CN1033013A - Butylene oxidation-dehydrogenation catalyst - Google Patents

Butylene oxidation-dehydrogenation catalyst Download PDF

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CN1033013A
CN1033013A CN 86108152 CN86108152A CN1033013A CN 1033013 A CN1033013 A CN 1033013A CN 86108152 CN86108152 CN 86108152 CN 86108152 A CN86108152 A CN 86108152A CN 1033013 A CN1033013 A CN 1033013A
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catalyst
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butylene
general formula
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CN1013247B (en
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周望岳
陈献诚
张国栋
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JINZHOU PETROLEUM REFINERY JINZHOU PETROCHEMICAL INDUSTRY Co
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JINZHOU PETROLEUM REFINERY JINZHOU PETROCHEMICAL INDUSTRY Co
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Abstract

Butylene oxidation-dehydrogenation catalyst the invention belongs to olefin oxidation dehydrogenation system alkadienes catalyst.The present invention is that a kind of general structure is Aa 2+Bb 2+Cc 3+Fe d 3+O 4X[α (γ)-F 2O 3] the spinel-type catalyst, in the formula, X=10～60% (weight).When this catalyst is used for fluidized-bed reactor, be 360～370 ℃ in reaction temperature, butylene air speed 300h -1, when water alkene ratio was 8～10 (mol ratios), the butadiene yield was 62～68%, selectivity is 90～92%.

Description

Butylene oxidation-dehydrogenation catalyst
The invention belongs to olefin oxidation dehydrogenation system alkadienes catalyst.
The reaction that butylene oxidation-dehydrogenation generates butadiene is that early sixties just comes out, and the different molybdenum systems that form, tin system, antimony system and Fe-series catalyst all have suitable catalytic activity to this reaction.But activity, the selectivity of molybdenum series catalyst are lower, and have quite a large amount of poisonous oxygenatedchemicals to generate.Though tin system, antimony-based catalyst have higher activity, there is toxic byproduct still a lot.
Olefin oxidation dehydrogenation Fe-series catalyst, that adopt the earliest is AB 2O 4Spinelle type composite oxides (USP.3,270,080), wherein A is generally Mg 2+, Zn 2+, Co 2+And Ni 2+Deng bivalent metal ion, B is Fe 3+Ion.
With Cr 3+Improve Mg 2+Fe 3+ 2O 4The stability of type catalyst is at first by invention (USP3,450,788 such as W.L.Kehl; 3,595,810), its general formula is Zn aCr bFe cO 4In: a is 0.1～3, and b is＞0～2, and C is＞0～3.And propose best prescription and consist of a and be about 1, b is 0.1～1.8, and C is 0.25～1.9, and b+c=2, and total ratio meets ZnCr bFe 2-bO 4Spinel structure form.The specific surface of catalyst＞0.1 meter 2/ gram, the best is 1 meter 2/ gram.Its patent right comprises that also the catalyst of above-mentioned prescription is in activating under 400～600 ℃ in oxygen containing inert gas atmosphere.300～500 ℃ of reaction temperatures, the reaction time is no less than 30 minutes.Press activation condition regeneration subsequently again.It is that oxygen alkene is than 0.2～2.5(mole that raw material is formed), water alkene is than 5～30(mole).The butylene gas space velocity is 450h -1
Lanzhou Chemicophysics Inst., Chinese Academy of Sciences once reported the result of the test of butylene oxidation-dehydrogenation with Fe-series catalyst, used ZnCrFeO 4Type has carrier (SiO 2) or unsupported catalyst Zn aCr bFe cO 4In, a=1, b=0.25～1, c=1～1.75, the b+c=2(petrochemical industry, 1979 731 pages), reaction condition is: 360～420 ℃ of reaction temperatures, butylene air speed 80～120h -1, oxygen alkene is than 0.8～1.0, and water alkene is than 10～16(mole), 500 hours reaction result of secondary accumulative total, butadiene once through yield 65～70%, selectivity 89%.
