CN105749928A - Supported catalyst used for butylene oxidative dehydrogenation to prepare butadiene, and preparation method thereof - Google Patents
Supported catalyst used for butylene oxidative dehydrogenation to prepare butadiene, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a supported catalyst used for butylene oxidative dehydrogenation to prepare butadiene, and a preparation method thereof. The method is characterized in that the butylene oxidative dehydrogenation catalyst is prepared through co-precipitation, dipping, roasting modification and grinding molding steps, and the general formula of the prepared catalyst is AaBbCcDd.FexOe, wherein A is one of Cu, Zn, Cr and Ni, B is one of Co, Mn, Mo and Sn, C is one of Ca, Sr, Ba and Mg, and D is W. The catalyst is used in fixed bed butylene oxidative dehydrogenation for preparing butadiene, the butadiene yield is 77-82%, and the butadiene selectivity is 92-95%.
Description
Technical field
The present invention relates to a kind of loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene and preparation method thereof, belong to catalysis technical field.
Background technology
1,3-butadiene is petrochemical industry base stock and the important monomer producing high molecular synthetic material, and the status in petrochemical industry olefin feedstock is only second to ethylene and propylene.Have in synthetic rubber and organic synthesis etc. and have been widely used, the multiple rubber products such as butadiene rubber (BR), butadiene-styrene rubber (SBR), nitrile rubber, SBS elastomer (SBS), acrylonitrile-butadiene-styrene (ABS) (ABS) resin can be synthesized, additionally can be used for producing adiponitrile, hexamethylene diamine, nylon66 fiber, 1, the Organic chemical products such as 4-butanediol and be used as bonding agent, gasoline additive etc., purposes is very extensive.
The source of world's butadiene mainly has two kinds, and one is from oil plant C4(normal butane and n-butene) fraction dehydrogenation obtains；Another is the mixing C from ethylene cracker by-product4In fraction, extracting obtains, and method for extracting is cheap, economically preponderates, and is always up the main source of butadiene, accounts for the 90% of butadiene total output.But in recent years, due to the lighting of the developed country such as Middle East and America and Europe ethylene cracking material, ethylene cracker is by-product butadiene no longer.And the fast development of auto industry makes the demand to rubber increase severely gradually, the demand as elastomeric primary raw material butadiene also grows with each passing day.Owing to the reason of these two aspects causes that butadiene is in great short, big bulge in price.Therefore, by oil refining apparatus and ethylene unit by-product Oxidative Dehydrogenation of Butene into Butadiene, it is high added value butadiene by the butenc of low value, not only meets the market demand, and improve economic benefit and the competitiveness of enterprise, it is considered as the following important process route producing butadiene gradually.
The preparation method that Chinese patent CN102716754A discloses a kind of butadiene catalyst made by butylene oxidation dehydrogen for fluidized-bed reactor, the method by metal precursor and alkaline matter 10～90 DEG C, pH be 5～11 times slurries being obtained by reacting containing insoluble compound, by slurries filtration and wash to pH be 7～7.5；Adding appropriate binding agent, deionized water and stirring, regulating slurry solid content is 10%～50%；Gained slurry carries out spray drying granulation by spraying drying granulating equipment, feeding temperature be 200 DEG C～400 DEG C, outlet temperature be 100 DEG C～160 DEG C, obtain catalyst microspheres；By catalyst microspheres dry 1～24h, roasting 4～24h at 500 DEG C～900 DEG C at baking temperature 80 DEG C～200 DEG C, obtain finished catalyst.The formula obtaining catalyst is FeXaYbZcOdWherein X is one or more in Ni, Co, Zn, Cu, Sn, Mn, Y is one or more in Bi, Mo, Cr, V, La, Zr, Z is one or more in Mg, Ca, Sr, Ba, a is 0.1～3, b is 0～1, and c is 0～1, and the value of d meets the valent requirement of other metallic element.This catalyst delays Oxidative Dehydrogenation butadiene for butylene, at temperature 300～400 DEG C, normal pressure, water/alkene mol ratio 6～16, oxygen/alkene mol ratio 0.4～1.0, butylene volume space velocity 100～600h-1When, butadiene productivity is 76%～86%, and butadiene selective is 94～97%.The shortcoming of this catalyst is that treating capacity is less, and full airspeed is only 600h-1；It addition, this catalyst has only carried out the evaluation test of 6h, the stability of catalyst can not be guaranteed.
