CN1013247B - Butylene oxidation-dehydrogenation catalyst - Google Patents
Butylene oxidation-dehydrogenation catalystInfo
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- CN1013247B CN1013247B CN 86108152 CN86108152A CN1013247B CN 1013247 B CN1013247 B CN 1013247B CN 86108152 CN86108152 CN 86108152 CN 86108152 A CN86108152 A CN 86108152A CN 1013247 B CN1013247 B CN 1013247B
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Abstract
The present invention relates to a catalyst preapred by oxidation and dehydrogenation of butylene, which belongs to a catalyst for diene, which is prepared by oxidation and dehydrogenation of butylene. The present invention is a spinel-type catalyst, whose structural general formula is Aa<2+>Bb<2+>Cc<3+>Fed<3+>O4. X[alpha(gamma)-Fe2O3]. In the structural general formula, X is equal to 10 to 60 wt. %. When the catalyst is used for a fluidized-bed reactor with the butylene air speed of 300h<-1> and the water-butylene ratio (molar ratio) of 8 to 10 at the reaction temperature of 360 to 370 DEG C, butadiene has the yield of 62 to 68% and the selectivity of 90 to 92%.
Description
The invention belongs to olefin oxidation dehydrogenation system diolefine catalyzer.
The reaction that butylene oxidation-dehydrogenation generates divinyl 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 oxygenatedchemicalss 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 divalent-metal ion, B is Fe
3+Ion.
With Cr
3+Improve Mg
2+Fe
3+ 2O
4The stability of type catalyzer is at first by invention (USP3,450,788 such as W.L.Kehl; 3,595,810), its general formula 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 catalyzer＞0.1 meter
2/ gram.Its patent right comprises that also the catalyzer of above-mentioned prescription is in activating under 400～600 ℃ in oxygen containing inert gas atmosphere.300～500 ℃ of temperature of reaction, the reaction times 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
U.S. Petro-Tex company adopts the adiabatic reactor reactor, carry out the reaction of butylene oxidation-dehydrogenation system divinyl, the reactor outlet temperature is 580～620 ℃, water alkene is than being the 14-16(mol ratio), its reaction result is: divinyl yield 60%, selectivity 93%, oxygenatedchemicals production rate 0.7%, alkynes production rate 0.26%.
Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences once reported the test-results of butylene oxidation-dehydrogenation with Fe-series catalyst, used ZnCrFe
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 complex, 1979 731 pages), reaction conditions is: 360～420 ℃ of temperature of reaction, 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, divinyl 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 physical 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 (about 5%) α-Fe
2O
3Have the stability that helps improve iron acid zinc catalyst.
The objective of the invention is: the new texture zinc ferrite type catalyzer of developing a kind of high reactivity, highly selective, high mechanical strength, non-regeneration type.Be characterized in except that the wustite that contains spinel structure, still containing a certain amount of α-Fe
2O
3, carry out the butylene oxidation-dehydrogenation reaction in the plate washer fluidized-bed reactor that makes it to be adapted to lead.Compare with the adiabatic reactor that the U.S. adopts, the advantage of fluidized-bed is that catalyst loading and unloading is convenient, and temperature of reaction can be hanged down 200～250 ℃, can avoid the by product that may generate under the high temperature.But adopt fluidized-bed that the catalytic activity and the physical strength of catalyzer are had higher requirement.
It is A that the present invention develops structural formula with this purpose
2+ aB
2+ bC
2+ cD
3+ dO
4X[α (γ)-Fe
2O
3] wustite-iron oxide type butylene oxidation-dehydrogenation catalyst, make it to adapt to the requirement of guiding plate washer fluidized-bed.
Detailed description of the present invention.
The present invention is Chrome-free or low chromium content.The butylene oxidation-dehydrogenation system divinyl of high oxidation iron ratio wustite-ferric oxide composite catalyst.This catalyzer is with A
2+(A represents Zn or Mg) Fe
2O
4And Fe
2O
3Be main body, and contain II on the periodic table of elements
A, II
B, III
BMore than one elementary composition composite oxides with VIII family.II
ASelect among the Ca of family, Sr and the Ba a kind of, II
BAnd VI
BIn Cd, Cr, Mo and W in select one or two kind, select one among Ni of VIII family and the Co.
Oxide compound that Li, P, As, Sb, Bi, La, Ce, Pr, Nd, Sm, Eu, Dy, Er are arranged and Cl as promotor
-Deng.
Total body catalyst consists of:
A
2+ aB
2+ bC
2+ 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, Bi, La, Ce, Pr, Nd, Sm, Eu, Dy, Er etc., and D is Fe, and a is 0.8～1.0, and b is 0～1.0, and c is 0.01～0.8, and d is 1.2～2.0; X is about 60%(weight).
