CN1072110A - Butylene oxidation dehydrogenation catalyst for fluidized bed - Google Patents

Butylene oxidation dehydrogenation catalyst for fluidized bed Download PDF

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CN1072110A
CN1072110A CN91110590A CN91110590A CN1072110A CN 1072110 A CN1072110 A CN 1072110A CN 91110590 A CN91110590 A CN 91110590A CN 91110590 A CN91110590 A CN 91110590A CN 1072110 A CN1072110 A CN 1072110A
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刘俊声
李树本
陈献诚
林景治
杨凤琨
兰人杰
周士相
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

Butylene oxidation dehydrogenation catalyst for fluidized bed belongs to olefin oxidation dehydrogenation system alkadienes catalyst.The present invention is made of the composite oxides of ferrite-iron oxide.Its general structure is:
A a 2+B b 2+Fe 2 3+O 4Z (α-Fe 2O 3), A is selected from Zn, Mg in the formula, Cd, B are selected from Ba, Zn, Ni, Ca, Mg, a+b=1, Z=20-70% (weight).When this catalyst was used for butylene oxidation-dehydrogenation system butadiene shelf fluidized bed reactor, the butadiene yield was 66-75%, and butene conversion 70-80% generates butadiene selectivity 92-94%.

Description

Butylene oxidation dehydrogenation catalyst for fluidized bed
The present invention relates to olefin oxidation dehydrogenation system alkadienes with iron system spinel class catalyst, be specially adapted to deflector apron fluid bed butylene oxidation-dehydrogenation system butadiene process.
The butylene oxidation-dehydrogenation system butadiene reaction that this century, early sixties came out is quickened by the catalyst of multiple different systems, as molybdenum system, tin system, antimony system and iron system.In these catalyst systems, Fe-series catalyst is because of having relatively mild reaction condition, advantages of high catalytic activity and more single-minded selectivity and extremely people's attention.
USP3,270,080 may be the butylene oxidation-dehydrogenation Fe-series catalyst of reporting the earliest.This catalyst is the composite oxides with spinel structure, and its general formula is AB 2O 4, wherein A is generally Mg 2+, Zn 2+, Co 2+And Ni 2+Deng bivalent metal ion, B is Fe 3+Ion.But performance is not really stable.
(USP.3,450,788 such as W.L.Kell; 3,595,810) find to use Cr 6+Can improve Mg effectively 2+Fe 3+ 2O 4The stability of type Fe-series catalyst.The general formula of this class catalyst is Mg aCr bFe cO 4Or Zn A 'Cr B 'Fe C 'O 4, a wherein, a '=0.1～3; B, b '＞0～2, C＞0～3.The optimum formula that this patent is recommended consists of a, and a ' is 1, and b, b ' are 0.1～1.8, and c, c ' are 0.25～1.9, and b+c=2, and b '+c '=2 are to guarantee catalyst ZnCr B 'Fe 2-b 'O 4Or MgCr bFe 2-bO 4Structure with spinelle.The specific surface of catalyst＞0.1 meter 2/ gram, best 1 meter 2/ gram.This patent right also requires: the catalyst that comprises above-mentioned prescription is in activating in oxygen containing inert gas atmosphere under 400～600 ℃; 300～500 ℃ of reaction temperatures, the reaction time is no less than 30 minutes, and presses activation condition regeneration; 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 -1Deng.
Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences once reported the ZnCrFeO of carrier 4/ SiO 2Catalyst or carrier-free Zn aCr bFe cO 4Catalyst (a=1 wherein, b=0.25～1, c=1～1.75, result of study b+c=2), 360～420 ℃ of reaction temperatures, butylene air speed 80～120h -1, oxygen alkene is than 0.8～1.0(mole), water alkene is than 10～16(mole), reaction (secondary accumulative total) result was a butadiene once through yield 65～70% in 500 hours, selectivity 89%(petrochemical industry, 1979 years 731 pages).Thereafter, this research institute to develop structural formula again be A 2+ aB 2+ bC 2+ cFe 3+ dO 4X| α (γ)-Fe 2O 3| ferrite-iron oxide type butylene oxidation-dehydrogenation catalyst (Chinese patent 86108152), A represents Zn, Mg etc. in the formula, B represents Ca, Ba, Sr and Ni etc., C represents Cr, Ni, Bi, La, Ce, Pr, Nd, Sa, Eu, Dy and Er etc.; A=0.0～1.0, b=0～1.0, c=0.01～0.8, d=1.2～2.0; X is 0～60%(weight).
