CN104549302B - Ferrate catalyst as well as preparation method and application thereof - Google Patents
Ferrate catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a ferrate catalyst as well as a preparation method and application thereof. The catalyst has a general formula of x(FeAaDbEcOd)/yZ and is prepared by the following steps: (1) dissolving a precursor compound of components in addition to halogen E in a solution to obtain mixed slurry; (2) adding a precipitant into the mixed slurry until the pH value is 7.0-11.0 to obtain precipitation slurry; (3) filtering to obtain a filter cake; (4) uniformly mixing the filter cake with the precursor compound solution of halogen E, and roasting to obtain the catalyst. When the catalyst is applied to oxidative dehydrogenation reaction of butene to butadiene, the butene conversion rate and the butadiene selectivity are remarkably improved.x(FeAaDbEcOd)/yZ.
Description
Technical field
The present invention relates to a kind of catalyst for preparing butadiene with butylene oxo-dehydrogenation, this catalyst has high butylene
Conversion ratio and butadiene selective.The invention still further relates to the preparation method of this catalyst and its in Oxidative Dehydrogenation of Butene for fourth two
Application in alkene reaction.
Background technology
Butadiene is the maximum monomer of consumption in China Synthetic Rubber Industry, is also to produce synthetic resin and Organic Chemicals
Important intermediate.Butadiene can be used for preparing butadiene-styrene rubber, butadiene rubber, nitrile rubber, neoprene and abs resin etc., few
Measure for producing sulfolane, 1,4- butanediol, adiponitrile, hexamethylene diamine, butadiene oligomer and pesticide captan etc..Butadiene is also
Can be used as binding agent, gasoline additive etc., purposes is quite varied.Asia has become as the major demands of world's butadiene
Ground, and the demand of annual butadiene is all in stable growth.
Butadiene is mainly obtained by the extracting of naphtha pyrolysis by-product in the market.But it is light to be as ethylene raw
The development of matter and the development of olefin hydrocarbon making by coal technology, the amount of naphtha cracker complex there will be no big growth, this imply that not
Carry out butadiene yield and will can not meet growing butadiene demand, market butadiene breach can be increasing, need to develop
The new butadiene production technique not relying on olefin cracking.
Early in the sixties in 20th century, the technology of Oxidative Dehydrogenation of Butene into Butadiene achieves industrialization, catalyst frequently with
Iron spinel catalyst.For example, U.S. petro-tex company discloses a kind of butylene oxygen of use iron spinel catalyst
Fluidized dehydrogenation technique, up to 78%～80%, butadiene selective is 92%～95% to butene conversion.
China also have developed a series of Fe-series catalyst such as b-02, h-198, w-201 in the eighties in last century, and in work
Industry is succeeded application in producing.Using iron spinel catalyst, advantage is oxygen-containing organic compound in the by-product generating
Content is less, and wastewater treatment is simple, but its shortcoming is to be easier complete oxidation.Therefore, how to improve ferrite
Selectivity of catalyst is crucial.
Ferrate catalyst has spinelle afe2o4(a is zn, co, ni, mg, cu etc.) structure, by the oxygen of iron ion
In change, reduction and crystal, the interaction of oxonium ion and gaseous oxygen, can be used for oxidative dehydrogenation.Wherein zinc ferrite, ferrum
Sour magnesium and Manganese Ferrite etc. are usually used in butylene oxidation-dehydrogenation reaction, and zinc ferrite is urged higher than other ferrites to the selectivity of butadiene
Agent (f.-y.qiu, l.-t.weng, e.sham, p.ruiz, b.delmon, appl.catal., 51 volume, page 235,1989
Year).
The preparation process of ferrate catalyst, catalyst elements composition all can affect greatly to catalyst performance, lead to
Cross and improve preparation process, add beneficial metallic element, or pretreatment and post processing are carried out to catalyst, catalysis can be improved
Activity in oxidative dehydrogenation for the agent and the selectivity to butadiene.
For example, petro-tex petro-chemical corporation, in United States Patent (USP) us3, reports in 937,748 with ammonia as precipitant,
Iron acid zinc catalyst is prepared by coprecipitation, compared with the ferrate catalyst of high-temperature solid phase reaction method preparation, has more
Good activity and longer service life.Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences Chinese patent cn1033013,
Report in cn1072110 and cn1088624c and be used ammonia as precipitant, ferrate catalyst is prepared by coprecipitation,
Describe formula, preparation process condition and catalyst reaction technological parameter of ferrate catalyst etc. in detail to catalyst performance
Impact.
In addition, by adding other active components in iron acid zinc catalyst, such as ni, co, ba, sr, k, mo, bi etc., can
To improve the performance of catalyst further.Some metals can substitute ferrum in iron acid zinc catalyst or zinc enters spinelle
Skeleton, the activity and selectivity of catalyst is greatly improved, when particularly replacing ferrum with al or cr, catalyst activity
Raising more substantially (j.mol.catal.a, volume 125, page 53,1997).
Describe in United States Patent (USP) us4,058,577 to divide it when with the addition of appropriate manganese carbonate group in iron acid zinc catalyst
Afterwards, the stability of catalyst, activity and selectivity are all substantially improved.
