CN106861752A - Solid catalyst and its preparation and application for ethanol synthesis butadiene - Google Patents
Solid catalyst and its preparation and application for ethanol synthesis butadiene Download PDFInfo
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Abstract
The present invention relates to a kind of solid catalyst for ethanol synthesis butadiene, it includes：Mesoporous silicon carrier and the oxidation activity component comprising transition metal silicate being carried on the mesoporous silicon carrier and the condensation dehydration activity component comprising transition metal oxide；Wherein, the quality meter based on the mesoporous silicon carrier, the content of the transition metal in the oxidation activity component is 0.5wt% 25.0wt%；The content of the transition metal in the condensation active component is 0.5wt% 10.0wt%.The invention further relates to the preparation method of above-mentioned solid catalyst.Catalyst prepared by the inventive method eliminates the adverse effect between the transition metal in oxidation activity component and condensation active component, so as to improve the Activity and stabill of catalyst, while catalyst has good water resistance.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to it is a kind of for ethanol synthesis butadiene solid catalyst and
Its preparation and application.
Background technology
At present, the source of world's butadiene mainly has two kinds.One kind is from oil plant C4Cut dehydrogenation is obtained, the method mesh
Preceding uses in the abundant a few countries of some butane, Butene.Another is from ethylene cracker by-product
Mixing C4Extracting is obtained in cut, and this method is cheap, economically dominant, is the main next of current butadiene in the world
Source.But, recently as petroleum resources as the increasingly depleted and shale gas exploitation of non-renewable resources bring to 1,3-
The impact that butadiene yield declines, develops new butadiene production processing route significant.
The research that alcohol catalysis prepare butadiene can trace back to for 20 beginnings of the century.Alcohol catalysis prepare butadiene catalysis used
The species of agent has：US 2438464 discloses a kind of load thorium oxide on silica or the catalyst prepared by zinc oxide；US
A kind of 2357855 mixture catalyzers for disclosing silica and magnesia；US 2436125 discloses one kind and is deposited on silica gel
On zirconium or thorium oxide catalyst.In the above-mentioned methods, the conversion ratio that alcohol catalysis prepare butadiene is 30~50%, choosing
Selecting property is 40~60%.It can be seen that, the conversion ratio that above-mentioned alcohol catalysis prepare ethanol in the method for butadiene is relatively low and butadiene
Selectivity is relatively low.CN103038196A discloses the catalyst prepared containing the metals such as metallic copper silver gold and titanium Zirconium oxide,
The conversion ratio that its one-step method catalysis ethanol prepares butadiene is 34%, and selectivity is 72%.Although the catalyst that the patent is provided
The selectivity of butadiene is improve to a certain extent, but the conversion ratio of ethanol still could not be realized breaking through.
The process of ethanol synthesis butadiene is mainly completed by steps such as oxidation, condensation and dehydrations.It is described in the above method
Catalyst all has that butadiene selective is low and short life, main reason is that the reaction is multistep cascade reaction,
High catalytic activity needs good cooperation between each component, and one is the screening of active component, and two is existing process for synthetic catalyst
All it is that the active component with oxidation and condensation function is together carried on carrier by load method, this can cause oxidation with contracting
Mutually generation influence between the active component of function is closed, so as to influence selectivity and the life-span of butadiene.
Therefore, be badly in need of at present research and development it is a kind of for ethanol synthesis butadiene with ethanol conversion is high, butadiene
Solid catalyst and its preparation and application of selectivity height and long lifespan.
The content of the invention
The technical problems to be solved by the invention are directed to above-mentioned the deficiencies in the prior art, there is provided a kind of for ethanol synthesis
Solid catalyst of butadiene and preparation method thereof.Oxidation activity component and condensation in catalyst prepared by the inventive method is de-
Water active component is carried on carrier in the form of compound, this eliminates the transition metal in two kinds of active components
Between the directly contact adverse effect that is likely to form alloy and is produced to catalyst activity, so as to improve catalyst activity and
Stability, while catalyst of the present invention also has good water resistance.