Because butylene oxidation-dehydrogenation iron system spinel catalyst has been introduced Cr 3+, make the stability of catalyst improve beyond example, activity of such catalysts and selectivity have also reached rare level, but from harsher eye, existing butylene oxidation-dehydrogenation catalyst also exists some defectives, and some then is discomforting, for example: Cr 3+To the potential impact that human and environment caused, activity of such catalysts and selectivity also have leeway of improving or the like.
The objective of the invention is to overcome the deficiency of prior art, and a kind of have more high activity and selectivity, high mechanical properties are proposed, the ferrite iron monoxide type olefin oxidation dehydrogenation of non-regeneration type, the more direct purpose of the present invention are that this catalyst is used for the butylene oxidation-dehydrogenation reaction.
Detailed description of the present invention:
The present invention is not for containing Cr 3+Use ferrite-iron oxide composite oxide catalysts etc. the butylene oxidation-dehydrogenation of non-iron trivalent metal ion, its main assembly is
A is a kind of divalent metal element in the periodic table in the formula, is selected from Zn, Mg, Cd, Pb etc.; B has been the metal of co-catalyst effect, can choose in some divalent metal element in periodic table, as: Ba, Wi, Zn, Mg, Sr, Co, Ca and Mn etc., but A, B are different elements.0.0＜a in the formula＜1.0,0.0＜b＜1.0, a+b=1.Z is a 5-70%(weight).
Purpose of the present invention can also realize by following measure:
When the catalyst general formula is Zn aCa bFe 2O 4Z| α-Fe 2O 4| the time, a=0.8-0.95, b+a=1, Z=10-70%(weight).
When the catalyst general formula is Zn aCa bFe 2O 4Z| α-Fe 2O 4| the time, a=0.85-0.95, b+a=1, Z=25-45%(weight), specific surface area of catalyst is 15-30m 2/ g.
When the catalyst general formula is Zn aMg bFe 2O 4Z| α-Fe 2O 4| the time, α=0.5-0.9, b+a=1, Z=10-70%(weight).
When the catalyst general formula is Zn aMg bFe 2O 4Z| α-Fe 2O 4| the time, a=0.7-0.9, b+a=1, Z=25-45%(weight).
When the catalyst general formula is Zn aWi bFe 2O 4Z| α-Fe 2O 4| the time, a=0.5-0.9, b+a=1, Z=10-70%(weight).
Preparation of catalysts comprises processes such as co-precipitation, mixing and decomposition activation.The precipitating reagent that co-precipitation is used is generally NH 4OH or NH 4OH and (NH 4) 2CO 3Mixture.Coprecipitation mode can be with being added drop-wise to alkaline precipitating agent the positive precipitation method that the pH value is changed from small to big, and also available the catalyst ingredients solution splashed into the anti-precipitation method in the alkaline solution.The pH value of precipitation terminal point is different and different with forming, and generally changes between 5-11.Use when just precipitating precipitating reagent to add speed and add 1% to 10% of required precipitating reagent total amount as per minute.In coprecipitation process or after co-precipitation finishes, add one or more hydroxyl organic compound or derive from the starchy material of plant, as: unary alcohol, polyalcohols, water-soluble polyvinyl alcohol or sesbania powder, starch etc., its consumption accounts for 0.1～2% of catalyst weight.
The suitable consumption of sesbania powder is 0.5～1%(weight of catalyst weight).
The raw material salt solution concentration is counted the 8-100 grams per liter with the metal ion total concentration during precipitation.
Precipitating reagent concentration: NH + 4Be 0.8-5.0 molar concentration, CO = 3Be the 0.0-0.1 molar concentration.
When catalyst prepares with coprecipitation, make precipitating reagent with ammoniacal liquor or ammonium carbonate, precipitation terminal point pH=7-9, after precipitation finished, colloidal precipitation was ground through colloid mill.
Adopt the mixed aqueous solution of ammoniacal liquor and ammonium carbonate to make precipitating reagent, CO in the precipitating reagent = 3Ion concentration is≤0.1 molar concentration.
The colloid of post precipitation needs through overaging, and aging temperature is selected between 30-90 ℃, ageing time 15-80 minute.
Above-mentioned ageing process can be divided into for two steps, and first step 50-90 ℃, the time was cooled to 30-40 ℃ of second step subsequently in 60 minutes.
Filter cake after aging should wash several times, and each water consumption is 10% to 100% of raw material salt solution preparation water consumption, and temperature of washing water is 30-80 ℃, and the filter cake pH value after the control washing is between the 7-8.8.
Filter cake after washing, filter are done is dry under 50-120 ℃, and the time is 24-72 hour.