United States Patent (USP) us4,083,884 reports by adding 1%～3% (weight ratio) calcium oxide to ferrate catalyst
In, the by-products such as acetaldehyde in byproduct of reaction, furan and acrylic aldehyde can be reduced.
United States Patent (USP) us4, after 332,972 report interpolation 1.5wt% zinc carbonate in iron acid zinc catalyst, catalyst
Conversion ratio and selectivity all have a distinct increment, reaction 572 hours after, butene conversion be 71.9%, butadiene selective be
93.6%.
Catalyst is carried out with the performance that suitable activation processing also can improve catalyst.For example, United States Patent (USP) us4,150,
064 reports using vapor in 450 DEG C about activation iron acid zinc catalysts, can lift conversion ratio and the selection of catalyst
Property.
Although the studies above has been made significant headway in lifting ferrate catalyst aspect of performance, the raw material due to no matter
Butylene or all easily generation deep oxidation reactions at the reaction temperatures of product butadiene, generate by-product co2And co, so existing
The leeway no matter some ferrate catalysts are still improved to butadiene selective or the conversion ratio reacting.
Therefore, this area remains a need for developing a kind of ferrate catalyst for preparing butadiene with butylene oxo-dehydrogenation, should
Catalyst not only has high butene conversion and butadiene selective, and anti-carrying out dehydrogenation using this ferrate catalyst
At a temperature of answering, raw material butylene and product butadiene occur the temperature of deep oxidation can be improved.
Content of the invention
One goal of the invention of the present invention is to provide a kind of catalyst for preparing butadiene with butylene oxo-dehydrogenation, and this is urged
Agent has high butene conversion and butadiene selective.
Another goal of the invention of the present invention is to provide a kind of preparation method of described catalyst, with existing preparation method
Compare, with the catalyst that the method is obtained, there is higher butene conversion and butadiene selective.
Another goal of the invention of the present invention is to provide described ferrate catalyst in preparing butadiene with butylene oxo-dehydrogenation
Purposes in reaction.
Therefore, it is an aspect of the invention to provide a kind of ferrate catalyst, it includes carrier band on a catalyst support
There is the catalyst of following general structure:
feaadbecod
Wherein,
A is mg atom, zn atom or both atoms with the mixture of arbitrary proportion；
D is selected from one of ni atom, co atom, mn atom, ca atom, mo atom or v atom or more kinds of former
Son；It is preferably one or more of ni atom, co atom, mn atom or v atom.
E is halogen atom, is selected from one of f atom, cl atom, br atom or more kinds of atoms；It is preferably
Cl atom.
A=0.01～0.6；
B=0～0.30；
C=0.001～0.01；
D is the number meeting each atomic valence.
Another aspect of the present invention is related to a kind of preparation method of above-mentioned catalyst, and it comprises the steps:
(1) precursor compound of the required component in addition to halogen e is dissolved in solution, obtains mixed slurry；
(2) add precipitant in mixed slurry, be 7.0～11.0 to ph value, be precipitated slurry；
(3) precipitate slurry filtered, wash, obtain filter cake；
(4) filter cake is mixed homogeneously with the precursor compound solution of halogen e, and dry, roasting, obtain catalyst.
Preferably 550～700 DEG C of the sintering temperature of step (4), more preferably 580～680 DEG C.
Another aspect of the invention is related to the above-mentioned catalyst prepared with the inventive method in gas phase oxidation of butene dehydrogenation system
Purposes in standby butadiene reaction.
Specific embodiment
1.Ferrate catalyst
The present invention relates to a kind of ferrate catalyst, it is applied in the reaction that butadiene is prepared in gas phase oxidation of butene dehydrogenation,
Described ferrate catalyst can make this reaction have improved butene conversion and butadiene selective.
Ferrate catalyst of the present invention is to carry the composite oxides on a catalyst support with following general structure:
feaadbecod
Wherein,
A is mg atom, zn atom or both atoms with the mixture of arbitrary proportion.
A=0.01～0.6, preferable a=0.05～0.5, more preferable a=0.1～0.4.In an example of the present invention, a be by
0.01,0.6,0.05,0.5,0.1 with the 0.4 any number scope being formed as end points.
D is selected from one of ni atom, co atom, mn atom, ca atom, mo atom or v atom or more kinds of former
Son；It is preferably one or more of ni atom, co atom, mn atom or v atom.In a preferable example of the present invention,
Described d is the mixing atom of mn atom and ni and/or co, and its mn atom is 10:1～1 with the mole mixture ratio of ni and/or co:
10, preferably 5:1～1:5, more preferably 2:1～1:2, preferably 1.5:1～1:1.5.
B=0～0.30, preferably b=0.02～0.20, more preferably b=0.05～0.15, preferably b=0.08～0.10.At this
In one preferable example of invention, described b is by any two conduct in 0.02,0.20,0.05,0.15,0.08 and 0.10
The numerical range that end points is formed.
E is halogen, and for example it is selected from one of f atom, cl atom, br atom or more kinds of atoms；It is preferably cl
Atom.
C=0.001～0.01, preferably 0.003～0.009, more preferably 0.005～0.008.At one of the present invention relatively
In good example, c be formed as end points by following any two value numerical range 0.001,0.01,0.003,0.009,
0.005 and 0.008, for example, it can be 0.003-0.005 or 0.008-0.01.