Preparation of catalysts, except that adopting coprecipitation method commonly used, also part adopts hybrid system, and co-precipitation is generally NH with precipitation agent
4OH and (NH
4)
2CO
3, with NH
4OH is main.The just precipitation that coprecipitation mode has the dropping alkaline precipitating agent that stock 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 strength of solution is counted 10～50 grams per liters with metal ion content.
Precipitation agent concentration is 1.0～6.0 volumetric molar concentrations.
When just precipitating, precipitation agent adding speed control reached to give in 10～100 minutes decides endpoint pH.Sedimentary endpoint pH is looked and is formed difference, in 4～11 variations.
Post precipitation, filter cake washing 2～6 times, each water consumption is 1/10th to times of raw material salt solution preparation water, the washing water water temperature is room temperature～80 ℃.
Raw material salt solution preparation water and gelatinous precipitate bath water can be used deionized water, distilled water, the tap water of also available low alkali ion content.
Filter cake after washing, filter are done is dry under 60～110 ℃, and be 24～48 hours time of drying.
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 thermal barrier, also can be the stack gas of 5～10% oxygen concns.
A
2+ aB
2+ bCr
cFe
2-cO
4X-Fe
2O
3The type catalyzer is when with Zn
2+Or Mg
2+Expression A
2+ aB
2+ bThe time, the catalyzer behind 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
cFe
2-cO
4(by the relative intensity size sequence):
2.54,1.49,2.99,1.62,2.11 and 1.72A
Mg
aCr
cFe
2-cO
4(by the relative intensity size sequence):
2.52,1.47,4.83,2.09,1.61 and 2.96A
α-Fe
2O
3(by the relative intensity size sequence):
2.51,2.69,1.48,1.69,1.84 and 1.45A
γ-Fe
2O
3(by the relative intensity size sequence):
2.52,2.95,1.61,3.75,2.09 and 1.70A
When with Ni
2+, Ca
2+, Ba
2+, Co
2+Replace Zn Deng part
2+Or Mg
2+The time, also have the spectrum peak of other features d value on the X-ray diffracting spectrum.
The specific surface of catalyzer is 10～40 meters
2/ gram.
Adopt catalyzer of the present invention, under suitable reaction conditions, n-butene can highly transform, height selectively changes into divinyl.
When making reaction raw materials, just, Trimethylmethane do not transformed by catalyzer of the present invention with c4 fraction; Iso-butylene will generate oxygenatedchemicals and deep oxidation product to transform with the similar transformation efficiency of n-butene; When iso-butylene 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 iso-butylene 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 vapor 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 is 6～15(mol ratio).In guiding plate washer fluidized-bed reactor, water alkene ratio is 8～12(mol ratio), generally adopt 8～10, can obtain the reaction result of anticipation.
In the present invention, temperature of reaction 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 duration of contact.
The catalyst bed stressor layer is advisable with normal pressure～1.0 gauge pressures (normal atmosphere).Every increase 0.1 normal atmosphere of bed layer pressure, butene conversion will descend 0.3～0.5%.
Advantage that the present invention is compared with prior art had or positively 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
zThe O(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.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 catalyzer guaranteed that also this catalyzer is for adapting to guiding plate washer fluidized-bed necessary mechanical strength.
Compare with existing adiabatic reactor butylene oxidation-dehydrogenation technology, on the reaction conditions of the present invention, temperature of reaction 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 divinyl 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 conditions 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 catalyzer form, preparation technology and reaction conditions.
Example 1:
124.0 gram Zn(NO
3)
26H
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 10 minutes after-filtration, 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 110 ℃ of homothermic drying in oven 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 conditions can obtain divinyl once through yield 87.0% down, the butylene per pass conversion is 97.4%, the selectivity of generation divinyl is 89.3%.
Example 2
The dosage of zinc salt, chromic salts and molysite and example 1 are together.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 65 ℃ 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 divinyl yield: 86.2%, butene conversion: 94.7%, divinyl 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 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 temperature of reaction: 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 divinyl 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 left standstill 2 hours after-filtration under 75 ℃, filter cake is washed 5 times with 40 ℃ distillation, and each water consumption is 0.2 liter.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: divinyl yield=87.6% having with example 1, butene conversion 96.9%, the selectivity that generates divinyl 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 catalyzer that 20～60 mesh sieves divide on the guiding plate washer fluidized-bed of 20 millimeters of diameters, is 360 ℃, butylene air speed 350 hours in temperature of reaction
-1, oxygen alkene is than for the 0.68(mol ratio), water alkene is than being the 12(mol ratio) and normal pressure under continuous operation 150 hours, average result is: divinyl 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: divinyl 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)
3, 9H
2O and 294.0 gram Fe(NO
3)
39H
2The solution of O is loaded in the separating funnel of 2 liters of molten amounts.Another capacity is that the 0.6 liter of concentration of packing in 1 liter the separating 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 separating 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, filter cake washing three times, 0.4 liter of each water consumption.Other are with example 6.Reaction result is: divinyl 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 temperature of reaction is that 400 ℃ of gained reaction results are: divinyl yield=65.2%, selectivity=90.6% of butene conversion=72.0% and generation divinyl.