But, which kind of Fe-series catalyst no matter, its structure all belongs to AB 2O 4Spinel structure, and mechanical strength is relatively poor.
Relevant butylene oxidation-dehydrogenation α-Fe in the ferrate catalyst 2O 3Effect, only Rennard etc. (J.Catal., 21(1971), 282) and Wang Hanqing etc. (Chinese science, 9(1979), 875) once mentioned, and proposed a small amount of (5%) left and right sides α-Fe 2O 3Have help to improve Tie Suan ?the stability of catalyst.
The objective of the invention is: develop a kind of high activity.The new construction Tie Suan of high selectivity, high mechanical properties, non-regeneration type ?the type catalyst.Make it to be adapted to lead and carry out the butylene oxidation-dehydrogenation reaction in the plate washer fluidized-bed reactor.The advantage of fluid bed is that catalyst loading and unloading is convenient, and reaction temperature can be hanged down 200～250 ℃, can avoid the accessory substance that may generate under the high temperature.But adopt fluid bed that the catalytic activity and the mechanical strength of catalyst are had higher requirement.
It is A that the present invention develops structural formula with this purpose 2+ aB 2+ bC 3+ cD 3+ dO 4X (α (γ)-Fe 2O 3) ferrite-iron oxide type butylene oxidation-dehydrogenation catalyst, make it to adapt to the requirement of guiding plate washer fluid bed.
Detailed description of the present invention.
The present invention is that the butylene oxidation-dehydrogenation system butadiene of Chrome-free or low chromium content, high oxidation iron ratio is with ferrite-iron oxide composite catalyst.This catalyst is with ZnFe 2O 4And Fe 2O 3Be main body, and contain II on the periodic table of elements A, II B, III BThe composite oxides of forming with more than one element of VIII family.II AFamily mainly comprises Mg, Ca, Sr and Ba, II BFamily mainly comprises Zn and Cd, VI BFamily mainly refers to Cr, Mo and W, and VIII family mainly is Ni and Co.
Oxide that Li, P, As, Sb, Bi, La, Ce, Pr, Nd, Sm, Eu, Dy, Er are arranged and Cl as co-catalyst -Deng.
Total body catalyst consists of:
A 2+ aB 2+ bC 3+ cD 3+ dO 4·X〔α（γ）-Fe 2O 3〕
A represents Zn, Mg etc. in the formula, and B represents Ca, Ba, Sr and Ni etc., and C represents Cr, Ni, Bi, La, Ce, Pr, Nd, Sm, Eu, Dy and Er etc.; A is 0.0～1.0, and b is 0～1.0, and c is 0.01～0.8, and d is 1.2～2.0; X is 0～60%(weight).
Preparation of catalysts, except that adopting coprecipitation commonly used, also part adopts mixing method, and co-precipitation is generally NH with precipitating reagent 4OH and (NH 4) 2CO 3, with NH 4OH is main.The just precipitation that coprecipitation mode has the dropping alkaline precipitating agent that material liquid pH value is changed from small to big, also available anti-precipitation is just to be precipitated as the master.
The raw material salt solution concentration is counted 10～50 grams per liters with metal ion content.
Precipitating reagent concentration is 1.0～6.0 molar concentrations.
When just precipitating, precipitating reagent adding speed is controlled to reach in 10～100 minutes to give decides endpoint pH.The endpoint pH of precipitation is looked and is formed difference, in 4～11 variations.
Post precipitation, filter cake are washed Polyester 2～6 times, and each water consumption is 1/10th to times of raw material salt solution preparation water, wash Polyester water water temperature and be room temperature～80 ℃.
Raw material salt solution preparation water and gelatinous precipitate are washed the Polyester water and can be used deionized water, distilled water, the running water of also available low alkali ion concentration.
Dry under 60～110 ℃ through the filter cake of washing Polyester, filter after doing, be 24～48 hours drying time.
Dried filter cake, be warming up to 600～700 ℃ after, stopped 6～24 hours, reduce to 100 ℃ of dischargings then.Heating can be an air with heat carrier, also can be the flue gas of 5～10% oxygen concentrations.