D is the number meeting each atomic valence.
The catalyst carrier being applied to the present invention can be any suitable oxide catalyst supports.In the present invention one
In individual example, described oxide catalyst supports are selected from aluminium oxide, silicon oxide, zirconium oxide, magnesium oxide or sial composite oxides
One or more of；Be preferably one of silicon oxide or aluminium oxide or both with arbitrary proportion formed mixture.
In a preferable example of the present invention, present invention carrier band ferrate catalyst on a catalyst support have as
Lower formula:
X(feaadbecod)/yz
Wherein, a, d, e and a, b, c and d are as defined above；
Z represents described catalyst carrier；
X, y represent ferrate catalyst and the amount of carrier z, y/x=0:1～4:1(weight ratio), preferably 0:1～3:1(weight
Amount ratio), more preferably y/x=0.5:1～2:1(weight ratio), preferably 0.5:1～1.5:1, preferably 0.5:1～1:1.
In catalyst of the present invention, catalyst is modified using micro halogen auxiliary agent e, the mode that halogen auxiliary agent e adds
It is to improve the butene conversion of catalyst of the present invention and a key point of butadiene selective with addition.As example below
As proving with comparative example, when the addition of halogen e or feed postition are outside the scope of the present invention, the conversion ratio of butylene
And/or the selectivity of butadiene will decline.
2.The preparation method of ferrate catalyst
A. the ferrate catalyst of the present invention can be obtained using following method:
(1) precursor compound of component in addition to halogen e is dissolved in solution, obtains mixed slurry
According to the difference of method and step, described precursor compound can be water miscible, fat-soluble, insoluble.?
In an example of the present invention, use water as reaction medium, it is therefore desirable to described precursor compound is water miscible.Suitable
The not limiting example of water-soluble precursor compound has, the water-soluble nitrate of for example described metallic element, chloride,
Sulfate etc., preferably nitrate.
In a preferable example of the present invention, using ferric nitrate (such as Fe(NO3)39H2O), zinc nitrate (such as six water
Close zinc nitrate), manganese nitrate, magnesium nitrate (such as magnesium nitrate hexahydrate) and/or nickel nitrate (such as Nickelous nitrate hexahydrate) be as institute
State lead compound.
In a preferable example of the present invention, the nitrate that metallic element is used as described precursor compound, this
A little nitrate may be dissolved in formation aqueous solution in water, and the concentration of aqueous solution of formation is without particular limitation, as long as its metallic element
Amount meets the ratio requirement of final ferrate catalyst.
In another preferable example of the present invention, the described step forming mixed slurry includes: weighs ferric nitrate, nitric acid
Zinc, manganese nitrate, are dissolved in water, and ferrum, zinc, the mol ratio of three kinds of metallic elements of manganese are 1:0.2～0.5:0.01～0.02.
In another preferable example of the present invention, the described step forming mixed slurry includes: weighs ferric nitrate, nitric acid
Zinc, magnesium nitrate, nickel nitrate, are dissolved in water, and ferrum, zinc, magnesium, the mol ratio of four kinds of metallic elements of nickel are 1:0.01～0.1:0.2
～0.5:0.01～0.04.
(2) add precipitant in mixed slurry, be 7.0～11.0 to ph value, be precipitated slurry
The inventive method includes the step adding precipitant in the mixed slurry that upward step obtains.Described precipitant is no
Special restriction, can be any precipitant known in the art.In a preferable example of the present invention, described precipitant choosing
From hydroxide (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium hydroxide etc.), ammonia, pyridine, trimethylamine, bicarbonate
Ammonium, ammonium carbonate or its two or more mixture of being formed with arbitrary proportion.In an example of the present invention, described precipitation
Agent uses in form of an aqueous solutions.
After adding precipitant, the ph of the mixed slurry of the present invention is controlled preferably control 7.2 in 7.0～11.0, ph～
10.8, it is preferably controlled in 7.5～9.5, more preferably control 7.8～9.2.
In an example of the present invention, the scope of described ph be by 7.0,11.0,7.2,10.8,7.5,9.5,7.8,
The numerical range that any two in 9.2 is formed as end points.
The settling step of the present invention is a kind of conventional chemical reaction step in itself.Those of ordinary skill in the art according to
Its Professional knowledge can easily carry out suitable precipitation operation.For example, can be stirred in Deca precipitant, to ensure simultaneously
Precipitant is sufficiently mixed with metal nitrate, is precipitated slurry mix etc..
(3) precipitate slurry filtered, wash, obtain filter cake.
After the mixed slurry being precipitated, the inventive method also includes filtering, washs.Specific filtration, washing are these
Method known to field.After having read present disclosure, those of ordinary skill in the art is readily determined tool
The suitable method and step of body.The deionized water of the most handy 30～50 DEG C of washing, washing times are to be advisable no less than secondary.
(4) filter cake is mixed homogeneously with the precursor compound solution of halogen e, dry roasting, obtain catalyst.
