CN108144604A - Using amino acid as 1,3- butadiene oxidation 3,4- butadiene monoxide efficient silver catalysts of directed agents and preparation method thereof - Google Patents
Using amino acid as 1,3- butadiene oxidation 3,4- butadiene monoxide efficient silver catalysts of directed agents and preparation method thereof Download PDFInfo
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- CN108144604A CN108144604A CN201711485903.3A CN201711485903A CN108144604A CN 108144604 A CN108144604 A CN 108144604A CN 201711485903 A CN201711485903 A CN 201711485903A CN 108144604 A CN108144604 A CN 108144604A
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- silver
- butadiene
- catalyst
- amino acid
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- 239000012266 salt solution Substances 0.000 claims description 4
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- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
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- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B01J37/02—Impregnation, coating or precipitation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- 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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- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
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Abstract
The invention discloses a kind of using amino acid as the 1 of directed agents, 3 butadiene oxidation systems 3, the preparation method of the silver catalyst of 4 butadiene monoxides, the amino acid that this method adds certain content in catalyst preparation is silver-colored active component, alkali metal and/or the load directed agents of alkaline-earth metal and/or transition metal isoreactivity auxiliary agent, makes silver-colored isoreactivity component in α Al2O3Surface forms the film that uniform protrusion is distributed with.The active good, high selectivity of silver catalyst disclosed by the invention, the advantages that stability is good.The present invention is without carrying out existing preparation process and mode excessively complicated change, so that it may realize the membranaceous distribution of the elements such as active component silver in silver catalyst.This method is easy to operate, of low cost, controllability is strong, easily prepared, meets and selectivity is improved under high activity, and be obviously improved the requirement of stability.
Description
Technical field
The invention belongs to catalyst preparations and application field, and in particular to a kind of using amino acid as 1, the 3- fourths two of directed agents
Alkene aoxidizes 3,4- butadiene monoxides efficient silver catalyst processed and preparation method thereof.
Background technology
In epoxidation reaction of olefines, the reaction mixture gas containing alkene and oxygen is contacted with catalyst, in certain reaction
Under the conditions of produce the by-products such as epoxide and a small amount of carbon dioxide, water.
So far, silver catalyst is still unique effective catalysis of industrial alkene epoxidation production epoxide
Agent.In the prior art, silver catalyst is also usually co-deposited with it in carrier other than including silver-colored ingredient with one or more
On other elements, carrier is usually made of Alpha-alumina that is heat safe, having suitable specific surface and pore structure.Except desilver
The other elements being deposited on carrier play the role of auxiliary agent or coassist agent, for improving the catalytic performance of silver catalyst.It closes
The alpha-alumina supports of suitable pore structure can not only promote deposition of the active component on carrier, but also can improve silver catalyst
Catalytic performance, this is because suitable pore structure can provide enough spaces for epoxidation reaction of olefines, make reaction heat and
When spread out, be on the other hand also beneficial to target product epoxide and be desorbed in time.Therefore, the performance of silver catalyst remove and
The composition and preparation method of catalyst have outside important relationship, and also and the pore structure of alpha-alumina supports has important relationship.
Patent CN200780009922.7 using petroleum coke, polyolefin, walnut parting etc. can burnout materials by hole introduce α-
Alumina support.But can burnout materials remove after, have metal oxide residual in the carrier, these residues can
The performance of catalyst can greatly be weakened, and changed quite greatly between the actual constituent of residue batch, cause its predictability cannot
It is satisfactory.United States Patent (USP) 2004/0110973A1 also discloses one kind and is used to prepare appropriate bore by two kinds of alpha-alumina fine particles
The method of the alumina support of diameter.Chinese patent CN102145306A selects the gibbsite of carse, medium and small different grain size grade
Prepare carrier.A kind of preparation method of alpha-alumina supports is disclosed in patent application CN102133544A, including mixing industry
α-gibbsite, a false water aluminium oxide, 0~30% burn out carbonaceous material, 0~2.5% alkali salt, 0~3%
Fluoride, binding agent and water, the percentage is based on the gross mass of raw alumina, wherein α-gibbsite and vacation one
The weight ratio of water aluminium oxide is 1~4:1, the total amount of binding agent and water is the 15~30% of alumina raw material total weight；Then it passes through
It crosses extrusion forming, drying and roasting and obtains the alpha-alumina supports.In the invention, using 0~30% burn out it is carbon containing
The carbon monoxide and/or carbon dioxide gas of material release carry out reaming；Using 0~3% fluoride as mineralizer, with profit
In aluminium hydroxide to the crystal transition of aluminium oxide.The adjustable silver catalysis of catalytic performance can be prepared by these above-mentioned carriers
Agent.
