken intensity is 30-200N/, preferably 40-160N/；Specific surface is 0.3-2.5m2/ g, preferably 0.6-2.0m2/ g, into one
Step is preferably 1.55-1.9m2/g；Water absorption rate is 30-80%, preferably 40-70%, further preferably 50-70%；Kong Rongwei
0.30-0.90ml/g, preferably 0.40-0.75ml/g, further preferably 0.50-0.70ml/g；Average crystalline size is
2.0-5.0μm。
In the present invention, the side crush intensity of carrier uses II type intelligence detector for strength of particles of DL, chooses carrier sample
Product are averaged to obtain after measuring radial crushing strength；Water absorption rate is measured by densimetry；Specific surface area is inhaled using nitrogen physisorption
Attached BET method measurement；Kong Rong is using pressure mercury method measurement.
According to another aspect of the present invention, described the present invention also provides a kind of ethylene epoxidizing silver catalyst
Silver catalyst includes the active component silver of carrier and load on this carrier, wherein the carrier is α-oxygen provided by the invention
Change alumina supporter.
A preferred embodiment according to the present invention, the present invention also provides a kind of silver catalysis of ethylene epoxidizing
Agent, the silver catalyst include:
A) alpha-alumina supports provided by the invention；
B) silver being deposited in the alpha-alumina supports；
C) alkali metal and/or alkaline-earth metal or the compound based on alkali metal and/or alkaline-earth metal；
D) rhenium metal and/or the compound based on rhenium；And
E) optionally, the coassist agent element of rhenium selected from one of chromium, molybdenum, tungsten and manganese or various metals, and/or is selected from
Compound based on one of chromium, molybdenum, tungsten and manganese or various metals.
According to the present invention, in above-mentioned silver catalyst, the total weight based on the silver catalyst, silver-colored mass content is 5-
37%, preferably 8-32%；The mass content of alkali metal is 5-3000ppm, preferably 10-2000ppm；The quality of alkaline-earth metal
Content is 50-20000ppm, preferably 100-15000ppm；The mass content of rhenium metal is 10-2000ppm, preferably 100-
1500ppm；Coassist agent content is calculated as 0-1500ppm, preferably 0-1000ppm with the metal in coassist agent.
Silver catalyst of the invention can be prepared in a conventional manner, by golden with a kind of Ag-containing compound, organic amine, alkali
The solution for belonging to auxiliary agent, base earth metal promoter, rhenium-containing auxiliary agent and its optional coassist agent impregnates above-mentioned alpha-alumina supports to prepare.
Wherein, the organic amine compound can be for suitable for any organic amine for preparing ethylene oxide silver catalyst
Compound, if the organic amine compound can with silver compound formed argent-amine complex, for example, can selected from pyridine,
One of butylamine, ethylenediamine, 1,3- propane diamine and ethanol amine are a variety of, preferably the mixture of ethylenediamine and ethanol amine.
The alkali metal promoter can be the compound or its any one compound of lithium, sodium, potassium, rubidium or caesium, such as it
Nitrate, sulfate or hydroxide or aforesaid compound two or more any combination, preferably sulphur
Sour caesium and/or cesium nitrate.
The base earth metal promoter can be the compound of magnesium, calcium, strontium or barium, such as their oxide, oxalates, sulfuric acid
Two or more any combination of salt, acetate or nitrate or aforesaid compound, the preferably chemical combination of barium or strontium
Object, more preferably barium acetate and/or strontium acetate.The base earth metal promoter can be applied to prior to, concurrently with, or after immersion silver
On carrier, it can also be immersed on carrier after silver compound is reduced.
The rhenium auxiliary agent can be the oxide, perrhenic acid, perrhenate of rhenium, or mixtures thereof, preferably perrhenic acid and/
Or perrhenate, such as perrhenic acid, perrhenic acid caesium and ammonium perrhenate etc..