The method of mixing can be churned mechanically method or the side of other generally acknowledged solids and liquid mixing
Method.The precursor compound of halogen e can be the ammonium salt containing halogen, slaine or Organic substance.Preferably comprise the ammonium of halogen
Salt or slaine.Particularly preferably cation is the slaine containing halogen of ferrum, zinc or magnesium.
The not limiting example of described halogen e precursor compound has, such as ammonium chloride, iron chloride, ferrous chloride, chlorination
Zinc, magnesium chloride or its mixture of two or more.When the use of cation is ferrum, the metal containing halogen of zinc or magnesium
Salt, should corresponding deduction now introduces when forming described filter cake the amount of ferrum, zinc or magnesium cation, thus making the catalysis obtaining
Agent has required composition.
After solid is mixed homogeneously with the precursor compound solution of halogen e, the mixture of solid and liquid is dried simultaneously
Roasting, obtains catalyst.
Preferably 50～300 DEG C of the baking temperature of step (4), more preferably 90～150 DEG C.
In a preferable example of the present invention, the inventive method also includes pulverizing the solid obtaining after drying, is mixed into 1
～5 weight %, preferable 2～4 weight %, the powdered graphite of more preferable 2.5～3.5 weight %, with aftershaping.
Suitable catalyst shape is without particular limitation, can be any shape known in the art, for example, cube
Type, square build, column type, ball-type, trilobal cross etc..
Subsequently roasting is carried out in oxygen-containing atmosphere to the solid of molding, sintering temperature is 500～700 DEG C, roasting time is
0.5～24 hour.
Applicable oxygen-containing atmosphere is without particular limitation, if its oxygen content be more than 5 volumes %, preferably greater than 8 volumes %, remaining
Measure as noble gases.
Preferably 520～680 DEG C of the temperature of roasting, more preferably 580～650 DEG C.In a preferable example of the present invention,
Described roasting is in the temperature being formed by any two temperature in 500 DEG C, 700 DEG C, 520 DEG C, 680 DEG C, 580 DEG C and 650 DEG C
In the range of carry out.
Preferably 1～20 hour time of roasting, more preferably 2～10 hours, preferably 3～8 hours, preferably 4～6 is little
When.In an example of the present invention, described roasting continue by 1 hour, 20 hours, 2 hours, 10 hours, 3 hours, 8 hours, 4
The time period that hour is formed for end points with any two in 6 hours.
3.The purposes of ferrate catalyst of the present invention
Ferrate catalyst of the present invention is suitable for gas phase oxidation of butene dehydrogenation and prepares butadiene reaction.Suitable reaction include as
Lower step: raw material butylene is mixed with vapor, air and diluent gas, passes through beds after preheating, carry out oxygen
Fluidized dehydrogenation reacts；The condition of reaction is 250～550 DEG C of temperature, and reaction velocity is 100～1000h for raw material butylene-1, instead
Should in gas butylene molar concentration 1～20%, butylene: oxygen: vapor: the mol ratio of carrier gas is 1:0.2～2:1～20:0
～20；Carrier gas is one of nitrogen, argon, helium.
In an example of the present invention, described gas phase oxidation of butene dehydrogenation is prepared butadiene reaction and is comprised the steps:
By raw material butylene and vapor, air and dilute gas mixture, pass through beds after preheating, carry out oxidative dehydrogenation
Reaction；Reaction condition is: 300～450 DEG C of temperature, and reaction raw materials air speed for butylene is 300～600h-1, butylene mole
Concentration 4～12%, butylene: oxygen: vapor: the mol ratio of carrier gas is 1:0.5～1.0:3～16:0～10；Carrier gas is nitrogen
Gas.
In the reaction that butadiene is prepared in gas phase oxidation of butene dehydrogenation of the present invention, its beds uses the inventive method
Prepared ferrate catalyst.
Described raw material butylene is one of 1-butylene, trans-butene -2, cis-butene -2, two kinds or these three butylene
The mixture of isomer.
Below, further illustrate the present invention in conjunction with the embodiments.In the examples below that, it is calculated using equation below
" conversion ratio of butylene " and " selectivity of butadiene ":
The conversion ratio (%) of butylene=[amount of butylene before (amount of butylene after the amount-reaction of butylene before reaction)/reaction] ×
100%
The selectivity (%) of butadiene=(amount of the butylene of amount/reaction of butadiene that reaction generates) × 100%
Embodiment 1
1. prepare catalyst
Weigh 404 grams of Fe(NO3)39H2Os, 134 grams of zinc nitrate hexahydrates, 7.08 grams of calcium nitrates, be dissolved in 1000ml25 DEG C
In distilled water, ferrum, zinc, the mol ratio of three kinds of metallic elements of calcium are 1:0.45:0.03, then add 100 grams of oxygen again in solution
Change aluminium powder, stirring makes powder be uniformly dispersed；To in above-mentioned solution, Deca concentration is the sodium hydroxide solution of 2mol/l, to solution
Ph value is 9.0.After being added dropwise to complete, serosity is warming up to 70 DEG C and stirs 1 hour, be subsequently cooled to 25 DEG C, filter and use distilled water
Wash to neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens and is dried 24 hours.Solid after drying, through milling, sieving, obtains
To the granule less than 150 mesh.