Catalyst behind the high-temperature activation has clear and definite crystal phase structure.The feature d value of its x-ray diffraction collection of illustrative plates is:
Zn aCr bFe 2-bO 4(by the relative intensity size sequence):
2.54,1.49,2.99,1.62,2.11 and 1.72
Mg aCr bFe 2-bO 4(by the relative intensity size sequence):
2.52,1.47,4.83,2.09,1.61 and 2.96
Figure 861081528_IMG2
α-Fe 2O 3(by the relative intensity size sequence):
2.51,2.69,1.48,1.69,1.84 and 1.45
Figure 861081528_IMG3
γ-Fe 2O 3(by the relative intensity size sequence):
2.52,2.95,1.61,3.75,2.09 and 1.70
Figure 861081528_IMG4
The specific surface of catalyst is 10～40 meters 2/ gram.
Adopt catalyst of the present invention, under suitable reaction condition, n-butene can highly transform, and highly selective changes into butadiene.
When making reaction raw materials, just, iso-butane do not transformed by catalyst of the present invention with c4 fraction; Isobutene will generate oxygenatedchemicals and deep oxidation product to transform with the similar conversion ratio of n-butene; When isobutene is 0.3～3.0(mole as impurity, its content of n-butene raw material) during %, the amount that is converted into oxygenatedchemicals is very few, is 10～20% of isobutene in the charging, or accounts for 15～30% of converted isobutylene, is acetone more than 90% of relative quantity wherein.
In oxidative dehydrogenation process, oxygen donator of n-butene raw material and certain mol proportion (as air) and water vapour together pass through beds.
In the present invention, oxygen alkene is than adopting 0.5～0.9(mol ratio), optimum range is 0.6～0.75.
In the present invention, water alkene ratio be 6～15(rub  dental caries  T closely question cangue horsefly egg Chuo dice  foretell from ζ bangs school   ┍ appoint～the 12(mol ratio), generally adopt 8～10, can obtain the reaction result of anticipation.
In the present invention, reaction temperature is 250～450 ℃, and optimum range is 300～380 ℃.
N-butene air speed (GHSV) is 200～1000 hours -1, with 250～500 hours -1Be best air speed scope.Be 0.08～2 second time of contact.
The catalyst bed stressor layer is advisable with normal pressure～1.0 gauge pressures (atmospheric pressure).Every increase 0.1 atmospheric pressure of bed layer pressure, butene conversion will descend 0.3～0.5%.
Advantage that the present invention is compared with prior art had or good effect.Butylene oxidation-dehydrogenation catalyst of the present invention is by A 2+ aB 2+ bC 3+ cFe 3+ dO 4And α-Fe 2O 3, γ-Fe 2O 3Three parts are formed, and it is different from existing catalyst technology.With Zn xCr yFe 2O 4(preferred example is x=1.0, y=0.2～0.8, z=2-y) and Zn aCr bFe 2-bO 4X (α (γ)-Fe 2O 3) compare, work as a=x, b=y, during 2-y=2-b, the latter has the stability of higher butylene oxidation-dehydrogenation activity, selectivity and long-term operation than the former, and the present invention is preparation A 2+ aB 2+ bC 3+ cFe 3+ dO 4X (α (γ)-Fe 2O 3) the designed catalyst preparation process of type catalyst guaranteed that also this catalyst is for adapting to guiding plate washer fluid bed necessary mechanical strength.
Compare with existing adiabatic reactor butylene oxidation-dehydrogenation technology, on the reaction condition of the present invention, reaction temperature can be hanged down 200～250 ℃, and water alkene is than low 4～6(mol ratio); On the reaction result that the present invention obtained, the oxygenatedchemicals production rate hangs down about 30% (to unit butadiene growing amounts) and does not have organic acid and generates, and the alkynes production rate is about 1/20 of an adiabatic reactor butylene oxidation-dehydrogenation.