1,3- butadiene epoxidation 3,4- butadiene monoxides (EpB) are the Eastman Chemical companies nineties in last century
The novel catalytic reaction technology succeeded in developing, it is the up to the present another utilization molecular oxygen catalysis epoxy in addition to ethylene
Change the course of industrialization of alkene.Its main reaction formula is represented by：
Monnier has found butadiene in the Ag/Al using Cs, Cl as auxiliary agent first2O3On can be oxidized to high selectivity
EpB.The addition of CsCl makes silver catalyst activity be greatly improved, and butadiene conversion and EpB selectivity are respectively from 1% He
50% improves to 15% and 95%.EpB is also referred to as 1,3-butadiene base 3,4- epoxy butanes (VO), since it is with unique molecule
Structure, i.e. intramolecular have there are one end position double bond and an epoxy group simultaneously, and chemical property is very active, and derivative is even more
It is related to the multiple fields such as large, fine and special chemical article, is known as novel chemical intermediate.Butadiene is urged in silver in recent years
Epoxidation reaction in agent by enterprise and scholar very big concern.But the dynamics research report about the reaction is seldom,
Have focused largely on catalyst preparation, the patent of invention of 1,3- butadienyl 3,4- epoxy butane recovery process and about Cs, Cl
Research of facilitation of auxiliary agent etc..
Monnier etc. is had studied by adding in the experiments such as various products and reacting condition object partial pressure in the reaction in CsCl-
Ag/Al2O3The kinetics of upper butadiene epoxidation and18The kinetic isotope effect of O labels, it is proposed that double activated position
Mechanism, i.e. butadiene no auxiliary agent silver surface adsorb active sites and oxygen in the silver surface adsorption potential for having auxiliary agent；Think simultaneously
The rate controlling step of reaction is the desorption of product EpB, not such as the absorption 1 in 1,3-butadiene epoxidation, 3- fourths two
The surface intercalation reaction of alkene and absorption oxygen is rate controlling step.Butadiene is investigated in Ba-Cs-Cl-Ag/Al2O3On epoxidation
Reaction, research shows that, the Ag catalyst using Ba, Cs, Cl as auxiliary agent has preferable butadiene conversion and VO selectivity, and three
There may be synergistic effects between person.
Invention content
For the Ag/Al currently used for 1,3- butadiene oxidation 3,4- butadiene monoxides2O3Catalyst choice decline compared with
Soon, the shortcomings of stability is bad, the present invention, which provides a kind of react 1,3-butadiene oxidation 3,4- of system butadiene monoxides, has selection
Property it is high, stability is good, service life is long the advantages that Ag/Al2O3Catalyst and preparation method thereof.
In view of the situation of the above-mentioned prior art, the present inventor has carried out extensive depth in silver catalyst and its preparation process field
The research entered, research are found：In the preparation process of silver catalyst, suitable amino acid is added as load directed agents, it can be with
Precipitate silver-colored isoreactivity compositional selecting, in α-Al2O3Surface forms the film that uniform protrusion is distributed with.Be conducive to improve silver-colored catalysis
The catalytic performance of agent.By loading type silver catalyst prepared by this method for being catalyzed 1,3- butadiene oxidation 3,4- epoxy fourths
During alkene, activity increases, it is often more important that selectivity is significantly improved, and stability and service life obtain very big carry
It is high.
The present invention specifically adopts the following technical scheme that solution above-mentioned technical problem：
The present invention provides a kind of efficiently silver-colored using amino acid as the 1,3- butadiene oxidation 3,4- butadiene monoxides of directed agents
Catalyst, the catalyst is with α-Al2O3For carrier, silver is for active component, alkali metal and/or alkaline-earth metal and/or transition metal
The film of uniform protrusion is distributed in carrier surface formation for auxiliary agent, active component and auxiliary agent.
The mass percentage of the above-mentioned preferred active component silver of catalyst of the present invention is 1~50%, more preferable 15~25%,
Adjuvant component content is 10~1000ppm, more preferable 100~300ppm.