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.In 85 ℃ aging 0.5 hour down, naturally cooling and leave standstill 5 hours after-filtration then.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.Divinyl 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 temperature of reaction
-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: divinyl 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 and boil and make filtered while hot after its boiling half an hour.Wash three times, use 50 milliliters of distilled water at every turn.All the other are with example 1, and evaluation result is: divinyl yield 60%, selectivity 80%.
Example 12
In 1 liter of distilled water, dissolve in Fe(NO in succession
3)
39H
2The O171.2 gram.Ni(NO
3)
26H
2O11.7 gram, Zn(NO
3)
26H
2O 45.0 gram and Mg(NO
3)
26H
2The O5.2 gram.Stir down, being added dropwise to concentration is 10%(weight) sal volatile to pH=8.5.Other conditions are with example 8.(other reaction conditionss are with example 1) carries out the butylene oxidation-dehydrogenation evaluation under 345 ℃, the divinyl 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, after washing 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 temperature of reaction was 400 ℃, obtaining the divinyl 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, naturally cooling left standstill 2 hours subsequently.Filter after scouring 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 fluidized-bed and pressurization static bed catalyst activity, selectivity and estimation of stability.
On the guiding plate washer fluidized-bed of 20 millimeters straight warps, adopt 360-370 ℃ of temperature of reaction, butylene air speed 350 hours
-1, oxygen alkene is than 0.68(mol ratio) and water alkene than 12(mol ratio) and non-pressurized reaction conditions, continuous operation 1012 hours, the average response result is: divinyl 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 conditions is: temperature of reaction=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 a gauge pressure 9.8 * 10
4Carry out butylene oxidation-dehydrogenation reaction 1000 hours during Pa continuously, its average result and net result all are: divinyl 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 tap water.Take by weighing ZnO 163.6 gram and Cr(OH)
329.1 gram adds a certain amount of low Na
+Tap 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 aging 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 ℃ stack gas.On guiding plate washer fluidized-bed, be that 360～370 ℃, butylene air speed are 300h in temperature of reaction
-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, continuous operation 1380 hours, divinyl once through yield are 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 tap 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 naturally cooling left standstill 3 hours then.Filter, with 65 ℃ of low Na
+Tap 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
+Tap water stirs pulp with ZnO, adds to Fe(OH then)
3Cr(OH)
3In the coprecipitated thing, make its thorough mixing even.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 fluidized-bed, and reaction conditions is with example 14, and the gained result is: divinyl 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 mutual relationship between them.
Claims (3)
1, a kind of butylene oxidation-dehydrogenation system divinyl 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], in the formula: A is selected from Zn and Mg, and B is Ni, and C is selected from Cr and Ce; A=0.8～1.0, b=0～1.0, c=0.01～0.8, d=1.2～2.0; X is about 60% (weight), and the specific surface area of catalyzer is 10～40m
2/ g.
2, catalyzer as claimed in claim 1, wherein catalyzer adopts the coprecipitation method preparation, makes precipitation agent with ammoniacal liquor or volatile salt.
3, catalyzer as claimed in claim 2, wherein with the exsiccant filter cake under 600-700 ℃, place the large flue gas that contains oxygen 5-10% to handle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86108152 CN1013247B (en) | 1986-11-27 | 1986-11-27 | Butylene oxidation-dehydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 86108152 CN1013247B (en) | 1986-11-27 | 1986-11-27 | Butylene oxidation-dehydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1033013A CN1033013A (en) | 1989-05-24 |
| CN1013247B true CN1013247B (en) | 1991-07-24 |
Family
ID=4803823
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108152 Expired CN1013247B (en) | 1986-11-27 | 1986-11-27 | Butylene oxidation-dehydrogenation catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1013247B (en) |
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| CN103055871A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same |
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|---|---|---|---|---|
| CN103055871A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same |
| CN103055871B (en) * | 2011-10-24 | 2015-07-01 | 中国石油化工股份有限公司 | Method for preparing butadiene from C4 aliphatic hydrocarbons by oxidative dehydrogenation and catalyst used by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1033013A (en) | 1989-05-24 |
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