The coassist agent of the rhenium auxiliary agent can be the compound of any transition metal or several transition gold in the periodic table of elements
Belong to the mixture of compound, one of preferred chromium, molybdenum, tungsten and manganese or various metals, and/or based in chromium, molybdenum, tungsten and manganese
The compound of one or more elements, such as chromic acid, chromic nitrate, wolframic acid, wolframic acid caesium, molybdic acid, ammonium molybdate, mangaic acid and potassium permanganate
Deng one of or it is a variety of.Rhenium auxiliary agent and its coassist agent can be applied on carrier prior to, concurrently with, or after immersion silver, can also
To be immersed on carrier after silver compound is reduced.As being added obtained by rhenium auxiliary agent and its coassist agent can be further improved
The stability of the activity of silver catalyst, selectivity and activity and selectivity.Wherein, " optionally, the coassist agent of rhenium auxiliary agent " table
It is bright, it can be the coassist agent of rhenium-containing auxiliary agent, or the not coassist agent of rhenium-containing auxiliary agent.
A specific embodiment according to the present invention, the preparation method of the silver catalyst include the following steps:
(1) with containing sufficient amount silver compound, organic amine, alkali metal promoter, base earth metal promoter, rhenium-containing auxiliary agent and its altogether
The solution of auxiliary agent impregnates above-mentioned porous alpha-alumina supports；
(2) maceration extract, dry impregnated carrier are filtered off；With
(3) containing activating in oxygen gas mixture to step (2) resulting vehicle, the silver catalyst is made.
In the preparation of silver catalyst of the present invention, is mixed with silver nitrate with ammonium oxalate solution generate silver oxalate, oxalic acid first
Silver is dissolved in organic amine and argentamine liquid is made, and adds above-mentioned auxiliary agent and is made into maceration extract；Then above-mentioned with the maceration extract dipping prepared
Alpha-alumina supports drain, in the nitrogen oxygen atmosphere of air stream or oxygen content no more than 21 weight % (such as oxygen-containing 8 weight %)
It is kept for 0.5-120 minutes within the temperature range of 180-700 DEG C, preferably 200-500 DEG C, the heat point of progress in preferably 1-60 minutes
Finished product silver catalyst is made in solution.
According to another aspect of the present invention, the present invention also provides a kind of ethylene methods, wherein this method packet
It includes and ethylene is subjected to second under the action of alpha-alumina supports provided by the present invention and/or silver catalyst provided by the invention
Alkene epoxidation reaction, obtains ethylene oxide.Wherein, ethylene oxidation reactions device can carry out epoxidation reaction to be any
Device.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
The present invention is described further below with reference to embodiment, but the scope of the invention is not limited to these embodiments.
It is primality that various silver catalysts of the invention with laboratory reactor (following letter " micro- anti-") evaluating apparatus test its
Energy and stability.The reactor that micro anti-evaluation device uses is the stainless steel tube of internal diameter 4mm, and reactor is placed in heating mantle.It urges
The admission space of agent is 1ml, and there is inert filler in lower part, catalyst bed is made to be located at the flat-temperature zone of heating mantle.
The determination condition for the activity and selectivity that the present invention uses is as follows:
Reaction gas forms (mol%)
METHOD FOR CONTINUOUS DETERMINATION reactor enters after stably reaching above-mentioned reaction condition, exit gas forms.Measurement result carries out body
Product calculates selectivity after shrinking correction as follows:
Wherein Δ EO is to work off one's feeling vent one's spleen poor with inlet gas ethylene oxide concentration, takes the average conduct of 10 groups or more test datas
The test result on the same day.
In the following embodiments, the side crush intensity of alumina support uses II type intelligence detector for strength of particles of DL,
Alumina support sample is chosen, is averaged to obtain after measuring radial crushing strength；Water absorption rate is measured by densimetry；Specific surface
Product is measured using nitrogen physisorption BET method；Pore size distribution is using pressure mercury method measurement.
Carrier prepares comparative example 1
This preparation comparative example is used to illustrate the preparation of reference alumina carrier
By 25-300 μm of three water α-A12O3380g, 10-100 μm of one water A1 of vacation2O3220g, magnesium fluoride 20g and nitre
Sour barium 4g is put into blender and is uniformly mixed, and is transferred in kneader, be added 22g petroleum coke and 200ml dust technology (nitric acid: water=
1:5, weight ratio), it is kneaded into extrudable molding paste.Extrusion molding is outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm
Seven apertures in the human head column is dried 2 hours or more at 80-120 DEG C, and free water content is made to be reduced to 10 weight % or less.It is pinched above-mentioned
Carrier after synthesis type is put into top-hat kiln, is increased to 1400 DEG C from room temperature through 33 hours, and it is small that 5 are calcined under the conditions of 1400 DEG C
When, obtain white α-A12O3Carrier.The carrier physical data measured is as shown in table 1 below.