Realize mode of the present invention and most preferred embodiment.
The following corresponding reaction result of composition, preparation process, reaction condition and gained that gives an actual example and be used for enumerating catalyst system therefor of the present invention, but do not limit the present invention by more suitable catalyst form, preparation technology and reaction condition.
Example 1:
124.0 gram Zn(NO 3) 26E 2O, 41.5 gram Cr(NO 3) 39H 2O and 293.5 gram Fe(NO 3) 39H 2O is dissolved in 2 liters of distilled water, and adding concentration with fast speeds under constantly stirring is 13%(weight) NH 4OH solution made the pH value of precipitated solution reach 9 in 5 minutes.Stir after 10 minutes and filter, filter cake is given a baby a bath on the third day after its birth inferior with 65 ℃ hot distilled water, and each water consumption is 0.4 liter, and the filter cake after filter is done is put into the drying in oven of 110 ℃ of constant temperature and spent the night, and moves into muffle furnace then, is warming up to 650 ℃ of activation 10 hours.The cooling back is taken out broken, sifts out 20-60 order sample for activity rating.At catalyst-assembly is on the thermostatic type fixed bed of 5-10 milliliter, is 400 hours in 360 ℃, butylene air speed -1, oxygen alkene is than for the 0.7(mole), water alkene is than being the 12(mole) reaction condition can obtain butadiene once through yield 87.0% down, the butylene conversion per pass is 97.4%, the selectivity of generation butadiene is 89.3%.
Example 2
?the dosage of salt, chromic salts and molysite and example 1 with.Add NH 4After OH solution to the pH value of mother liquor is 9, is heated to 90 ℃ and stirred 30 minutes.Filter cake is given a baby a bath on the third day after its birth inferior with 650 ℃ of distilled water, each water consumption is 0.4 liter.Filter cake is broken after 10 hours in 110 ℃ of dryings, 650 ℃ of activation, sieve, get 20～60 mesh sieve branches and carry out the butylene oxidation-dehydrogenation activity rating, appreciation condition is with example 1, and reaction result is the butadiene yield: 86.2%, butene conversion: 94.7%, butadiene selectivity: 91.0%.
Example 3
In 1 liter of distilled water, dissolve in 24.8 gram Zn(NO 3) 26H 2O, 8.3 gram Cr(NO 3) 39H 2O and 58.7 gram Fe(NO 3) 39H 2O.Under agitation dripping concentration is 13%(weight) NH 4OH solution added and to make mother liquor terminal point pH=8.5 in 40 minutes.Filter the back and at room temperature wash Polyester three times with distilled water, each water consumption is 0.1 liter.Be filtered to dried filter cake and put into baking oven, 120 ℃ are spent the night.Dried filter cake in muffle furnace in 650 ℃ of following calcinations 10 hours.Through broken, sieve, get the sample that the 20-60 mesh sieve divides and carry out activity rating.Appreciation condition is a reaction temperature: 380 ℃, butylene air speed 120 hours -1, oxygen alkene ratio: the 0.70(mol ratio) and water alkene ratio: in the time of the 8(mol ratio), the butadiene yield be 65.6%, butene conversion is 79.1%, selectivity is 82.9%.
Example 4
Take by weighing Zn(NO 3) 26H 2O 124.0 grams, Cr(NO 3) 39H 2O 41.5 gram and Fe(NO 3) 39H 2O 332.0 gram adds distilled water and makes its dissolving for 2 liters, and under agitation adding concentration in 15 minutes is 10%(weight) NH 4OH solution makes terminal point pH=9.This gelatinous precipitate is filtered after leaving standstill 2 hours under 75 ℃, and filter cake is washed 5 times with 40 ℃ distillation, and each water consumption is 0.2 liter, and the baking oven of filtering 110 ℃ of dried gained filter cake immigration constant temperature at last spends the night.650 ℃ of calcinations 10 hours and through broken, gained 20～60 mesh sieve divided catalyst samples sieve, gained butylene oxidation-dehydrogenation reaction result is under the identical appreciation condition: butadiene yield=87.6% having with example 1, butene conversion 96.9%, the selectivity that generates butadiene is 90.6%.