Chinese patent CN1184705A discloses a kind of fluid bed iron group catalyst for producing butadiene by oxidative dehydrogenation of bytylene, and this catalyst is by three kinds or more bivalent metal ion and Fe3+Composition, its general structure is, Aa 2+Bb 2+Cc 2+Fe2O4·X(α-Fe2O3), (when catalyst Formula is: ZnaCab-CoeFe2O4·X(α-Fe2O3) time, a=0.8-0.9, a+b+c=1, X=15-65% (weight).Formula ZnaCabCocFe2O4·X(α-Fe2O3) in, a=0.8-0.9, b=0.03-0.08, a+b+c=1, X=20-40% (weight)) A is Zn in formula, B is selected from Mg, Ca, Sr, one or both elements in Ba, the C a kind of element in Ni, Co, a=0.1-0.9, b=0.01-0.1, a+b+c=1, X=15-65% (weight).It is characterized in that doing precipitant with ammonia, precipitation terminal pH is 8.2～8.7, and precipitation aging temperature is 50～95 DEG C, time 30min, filtration washing, after filtration, filter cake and 100～120 DEG C dry, time is 12～24h, and activation temperature is 640～700 DEG C, and the time is 10～20h.When this catalyst is for Oxidative Dehydrogenation of Butene into Butadiene shelf fluidized bed reactor, at temperature 310～420 DEG C, normal pressure, water/alkene mol ratio 8～12, oxygen/alkene mol ratio 0.56～0.9, butylene volume space velocity 150～600h-1When, butadiene yield is 70～85%, and butadiene selective is 93～96%, and the shortcoming of this catalyst is to be only applied to the shelf fluidized bed reactor being raw material with n-butene.
Chinese invention patent CN103055890A discloses the iron catalyst of a kind of n-butene oxidative dehydrogenation butadiene, it is characterized in that this catalyst is with Fe for main component, with Mg, Zn and extraction element are auxiliary agent, the quality group of catalyst becomes 48.80～60.53wt%Fe, 0.01～18.0%Mg, 0.0～15.0wt%Zn, it is 0.0～5.0wt% with other described element gross mass, all the other are oxygen element, other element is selected from Ba, Ca, Ni, Co, Cu, Cr, p, Si, Al, V, Ti, Mo, Sn, Sb, Zr, Mn, one or more in K and rare earth element.When this catalyst is used for fixing bed Oxidative Dehydrogenation of Butene into Butadiene, at temperature 260～445 DEG C, normal pressure, water/alkene mol ratio 12～25, oxygen/alkene mol ratio 0.42～0.90, butylene volume space velocity 180～600h-1When, the yield of butadiene is only up to 72.8%.The shortcoming of this catalyst is that treating capacity is less, and full airspeed is only 600h-1；It addition, the butadiene yield of this catalyst is relatively low.
Chinese invention patent CN102824914A discloses a kind of method for n-butene oxidative dehydrogenation butadiene, and the method utilizes cobalt and magnesium elements to modifiy the oxidative dehydrogenation for n-butene of the prepared iron acid zinc catalyst.But this catalyst is only applicable to n-butene, at temperature 400～450 DEG C, unstripped gas: air: water vapour volume ratio is 1:4:16, butylene volume space velocity 500～700h-1When, the yield of butadiene is only up to 77.8%.The treating capacity of catalyst is also less.
CN101674883 discloses a kind of iron acid zinc catalyst, combine with simple zinc ferrite, it is difficult to reach desirable catalytic effect, and catalyst is for fixed bed reactors, beds temperature rise is serious, energy consumption is high, can not solve catalyst wear problem on fluidized-bed reactor simultaneously.