Dried filter cake is warmed up to 580-720 ℃ of activation, keeps constant temperature 5-24 hour, cools to 100 ℃ then with bottom discharge.Heating can be main or based on the device of heat exchange pattern, when being main with heat exchange pattern, thermophore can be selected oxygen containing non-ignitibility mist for use in order to the heat radiation mode, as the flue gas of air or oxygen and inert gas gaseous mixture or 5-10% oxygen concentration etc.
When catalyst of the present invention is containing when activating in the flue gas that oxygen is 5-10%, activation temperature is 560-720 ℃, and soak time is 8-20 hour.
Catalyst behind the high-temperature activation has definite crystal phase structure.The characteristic peak d value of its x-ray diffraction collection of illustrative plates is:
Zn aFe 2O 4(by the relative intensity size sequence)
2.54,1.94,2.90,2.10,1.62 and 1.73A
Mg aFe 2O 4(by the relative intensity size sequence)
2.52,1.47,4.82,2.09,1.61 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
The specific surface of catalyst is a 15-40 rice 2/ gram.
When using catalyst of the present invention to make reaction raw materials with n-butene, under suitable reaction condition, n-butene can highly transform, highly selective generates butadiene, just, iso-butane is not transformed by catalyst of the present invention, isobutene generation deep oxidation generates COx or changes into oxygenatedchemicals, and it is similar that its conversion rate and n-butene change into the speed of butadiene.Therefore, when containing the 0.3-3.0%(mole in the n-butene raw material) isobutene impurity the time, reactant mainly is an acetone under suitable reaction condition, other oxygenatedchemicals growing amounts are very few.
Use catalyst of the present invention to carry out the butylene oxidation-dehydrogenation reaction, raw material is n-butene, oxygen donator (as air) and water vapour, the proportion of raw material is: oxygen alkene is than adopting the 0.5-1.0(mol ratio), optimum range is 0.55-0.70, water alkene is than being the 6-14(mol ratio), generally adopt 8-10 on the deflector apron fluidized-bed reactor, to obtain desired result.
On the deflector apron fluidized-bed reactor, the reaction temperature that the present invention selects for use is 280-450 ℃, and optimum range is 300-380 ℃.
On the deflector apron fluidized-bed reactor, it is 200-1000 hour that the present invention adopts n-butene air speed (GHSV) -1, with 250-450 hour -1Be optimum range.Be 0.08-2 second time of contact.
On the deflector apron fluidized-bed reactor, the catalyst bed stressor layer is with normal pressure-0.1MPa(gauge pressure) be advisable, the every increase of bed layer pressure 0.01MPa, butene conversion is with decline 0.3-0.5%.
Advantage that the present invention is compared with prior art had or good effect:
The present invention does not contain the trivalent metallic element beyond the deironing, is by divalent metal and Fe more than two kinds or two kinds 3+Ferrite iron monoxide composite oxide catalysts in conjunction with generating is different from existing catalyst.Catalyst of the present invention and Zn xCr yFe zO 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 4| (a=x, b=y is during z-y=2-b) compares, and has the stability of higher butylene oxidation-dehydrogenation activity, selectivity and long-term operation.And has suitable deflector apron fluid bed necessary mechanical strength.
Fluid catalyst technology of the present invention is compared with existing adiabatic reactor butylene oxidation-dehydrogenation technology, under the reaction condition that is adopted, reaction temperature can be hanged down 200-250 ℃, water alkene is than low 4-6(mol ratio), the reaction result of obtaining, the oxygenatedchemicals production rate is low not to detect organic acid more than 30% (to unit butadiene growing amount) in the product, the alkynes production rate is about 1/20 of an adiabatic reactor butylene oxidation-dehydrogenation.
Catalyst technology of the present invention is compared with existing shelf fluidized bed butylene oxidation-dehydrogenation technology, under close reaction condition, can obtain higher by 5% than existing technology butadiene yield, the result of butadiene selectivity high 2%, and catalyst does not contain Cr in forming 3+Etc. harmful trivalent metal.
The present invention is preparation A 2+ aB 2+ bFe 3+ 2O 4Z| α-Fe 2O 3The ︱ Catalyst Design rational preparation technology, guarantee that this catalyst is easy to amplify to produce and the necessary mechanical strength that turns round on industrial deflector apron fluid bed.
Realize mode of the present invention and most preferred embodiment
Composition, preparation process, reaction condition and the obtained corresponding result of the test of the catalyst that the example of enumerating below only is used for illustrating that the present invention uses are not made of preparation technology and reaction condition better catalyst but do not limit the present invention.