Example 5
In 3 liters of distilled water, dissolve in 246.4 gram Zn(NO in succession 3) 26H 2O, 156.4 gram Cr(NO 3) 39H 2O and 588.0 gram Fe(NO 3) 39H 2Behind the O.Drip 14%(weight with fast speed) NH of concentration 4OH solution reaches 9 until the pH of precipitated liquid value.It is inferior to give a baby a bath on the third day after its birth with 70 ℃ distilled water after filtering, and each water yield is 0.4 liter.Filter cake after filter is done at last is following dry 30 hours in 120 ℃.Dried filter cake moves to muffle furnace, 650 ℃ of calcinations 10 hours.Getting catalyst that 20～60 mesh sieves divide on the guiding plate washer fluid bed of 20 millimeters of diameters, is 360 ℃, butylene air speed 350 hours in reaction temperature -1, oxygen alkene is than for the 0.68(mol ratio), water alkene is than being the 12(mol ratio) and normal pressure turned round 150 hours continuously down, average result is: butadiene yield 71%, butene conversion 78% and selectivity 91%.
Example 6
Fe(NO 3) 39H 2O 592.5 grams, Cr(NO 3) 39H 2O 83.9 gram and Zn(NO 3) 26H 2O 246.4 grams are dissolved in 3 liters of distilled water in succession.Adding concentration under constantly stirring in 20 minutes is 10%(weight) ammoniacal liquor make pH=9.Filter the back and wash once for 0.4 liter with distilled water earlier, add 0.4 liter of distilled water making beating again and be heated to 85 ℃, left standstill 2 hours.Filter and with 60 ℃ thermal distillation washing twice, water consumption is 2 liters at every turn.Filter cake moved in the muffle furnace in 650 ℃ of following calcinations 10 hours then in 110 ℃ times dry 20 hours.In 340 ℃, butylene air speed 400 hours -1, oxygen alkene is than 0.70(mol ratio), water alkene is than 12(mol ratio) and normal pressure under evaluation result be: butadiene yield=84.7%, butene conversion=90.4%, selectivity=93.7%.
Example 7
1 liter is dissolved with 123.2 gram Zn(NO 3) 26H 2O, 15.7 gram Cr(NO 3) 39H 2O and 294.0 gram Fe(NO 3) 39H 2The solution of O is loaded in the separatory funnel of 2 liters of molten amounts.Another capacity is that the 0.6 liter of concentration of packing in 1 liter the separatory funnel is 13%(weight) NH 4OH solution.Get the beaker of 3 liters of capacity, in put a small amount of distilled water and begin and stir.Under agitation regulate the flow velocity of two kinds of solution in two separatory funnels, make its in 20～30 minutes and stream add, give and decide terminal point pH=9.Filter immediately after adding, filter cake adds 0.4 liter of distilled water and left standstill under 85 ℃ 3 hours, and filter cake is washed Polyester three times, 0.4 liter of each water consumption.Other are with example 6.Reaction result is: butadiene yield=71.0%, butene conversion=74.8%, selectivity=95.0%.
Example 8
64.2 gram Mg(NO 3) 26H 2O, 192.3 gram Fe(NO 3) 39H 2O and 10.0 gram Cr(NO 3) 39H 2O dissolves in 1 liter of distilled water in succession, stirs to add 14%(weight down) NH of concentration 4OH solution, terminal point pH=11.It is inferior to give a baby a bath on the third day after its birth under room temperature with distilled water after filtering, and each water consumption is 0.2 liter.Other are with example 1.In reaction temperature is that 400 ℃ of gained reaction results are: butadiene yield=65.2%, selectivity=90.6% of butene conversion=72.0% and generation butadiene.