US Patent No. 3450788 and US3450787 describe multiple different spinel structure ferric chromate butylene oxidation-dehydrogenation catalyst.Wherein spinelle ferric chromate catalyst has good Oxidative Dehydrogenation of Butene into Butadiene reactivity worth, and butylene one way molar yield is 70%, and butadiene molar selectivity is up to 92%.
The preparation method that Chinese patent CN1033013, CN101674883 and CN1184705 etc. describe the butadiene catalyst made by butylene oxidation dehydrogen based on ferrite.On these catalyst, the molar yield of butylene is generally 70-80%, and butadiene molar selectivity is 89-93%.Wherein partial monopoly once obtained commercial Application at home, but was limit by butadiene demand and technological level at that time, was forced to stop production.
The purpose of the present invention is contemplated to provide a kind of novel high conversion and selective butadiene catalyst made by butylene oxidation dehydrogen and preparation method.
Summary of the invention
It is an object of the invention to adopt the sedimentation method and infusion process to prepare a kind of loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene and preparation method thereof.
For achieving the above object, the invention provides a kind of loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene, described loaded catalyst is represented by formula (I):
AaBbCcDd·FexOe(I)
Wherein: A is Cu, Zn, Cr or Ni；B is Co, Mn, Sn or Mo；C is Ca, Sr, Ba or Mg；D is W；A is 1～7, and b is 0.05～0.4, and c is 0.01～0.6, and d is 0.01～0.1, and x is 3～16, and e takes the numerical value meeting valency requirements.
Loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein a preferably 3～5, b preferably 0.1～0.2, c preferably 0.1～0.4, d preferably 0.04～0.07, x preferably 6～12.
The preparation method that present invention also offers a kind of loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene, comprises the steps:
(1) metal precursor A, B, C are ground to respectively the microspheroidal of 40～100 orders, by ground metal precursor B, C mix homogeneously, ground metal precursor A are divided into two parts；
(2) configuration concentration is the iron nitrate solution of 0.1～2mol/L, under agitation, first part of metal precursor A is joined in iron nitrate solution, react 30-90 minute, add the metal precursor B, the C that mix, add second part of metal precursor A after reacting 30-90 minute, add binding agent and activated carbon after reacting 20～80 minutes, obtain the sedimentary slurry of presoma；
(3) stirring slurry is after 20～60 minutes, adds ammonia in slurry, and regulating slurry pH value is 7.5～10.0；
(4) being placed in by obtained slurry in step (3) under the environment of 80～95 DEG C and carry out heat modification, modification time is 60～180 minutes；
(5) filter, use washings filtering stock, make slurry pH value reach 7～7.5；
(6) slurry, roasting 6～12 hours at 100～200 DEG C, roasting 4～8 hours at 200～300 DEG C, roasting 1～4 hour at 300～400 DEG C, roasting 1～4 hour at 400～500 DEG C are filtered；
(7) the product grinding screening after roasting in step (6) being taken 60～100 orders, impregnate in the solution of metal precursor D, dipping temperature is 15～95 DEG C, and dip time is 1～24 hour；
(8) dry 4～12 hours at 100～160 DEG C, activate 6～24 hours at 400～550 DEG C, obtain the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene；
Wherein, A is Cu, Zn, Cr or Ni；B is Co, Mn, Mo or Sn；C is Ca, Sr, Ba or Mg；D is W；The mol ratio of A:B:C:D is 1～7:0.05～0.4:0.01～0.6:0.01～0.1.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (1), metal precursor A is preferably divided into first part of 60～80% and second part of 20～40% by weight percentage.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said metal precursor A, B, C are preferably selected from least one in the group being made up of their nitrate, chloride, sulfate, oxide respectively.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said metal precursor solution D is preferably the ammonium tungstate of 0.01～0.6mol/L.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said metal precursor solution D is preferably the ammonium tungstate of 0.1～0.3mol/L.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said binding agent is preferably selected from least one in the group being made up of sesbania powder, polyacrylamide, methylcellulose, polyvinyl alcohol.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the addition of wherein said binding agent is preferably the 0.1～3% of metal precursor gross mass, and the addition of described activated carbon is preferably the 0.5～5.0% of metal precursor gross mass.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the addition of wherein said binding agent is preferably the 0.5～2% of metal precursor gross mass, and the addition of described activated carbon is preferably the 1～3% of metal precursor gross mass.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the pH value in wherein said step (3) is preferably 8.0～9.0.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the concentration of wherein said iron nitrate solution is preferably 0.4～1.2mol/L.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (2), preferred reaction adds binding agent and activated carbon after 40～60 minutes.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (4), modification time is preferably 90～120 minutes.
The preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (7), dip time is preferably 8～16 hours.
The preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (5), washings are preferably selected from least one in the group being made up of deionized water, distilled water, desalted water, tap water.
The preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, butene feedstock wherein used is 1-butylene, cis-2-butene or Trans-2-butene.
The preparation method of catalyst of the present invention is first metal precursor used to be ground, and is 60～80% and 20～40% two part by metal precursor A parts by weights, and substep adds, by metal precursor B and C mix homogeneously.Each active component homogeneous nucleation in catalyst preparation process can be enable, improve the stability of catalyst；It addition, catalyst preparation process adds pro-oxidant tungsten, the activity of catalyst can be effectively increased.Catalyst is at 600～1000h-1Air speed under, reaction 500h after still can obtain higher butadiene productivity.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, but the present invention is not by the restriction of following embodiment.The change of any design without departing from the present invention and category, is within the scope of the present invention.
Embodiment 1
(1) first, metal precursor A copper sulfate 996g, B cobalt nitrate 58.5g, C calcium chloride 66g is ground to the microspheroidal of 40 orders；Secondly, copper sulfate is divided into 598g and 398g two parts in the ratio of 60% and 40%.By cobalt nitrate and calcium chloride mix homogeneously.
(2) iron nitrate solution of 20L0.4mol/L is configured, under agitation, the copper sulfate of 598g is added gradually in iron nitrate solution, react 30 minutes, it is slow added into the mixture of cobalt nitrate and calcium chloride, add the copper sulfate of 398g after reacting 90 minutes, after reacting 40 minutes, add activated carbon 90g, sesbania powder 44g；
(3) ammonia of dropping 15% in stirring 30 minutes backward slurries of slurry, regulating slurry pH value is 8.0；
(4) slurry is placed under 85 DEG C of constant temperature and slurry is carried out heat modification 90 minutes；
(5) filter slurry and use distilled water wash slurry, making slurry pH value reach 7.0；
(6) slurry, modification by calcination 12 hours at 140 DEG C, modification by calcination 7 hours at 240 DEG C, modification by calcination 3 hours at 360 DEG C, modification by calcination 2 hours at 470 DEG C are filtered；
(7) catalyst after modification by calcination grinds screening and takes the catalyst of 60～100 orders, and the catalyst after screening impregnates 10 hours in the ammonium tungstate solution of 2L0.3mol/L, and dipping temperature is 70 DEG C.