Example 1 is with 341 gram Fe(WO 3) 39H 2O, 113 gram Zn(NO 3) 26H 2O and CaO2.4 gram, sesbania powder 1 gram is dissolved in 1 liter of distilled water successively, the following 13%(weight that splashes into of quick stirring) the ammoniacal liquor and the mixed solution (1: 0.5) of 1% ammonium carbonate, whole precipitation process was finished in 10 minutes, precipitation terminal point pH=9.0, the heat ageing precipitation, in 90 ℃ of following constant temperature 30 minutes, leave standstill filtration in a hour, filter cake is with distilled water washing four times, each with 0.5 liter of distilled water, 60 ℃ of temperature.Filter cake after the washing moved into down in the muffle furnace calcination after dry 24 hours 10 hours, 650 ℃ of furnace temperature at 110 ℃.With catalyst breakage, sieve is got 20-60 mesh sieve branch, is on the flow-type constant temperature fixed bed of 10ml in the catalyst loading amount, in 360 ℃ of reaction temperatures, and butylene air speed 400 hours -1, oxygen alkene is than 0.68(mole), water alkene is than 12(mole) reaction condition under can obtain butadiene once through yield 83.4%, butylene conversion per pass 88.7% generates the result of butadiene selectivity 94.0%.
Example 2, the raw material consumption is identical with example 1, and precipitation is reached home behind the pH=9, continues to stir 10 minutes, filters.Filter cake is used 0.5 liter of distilled water with 65 ℃ of distilled water washings four times at every turn.Filter cake descended 650 ℃ of activation taking-ups after 10 hours dry 18 hours in 10 ℃.Broken, sieve, collect 20-60 mesh sieve branch and carry out the butylene oxidation-dehydrogenation activity rating, appreciation condition is with example 1.Reaction result is a butadiene yield 85.0%, and butene conversion 92.0% generates butadiene selectivity 92.3%.
Example 3,885 gram Fe(NO 3) 39H 2O, 285 gram Zn(NO 3) 26H 2O and 7.8 gram Ca(OH) 2Be dissolved in 3 liters of distilled water, co-precipitation under the room temperature, precipitating reagent is a 13%(weight) ammoniacal liquor, the precipitation endpoint pH is 8.5, precipitation ends and adds sesbania powder 2.5 grams, continues to stir 10 minutes, is heated to 80 ℃ of constant temperature 30 minutes, leaves standstill filtration in a hour.Filter cake is used 0.5 liter of 60 ℃ of distilled water with distilled water washing five times at every turn, and filter cake descended dry 24 hours at 110 ℃, and 670 ℃ activate 12 hours, get 20-60 mesh sieve branch after catalyst breakage is sieved and carry out the butylene oxidation-dehydrogenation activity rating, and condition is with example 1.Butadiene yield 73.0%, butene conversion 78.7%, butadiene selectivity 92.8%.
Example 4,430 gram Fe(NO 3) 39H 2O, 39.0 gram ZnO, 6.0 gram CaCl 2Be dissolved in 1.5 liters of distilled water, the following 13%(weight that splashes into of quick stirring) the ammoniacal liquor and the mixed solution (10: 1) of 1% ammonium carbonate, precipitation process was finished in 15 minutes, precipitation terminal point pH=8.5, add polyvinyl alcohol 1.5 grams, stirred 15 minutes, and filtered, filter cake is washed 5 times with distillation, at every turn with 0.5 liter of 60 ℃ of distilled water, filter cake grinds through colloid mill, moves into down in the muffle furnace calcination after dry 30 hours 10 hours, 650 ℃ of activation temperatures at 110 ℃.With catalyst breakage, sieve, get 20-60 mesh sieve branch and on φ 20m/m quartz baffle fluid bed, estimate, condition is 360 ℃ of reaction temperatures, butylene air speed 400 hours -1, oxygen alkene is than 0.68(mol ratio), water alkene is than 12(mol ratio), obtaining butadiene yield 75.0%, butene conversion 84.7% generates butadiene selectivity 88.5%.
Example 5,1230 gram Fe(NO 3) 39H 2O, 165.9 gram ZnCl 2, 34 gram CaCl 2, 4 gram sesbania powder are dissolved in 3 liters of distilled water, stir and splash into 10%(weight down) and the sal volatile of concentration, up to pH=8.5, be heated to 85 ℃ of constant temperature 30 minutes, be cooled fast to room temperature, filter, with 65 ℃ of distilled water washing precipitations eight times, use 1 liter of distilled water at every turn.Filter is done the back extrusion and is become 3 * 6 millimeters short columns of φ, in the baking oven 110 ℃ dry 30 hours down, 650 ℃ of activation are 16 hours in the muffle furnace.Get 20-60 mesh sieve branch after catalyst breakage sieves and carry out the catalyst activity evaluation on the quartzy deflector apron fluid bed of φ 20m/m, experimental condition is 360 ℃ of butylene air speeds of reaction temperature 400 hours -1, oxygen alkene is than 0.68(mol ratio), water alkene is than 12(mol ratio), reaction result is a butadiene once through yield 78.4%, butene conversion 83.2%, butadiene selectivity 94.2%.