The present invention still further provides the efficient silver catalyst of above-mentioned 1,3- butadiene oxidations 3,4- butadiene monoxides
A kind of preparation method, this method comprises the following steps：
1) soluble silver salt solution and oxalic acid solution are mixed to get silver oxalate precipitate or directly weigh silver oxalate solid；
2) by ethylenediamine and ethanol amine 4-2 by volume:Solution is obtained after 1 mixing plus in water；
3) amino acid is taken to add in the solution that step 2) obtains, obtains the mixed solution containing amino acid；
4) silver oxalate that step 1) obtains is added in the amino acid solution that step 3) obtains, it is molten that clear complexing is made
Liquid；
5) it obtains addition auxiliary agent in complex solution to step 4) and maceration extract is made；
6) maceration extract that step 5) obtains is poured into the container for fill carrier supersaturation under vacuum to impregnate, is completed
After dipping, by product after the dipping being obtained by filtration it is aged, it is dry, activation after be made catalyst；
The amino acid is glycine, asparagine, lysine, glutamine, serine, threonine, cysteine, group
Propylhomoserin, arginine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, aspartic acid, paddy
It is one or more in propylhomoserin, methionine；The molar ratio of the amino acid and silver is 0.01-2, preferably 0.1-1.
In above-mentioned preparation method, the auxiliary agent is preferably the soluble salt solutions of Na, K, Mg, Ca, Ba, Cs, Ce, Re, Zr
It is one or more.
Conventional method progress can be used in product drying, activation after dipping in step 6), is done preferably at 80~120 DEG C
It is dry, activated in 200~400 DEG C of moving air, moving air flow be 10~100L/h, soak time 5~
300min。
1,3-butadiene oxidation system 3, the 4- epoxy butane silver catalysts prepared by as above step, with electron probe, sweep
It retouches the characterization methods such as Electronic Speculum or transmission electron microscope progress catalyst section grain form and size is characterized, it is possible to find in α-Al2O3
Surface forms the film that uniform protrusion is distributed with.Pass through thermogravimetric, O2- TPD analyses find that silver catalyst adsorption desorption is conducive to generation 1,
The ability enhancing of the oxygen of 3- butadiene epoxidations reaction.
XRF chemical constituent analyses are carried out by scraping different thin layers, the results showed that, oxidation silver content is kept in the catalyst
It is uniformly distributed, the thin layer maximum scraped is no more than 0.5 millimeter.Show that the content distribution of active component in the catalyst is equal enough
It is even.
It is a strong exothermal reaction, therefore it is anti-normally more to focus on this since 1,3-butadiene aoxidizes system 3,4- butadiene monoxides
Should in target product selectivity, and reaction is made to maintain the transform level of relatively low stabilization.
Catalyst of the present invention is being raw material using 1,3-butadiene content as 40~60%, reaction pressure 1~
2.5MPa, 150~250 DEG C of reaction temperature, 500~1500h of 1,3-butadiene unstripped gas gas space velocity-1Under conditions of catalytic
Energy evaluation test, evaluation result show that 1,3-butadiene conversion ratio is 18% or so, and 3,4- epoxy butanes are selectively not less than
95%.More than 30% catalyst life.
The remarkable advantage of technology of the present invention is：(1) distinguishing feature of catalyst of the present invention be by the use of amino acid as load
Directed agents make the components such as silver in α-Al2O3The film of uniform protrusion is distributed in crystal plane surface formation, can improve the 1,3- of catalyst
The selectivity of butadiene oxidation 3,4- butadiene monoxides；(2) components such as Ag in catalyst are regulated and controled as directed agents using amino acid
Load pattern so that catalyst performance is significantly improved.By the collective effect in terms of the two, the present invention ensure that
The technology of proposition is different from the characteristics of existing invention and technology：1) catalyst preparation technology of simple and regular；2) 1,3- butadiene
The selectivity of the target product of oxidation 3,4- epoxy butanes processed is stablized；3) catalyst life is longer.
Specific embodiment
Embodiment
Below will by specific embodiment, the invention will be further described, but the invention is not limited in these implement
Example.
Carrier used in the present invention is regular oxidation alumina supporter, and following preparation method can also be used and be prepared：By one
Quantitative gibbsite powder, a water alumina powder and account for the graphite powder that total alumina powder mass fraction is 1~20%
Calcium carbonate with 0.1~10% is uniformly mixed, and is added mass concentration and is carried out kneading for 1~30% dust technology, kneading time is
0.1~2h is finally molded on forming machine again, and carrier after molding is after room temperature dries 1~12h, then at 80~150
DEG C 1~8h of drying, last 800~1800 DEG C of 1~12h of roasting in Muffle furnace of the carrier of drying, obtains final carrier A, carries
The shape of body includes single-orifice type, porous type, honeycomb briquet type, cylinder, bunge bedstraw herb type etc..