(8) take out catalyst to dry 10 hours at 120 DEG C, activate 12 hours at 500 DEG C.The catalyst prepared mainly comprises as Cu4Co0.2Ca0.3W0.05·Fe8O16.6。
Embodiment 2
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.6mol/L, metal precursor is ground to the microspheroidal of 80 orders, precursor A is divided into 65% and 35% two part, adding respectively 90 minutes and the 40 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: copper sulfate 1245g, manganese sulfate 17g, strontium chloride 54g.Activated carbon 94g, polyacrylamide 94g is added after reacting 60 minutes.Stirring the ammonia dripping 15% in 40 minutes backward slurries, regulating slurry pH value is 9.0, and under 85 DEG C of constant temperature, slurry is carried out heat modification 90 minutes.Filter slurry and use tap water slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 6 hours at 180 DEG C, modification by calcination 8 hours at 220 DEG C, modification by calcination 3 hours at 380 DEG C, modification by calcination 2 hours at 490 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 12 hours in the ammonium tungstate solution of 2L0.2mol/L, and dipping temperature is 90 DEG C, takes out catalyst and dries 10 hours at 160 DEG C, activates 12 hours at 550 DEG C.Obtain finished catalyst, mainly comprise as Cu5Mn0.1Sr0.2W0.07·Fe12O23.4。
Embodiment 3
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L1.0mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 70% and 30% two part, adding respectively 70 minutes and the 70 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 893g, cobalt nitrate 88g, calcium chloride 44g.Activated carbon 125g, sesbania powder 25g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.Filter slurry and use desalted water filtering stock, making slurry pH value reach 7.2.Filter slurry, modification by calcination 12 hours at 150 DEG C, modification by calcination 4 hours at 290 DEG C, modification by calcination 2 hours at 380 DEG C, modification by calcination 2 hours at 470 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 15 hours in the ammonium tungstate solution of 2L, 0.05mol/L, and dipping temperature is 60 DEG C, takes out catalyst and dries 10 hours at 140 DEG C, activates 12 hours at 500 DEG C.Obtain finished catalyst, mainly comprise as Zn3Co0.3Ca0.2W0.01·Fe10O18.5。
Embodiment 4
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L0.5mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 75% and 25% two part, adding respectively 80 minutes and the 80 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 595g, stannous chloride 91g, magnesium chloride 81g.Activated carbon 105g, polyvinyl alcohol 60g is added after reacting 50 minutes.Stirring the ammonia dripping 25% in 50 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Filter slurry and use deionized water wash slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 8 hours at 190 DEG C, modification by calcination 6 hours at 260 DEG C, modification by calcination 4 hours at 340 DEG C, modification by calcination 4 hours at 420 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 10 hours in the ammonium tungstate solution of 2L, 0.3mol/L, and dipping temperature is 30 DEG C, takes out catalyst and dries 10 hours at 130 DEG C, activates 12 hours at 440 DEG C.Obtain finished catalyst, mainly comprise as Zn2Sn0.4Mg0.04W0.04·Fe5O10.3。
Embodiment 5
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L0.9mol/L, metal precursor is ground to the microspheroidal of 80 orders, precursor A is divided into 80% and 20% two part, adding respectively 90 minutes and the 50 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 2083g, manganese sulfate 9g, barium chloride 21g.Activated carbon 280g, methylcellulose 20g is added after reacting 50 minutes.Stirring the ammonia dripping 25% in 50 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Filter slurry and use tap water slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 12 hours at 120 DEG C, modification by calcination 6 hours at 260 DEG C, modification by calcination 4 hours at 340 DEG C, modification by calcination 2 hours at 450 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 18 hours in the ammonium tungstate solution of 2L, 0.3mol/L, and dipping temperature is 50 DEG C, takes out catalyst and dries 10 hours at 110 DEG C, activates 12 hours at 500 DEG C.Obtain finished catalyst, mainly comprise as Zn7Mn0.05Ba0.1W0.05·Fe9O20.7。
Embodiment 6
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L1.1mol/L, metal precursor is ground to the microspheroidal of 100 orders, precursor A is divided into 65% and 35% two part, adding respectively 30 minutes and the 70 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: chromic nitrate 2400g, cobalt nitrate 88g, strontium chloride 14g.Activated carbon 140g, polyacrylamide 175g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.Filter slurry and use tap water slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 12 hours at 150 DEG C, modification by calcination 6 hours at 240 DEG C, modification by calcination 4 hours at 350 DEG C, modification by calcination 2 hours at 460 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 6 hours in the ammonium tungstate solution of 2L, 0.5mol/L, and dipping temperature is 80 DEG C, takes out catalyst and dries 10 hours at 100 DEG C, activates 12 hours at 530 DEG C. and obtain finished catalyst, mainly comprise as Cr6Co0.3Sr0.05W0.06·Fe11O22.9。