Analyze the elementary composition of the granule obtaining using Dutch philips company pw2404x ray fluorescence spectrometer, record
Ferrum, zinc, calcium, the mol ratio of four kinds of metallic elements of aluminum are 1:0.44:0.025:0.98.
By 0.535 gram of chloride leach in 300ml distilled water, above-mentioned preparation is dispersed in less than the granule of 150 mesh
In ammonium chloride solution, ferrum element is 100:1 with the mol ratio of chlorine element, dries afterwards in 110 DEG C of baking ovens.
The solid obtaining after drying is mixed with graphite, graphite addition is the 3% of gross mass.By above-mentioned mixed powder
End is shaped to 20～40 mesh granules, and by the granule obtaining 600 DEG C of heat treatments 10 hours in air atmosphere, obtains catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test is to carry out in rustless steel tubular reactor (internal diameter 10mm, long 350mm), Catalyst packing body
Long-pending 15ml.Raw material 1-butylene is mixed with vapor, air, preheated to after 300 DEG C, by beds.Wherein 1- fourth
Alkene air speed is 400h-1, 350 DEG C of reaction temperature, the mol ratio of air and butylene is 3.3, and the mol ratio of vapor and butylene is 16,
After reaction is stablized for 100 hours, tail gas is used with gas chromatogram on-line analyses, 1-butylene conversion ratio is 88.5%, butadiene selective
95.8%.
Comparative example 1
1. prepare catalyst
Rate of charge and method according to embodiment 1 prepare ferrate catalyst, except for the difference that without component cl element.Claim
Take 404 grams of Fe(NO3)39H2Os, 134 grams of zinc nitrate hexahydrates, 7.08 grams of calcium nitrates, be dissolved in 1000ml25 DEG C of distilled water,
Ferrum, zinc, the mol ratio of three kinds of metallic elements of calcium are 1:0.45:0.03, then add 100 grams of alumina powders in solution again,
Stirring makes powder be uniformly dispersed；To in above-mentioned solution, Deca concentration is the sodium hydroxide solution of 2mol/l, to solution ph is
9.0.After being added dropwise to complete, slurry temperature is risen to 70 DEG C and stirs 1 hour, be subsequently cooled to 25 DEG C, filter and use distilled water wash
To neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens and is dried 24 hours.Solid after drying through milling, sieving be less than
The granule of 150 mesh,
Measure the elementary composition of the granule obtaining using instrument same as Example 1 and method, record ferrum, zinc, calcium, aluminum
The mol ratio of four kinds of metallic elements is 1:0.44:0.025:0.98.
Above-mentioned granule is mixed with graphite, graphite addition is the 3% of gross mass, and above-mentioned mixed solid forming is
20～40 mesh granules, and by the granule obtaining 600 DEG C of heat treatments 10 hours in air atmosphere, obtain catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test is that (internal diameter 10mm, long 350mm) is carried out, catalyst volume in rustless steel tubular reactor
15ml.Raw material 1-butylene is mixed with vapor, air, preheated to after 300 DEG C, by beds.Wherein 1-butylene
Air speed is 400h-1, 350 DEG C of reaction temperature, the mol ratio of air and butylene is 3.3, and the mol ratio of vapor and butylene is 16, instead
Answer 100 hours after stablizing, tail gas is used with gas chromatogram on-line analyses, 1-butylene conversion ratio is 81.5%, butadiene selective
92.8%.
Embodiment 2
1. prepare catalyst
Weigh 404 grams of Fe(NO3)39H2Os, 103 grams of magnesium nitrate hexahydrates, 14.6 grams of cobalt nitrates, be dissolved in 1000ml25 DEG C
In distilled water, ferrum, magnesium, the mol ratio of three kinds of metallic elements of cobalt are 1:0.40:0.05, then add 100 grams of oxygen again in solution
Change aluminium powder, stirring makes powder be uniformly dispersed；To in above-mentioned solution, Deca concentration is the sodium hydroxide solution of 2mol/l, to solution
Ph value is 9.5.After being added dropwise to complete, slurry temperature is risen to 70 DEG C and stirs 1 hour, be subsequently cooled to 25 DEG C, filter and with distilling
Water is washed to neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens and is dried 24 hours.Solid after drying through milling,
Screening, yields less than the granule of 150 mesh.
Measure the elementary composition of the granule obtaining using instrument same as Example 1 and method, record ferrum, zinc, cobalt, aluminum
The mol ratio of four kinds of metallic elements is 1:0.35:0.045:0.98.
0.47 gram of magnesium chloride is dissolved in 300ml distilled water, above-mentioned preparation is dispersed in chlorine less than the granule of 150 mesh
Change in magnesium solution, ferrum element is 200:1 with the mol ratio of chlorine element, dries afterwards in 110 DEG C of baking ovens.
The solid obtaining after drying is mixed with graphite, graphite addition is the 3% of gross mass, by above-mentioned mixed powder
End is shaped to 20～40 mesh granules, and by the granule obtaining 650 DEG C of heat treatments 4 hours in air atmosphere, obtains catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 1.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction temperature
370 DEG C of degree, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours, right
Tail gas gas chromatogram on-line analyses, 1-butylene conversion ratio is 87.2%, butadiene selective 94.3%.