Therefore, first aspect present invention provides a kind of solid catalyst for synthesizing butadiene for ethanol, it includes：It is situated between
Hole silicon carrier and the oxidation activity component comprising transition metal silicate being carried on the mesoporous silicon carrier and comprising mistake
Cross the condensation dehydration activity component of metal oxide；
Wherein, the quality meter based on the mesoporous silicon carrier,
The content of the transition metal in the oxidation activity component is 0.5wt%-25.0wt%, preferably
5.0wt%-10.0wt%；
The content of the transition metal in the condensation active component is 0.5wt%-10.0wt%, preferably
2.0wt%-10.0wt%.
In some preferred embodiments of the invention, transition metal and the contracting in the oxidation activity component
The mass ratio for closing the transition metal in active component is (2.5-10):1, preferably (4-5):1.Present inventor passes through
Cross research to find, control the transition metal and the transition metal being condensed in active component in the oxidation activity component
When catalyst obtained in the mass ratio of element is used for ethanol and converts butadiene processed, it is possible to achieve ethanol conversion higher and higher
Butadiene selective.
According to the present invention, the transition metal in the transition metal silicate is selected from the one kind or many in zinc, nickel, copper and cobalt
Kind；And/or
Transition metal in the transition metal oxide is selected from one or more in tantalum, hafnium, scandium and yttrium.
According to the present invention, the mesoporous silicon carrier is selected from Beta molecular sieves, SBA-15 molecular sieves, white carbon and silicon foam
One or more, preferably described mesoporous silicon carrier be Beta molecular sieves.
Second aspect present invention provides a kind of preparation method of solid catalyst described according to a first aspect of the present invention, its
Including：
Step A, the oxidation activity component comprising transition metal silicate and the condensation being carried on mesoporous silicon carrier are taken off
Water active component mixes with water, by stirring, centrifugal treating, white solid powder is obtained；
Step B, by the white solid powder through drying, calcination process, is obtained the solid catalyst.
In some embodiments of the invention, in step, the temperature of the stir process is 30-90 DEG C, the stirring
The time for the treatment of is 0.5-6h.
In other embodiments of the invention, in stepb, the temperature of the dried process is 80-120 DEG C, described
The temperature of calcination process is 400-600 DEG C.
According to the preparation method of solid catalyst of the present invention, the oxidation activity group comprising transition metal silicate
The preparation method divided includes：Transition metal silicate precursor is added drop-wise in the aqueous solution of silicon-containing compound, by stirring, centrifugation
And dried process, the oxidation activity component comprising transition metal silicate is obtained；It is preferred that before the transition metal silicate
The mol ratio of the element silicon in transition metal in body and the silicon-containing compound is 0.5-5, more preferably 2.3-5.
In some embodiments of the invention, the transition metal silicate precursor is selected from the corresponding nitrate of transition metal
And/or chloride, it is preferably selected from one or more in zinc, nickel, copper or the corresponding nitrate of cobalt and/or chloride.
In other embodiments of the invention, the silicon-containing compound is selected from silane, siloxanes, sodium metasilicate and silicic acid second
One or more in ester.
According to the preparation method of solid catalyst of the present invention, the oxidation activity group comprising transition metal silicate
The temperature of stir process described in the preparation method divided is 60-100 DEG C, and the time of the stir process is 6-24h；The drying
The temperature for the treatment of is 80-200 DEG C.
According to the preparation method of solid catalyst of the present invention, the condensation dehydration being carried on mesoporous silicon carrier is lived
The preparation method of property component includes：Mesoporous silicon carrier is impregnated using transition metal oxide precursor solution, by dried process, system
Obtain the condensation dehydration activity component being carried on mesoporous silicon carrier.
In some embodiments of the invention, the transition metal oxide precursor includes the corresponding nitric acid of transition metal
One or more in salt, chloride and organic salt；It is preferred that the transition metal oxide precursor is selected from tantalum, hafnium, scandium or yttrium pair
One or more in nitrate, chloride and the organic salt answered；More preferably described transition metal oxide precursor is ethanol tantalum.