Embodiment 1
Weigh silver nitrate 11.5g and be dissolved in 40ml deionized waters and obtain silver nitrate solution, oxalic acid 4.6g be dissolved in 15ml go from
Oxalic acid solution is obtained in sub- water, solvent silver nitrate solution is poured slowly into oxalic acid solution, generates white silver oxalate precipitate.It will
Precipitation filters, and filter cake is washed till neutrality, and it is 4 to be dissolved in volume ratio:1 ethylenediamine, ethanol amine and glycine, threonine, leucine
In the mixed solution of water, clear light brown complex solution is made.Weigh cesium nitrate 0.5g be dissolved in it is standby in 100ml deionized waters
With, weigh 0.25g ammonium perrhenates be dissolved in it is spare in 100ml deionized waters.Measure 1.8ml cesium nitrates solution, 1.2ml ammonium perrhenates
Solution is poured into above-mentioned complex solution, is shaken up.It weighs silver-colored carrier A10g and supersaturation dipping 0.5h is carried out under vacuumized conditions, so
The carrier after dipping is filtered out afterwards, 10h is aged in room temperature, then at 110 DEG C of drying 6h, 45min is activated under 260 DEG C of air atmospheres,
Obtain finished catalyst A.
The composition of catalyst A is：Ag-Cs-Re/Al2O3, wherein mass percentage of each component in terms of oxide be：
Ag2O：22.1%, Cs2O：300ppm, ReO2：100ppm, remaining is aluminium oxide.By scanning electron microscopic observation, find in α-Al2O3
Crystal plane surface forms the film of uniformly protrusion distribution.Projection portion equivalent particle size is uniform, in 20-30nm.
The catalytic activity test of catalyst A：Using 10ml fixed bed minisize reaction evaluation systems, 10 milliliters are taken to be ground to 20
The catalyst A of~40 mesh, which is fitted into the stainless steel reactor that internal diameter is 5mm, carries out the test of 1,3- butadiene epoxidations reactivity worth.
Reaction condition is：Unstripped gas contains 1,3-butadiene 50%, and the total volume air speed of unstripped gas is 4000h-1, reaction pressure is
1.8MPa, reaction temperature are 220 DEG C, carry out the successive reaction of 1,3-butadiene oxidation.Each hour carries out a chromatography and takes
Sample is analyzed, and 10 samples are one group of calculating average value.The catalytic activity test result of catalyst A is shown in Table 1.
Embodiment 2
Silver oxalate 12.0g is weighed, alleged silver oxalate is dissolved in the mixed solution of ethylenediamine, ethanol amine, asparagine and water
In, chartreuse complex solution is made.Zirconium oxycarbonate 1.2g is made into 1ml solution and pours into above-mentioned complex solution, takes nitre
Sour caesium solution 0.9ml, measurement ammonium perrhenate solution 2.3ml are equally injected in above-mentioned solution.Silver-colored carrier A10g is weighed to vacuumize
Under the conditions of carry out supersaturation dipping 2h, then the carrier after dipping is filtered out, room temperature be aged 10h, then at 120 DEG C drying 4h,
60min is roasted under 280 DEG C of air atmospheres, obtains finished catalyst B.
The composition of catalyst B is：Ag-Cs-Re-Zr/Al2O3, wherein mass percentage of each component in terms of oxide
For Ag2O：21.4%th, Cs2O：200ppm、ReO2：200ppm、ZrO2：0.3%, remaining is aluminium oxide.It is seen by scanning electron microscope
It examines, finds in α-Al2O3Crystal plane surface forms the film of uniformly protrusion distribution.Projection portion equivalent particle size is uniform,
In 20-30nm.
For catalyst B evaluation conditions with embodiment 1, experimental result is shown in Table 1.