Embodiment 7
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L1.3mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 60% and 40% two part, adding respectively 60 minutes and the 60 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: chromic nitrate 1200g, manganese sulfate 68g, magnesium chloride 101g.Activated carbon 260g, sesbania powder 100g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.Filter slurry and use deionized water wash slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 8 hours at 150 DEG C, modification by calcination 4 hours at 280 DEG C, modification by calcination 3 hours at 370 DEG C, modification by calcination 2 hours at 450 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 16 hours in the ammonium tungstate solution of 2L, 0.2mol/L, and dipping temperature is 40 DEG C, takes out catalyst and dries 10 hours at 110 DEG C, activates 12 hours at 470 DEG C.Obtain finished catalyst, mainly comprise as Cr3Mn0.4Mg0.5W0.05·Fe13O23.5。
Embodiment 8
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.7mol/L, metal precursor is ground to the microspheroidal of 40 orders, precursor A is divided into 70% and 30% two part, adding respectively 50 minutes and the 30 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: nickel nitrate 1450g, ammonium dimolybdate 34g, strontium chloride 160g.Activated carbon 220g, methylcellulose 130g is added after reacting 60 minutes.Stirring the ammonia dripping 18% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Filter slurry and use deionized water wash slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 6 hours at 190 DEG C, modification by calcination 6 hours at 260 DEG C, modification by calcination 4 hours at 300 DEG C, modification by calcination 4 hours at 400 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 12 hours in the ammonium tungstate solution of 2L, 0.1mol/L, and dipping temperature is 70 DEG C, takes out catalyst and dries 10 hours at 100 DEG C, activates 12 hours at 420 DEG C. and obtain finished catalyst, mainly comprise as Ni5Mo0.2Sr0.6W0.02·Fe14O26.8。
Embodiment 9
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 3L2.0mol/L, metal precursor is ground to the microspheroidal of 100 orders, precursor A is divided into 65% and 35% two part, adding respectively 90 minutes and the 40 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: copper sulfate 249g, manganese sulfate 8.5g, strontium chloride 26.6g.Activated carbon 135.4g, polyacrylamide 81.2g is added after reacting 60 minutes.Stirring the ammonia dripping 10% in 40 minutes backward slurries, regulating slurry pH value is 10.0, and under 85 DEG C of constant temperature, slurry is carried out heat modification 90 minutes.Filter slurry and with tap water and distilled water wash slurry, make slurry pH value reach 7.0.Filter slurry, modification by calcination 12 hours at 100 DEG C, modification by calcination 6 hours at 400 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 12 hours in the ammonium tungstate solution of 5L0.01mol/L, and dipping temperature is 90 DEG C, takes out catalyst and dries 10 hours at 160 DEG C, activates 12 hours at 550 DEG C.Obtain finished catalyst, mainly comprise as Cu1Mn0.05Sr0.1W0.01·Fe6O10.2。
Embodiment 10
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L1.2mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 70% and 30% two part, adding respectively 70 minutes and the 70 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 2082.5g, cobalt nitrate 116.4g, calcium chloride 87.6g.Activated carbon 71.3g, sesbania powder 7.2g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.Filter slurry and with desalted water and distilled water wash slurry, make slurry pH value reach 7.2.Filter slurry, modification by calcination 12 hours at 150 DEG C, modification by calcination 4 hours at 290 DEG C, modification by calcination 2 hours at 380 DEG C, modification by calcination 2 hours at 470 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 15 hours in the ammonium tungstate solution of 2L, 0.2mol/L, and dipping temperature is 60 DEG C, takes out catalyst and dries 4 hours at 160 DEG C, activates 6 hours at 550 DEG C.Obtain finished catalyst, mainly comprise as Zn7Co0.4Ca0.4W0.1·Fe12O25.9。
Embodiment 11