According to the preparation method of solid catalyst of the present invention, the condensation dehydration being carried on mesoporous silicon carrier is lived
Property component preparation method in, the temperature of the dried process is 60-100 DEG C, and the time of the dried process is 3-6h.
In some specific embodiments of the invention, the preparation method of the solid catalyst comprises the following steps：
(1) preparation of oxidation activity component：First, it is respectively configured certain density Transition metal salt solution and siliceous
The aqueous solution of compound, wherein, the mol ratio of the element silicon in metallic element and silicon-containing compound in transition metal silicate
It is 0.5-5；Then, under stirring at normal temperature, Transition metal salt solution is added dropwise in the aqueous solution of silicon-containing compound, this
When, constantly there is white suspension particles generation；Then 60-100 DEG C is warming up to, 6-24h, centrifuge washing white precipitate, in 80- is stirred
200 DEG C of drying, obtain oxidation activity component.
(2) preparation of the condensation dehydration activity component being carried on mesoporous silicon carrier：By the mistake in transition metal oxide
The corresponding salt of metal is crossed to be dissolved in deionized water or isobutanol；Appropriate mesoporous silicon carrier is subsequently adding, mixed solution is formed, its
In, the mesoporous silicon carrier includes one or more in white carbon, pure silicon Beta molecular sieves, SBA-15 and silicon foam；Should
Mixed solution is heated to water or isobutanol and evaporates 3-6h at 60-100 DEG C so that solvent evaporation is dry, obtains white powder；Wherein,
It is 0.5wt%-10.0wt% that load capacity of the transition metal on silicon carrier is calculated in mass percent.
(3) combination of oxidation activity component and the condensation dehydration activity component being carried on mesoporous silicon carrier：By step (1)
The condensation dehydration activity component that what the oxidation activity component and step (2) for obtaining were obtained be carried on mesoporous silicon carrier add go from
In sub- water, 0.5-6h is stirred at 30-90 DEG C, white solid powder is obtained after centrifugation, wherein, the mistake in oxidation activity component
It is by percentage to the quality 0.5wt%-25.0wt% to cross load capacity of the metallic element on silicon carrier.
(4) by step C gained white powder 80-120 DEG C dry after, in 400-600 DEG C roasting, through compressing tablet, crushing,
Sieving, is obtained final heterogeneous solid catalyst.
Third aspect present invention provides a kind of solid catalyst described according to a first aspect of the present invention or according to this hair
The application of solid catalyst prepared by bright second aspect methods described in ethanol synthesis butadiene, it includes：Ethanol is water-soluble
Liquid in the presence of solid catalyst, it is oxidized, condensation and dehydration, be obtained butadiene.
According to application of the present invention, the mass concentration of the ethanol water is 50wt%-99wt%, mass space velocity
It is 0.1-2h-1, the temperature of the reaction is 300-400 DEG C, preferably 325-350 DEG C；The time of the reaction is 8-30h.
In some specific embodiments of the invention, application bag of the solid catalyst in ethanol synthesis butadiene
Include following steps：
(1) material liquid is that mass concentration is the ethanol water of 50wt%-99wt%, and air speed is 0.1-2h-1, in indifferent gas
Under the carrying of body, fixed bed reactors are entered after preheated device gasification；
(2) under catalyst action at 300-400 DEG C there is oxidation, condensation and dehydration, one-step method system in material liquid
Obtain butadiene；
(3) product is separated by adjusting temperature, and gas-phase product is mainly butadiene, cold at a certain temperature
But acetaldehyde byproduct reenters reactor and is reacted as raw material；
(4) reacted catalyst in the original location under the conditions of, be passed through air in 400-600 DEG C of roasting regeneration.
Solid catalyst provided by the present invention for ethanol synthesis butadiene and preparation method thereof has the following advantages that：
(1) catalyst has good water resistance, and the ethanol that can be obtained with non-grain biomass ferment is raw material life
Butadiene is produced, alcohol fermentation liquid technical maturity, wide material sources are conducive to energy sustainable development.