Embodiment 3
Weigh silver nitrate 13.0g, ammonium oxalate 7.3g is dissolved in 100.0g and is heated to 50 DEG C of deionized water to be made into ammonium oxalate molten
The silver nitrate weighed up is slowly dissolved in ammonium oxalate solution by liquid, generates white silver oxalate precipitate.Precipitation is filtered out and is dissolved in second two
Amine, ethanol amine, lysine, histidine and water mixed solution in, light blue black transparent complex solution is made.Weigh sodium nitrate
0.032g, zirconyl nitrate 1.5g are made into 2ml solution and pour into above-mentioned complex solution respectively, and it is same to measure ammonium perrhenate solution 3.4ml
Sample is injected in above-mentioned solution.It weighs silver-colored carrier A10g and supersaturation dipping 5h is carried out under vacuumized conditions, it then will be after dipping
Carrier filters out, and 20h is aged in room temperature, then at 100 DEG C of drying 20h, roasts 10min under 300 DEG C of air atmospheres, obtains finished catalyst
C。
The composition of catalyst C is：Ag-Na-Re-Zr/Al2O3, wherein mass percentage of each component in terms of oxide
For：Ag2O：18.3%, Na2O：0.05%, ReO2：300ppm, ZrO2：0.25% remaining be aluminium oxide.It is seen by scanning electron microscope
It examines, finds in α-Al2O3Crystal plane surface forms the film of uniformly protrusion distribution.Projection portion equivalent particle size is uniform,
In 20-30nm.
For catalyst C evaluation conditions with chromatography with embodiment 1, reactivity worth the results are shown in Table 1.
Analysis result shows the catalyst series after successive reaction 60 days, and system 3,4- epoxy fourths are aoxidized to 1,3-butadiene
The selectivity of alkane does not significantly decrease, and shows good stability.
The 1,3- butadiene oxidation response data tables of 1 different catalysts of table
Claims (6)
1. a kind of efficient silver catalyst of 1,3-butadiene oxidation system 3,4- butadiene monoxides, which is characterized in that with α-Al2O3To carry
Body, silver is active component, alkali metal and/or alkaline-earth metal and/or transition metal is auxiliary agent, active component and auxiliary agent in carrier table
Face forms the film that uniform protrusion is distributed with.
2. efficient silver catalyst according to claim 1, which is characterized in that the mass percentage of active component silver is 1
~50%, adjuvant component content is 10~1000ppm.
3. efficient silver catalyst according to claim 1, which is characterized in that the mass percentage of active component silver is 15
~25%, adjuvant component content is 100~300ppm.
4. a kind of preparation side of the efficient silver catalyst of 1,3- butadiene oxidations 3,4- butadiene monoxides described in claim 1
Method, which is characterized in that
1) soluble silver salt solution and oxalic acid solution are mixed to get silver oxalate precipitate or take silver oxalate solid；
2) by ethylenediamine and ethanol amine 4-2 by volume:Solution is obtained after 1 mixing plus in water；
3) amino acid is taken to add in the solution that step 2) obtains, obtains the mixed solution containing amino acid；
4) silver oxalate precipitate that step 1) obtains is added in the amino acid solution that step 3) obtains, it is molten that clear complexing is made
Liquid；
5) it obtains addition auxiliary agent in complex solution to step 4) and maceration extract is made；
6) maceration extract that step 5) obtains is poured into the container for fill carrier supersaturation under vacuum to impregnate, completes dipping
Afterwards, by product after the dipping being obtained by filtration it is aged, it is dry, activation after be made catalyst；
The amino acid is glycine, asparagine, lysine, glutamine, serine, threonine, cysteine, organizes ammonia
Acid, arginine, alanine, valine, leucine, isoleucine, phenylalanine, tryptophan, tyrosine, aspartic acid, paddy ammonia
It is one or more in acid, methionine；The molar ratio of the amino acid and silver is 0.01-2.
5. preparation method according to claim 4, which is characterized in that the molar ratio of the amino acid and silver is 0.1-1.
6. preparation method according to claim 4, which is characterized in that the auxiliary agent for Na, K, Mg, Ca, Ba, Cs, Ce,
The soluble salt solutions of Re, Zr it is one or more.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208321A (en) * | 2005-05-09 | 2008-06-25 | 科学设计有限责任两合公司 | Nanometer scale restructuring of alumina carrier surface and catalysts for the production of alkene oxides |
| CN105916577A (en) * | 2013-12-19 | 2016-08-31 | 科学设计有限公司 | High-concentration silver solutions for ethylene oxide catalyst preparation |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101208321A (en) * | 2005-05-09 | 2008-06-25 | 科学设计有限责任两合公司 | Nanometer scale restructuring of alumina carrier surface and catalysts for the production of alkene oxides |
| CN105916577A (en) * | 2013-12-19 | 2016-08-31 | 科学设计有限公司 | High-concentration silver solutions for ethylene oxide catalyst preparation |
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Application publication date: 20180612 |