Example 6,640.5 gram Fe(NO 3) 39H 2O, 118.0 gram Zn(NO 3) 26H 2O, 187.0 gram Ca(NO 3) 24H 2O is dissolved in 2 liters of distilled water, stirs fast to splash into 13%(weight down) NH of concentration 4OH solution, up to pH=9, be heated to 90 ℃ of constant temperature half an hour, left standstill 3 hours, filter, with 60 ℃ of distilled water washing 5 times, use 0.5 liter at every turn, filter cake enters 120 ℃ in baking oven and moves in the muffle furnace 670 ℃ of activation 10 hours down after dry 24 hours, on 10ml flow-type constant temperature fixed bed, estimate, the result is a butadiene yield 58.8%, butene conversion 61.8%, butadiene selectivity 95.1%.
Dissolve in Fe(NO in succession in 7,1 liters of distilled water of example 3) 39H 2The O322.6 gram, Zn(NO 3) 26H 2The O95.0 gram, Cd(NO 3) 24H 2O24.6 gram, sesbania powder 2 grams, under the room temperature, adding concentration in half an hour is 13%(weight) ammoniacal liquor, add in the ammoniacal liquor process and constantly stir, precipitation terminal point pH=9.The heat ageing precipitation, in 90 ℃ of following constant temperature 20 minutes, left standstill 2 hours, filter, with 50 ℃ of distilled water washing precipitations 3 times, each with 0.5 liter of distilled water, filter cake enters in 110 ℃ of baking ovens dry 24 hours, and 660 ℃ of activation are 8 hours in the muffle furnace, on 10ml flow-type constant temperature fixed bed, estimate, the result is a butadiene yield 61.0%, and butene conversion 73.1% generates butadiene selectivity 83.5%.
Example 8,387.0 gram Fe(NO 3) 39H 2O, 110.5 gram Mg(NO 3) 26H 2O, 14.8 gram Cd(NO 3) 24H 2O is dissolved in 1.5 liters of distilled water, the following 13%(weight that splashes into of quick stirring) ammoniacal liquor, precipitation process was finished at 15 minutes, precipitation terminal point pH=10.5 adds polyvinyl alcohol 1.5 grams, and stirring heated up after 20 minutes wears out, in 90 ℃ of following constant temperature 30 minutes, filter while hot, filter cake is used 0.5 liter of 60 ℃ of distilled water with distillation washing 4 times at every turn.Filter cake after the washing moves into dried overnight in 110 ℃ of baking ovens, and activation is 12 hours in 650 ℃ muffle furnace.With catalyst breakage, sieve is got 20-60 mesh sieve branch, estimates on 10ml flow-type constant temperature fixed bed, and the result is a butadiene yield 58.5%, butene conversion 71.7%, butadiene selectivity 81.6%.
Dissolve in Fe(NO in succession in 9,1 liters of distilled water of example 3) 39H 2The O338.0 gram, Zn(NO 3) 26H 2The O99.6 gram, MnCO 39.6 gram splashes into 10%NH under room temperature stirs fast 4OH(weight), until pH=9, finish ammonification, last 30 minutes, add farina 1.5 grams, stir, material is heated to 85 ℃, constant temperature 20 minutes leaves standstill filtration in 2 hours.Filter cake is used 0.5 liter of distilled water with 65 ℃ of distilled water washing four times at every turn, and filter cake grinds through colloid mill and was placed in 110 ℃ of baking ovens dry 24 hours, and dried filter cake activates 10 hours in muffle furnace, 650 ℃ of temperature.The catalyst that 20-60 mesh sieve branch is got in fragmentation, sieve carries out the butylene oxidation-dehydrogenation activity rating, and the result is a butadiene yield 53.0%, and butene conversion 57.3% generates butadiene selectivity 92.5%.
Dissolve in Fe(NO in succession in 10,3 liters of distilled water of example 3) 39H 2The O1024 gram, Zn(NO 3) 26H 2The O338 gram, CaCl 28 grams, sesbania powder 4.5 grams, adding concentration under the room temperature in 50 minutes is 13%(weight) ammoniacal liquor, and constantly stir, precipitation terminal point pH=8.5, heat ageing are deposited in 90 ℃ of following constant temperature half an hour, naturally leave standstill after 3 hours and filter, filter cake washing 5 times, each with 0.5 liter of the distilled water (concentration 0.1%) that contains ammonium carbonate, 60 ℃ of temperature.The short column that the back extrusion becomes 3 * 6 millimeters of φ is done in filter, 105 ℃ moved into the interior calcination of muffle furnace 12 hours down in dry 24 hours then, 650 ℃ of furnace temperature are sieved the strip catalyst fragmentation, get 20-60 mesh sieve branch and carry out catalyst activity, selective evaluation and long-term operation stability test at fluid bed.