(2) in the preparation process of the catalyst, it is oxidation activity component to use transition metal silicate, is compared using height
The transition metal oxide of the mesoporous silicon load of surface area and large aperture is condensation dehydration activity component, eliminates transition metal silicon
Issuable unfavorable factor between hydrochlorate and transition metal oxide, favourable mass transfer slow down the generation of carbon distribution, and both is total to
It is same to realize ethanol high conversion, butadiene high selectivity, and catalyst life is long.
(3) process for synthetic catalyst of the present invention is simple, it is easy to operate, it is easy to which scale is amplified, and whole technical process environment
It is friendly.
(4) catalyst preparation process of the present invention is simple, and catalysis activity is good, and butadiene, work are prepared for catalysis ethanol
Skill process is simple, easily operated, and required equipment is simple, with good industrial applications prospect.
Specific embodiment
To make the present invention easier to understand, the present invention is described in detail below in conjunction with embodiment, these embodiments are only
Serve illustrative, it is not limited to range of application of the invention, NM specific experiment method in the following example, generally
Carried out according to normal experiment method.
Ethanol conversion (%)=(nThe ethanol added before reaction-nRemaining ethanol after reaction)/nThe ethanol added before reaction× 100%；
Butadiene selective (%)=2nButadiene in product/(nThe ethanol added before reaction-nRemaining ethanol after reaction) × 100%；
Wherein, n is the molal quantity of raw material or product.
Embodiment
Embodiment 1
First, the preparation of solid catalyst
(1) 2.1g Zn (NO are taken3)2·6H2O and 1g Na2SiO3·9H2O, is dissolved in 100mL deionized waters respectively.Stirring
Under conditions of mixing, by Zn (NO3)2The aqueous solution is added dropwise to Na2SiO3In solution, 100 DEG C are warming up to, stir 12h, will obtained
White powder overnight dried at 110 DEG C, be then calcined 4h under the conditions of 500 DEG C, it is 2.3 that Zn/Si mol ratios are obtained:1 silicon
Sour zinc active component；
(2) in the 100mL isobutanols by the addition of 5g Beta molecular sieves dissolved with 0.224g ethanol tantalums, heating stirring to solvent
Volatilization is dry, after the white powder that will be obtained dries 8h at 160 DEG C, the Ta-Beta activearms that tantalum load capacity is 2wt% has been obtained
Point；
(3) the Ta-Beta active components that the zinc silicate and step (2) for obtaining step (1) are obtained add 100mL deionizations
In water, 2h is stirred at 35 DEG C, the powder sample that will be obtained dries 12h at 110 DEG C, and 10wt% is obtained after 500 DEG C of calcining 3h
Zn-2wt%Ta-Beta catalyst, is abbreviated as 10Zn-2Ta-Beta.
2nd, catalysis of solid catalyst ethanol synthesis butadiene reaction
The quartz glass tube fixed bed reactors that gained 1g 10Zn-2Ta-Beta catalyst loads 8mm × 400mm are entered
Row catalytic reaction.Wherein, ethanol raw material liquid concentration is 99wt%；Mass space velocity is 0.5gg-1·h-1；Carrier gas N2Flow velocity is
10ml·min-1；Reaction temperature is 350 DEG C, and the reaction time is 8h.Specific experiment the results are shown in Table 1.
Embodiment 2
The catalytic reaction time is 30h to embodiment 2 as different from Example 1, and remaining reaction condition is same as Example 1.
Specific experiment the results are shown in Table 1.
Embodiment 3
Embodiment 3 prepares catalyst 5wt%Zn-2wt%Hf-Beta as different from Example 2, is abbreviated as 5Zn-
2Hf-Beta, remaining reaction condition is same as Example 2.Specific experiment the results are shown in Table 1.
Embodiment 4
The temperature of the catalytic reaction as different from Example 3 of embodiment 4 is 325 DEG C, remaining reaction condition and the phase of embodiment 3
Together.Specific experiment the results are shown in Table 1.