Example 9
481.5 gram Fe(NO 3) 39H 2O, 68.2 gram Cr(NO 3) 39H 2O, 87.75 gram Mg(NO 3) 26H 2O and 101.25 gram Zn(NO 3) 26H 2O is dissolved in 2 liters of distilled water in succession, adds NH under the condition identical with example 8 4OH becomes glue.Wore out 0.5 hour down in 85 ℃, cool off naturally then and leave standstill after 5 hours and filter.Filter cake is given a baby a bath on the third day after its birth inferior, uses 0.15 liter of distilled water at every turn.Other preparation process and appreciation condition are with example 8 butadiene yield=80.1%.Selectivity=89.4%.
Example 10
In 2.5 liters of distilled water, dissolve in 427.0 gram Fe(NO in succession 3) 39H 2O, 60.4 gram Cr(NO 3) 39H 2O and 154.8 gram Mg(NO 3) 2, 6H 2O.Stirring and dripping concentration down is 13%(weight) ammoniacal liquor, added to pH=11 in 20 minutes and stop, other processes are with example 8.Dried filter cake is in 780 ℃ of following calcinations 10 hours, is that 320 ℃, butylene air speed are 400 hours in reaction temperature -1, oxygen alkene is than for the 0.65(mol ratio), water alkene is than being the 12(mol ratio) and normal pressure under carry out the butylene oxidation-dehydrogenation evaluation, its result is: butadiene yield=35.1%, butene conversion=36.7% and selectivity=95.6%.
Example 11
79.5 gram Fe(NO 3) 39H 2O, 33.4 gram Zn(NO 3) 26H 2O and 12.2 gram Ce(NO 3) 36H 2O is dissolved in 0.5 liter of distilled water.Stir that to add concentration down be 13%(weight) ammoniacal liquor to pH=9, add in the process of ammoniacal liquor, keeping temperature is 30 ℃.Add behind the ammoniacal liquor precipitated liquid is heated to boil and make its boiling half an hour after filter while hot.Wash three times, use 50 milliliters of distilled water at every turn.All the other are with example 1, and evaluation result is: butadiene yield 60%, selectivity 80%.
Example 12
In 1 liter of distilled water, dissolve in Fe(NO in succession 3) 39H 2O 171.2 grams.Ni(NO 3) 26H 2O 11.7 grams, Zn(NO 3) 26H 2O 45.0 gram and Mg(NO 3) 26H 2O 5.2 grams.Stir down, being added dropwise to concentration is 10%(weight) sal volatile to pH=8.5.Other conditions are with example 8.(other reaction conditions are with example 1) carries out the butylene oxidation-dehydrogenation evaluation under 345 ℃, the butadiene yield be 76.0%, butene conversion be 80.9% and selectivity be 93.9%.
Example 13
Make 2 liters to include 350.1 gram Fe(NO by example 12 usefulness sal volatiles 3) 39H 2O, 21.9 gram Ni(NO 3) 26H 2O, 9.7 gram Mg(NO 3) 26H 2O and 84.1 gram Zn(NO 3) 26H 2The solution of O generates precipitation, terminal point pH=9.After filtration, wash after Polyester and filter do, evenly sneak into and be dissolved with 2.6 gram LiNO 3The aqueous solution.Drying, 650 ℃ of calcinations were got 20-60 mesh sieve branch and are carried out the butylene oxidation-dehydrogenation activity rating after 10 hours.The same example of other appreciation conditions.When reaction temperature was 400 ℃, obtaining the butadiene yield was 71.7%, and butene conversion is 78.3%, selectivity 91.6%.
Example 14
In 10 liters of distilled water, dissolve in Fe(NO in succession 3) 39H 2O 1399.8 grams, Cr(NO 3) 39H 2O 149.8 gram and Zn(NO 3) 26H 2O 556.3 grams.Adding concentration under constantly stirring in 30 minutes is 13%(weight) ammoniacal liquor make terminal point pH=9.Stir half an hour down in 80 ℃ before filtering, cooling was left standstill 2 hours naturally subsequently.Wash Polyester after the filtration 5 times, use 2 liters of 60 ℃ of distilled water at every turn.The short column that the back extrusion becomes 3 * 6 millimeters of φ is done in filter, and drying is 30 hours under 110 ℃, moves into muffle furnace then in 680 ℃ of calcinations 16 hours.Take out the strip catalyst fragmentation and sieve, get 20-60 mesh sieve branch and carry out fluid bed and pressurization static bed catalyst activity, selectivity and estimation of stability.