Evaluation test and stability test are all carried out on 20 millimeters quartzy deflector apron fluid beds of φ, and experimental condition is reaction temperature 340-360 ℃, butylene air speed (GHSV) 400 hours -1Oxygen alkene is than 0.65-0.68(mol ratio), water alkene is than 12(mol ratio), turned round 1000 hours continuously under condition of normal pressure, average response is butadiene once through yield 66% as a result, butene conversion 70.6%, selectivity 93.5%, oxygenatedchemicals production rate 0.6%(is to butene feed), be mainly acetone, do not detect organic acid.Generate alkynes content 27ppm in the gas.
Dissolve in Fe(NO in succession in 11,1 liters of distilled water of example 3) 29H 2The O339.3 gram, Zn(NO 3) 26H 2The O108.7 gram, CaCl 26.0 gram, sesbania powder 1.5 gram is made solution, with 13%(weight) ammoniacal liquor splash into simultaneously in the container of a belt stirrer and carry out co-precipitation, adjust the speed that splashes into of two kinds of solution, when nitrate solution was dripped off, the pH value of precipitation was near 9.Thermal precipitation to 85 ℃, constant temperature 1 hour leaves standstill after 2 hours and filters.Filter cake washs 5 times through 65 ℃ distilled water, uses 0.3 liter of distilled water at every turn.Precipitation filter is done the back 115 ℃ baking oven inner drying 24 hours, 650 ℃ of calcinations are 12 hours in muffle furnace, get the screening of 20-60 purpose after catalyst breakage is sieved and estimate on flow-type constant temperature fixed bed, obtain butadiene yield 78.5%, butene conversion 84.2%, butadiene selectivity 93.2% result.
Example 12,84.5 gram Fe(NO 3) 39H 2O, 26.5 gram Zn(NO 3) 36H 2O, 7.5 gram CaO are dissolved in 0.5 liter of distilled water, stir that to add concentration down be 13%(weight) ammoniacal liquor to pH=8.5, precipitation is heated to 90 ℃ of constant temperature half an hour, filters while hot.Wash 4 times, use 60 ℃ of distilled water 100ml at every turn, all the other are with example 1.Butadiene yield 71.2%, butene conversion 77.1%, selectivity 92.3%.
Example 13, Cd(NO 3) 24H 2The O90.2 gram, Ca(NO 3) 24H 2The O17.3 gram, Fe(NO 3) 39H 2The O295.3 gram is dissolved in 1 liter of distilled water, the following 13%(weight that splashes into of quick stirring) ammoniacal liquor is until pH=9, heat ageing, when reaching 85 ℃, temperature adds farina 2 grams, continue to stir constant temperature half an hour, leave standstill after 2 hours and filter, with 65 ℃ of hot distilled water washing precipitations 4 times, 0.3 liter of each water consumption.Filter cake is drained and was placed in 110 ℃ of baking ovens 18 hours, transfers in the muffle furnace calcination then 10 hours, and temperature is 650 ℃, the catalyst breakage sieve is got the screening of 20-60 purpose estimate butadiene yield 53.4%, selectivity 89.8% on flow-type constant temperature fixed bed.
Dissolve in Fe(NO in example 14,1 premium on currency 3) 39H 2The O280 gram, Zn(NO 3) 26H 2The O77.3 gram, Ni(NO 3) 26H 2The O25.2 gram, sesbania powder 1.3 grams, stir and to pluck down that to add concentration be 13%(weight) ammoniacal liquor and 1%(weight) mixed solution (3: 1) of ammonium carbonate, control 25 minutes and add to pH=8.5, finish precipitation, other processes are with example 5, butadiene yield 74.4%, butene conversion 86.8%, butadiene selectivity 85.7%.
Example 15 is dissolved in Zn(NO in 1 liter of distilled water 3) 26H 2The O105.5 gram, Mg(NO 3) 26H 2O22.5 gram and Fe(NO 3) 39H 2O355.2 gram, farina 2.0 grams stir fast in 50 ℃ and to splash into 13%(weight down) ammoniacal liquor, pH=9 when precipitation finishes, leave standstill filtration in 1 hour,, divide five washing precipitations with 2 liters of 65 ℃ of distilled water, filter cake 110 ℃ dry 24 hours down, in the muffle furnace 680 ℃, activate 10 hours.With catalyst breakage, sieve, get 20-60 mesh sieve branch and on 10ml flow-type constant temperature fixed bed, estimate butadiene yield 68.3%, butene conversion 78.3%, butadiene selectivity 87.2%.