Embodiment 5
Ethanol water concentration is 90wt%, remaining reaction condition and embodiment 4 to embodiment 5 as different from Example 4
It is identical.Specific experiment the results are shown in Table 1.
Embodiment 6
Embodiment 6 prepares catalyst 5wt%Zn-2wt%Ta-SBA-15 as different from Example 5, is abbreviated as
5Zn-2Ta-SBA-15, remaining reaction condition is same as Example 5.Specific experiment the results are shown in Table 1.
Embodiment 7
Used carrier is white carbon to embodiment 7 as different from Example 6, and remaining reaction condition is same as Example 6.Tool
Body experimental result is shown in Table 1.
Embodiment 8
Embodiment 8 prepares catalyst 5wt%Ni-2wt%Ta- white carbons as different from Example 7, is abbreviated as
5Ni-2Ta- white carbons, remaining reaction condition is same as Example 7.Specific experiment the results are shown in Table 1.
Embodiment 9
Embodiment 9 as different from Example 8 Ta load capacity be 0.5wt%, remaining reaction condition and the phase of embodiment 8
Together.Specific experiment the results are shown in Table 1.
Embodiment 10
Embodiment 10 prepares catalyst 20wt%Zn-5wt%Hf- white carbons as different from Example 9, is abbreviated as
20Zn-5Hf- white carbons, remaining reaction condition is same as Example 9.Specific experiment the results are shown in Table 1.
Embodiment 11
Embodiment 11 prepares catalyst 20wt%Zn-5wt%Y- white carbons as different from Example 10, is abbreviated as
20Zn-5Y- white carbons, remaining reaction condition is same as in Example 10.Specific experiment the results are shown in Table 1.
Embodiment 12
Embodiment 12 prepares catalyst 20wt%Ni-5wt%Hf- white carbons as different from Example 10, writes a Chinese character in simplified form
It is 20Ni-5Hf- white carbons, remaining reaction condition is same as in Example 10.Specific experiment the results are shown in Table 1.
Embodiment 13
First, the preparation of solid catalyst
By 2.1g Zn (NO3)2·6H2O and the 100mL isobutanol solutions mixing dissolved with 0.224g ethanol tantalums, then by 5g
Beta molecular sieves are added in above-mentioned mixed liquor, and heating stirring is dry to solvent volatilization, and the white powder that will be obtained is in 160 DEG C of dryings
8h, 10wt%Zn-2wt%Ta-Beta (*) catalyst is obtained after 500 DEG C of calcining 3h, is abbreviated as 10Zn-2Ta-Beta (*).
2nd, catalysis of solid catalyst ethanol synthesis butadiene reaction
The quartz glass tube fixed bed reactors that gained 1g 10Zn-2Ta-Beta catalyst loads 8mm × 400mm are entered
Row catalytic reaction.Wherein, ethanol raw material liquid concentration is 99wt%；Mass space velocity is 0.5gg-1·h-1；Carrier gas N2Flow velocity is
10ml·min-1；Reaction temperature is 350 DEG C, and the reaction time is 8h.Specific experiment the results are shown in Table 1.
The ethanol of table 1 synthesizes butadiene catalyst evaluation result
From above-described embodiment as can be seen that the solid catalyst preparation process is simple of present invention offer, synthesizes for ethanol
The solid catalyst of butadiene has ethanol conversion high, and butadiene selective is high, and the features such as water-tolerant and long lifespan, it can
It is environment-friendly to ferment the ethanol solution for obtaining as raw material is efficiently synthesized butadiene with abiotic matter, it is a sustainable conjunction
Into the friendly process of butadiene.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used 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 is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, conversely, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. it is a kind of for ethanol synthesize butadiene solid catalyst, it includes：Mesoporous silicon carrier and it is carried on described mesoporous
The oxidation activity component comprising transition metal silicate on silicon carrier and the condensation dehydration activity comprising transition metal oxide
Component；
Wherein, the quality meter based on the mesoporous silicon carrier,
The content of the transition metal in the oxidation activity component is 0.5wt%-25.0wt%, preferably 5.0wt%-
10.0wt%；
The content of the transition metal in the condensation active component is 0.5wt%-10.0wt%, preferably 2.0wt%-
10.0wt%.