On the guiding plate washer fluid bed of 20 millimeters straight warps, adopt 360-870 ℃ of reaction temperature, butylene air speed 350 hours -1, oxygen alkene is than 0.68(mol ratio) and water alkene than 12(mol ratio) and the reaction condition of normal pressure, running is 1012 hours continuously, average response result and final result all are: butadiene once through yield=61%, butene conversion=68%, selectivity=90%, oxygenatedchemicals production rate 0.5%(is to butene feed), wherein there is not organic acid, unsaturated aldehyde is a trace.Alkynes content is about 20ppm in the generation gas.
In gauge pressure 9.8 * 10 4On the thermostatic type fixed bed of Pa, when reaction condition is: reaction temperature=350 ℃, butylene air speed 300 hours -1, oxygen alkene is than 0.70(mol ratio), water alkene is than 12(mol ratio), bed layer pressure is gauge pressure 9.8 * 10 4Carry out butylene oxidation-dehydrogenation reaction 1000 hours during Pa continuously, its average result and final result all are: butadiene once through yield=65%, butene conversion=72%, selectivity=90%, the oxygenatedchemicals production rate is that 0.6%(is to butene feed), oxygenatedchemicals is mainly acetone, and unsaturated aldehyde, copper are trace, and no organic acid generates.Alkynes concentration is about 20ppm in the generation gas.
Example 15
Steel cuttings 220.5 gram is dissolved in concentration and is 54% HNO 3In, the nitric acid dosage of 54% concentration is 2.5 liters.After all dissolving, adding distil water or low Na +6.5 liters in content running water.Take by weighing ZnO 163.6 gram and Cr(OH) 329.1 gram adds a certain amount of low Na +Running water or distilled water make the mixture of the two become the thin pulp shape.Add to stir giving in the pretipitatin jar that is added with iron liquid earlier down subsequently, treat that all dissolving back dropping concentration is 10%(weight) ammoniacal liquor, reach terminal point pH=9 in 30 minutes.Heat ageing half an hour, take advantage of heat filtering, with hot distilled water or low Na +Wash from the beginning 5 times, each water consumption is 3 liters.Filter is done, extrusion, 90 ℃ of dryings 36 hours, dry sample calcination 16 hours in 680 ℃ flue gas.On guiding plate washer fluid bed, be that 360～370 ℃, butylene air speed are 300h in reaction temperature -1, oxygen alkene ratio is 0.65～0.70(mol ratio), water alkene ratio is 8～10(mol ratio), bed layer pressure is 4.9 * 10 4The Pa(gauge pressure) time, turned round continuously 1380 hours, the butadiene once through yield is 62～68%, butene conversion 67～75%, and selectivity 90～92%, the oxygenate production rate is lower than 0.6%(to butene feed), it is formed with example 14.The alkynes production rate is that 0.01%(is to butene feed), wherein more than 90% vinylacetylene.This example is one of most preferred embodiment.
Example 16
1590 gram Fe(NO 3) 39H 2O and 113 gram Cr(NO 3) 39H 2O is dissolved in 5 liters of low Na +In the running water, stir that to add concentration down be 10%(weight) ammoniacal liquor, make coprecipitated thing reach terminal point pH=8 in 20 minutes.Coprecipitated thing is 80 ℃ of down aging half an hour, and cooling was left standstill 3 hours naturally then.Filter, with 65 ℃ of low Na +Running water is given a baby a bath on the third day after its birth inferior, and each water consumption is 1 liter.Claim ZnO 85 grams, with an amount of low Na +Running water stirs pulp with ZnO, adds to Fe(OH then) 3Cr(OH) 3In the coprecipitated thing, it is fully mixed.100 ℃ moved in the muffle furnace after dry 36 hours down, 680 ℃ of calcinations 16 hours.Fragmentation is got 20-70 mesh sieve branch and is estimated on guiding plate washer fluid bed, and reaction condition is with example 14, and the gained result is: butadiene yield 75%, butene conversion 80%, selectivity 94%.