Comparative example 2
1. prepare catalyst
Rate of charge and method according to embodiment 2 prepare ferrate catalyst, except for the difference that without component cl element.Claim
Take 404 grams of Fe(NO3)39H2Os, 103 grams of magnesium nitrate hexahydrates, 14.6 grams of cobalt nitrates, be dissolved in 1000ml25 DEG C of distilled water,
Ferrum, magnesium, the mol ratio of three kinds of metallic elements of cobalt are 1:0.40:0.05, then add 100 grams of alumina powders in solution again,
Stirring makes powder be uniformly dispersed；To in above-mentioned solution, Deca concentration is the sodium hydroxide solution of 2mol/l, to solution ph is
9.5.After being added dropwise to complete, slurry temperature is risen to 70 DEG C and stirs 1 hour, be subsequently cooled to 25 DEG C, filter and use distilled water wash
To neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens and is dried 24 hours.Solid after drying through milling, sieving be less than
The granule of 150 mesh,
Measure the elementary composition of the granule obtaining using instrument same as Example 1 and method, record ferrum, magnesium, cobalt, aluminum
The mol ratio of four kinds of metallic elements is 1:0.35:0.045:0.98.
Above-mentioned granule is mixed with graphite, graphite addition is the 3% of gross mass, and above-mentioned mixed solid forming is
20～40 mesh granules, and by the granule obtaining 650 DEG C of heat treatments 4 hours in air atmosphere, obtain catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 2.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction temperature
370 DEG C of degree, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours, right
Tail gas gas chromatogram on-line analyses, 1-butylene conversion ratio is 80.2%, butadiene selective 92.1%.
Embodiment 3
1. prepare catalyst
Weigh 404 grams of Fe(NO3)39H2Os, 29.7 grams of magnesium nitrate hexahydrates, 119 grams of zinc nitrates, be dissolved in 1000ml25 DEG C
In distilled water, ferrum, zinc, the mol ratio of three kinds of metallic elements of magnesium are 1:0.40:0.10, then add 100 gram two in solution again
Silicon oxide powder, stirring makes powder be uniformly dispersed；The Deca strong aqua ammonia in above-mentioned solution, is 9.0 to solution ph.It is added dropwise to complete
Afterwards, slurry temperature is risen to 70 DEG C to stir 1 hour, be subsequently cooled to 25 DEG C, filter and be washed with distilled water to neutrality.To obtain
Filter cake be placed in 120 DEG C of baking ovens be dried 24 hours.Solid after drying, through milling, sieving, yields less than 150 purposes
Grain.
Using instrument same as Example 1 and method mensure obtain catalyst elementary composition, record ferrum, zinc, magnesium,
The mol ratio of four kinds of elements of silicon is 1:0.35:0.051:0.1.65.
By 0.268 gram of chloride leach in 300ml distilled water, above-mentioned preparation is dispersed in less than the granule of 150 mesh
In ammonium chloride solution, the mol ratio of ferrum element and chlorine element is 200:1, dries afterwards in 110 DEG C of baking ovens.
The solid obtaining after drying is mixed with graphite, graphite addition is the 3% of gross mass, by above-mentioned mixed powder
End is shaped to 20～40 mesh granules, and by the granule obtaining 650 DEG C of heat treatments 4 hours in air atmosphere, obtains catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 1.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction temperature
370 DEG C of degree, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours, right
Tail gas gas chromatogram on-line analyses, 1-butylene conversion ratio is 86.8%, butadiene selective 95.0%.
Comparative example 3
1. prepare catalyst
Rate of charge and method according to embodiment 3 prepare ferrate catalyst, but without component cl element.Weigh
404 grams of Fe(NO3)39H2Os, 29.7 grams of magnesium nitrate hexahydrates, 119 grams of zinc nitrates, are dissolved in 1000ml25 DEG C of distilled water, ferrum,
Zinc, the mol ratio of three kinds of metallic elements of magnesium are 1:0.40:0.10, then add 100 grams of SiO 2 powders in solution again, stir
Mix and so that powder is uniformly dispersed；The Deca strong aqua ammonia in above-mentioned solution, is 9.0 to solution ph.After being added dropwise to complete, by slurry temperature
Rise to 70 DEG C to stir 1 hour, be subsequently cooled to 25 DEG C, filter and be washed with distilled water to neutrality.The filter cake obtaining is placed in 120
It is dried 24 hours in DEG C baking oven.Solid after drying, through milling, sieving, yields less than the granule of 150 mesh.
Measure the elementary composition of the granule obtaining using instrument same as Example 1 and method, record ferrum, zinc, magnesium, silicon
The mol ratio of four kinds of elements is 1:0.35:0.051:0.1.65.
Above-mentioned granule is mixed with graphite, graphite addition is the 3% of gross mass, and above-mentioned mixed solid forming is
20～40 mesh granules, and by the granule obtaining 650 DEG C of heat treatments 4 hours in air atmosphere, obtain catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 3.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction temperature
370 DEG C of degree, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours, right
Tail gas gas chromatogram on-line analyses, 1-butylene conversion ratio is 78.9%, butadiene selective 89.2%.