2. solid catalyst according to claim 1, it is characterised in that the transition metal in the transition metal silicate
Selected from one or more in zinc, nickel, copper and cobalt；And/or the transition metal in the transition metal oxide be selected from tantalum, hafnium,
One or more in scandium and yttrium.
3. solid catalyst according to claim 1 and 2, it is characterised in that the mesoporous silicon carrier is selected from Beta molecules
One or more in sieve, SBA-15 molecular sieves, white carbon and silicon foam, preferably described mesoporous silicon carrier is Beta molecular sieves.
4. in a kind of 1-3 according to claim solid catalyst described in any one preparation method, it includes：
Step A, the oxidation activity component comprising transition metal silicate and the condensation being carried on mesoporous silicon carrier is dehydrated and is lived
Property component mix with water, by stirring, centrifugal treating, be obtained white solid powder；
Step B, by the white solid powder through drying, calcination process, is obtained the solid catalyst.
5. preparation method according to claim 4, it is characterised in that in step, the temperature of the stir process is
30-90 DEG C, the time of the stir process is 0.5-6h；And/or
In stepb, the temperature of the dried process is 80-120 DEG C, and the temperature of the calcination process is 400-600 DEG C.
6. the preparation method according to claim 4 or 5, it is characterised in that the oxidation comprising transition metal silicate
The preparation method of active component includes：Transition metal silicate precursor is added drop-wise in the aqueous solution of silicon-containing compound, by stirring
Mix, be centrifuged and dried process, the oxidation activity component comprising transition metal silicate is obtained；It is preferred that the transition metal silicon
The mol ratio of the element silicon in transition metal in hydrochlorate precursor and the silicon-containing compound is 0.5-5, more preferably
2.3-5。
7. preparation method according to claim 6, it is characterised in that the transition metal silicate precursor is selected from transition gold
Belong to corresponding nitrate and/or chloride, be preferably selected from the one kind in zinc, nickel, copper or the corresponding nitrate of cobalt and/or chloride
Or it is various；
The silicon-containing compound is selected from one or more in silane, siloxanes, sodium metasilicate and silester；
It is preferred that the temperature of the stir process is 60-100 DEG C, the time of the stir process is 6-24h；The dried process
Temperature is 80-200 DEG C.
8. the preparation method according to any one in claim 4-7, it is characterised in that described to be carried on mesoporous silicon carrier
On the preparation method of condensation dehydration activity component include：Mesoporous silicon carrier is impregnated using transition metal oxide precursor solution,
By dried process, the condensation dehydration activity component being carried on mesoporous silicon carrier is obtained；
It is preferred that the transition metal oxide precursor is selected from the one kind in the corresponding nitrate of transition metal, chloride and organic salt
Or it is various；More preferably described transition metal oxide precursor is selected from tantalum, hafnium, scandium or the corresponding nitrate of yttrium, chloride and organic
One or more in salt；The further preferred transition metal oxide precursor is ethanol tantalum；
It is preferred that the temperature of the dried process is 60-100 DEG C；The time of the dried process is 3-6h.
9. solid catalyst in a kind of 1-3 according to claim described in any one or according to any one institute in right 4-8
Application of the solid catalyst of method preparation in ethanol synthesis butadiene is stated, it includes：By ethanol water in solid catalysis
In the presence of agent, it is oxidized, condensation and dehydration, be obtained butadiene.
10. preparation method according to claim 9, it is characterised in that the mass concentration of the ethanol water is
50wt%-99wt%；Mass space velocity is 0.1-2h-1；The temperature of the reaction is 300-400 DEG C, preferably 325-350 DEG C；Institute
The time for stating reaction is 8-30h.
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