Aforesaid various embodiments of the present invention also can adopt the implementer to think mass unit and relevant other unit easily, the importantly condition according to the invention of the correlation between them.

Claims (14)

1, a kind of butylene oxidation-dehydrogenation system butadiene ferrous acid saline catalyst is characterized in that its general structure is: A 2+ aB 2+ bC 3+ cFe 3+ dO 4X[α (γ)-Fe 2O 3], A comprises Zn, Mg etc. in the formula, and B comprises Ca, Ba, Sr and Ni etc., and C comprises Cr, Ni, Bi, La, Ce, Pr, Nd, Sm, Eu, Dy and Er etc.:
A=0～1.0, b=0～1.0, c=0.01～0.8, d=1.2～2.0; X=10～60% (weight), the specific area of catalyst are 10～40m 2/ g.
2, catalyst as claimed in claim 1 is characterized in that, when the general formula of catalyst is: Zn aCr cFe dO 4X (α (γ)-Fe 2O 3) time, a=1, c=0.05～0.6, c+d=2, X=10～60%(weight).
3, catalyst as claimed in claim 2 is characterized in that, general formula Zn aCr cFe dO 4X (α (γ)-Fe 2O 3) in, a=1, c=0.2～0.5, c+d=2, X=30～50%(weight), the specific area of catalyst is 15～25m 2/ g.
4, catalyst as claimed in claim 1 is characterized in that, when the catalyst general formula is Zn aMg bCr cFe dO 4X (α (γ)-Fe 2O 3) time, a=0.2～0.8, b=0.2～0.8, c=0.05～0.6, c+d=2, X=10～60%(weight).
5, catalyst as claimed in claim 4 is characterized in that, general formula Zn aMg bCr cFe dO 4X (α (γ)-Fe 2O 3) in, a=0.5～0.8, b=0.2～0.5, c=0.2～0.6, c+d=2, X=20～50%(weight).
6, catalyst as claimed in claim 1 is when the catalyst general formula is Zn aMg bNi cFe dO 4X (α (γ)-Fe 2O 3) time, a=0.2～0.8, b=0.1～0.7, c=0.1～0.3, c+d=2, X=10～60%(weight).
7, catalyst as claimed in claim 1 is characterized in that, in the coprecipitation process, makes precipitating reagent with ammoniacal liquor or ammonium carbonate.
8, catalyst as claimed in claim 1 is characterized in that, 30～90 ℃ of aging temperatures, hot water wash Polyester, 40～90 ℃ of hot water temperatures.
9, catalyst as claimed in claim 3 is characterized in that, adopts guiding plate washer fluidized-bed reactor.
As claim 3,9 described catalyst, it is characterized in that 10, reaction temperature is 280～450 ℃.
As claim 3,9 described catalyst, it is characterized in that 11, oxygen alkene ratio is 0.5～0.9(mol ratio).
As claim 3,9 described catalyst, it is characterized in that 12, water alkene ratio is 8～12(mol ratio).
As claim 3,9 described catalyst, it is characterized in that 13, butylene air speed (GHSV) is 200～1000h -1; Be 0.08～2 second time of contact.
14, a kind of ferrous acid saline catalyst that is used for butylene oxidation-dehydrogenation system butadiene is characterized in that, general formula is A 2+ aB 2+ bC 3+ cFe 3+ dO 4X (α (γ)-Fe 2O 3) catalyst, be to activate in 5～10% the flue gas in containing oxygen, activation temperature is 580～750 ℃.
CN 86108152 1986-11-27 1986-11-27 Butylene oxidation-dehydrogenation catalyst Expired CN1013247B (en)

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