Embodiment 4
1. prepare catalyst
Weigh 404 grams of Fe(NO3)39H2Os, 128.2 grams of magnesium nitrate hexahydrates, 14.87 grams of zinc nitrates, 7.53 grams of manganese nitrates,
8.72 grams of nickel nitrates, are dissolved in 1000ml25 DEG C of distilled water, and ferrum, zinc, magnesium, nickel, the mol ratio of five kinds of metallic elements of manganese are 1:
0.05:0.50:0.03:0.03, then adds 100 grams of SiO 2 powders again in solution, and stirring makes powder be uniformly dispersed；To
Deca 2m sodium hydroxide solution in above-mentioned solution, until solution ph is 8.5.After being added dropwise to complete, slurry temperature is risen to 70 DEG C
Stirring 1 hour, is subsequently cooled to 25 DEG C, filters and be washed with distilled water to neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens
It is dried 24 hours, the solid after drying, through milling, sieving, yields less than the granule of 150 mesh.
Using instrument same as Example 1 and method mensure obtain granule elementary composition, record ferrum, zinc, magnesium,
Nickel, manganese, the mol ratio of six kinds of elements of silicon are 1:0.042:0.42:0.022:0.029:1.65.
By 0.268 gram of chloride leach in 300ml distilled water, above-mentioned preparation is dispersed in less than the granule of 150 mesh
In ammonium chloride solution, the mol ratio of ferrum element and chlorine element is 200:1, then dries in 110 DEG C of baking ovens.
The solid obtaining after drying is mixed with graphite, graphite addition is the 3% of gross mass, by above-mentioned mixed powder
End is shaped to 20～40 mesh granules, and by the granule obtaining 650oc heat treatment 4 hours in air atmosphere, obtains catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 1.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction temperature
370 DEG C of degree, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours, right
Tail gas gas chromatogram on-line analyses, 1-butylene conversion ratio is 90.2%, butadiene selective 95.5%.
Comparative example 4
1. prepare catalyst
Rate of charge and method according to embodiment 4 prepare ferrate catalyst, but without component cl element.Weigh
404 grams of Fe(NO3)39H2Os, 128.2 grams of magnesium nitrate hexahydrates, 14.87 grams of zinc nitrates, 7.53 grams of manganese nitrates, 8.72 grams of nitric acid
Nickel, is dissolved in 1000ml25 DEG C of distilled water, and ferrum, zinc, magnesium, nickel, the mol ratio of five kinds of metallic elements of manganese are 1:0.05:0.50:
0.03:0.03, then adds 100 grams of SiO 2 powders again in solution, and stirring makes powder be uniformly dispersed；To in above-mentioned solution
Deca 2m sodium hydroxide solution, until solution ph is 8.5.After being added dropwise to complete, slurry temperature is risen to 70 DEG C and stirs 1 hour,
It is subsequently cooled to 25 DEG C, filter and be washed with distilled water to neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens dry 24 little
When.Solid after drying, through milling, sieving, yields less than the granule of 150 mesh.
Using instrument same as Example 1 and method mensure obtain granule elementary composition, record ferrum, zinc, magnesium,
Nickel, manganese, the mol ratio of six kinds of elements of silicon are 1:0.042:0.42:0.022:0.029:1.65.
Above-mentioned granule is mixed with graphite, graphite addition is the 3% of gross mass.Above-mentioned mixed solid forming is
20～40 mesh granules, and by the granule obtaining 650 DEG C of heat treatments 4 hours in air atmosphere, obtain catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test method is same as Example 4.Catalyst volume 15ml, 1-butylene air speed is 400h-1, reaction
370 DEG C of temperature, the mol ratio of air and butylene is 3.0, and the mol ratio of vapor and butylene is 16, after reaction is stablized for 100 hours,
Tail gas is used with gas chromatogram on-line analyses, 1-butylene conversion ratio is 82.3%, butadiene selective 93.2%.
Comparative example 5
1. prepare catalyst
Weigh 404 grams of Fe(NO3)39H2Os, 134 grams of zinc chloride, 7.08 grams of calcium nitrates, be dissolved in 25 DEG C of distillations of 1000ml
In water, ferrum, zinc, the mol ratio of three kinds of metallic elements of calcium are 1:0.45:0.03, then add 100 grams of aluminium oxidies again in solution
Powder, stirring makes powder be uniformly dispersed；To in above-mentioned solution, Deca concentration is the sodium hydroxide solution of 2 mol/l, to solution ph
It is worth for 9.0.After being added dropwise to complete, serosity is warming up to 70 DEG C and stirs 1 hour, be subsequently cooled to 25 DEG C, filter and washed with distillation
Wash to neutrality.The filter cake obtaining is placed in 120 DEG C of baking ovens and is dried 24 hours.Solid after drying, through milling, sieving, obtains
Granule less than 150 mesh.
Using instrument same as Example 1 and method mensure obtain catalyst elementary composition, record ferrum, zinc, calcium,
The mol ratio of four kinds of elements of aluminum is 1:0.44:0.025:0.98.
0.535 gram of ammonium nitrate is dissolved in 300ml distilled water, above-mentioned preparation is dispersed in less than the granule of 150 mesh
In ammonium chloride solution, ferrum element is 100:1 with the mol ratio of chlorine element, dries afterwards in 110 DEG C of baking ovens.