Carrier prepares embodiment 1
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 25-300 μm of three water α-A12O3190g, 10-100 μm of one water A1 of vacation2O3220g, 10-100 μm of vacation one
Water A12O3It is put into blender and is uniformly mixed in the product 190g, magnesium fluoride 20g and barium nitrate 4g that 550 DEG C of roastings obtain, be transferred to
In kneader, 22g petroleum coke and 200ml dust technology (nitric acid: water=1:5, weight ratio) is added, is kneaded into extrudable molding cream
Shape object.Extrusion molding is the seven apertures in the human head column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, is dried 2 hours at 80-120 DEG C
More than, so that free water content is reduced to 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, it is small through 33
When from room temperature be increased to 1400 DEG C, calcined 5 hours under the conditions of 1400 DEG C, obtain white α-A12O3Carrier.The carrier measured
Property is as shown in table 1 below.
Carrier prepares embodiment 2
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 10-100 μm of one water A1 of vacation2O3220g, 10-100 μm of one water A1 of vacation2O3In the production that 550 DEG C of roastings obtain
Object 380g, magnesium fluoride 20g and barium nitrate 4g be put into blender be uniformly mixed, be transferred in kneader, be added 22g graphite and
200ml dust technology (nitric acid: water=1:5, weight ratio), is kneaded into extrudable molding paste.Extrusion molding is outer diameter
The seven apertures in the human head column of 8.0mm, long 6.0mm, internal diameter 1.0mm are dried 2 hours or more at 80-120 DEG C, make free water content drop
As low as 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1400 from room temperature through 33 hours
DEG C, it is calcined 5 hours under the conditions of 1400 DEG C, obtains white α-A12O3Carrier.The carrier physical property measured is as shown in table 1 below.
Carrier prepares embodiment 3
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 25-300 μm of three water α-A12O3190g, 10-100 μm of one water A1 of vacation2O3220g, 10-100 μm of vacation one
Water A12O3It is put into blender and is uniformly mixed in the product 190g, magnesium fluoride 20g and barium nitrate 4g that 820 DEG C of roastings obtain, be transferred to
In kneader, 22g graphite and 200ml dust technology (nitric acid: water=1:5, weight ratio) is added, is kneaded into extrudable molding paste
Object.Extrusion molding be outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm seven apertures in the human head column, dried at 80-120 DEG C 2 hours with
On, so that free water content is reduced to 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33 hours
1400 DEG C are increased to from room temperature, is calcined 5 hours under the conditions of 1400 DEG C, obtains white α-A12O3Carrier.The carrier physical property measured
As shown in table 1 below.
Carrier prepares embodiment 4
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 10-100 μm μm of one water A1 of vacation2O3220g, 10-100 μm of one water A1 of vacation2O3It is obtained in 820 DEG C of roastings
Product 380g, magnesium fluoride 20g and barium nitrate 4g be put into blender be uniformly mixed, be transferred in kneader, be added 22g petroleum coke and
200ml dust technology (nitric acid: water=1:5, weight ratio), is kneaded into extrudable molding paste.Extrusion molding is outer diameter
The seven apertures in the human head column of 8.0mm, long 6.0mm, internal diameter 1.0mm are dried 2 hours or more at 80-120 DEG C, make free water content drop
As low as 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1400 from room temperature through 33 hours
DEG C, it is calcined 5 hours under the conditions of 1400 DEG C, obtains white α-A12O3Carrier.The carrier physical property measured is as shown in table 1 below.