Example 16 is with Mg(NO 3) 26H 2The O97.5 gram, Fe(NO 3) 39H 2The O170.7 gram, CaCl 24.7 gram is dissolved in 1 liter of distilled water, use 13%(weight under the room temperature) ammoniacal liquor and 1% ammonium carbonate (weight) mixed solution (3: 1) co-precipitation, precipitating reagent adding speed is the 20-30 ml/min, pH=11 when precipitation finishes adds sesbania powder 1 gram, heat ageing 30 minutes, 85 ℃ of temperature, filter while hot, filter cake washs four times with 60 ℃ of distilled water, 0.3 liter of each water.Filter cake in 110 ℃ of baking ovens dry 24 hours, 650 ℃ of activation are 10 hours in the muffle furnace.Get 20-60 mesh sieve divided catalyst on 10ml flow-type constant temperature fixed bed, butadiene yield 62.5%, butene conversion 66.1%, butadiene selectivity 94.5%.
It is 54% HMO that example 17, steel cuttings 215.5 gram are dissolved in concentration 3In, 2.5 liters of the nitric acid dosage of 54% concentration, steel cuttings all adds low Na after the dissolving +5 liters of dilutions of content running water (liquid 1) mix the low Na in back with 301.5 gram ZnO and 8.7 gram CaO +Running water furnishing thin pulp shape, and joining in the liquid 1 under the quick stirring treats that all the dissolving back drips the 10%(weight) ammoniacal liquor stop ammonification to pH=8.5 sesbania powder 12.5 gram furnishing pasty states be added in the precipitation, continue to stir 20 minutes, heat ageing half an hour, 85 ℃ of temperature are filtered while hot.With 65 ℃ of low Wa +Running water washing precipitation five times, each 3 liters, with the filter cake extrusion, 105 ℃ of dryings 48 hours move in the activation furnace then with 650 ℃ of flue gas calcinations 12 hours, carry out butylene oxidation-dehydrogenation test (catalyst 20-60 order) on the deflector apron fluid bed.360 ℃ of reaction temperatures, butylene air speed 300 hours -1, oxygen alkene is than 0.65-0.68(mol ratio), water alkene is than 8-10(mol ratio), bed layer pressure is 4.9 * 10 4The Pa(gauge pressure) time, butadiene once through yield 68.0%, butene conversion 74.6% generates butadiene selectivity 91.2%, the oxygenatedchemicals production rate is lower than 0.6%(to butene feed), the unsaturated aldehyde trace does not detect organic acid and generates.Alkynes content is about 25ppm in the generation gas.
It is 54% HMO that example 18, steel cuttings 120 gram are dissolved in 1.5 liters of concentration 3In, all dissolving back 3 liters of dilutions of adding distil water (A liquid) are respectively with 575.3 gram Zn(NO 3) 26H 2O and 11.9 gram CaCl 2Add in the A liquid, treat that it all drips 10%(weight in the dissolving back) ammoniacal liquor and 1%(weight) sal volatile (10: 1 are mixed), to pH=8.0, add sesbania powder 7.5 grams and continue to stir 20 minutes, all the other processes are with example 16.The butylene oxidation-dehydrogenation result is a butadiene once through yield 73.3%, and butene conversion 78.6% generates butadiene selectivity 93.2%, and the oxygenatedchemicals production rate is lower than 0.6%(to butene feed), the unsaturated aldehyde trace does not detect organic acid.Alkynes content is about 23ppm in the generation gas.
Aforesaid various embodiments of the present invention also can adopt the implementer to think that mass unit reaches relevant other unit easily.Key is that correlation and the manufacture craft process between the material meets condition of the present invention.

Claims (12)

1, a kind of butylene oxidation-dehydrogenation system butadiene ferrous acid saline catalyst is characterized in that by bivalent metal ion and Fe more than two kinds or two kinds 3+Form, its general structure is A a 2+B b 2+Fe 2O 42| α-Fe 2O 3|, A is selected from Zn, Ng, Cd in the formula, and B is selected from Ba, Ca, Zn, Ni, Mg, 0.0＜a in the formula＜1.0,0.0＜b＜1.0, a+b=1, Z=10-70% (weight), catalyst specific surface 10-40 rice 2/ gram.
2, catalyst as claimed in claim 1 is characterized in that when the catalyst general formula being: Zn aCa bFe 2O 4Z| α-Fe 2O 3| the time, a=0.8-0.95, b+a=1, z=10-70%(weight).