The solid obtaining after drying is mixed with graphite, graphite addition is the 3% of gross mass.By above-mentioned mixed powder
End is shaped to 20～40 mesh granules, and by the granule obtaining 600 DEG C of heat treatments 10 hours in air atmosphere, obtains catalyst.
2. pass through butylene dehydrogenation reaction evaluating catalyst performance
Catalytic performance test is to carry out in rustless steel tubular reactor (internal diameter 10mm, long 350mm), Catalyst packing body
Long-pending 15ml.Raw material 1-butylene is mixed with vapor, air, preheated to after 300 DEG C, by beds.Wherein 1- fourth
Alkene air speed is 400h-1, 350 DEG C of reaction temperature, the mol ratio of air and butylene is 3.3, and the mol ratio of vapor and butylene is 16,
After reaction is stablized for 100 hours, tail gas is used with gas chromatogram on-line analyses, 1-butylene conversion ratio is 88.5%, butadiene selective
95.8%.
Being compared by the result of the test of above embodiment and comparative example it can be seen that adopting the catalyst of the present invention, passing through
Add chlorine element or bromo element in ferrate catalyst, it is possible to increase the performance of catalyst, be applied to butylene oxidation-dehydrogenation
Reaction, butene conversion and butadiene selective are significantly improved.
By experiment above result it can also be seen that the addition opportunity of halogen has impact to the performance of final catalyst.When
Introduced during halogen hence it is evident that the goal of the invention of the present invention can not be reached using the method beyond the inventive method.
Claims (12)
1. a kind of carrier band ferrate catalyst on a catalyst support, it has a following general structure:
x(feaadbecod)/yz
Wherein,
A is mg atom, zn atom or both atoms with the mixture of arbitrary proportion；
D is selected from one of ni atom, co atom, mn atom, ca atom, mo atom or v atom or more kinds of atoms；
E is halogen, and it is selected from one of f atom, cl atom, br atom or more kinds of atoms；
A=0.01～0.6；
B=0～0.30；
C=0.001～0.01；
D is the number meeting each atomic valence；
Z is the catalyst selected from one or more of aluminium oxide, silicon oxide, zirconium oxide, magnesium oxide or sial composite oxides
Carrier；
Amount x, y of catalyst and carrier meets weight than y/x=0.5:1～4:1.
2. ferrate catalyst as claimed in claim 1 is it is characterised in that d is ni atom, co atom, mn atom or v atom
One or more of；E is one of cl atom, br atom or two kinds.
3. ferrate catalyst as claimed in claim 1 or 2,
It is characterized in that amount x, y of catalyst and carrier meets weight than y/x=0.5:1～3:1.
4. ferrate catalyst as claimed in claim 1 or 2 is it is characterised in that amount x, y of catalyst and carrier meets weight
Than y/x=0.5:1～2:1.
5. ferrate catalyst as claimed in claim 1 or 2 is it is characterised in that amount x, y of catalyst and carrier meets weight
Than y/x=0.5:1～1:1.
6. ferrate catalyst as claimed in claim 1 is it is characterised in that c=0.003～0.009.
7. ferrate catalyst as claimed in claim 1 is it is characterised in that c=0.005～0.008.
8. ferrate catalyst as claimed in claim 1 or 2 is it is characterised in that it is obtained with the following method:
(1) precursor compound of component in addition to halogen e is dissolved in solution, obtains mixed slurry, add in mixed slurry
Enter catalyst carrier；
(2) add precipitant in mixed slurry, be 7.0～11.0 to ph value, be precipitated slurry；
(3) obtain filter cake after filtering；
(4) filter cake is mixed homogeneously with the precursor compound solution of halogen e, roasting obtains catalyst.
9. a kind of preparation method of the ferrate catalyst as any one of claim 1-8, it comprises the steps:
(1) precursor compound of component in addition to halogen e is dissolved in solution, obtains mixed slurry, add in mixed slurry
Enter catalyst carrier；
(2) add precipitant in mixed slurry, be 7.0～11.0 to ph value, be precipitated slurry；
(3) obtain filter cake after filtering；
(4) filter cake is mixed homogeneously with the precursor compound solution of halogen e, roasting obtains catalyst.
10. method as claimed in claim 9 is it is characterised in that also included after step (3) before step (4): will filter
Cake is warming up to 120～250 DEG C of heat treatments 2～24 hours, and the sintering temperature of described step (4) is 550～700 DEG C.
11. methods as claimed in claim 9 are it is characterised in that also included after step (3) before step (4): will filter
Cake is warming up to 120～250 DEG C of heat treatments 2～24 hours, and the sintering temperature of described step (4) is 580～680 DEG C.
Purposes in preparing butadiene with butylene oxo-dehydrogenation reaction for the catalyst any one of 12. claim 1～8.
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| CN111054405A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene and preparation method thereof |
| CN111054407A (en) * | 2018-10-16 | 2020-04-24 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene by oxidative dehydrogenation of butylene |
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| CN114073953A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing butadiene through oxidative dehydrogenation of butylene and preparation method and application thereof |
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