Carrier prepares embodiment 5
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 25-300 μm of three water α-A12O3190g, 10-100 μm of one water A1 of vacation2O3220g, 10~100 μm of vacation
One water A12O3It is put into blender and is uniformly mixed in the product 190g, magnesium fluoride 20g and barium nitrate 4g that 1000 DEG C of roastings obtain, turn
Enter in kneader, 22g petroleum coke and 200ml dust technology (nitric acid: water=1:5, weight ratio) is added, is kneaded into extrudable molding
Paste.Extrusion molding is the seven apertures in the human head column of outer diameter 8.0mm, long 6.0mm, internal diameter 1.0mm, and it is small that 2 are dried at 80-120 DEG C
When more than, so that free water content is reduced to 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, through 33
Hour is increased to 1400 DEG C from room temperature, calcines 5 hours under the conditions of 1400 DEG C, obtains white α-A12O3Carrier.The carrier measured
Physical property is as shown in table 1 below.
Carrier prepares embodiment 6
This preparation embodiment is used to illustrate the preparation of alumina support provided by the invention
By 10-100 μm of one water A1 of vacation2O3220g, 10-100 μm of one water A1 of vacation2O3In the production that 1000 DEG C of roastings obtain
Object 380g, magnesium fluoride 20g and barium nitrate 4g be put into blender be uniformly mixed, be transferred in kneader, be added 22g graphite and
200ml dust technology (nitric acid: water=1:5, weight ratio), is kneaded into extrudable molding paste.Extrusion molding is outer diameter
The seven apertures in the human head column of 8.0mm, long 6.0mm, internal diameter 1.0mm are dried 2 hours or more at 80-120 DEG C, make free water content drop
As low as 10 weight % or less.By it is above-mentioned it is kneaded and formed after carrier be put into top-hat kiln, be increased to 1400 from room temperature through 33 hours
DEG C, it is calcined 5 hours under the conditions of 1400 DEG C, obtains white α-A12O3Carrier.The carrier physical property measured is as shown in table 1 below.
The preparation of catalyst
It weighs 140g silver nitrate to be dissolved in 150ml deionized water, weighs 64g ammonium oxalate and be dissolved in 520ml deionized water, fill
Divide dissolution, obtain silver nitrate solution and ammonium oxalate solution, mix two kinds of solution with vigorous stirring, generates white silver oxalate and sink
It forms sediment, aging 30 minutes or more, filtering was washed with deionized and is precipitated to no nitrate ion.About 60 weight % of filter cake argentiferous, contains
About 15 weight % of water.
70.0g ethylenediamine is dissolved in 75.0g deionized water, the silver oxalate filter cake of above method preparation is added, persistently stirs
Mixing dissolves silver oxalate all, sequentially adds 2.58g cesium nitrate, 6.22g barium acetate, 0.86g ammonium perrhenate and deionized water
So that solution gross mass is reached 400g, it is stand-by to be configured to maceration extract.
The support samples 20g of carrier preparation comparative example 1 and carrier preparation embodiment 1-6 preparation is taken respectively, and being put into can take out
In the container of vacuum, it is evacuated to 10mmHg or more, introduces above-mentioned maceration extract, keeps 30min, extra solution is removed in leaching.Leaching
Carrier after stain heats 3min in 450 DEG C of air stream, cooling, that is, silver catalyst is made.Silver catalyst number is carried with corresponding
Body is consistent.
The activity and selectivity of catalyst sample is measured under the conditions of previous process using microreactor evaluating apparatus, it is micro-
Anti- evaluation result is listed in table 2.
The physical data of 1 carrier of table
The performance of 2 catalyst of table
By data in Tables 1 and 2 it is known that the carrier provided according to the method for the present invention, improves specific surface area, water suction
Rate, Kong Rong reduce carrier average crystalline size, meanwhile, carrier also crushing strength with higher.By carrier system of the invention
The catalyst obtained, reaction temperature are substantially reduced and (improve reactivity), and simultaneous selection increases, and have wide answer
Use prospect.
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two
The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if stating one kind
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (12)
1. a kind of alpha-alumina supports, which is characterized in that the alpha-alumina supports pass through the method included the following steps and are made:
S1. the solid mixture with following component is prepared: one water A1 of vacation2O3, component A, can after-flame solid lubricant, fluorination
Then the solid mixture is mixed with binder and optional water, is mixed by object mineralizer and alkaline earth metal compound
Object；Wherein, component A is one water A1 of vacation2O3One water A1 of product of roasting or vacation2O3Product of roasting and three water α-A12O3；
S2. mixture obtained in step S1 is formed, obtains formed body；
S3. formed body obtained in step S2 is dried and is roasted, obtain the alpha-alumina supports.