3, catalyst as claimed in claim 2 is characterized in that, general formula Zn aCa bFe 2O 4Z| α-Fe 2O 3| in, a=0.85-0.95, b+a=1, z=25-45%(weight), specific surface area of catalyst is 15-30M 2/ g.
4, according to claim 1 catalyst be when the catalyst general formula be Zn aMg bFe 2O 4Z| α-Fe 2O 3| the time, a=0.5-0.9, b+a=1, z=10-70%(weight).
5, catalyst as claimed in claim 4 is characterized in that, general formula Zn aMg bFe 2O 4Z| α-Fe 2O 3| in, a=0.7-0.9, b+a=1, z=25-45%(weight).
6, catalyst according to claim 1 is when the catalyst general formula is Zn aNi bFe 2O 4Z| α-Fe 2O 3| the time, a=0.5-0.9, b+a=1, z=10-70%(weight).
7, a kind of general formula is the preparation method of the butadiene catalyst made by butylene oxidation dehydrogen of formula (I), adopts coprecipitation,
In the formula, A is selected from Zn, Mg, and Cd, B is selected from Ba, Ca, Zn, Ni, Mg is characterized in that: ammoniacal liquor or ammonium carbonate are made precipitating reagent, and the precipitation terminal point is pH=8-9; The precipitation aging temperature is 30-90 ℃, time 15-80 minute; Filter cake after washing, filter are done is dry under 50-120 ℃, and the time is 24-72 hour; Activation temperature is 580-720 ℃, time 5-24 hour; In coprecipitation process or after co-precipitation finishes, add following one or more hydroxyl organic compound or derive from the starchy material of plant: unary alcohol, polyalcohols, water-soluble polyvinyl alcohol or sesbania powder, starch etc., its consumption accounts for the 0.1-2% of catalyst weight.
8, as Preparation of catalysts method as described in the claim 7, it is characterized in that: activate in containing the flue gas that oxygen is 5-10%, activation temperature is 560-720 ℃, time 8-20 hour.
9, as Preparation of catalysts method as described in the claim 7, it is characterized in that adopting the mixed aqueous solution of ammoniacal liquor and ammonium carbonate to make precipitating reagent, CO in the precipitating reagent = 3Concentration be the 0.0-0.1 mole.
10, as Preparation of catalysts method as described in the claim 7, it is characterized in that: the precipitation aging temperature can be divided into for two steps, and first step 50-90 ℃, the time was cooled to 30-40 ℃ subsequently in 60 minutes.
11, as Preparation of catalysts method as described in the claim 7, it is characterized in that: the consumption of sesbania powder is the 0.5-1% of catalyst weight.
12, as the described catalyst of any one claim of claim 1 to 11, it is characterized in that: adopt the deflector apron fluidized-bed reactor, reaction temperature is 280-450 ℃; Oxygen alkene is than being the 8-12(mol ratio); Butylene air speed (GHSV) is 200-1000h -1; Be 0.08-2 second time of contact.
CN91110590A 1991-11-01 1991-11-01 Butylene oxidation dehydrogenation catalyst for fluidized bed Pending CN1072110A (en)

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CN102580749A (en) * 2012-02-02 2012-07-18 中石油东北炼化工程有限公司锦州设计院 Preparation technology of butadiene catalyst by oxidative dehydrogenation of butene
CN103285849A (en) * 2012-02-29 2013-09-11 北京安耐吉能源工程技术有限公司 Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation
CN103285848A (en) * 2012-02-29 2013-09-11 北京安耐吉能源工程技术有限公司 Dehydrogenation catalyst, preparation method and application thereof, and method for preparing cyclohexanone by cyclohexanol dehydrogenation
WO2014008865A1 (en) 2012-07-12 2014-01-16 上海碧科清洁能源技术有限公司 Butadiene catalyst for fluidized bed reactor prepared by oxidizing and dehydrogenating butylene, and preparation method and use thereof
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CN111054348A (en) * 2018-10-16 2020-04-24 中国石油化工股份有限公司 Process for producing butadiene
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WO2014008865A1 (en) 2012-07-12 2014-01-16 上海碧科清洁能源技术有限公司 Butadiene catalyst for fluidized bed reactor prepared by oxidizing and dehydrogenating butylene, and preparation method and use thereof
US9546118B2 (en) 2012-09-05 2017-01-17 China Petroleum & Chemical Corporation Catalyst for the oxidative dehydrogenation of butene to butadiene and preparation process thereof
US9731280B2 (en) 2012-11-21 2017-08-15 Shanghai Huayi Acrylic Acid Co. Ltd. Ferrite catalyst and preparation method thereof
CN105618064A (en) * 2014-11-26 2016-06-01 中国石油天然气股份有限公司 Preparation method of butylene oxidative dehydrogenation catalyst
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