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.8mol/L, metal precursor is ground to the microspheroidal of 80 orders, precursor A is divided into 80% and 20% two part, adding respectively 90 minutes and the 50 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 892.5g, manganese sulfate 16.9g, barium chloride 124.8g.Activated carbon 37.5g, methylcellulose 37.5g is added after reacting 50 minutes.Stirring the ammonia dripping 25% in 50 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Filter slurry and use tap water slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 12 hours at 120 DEG C, modification by calcination 6 hours at 260 DEG C, modification by calcination 4 hours at 340 DEG C, modification by calcination 2 hours at 450 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 18 hours in the ammonium tungstate solution of 3L, 0.1mol/L, and dipping temperature is 50 DEG C, takes out catalyst and dries 10 hours at 130 DEG C, activates 12 hours at 500 DEG C.Obtain finished catalyst, mainly comprise as Zn3Mn0.1Ba0.6W0.07·Fe16O27.8。
Embodiment 12
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 30L0.1mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 60% and 40% two part, adding respectively 60 minutes and the 60 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: chromic nitrate 2000g, manganese sulfate 34g, magnesium chloride 2g.Activated carbon 97.4g, sesbania powder 65g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.Filter slurry and with deionized water and tap water slurry, make slurry pH value reach 7.0.Filter slurry, modification by calcination 8 hours at 150 DEG C, modification by calcination 4 hours at 280 DEG C, modification by calcination 3 hours at 370 DEG C, modification by calcination 2 hours at 450 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 16 hours in the ammonium tungstate solution of 2L, 0.1mol/L, and dipping temperature is 40 DEG C, takes out catalyst and dries 10 hours at 140 DEG C, activates 12 hours at 450 DEG C.Obtain finished catalyst, mainly comprise as Cr5Mn0.2Mg0.01W0.04·Fe3O9.75。
Embodiment 13
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 22.5L0.4mol/L, metal precursor is ground to the microspheroidal of 40 orders, precursor A is divided into 70% and 30% two part, adding respectively 50 minutes and the 30 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: nickel nitrate 1160g, ammonium dimolybdate 25.5g, strontium chloride 66.5g.Activated carbon 97.8g, methylcellulose 73.3g is added after reacting 60 minutes.Stirring the ammonia dripping 18% in 60 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Filter slurry and use deionized water wash slurry, making slurry pH value reach 7.0.Filter slurry, modification by calcination 6 hours at 190 DEG C, modification by calcination 6 hours at 260 DEG C, modification by calcination 4 hours at 300 DEG C, modification by calcination 4 hours at 400 DEG C.Grind screening and take the catalyst of 60～100 orders.Catalyst after screening impregnates 12 hours in the ammonium tungstate solution of 3L, 0.2mol/L, and dipping temperature is 70 DEG C, takes out catalyst and dries 10 hours at 100 DEG C, activates 12 hours at 400 DEG C. and obtain finished catalyst, mainly comprise as Ni4Mo0.15Sr0.25W0.06·Fe9O18。
Comparative example 1
Preparing catalyst by the preparation process of embodiment 1, but metal precursor is not ground, precursor A copper sulfate is not drawn to points two parts, and cobalt nitrate, calcium chloride do not carry out premixing.Each metal precursor is added sequentially in the iron nitrate solution configured.
Comparative example 2
Catalyst preparation process presses embodiment 1, but does not add tungsten in catalyst preparation process.
Evaluating catalyst method of testing
In Catalyst packing prepared by embodiment and small-sized fixing stream flower beds reactor, with mixed butene for raw material, it is 380 DEG C in reaction temperature, butylene volume space velocity 800h-1, oxygen/alkene ratio is 0.7, and water/alkene ratio carries out catalyst when being 12 and evaluates continuously, and after plant running 500h, the butadiene productivity (%) of each catalyst and butadiene selective (%) result are in Table 1.
Table 1 butadiene productivity and selectivity
As can be seen from Table 1, the catalyst of embodiment 1～8 preparation is after reaction 500h, and the productivity of butadiene remains to reach 77～81%, and the selectivity of butadiene is 91～94%.The poor catalyst stability of comparative example 1 preparation, after 500h, the productivity of butadiene is only 23.8%, and the catalyst activity of comparative example 2 preparation is poor, and the productivity of initial reaction stage butadiene is only 48.3%.Metal precursor used is ground by the present invention, and is 60～80% and 20～40% two part by metal precursor A parts by weights, and substep adds, by metal precursor B and C mix homogeneously.Each active component homogeneous nucleation in catalyst preparation process can be enable, improve the stability of catalyst；After reaction 500h, the butadiene productivity of embodiment is still above 77.2%.Adding pro-oxidant tungsten in catalyst preparation process, be effectively increased the activity of catalyst, the butadiene productivity of embodiment is more than 77.8%.Activity is good.Comparative example 1 and 2 productivity and selectivity are decreased obviously, poor stability, and activity is low.