2. alpha-alumina supports according to claim 1, wherein the false water A12O3Product of roasting be a false water
A12O3The product roasted at 550-1000 DEG C.
3. alpha-alumina supports according to claim 1, wherein on the basis of the total weight of solid mixture, the vacation
One water A12O3Dosage be 10-55 weight %, preferably 15-45 weight %；The dosage of the component A is 40-85 weight %, excellent
It is selected as 55-80 weight %；It is described can after-flame solid lubricant dosage be 0.01-10 weight %, preferably 0.01-5 weight
Measure %；The dosage of the alkaline earth metal compound is 0.01-8 weight %, preferably 0.05-5 weight %；The fluoride-mineralization
The dosage of agent is 0.05-10 weight %, preferably 0.5-5 weight %；The additional amount of the binder is solid mixture gross weight
The 25-60 weight % of amount.
4. the alpha-alumina supports according to claim, wherein the false water A12O3Product of roasting dosage be group
Divide the 0.1~100wt%, preferably 50~100wt% of the total dosage of A.
5. alpha-alumina supports according to claim 1, wherein the false water A12O3Granularity be 10-100 μm, institute
State one water A1 of vacation2O3Product of roasting granularity be 10-100 μm, the three water α-A12O3Granularity be 25-300 μm.
6. alpha-alumina supports described in any one of -5 according to claim 1, wherein it is described can after-flame solid lubricant
It is one or more in petroleum coke, carbon dust, graphite, vaseline；The fluoride-mineralization agent be hydrogen fluoride, aluminum fluoride, ammonium fluoride,
One of magnesium fluoride, ice crystal are a variety of；The alkaline earth metal compound is oxide, nitrate, the acetic acid of strontium and/or barium
One of salt, oxalates and sulfate are a variety of.
7. alpha-alumina supports described in any one of -5 according to claim 1, wherein the binder is acid, the acid
It is provided in the form of the aqueous solution of acid, preferably aqueous solution of nitric acid, the weight ratio of nitric acid and water is 1 in the aqueous solution of nitric acid:
(1.25-10)。
8. alpha-alumina supports described in any one of -5 according to claim 1, wherein the binder and one water A1 of vacation2O3
It is all or part of to be provided in the form of Aluminum sol.
9. alpha-alumina supports described in any one of -5 according to claim 1, wherein the alpha-alumina supports have such as
Lower feature: α-A12O3Content is 90 weight % or more, and crushing strength is 30-200N/, preferably 40-160N/；Specific surface
For 0.3-2.5m2/ g, preferably 0.6-2.0m2/g；Water absorption rate is 30-80%, preferably 40-70%；Kong Rongwei 0.30-
0.90ml/g, preferably 0.40-0.75ml/g；Average crystalline size is 2.0-5.0 μm.
10. a kind of ethylene epoxidizing silver catalyst, the silver catalyst includes the active group of carrier and load on this carrier
Divide silver, which is characterized in that the carrier is alpha-alumina supports described in any one of claim 1-9.
11. ethylene epoxidizing silver catalyst according to claim 10, wherein the silver catalyst further include:
Alkali metal and/or alkaline-earth metal or compound based on alkali metal and/or alkaline-earth metal；
Rhenium metal and/or compound based on rhenium；And
Optionally, the coassist agent element of rhenium, selected from one of chromium, molybdenum, tungsten and manganese or various metals, and/or selected from based on chromium,
The compound of one of molybdenum, tungsten and manganese or various metals.
12. a kind of ethylene method, which is characterized in that this method comprises: by ethylene in any one of claim 1-9 institute
Ethylene ring is carried out under the action of silver catalyst described in any one of the alpha-alumina supports stated and/or claim 10-11
Oxidation reaction obtains ethylene oxide.
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| CN114433045A (en) * | 2020-11-05 | 2022-05-06 | 中国石油化工股份有限公司 | Alpha-alumina carrier, silver catalyst for ethylene epoxidation and ethylene oxidation method |
| CN115364835A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | Modified alpha-alumina carrier, silver catalyst and application |
| CN115364836A (en) * | 2021-05-20 | 2022-11-22 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method thereof, silver catalyst for ethylene epoxidation and ethylene oxidation method |
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