Claims (16)
1. the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene, it is characterised in that described loaded catalyst is represented by formula (I):
AaBbCcDd·FexOe(I)
Wherein: A is Cu, Zn, Cr or Ni；B is Co, Mn, Sn or Mo；C is Ca, Sr, Ba or Mg；D is W；A is 1～7, and b is 0.05～0.4, and c is 0.01～0.6, and d is 0.01～0.1, and x is 3～16, and e takes the numerical value meeting valency requirements.
2. the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that: a is 3～5, and b is 0.1～0.2, and c is 0.1～0.4, and d is 0.04～0.07, and x is 6～12.
3., for a preparation method for the loaded catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is the preparation method of the loaded catalyst described in claim 1 or 2, it is characterised in that comprise the steps:
(1) metal precursor A, B, C are ground to respectively the microspheroidal of 40～100 orders, by ground metal precursor B, C mix homogeneously, ground metal precursor A are divided into two parts；
(2) configuration concentration is the iron nitrate solution of 0.1～2mol/L, under agitation, first part of metal precursor A is joined in iron nitrate solution, react 30-90 minute, add the metal precursor B, the C that mix, add second part of metal precursor A after reacting 30-90 minute, add binding agent and activated carbon after reacting 20～80 minutes, obtain the sedimentary slurry of presoma；
(3) stirring slurry is after 20～60 minutes, adds ammonia in slurry, and regulating slurry pH value is 7.5～10.0；
(4) being placed in by obtained slurry in step (3) under the environment of 80～95 DEG C and carry out heat modification, modification time is 60～180 minutes；
(5) filter, use washings filtering stock, make slurry pH value reach 7～7.5；
(6) slurry, roasting 6～12 hours at 100～200 DEG C, roasting 4～8 hours at 200～300 DEG C, roasting 1～4 hour at 300～400 DEG C, roasting 1～4 hour at 400～500 DEG C are filtered；
(7) the product grinding screening after roasting in step (6) being taken 60～100 orders, impregnate in the solution of metal precursor D, dipping temperature is 15～95 DEG C, and dip time is 1～24 hour；
(8) dry 4～12 hours at 100～160 DEG C, activate 6～24 hours at 400～550 DEG C, obtain the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene；
Wherein, A is Cu, Zn, Cr or Ni；B is Co, Mn, Mo or Sn；C is Ca, Sr, Ba or Mg；D is W；The mol ratio of A:B:C:D is 1～7:0.05～0.4:0.01～0.6:0.01～0.1.
4. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that in described step (1), metal precursor A is divided into first part of 60～80% and second part of 20～40% by weight percentage.
5. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that described metal precursor A, B, C are respectively selected from least one in the group being made up of their nitrate, chloride, sulfate, oxide.
6. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that described metal precursor solution D is the ammonium tungstate of 0.01～0.6mol/L.
7. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 6, it is characterised in that described metal precursor solution D is the ammonium tungstate of 0.1～0.3mol/L.
8. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that described binding agent is at least one in the group selecting free sesbania powder, polyacrylamide, methylcellulose, polyvinyl alcohol to form.
9. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterized in that the addition of described binding agent is metal precursor gross mass 0.1～3%, the addition of described activated carbon is the 0.5～5.0% of metal precursor gross mass.
10. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 9, it is characterized in that the addition of described binding agent is metal precursor gross mass 0.5～2%, the addition of described activated carbon is the 1～3% of metal precursor gross mass.
11. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that the pH value in described step (3) is 8.0～9.0.
12. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that the concentration of described iron nitrate solution is 0.4～1.2mol/L.
13. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that in described step (2), reaction added binding agent and activated carbon after 40～60 minutes.
14. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that in described step (4), modification time is 90～120 minutes.
15. the preparation method of the loaded catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that in described step (7), dip time is 8～16 hours.
16. the preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that in described step (5), washings are at least one in the group selecting free deionized water, distilled water, desalted water, tap water to form.
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