CN105749930A - Catalyst used for butylene oxidative dehydrogenation to prepare butadiene, and preparation method thereof - Google Patents
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 catalyst used for butylene oxidative dehydrogenation to prepare butadiene, and a preparation method thereof. The method comprises the following steps: dividing a 40-100 mesh metal precursor A into 55-70wt% and 30-45wt%, and uniformly mixing metal precursors B, C and D, wherein A is one of Cu, Zn and Cr, B is one of Co, Mn, Ni and Mo, C is one of Ca, Sr, Ba and Mg, and D is W; gradually adding 55-70wt% of the metal precursor A to an iron nitrate solution, adding the metal precursors B, C and D, adding the remaining 30-45% of the metal precursor A, reacting above materials, and adding a binder to obtain a precursor precipitate slurry; adjusting the pH value of the slurry to 7.5-10; and carrying out thermal modification, washing the obtained product, carrying out spray molding to obtain catalyst microspheres, and carrying out roasting modification on the catalyst microspheres at 400-500DEG C for 6-12h to obtain the finished catalyst. The catalyst prepared through adopting the method has high catalysis activity and good stability.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method for Oxidative Dehydrogenation of Butene into Butadiene.
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)), in formula, A is Zn, 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, 0.01～18.0wt%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 the Catalysts and its preparation method providing a kind of novel high conversion and selective Oxidative Dehydrogenation of Butene into Butadiene.
Summary of the invention
The present invention provides the Catalysts and its preparation method of a kind of Oxidative Dehydrogenation of Butene into Butadiene.Adopt coprecipitation to prepare catalyst pulp, prepare a kind of Catalysts and its preparation method for Oxidative Dehydrogenation of Butene into Butadiene again through spray shaping.
For achieving the above object, the invention provides a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene, described catalyst is represented by formula (I):
AaBbCcDd·FexOe(I)
Wherein: A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C is Ca, Sr, Ba or Mg；D is W；A is 1～6, and b is 0.01～0.3, and c is 0.1～1.0, and d is 0.01～0.1, and x is 4～18, and e takes any number meeting valency requirements.
Catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein a preferably 3～5, b preferably 0.05～0.15, c preferably 0.3～0.6, d preferably 0.04～0.08, x preferably 7～13.
The preparation method that present invention also offers a kind of catalyst for Oxidative Dehydrogenation of Butene into Butadiene, comprises the steps:
(1) metal precursor A, B, C, D are ground to respectively the microspheroidal of 40～100 orders, by ground metal precursor B, C, D 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 metal precursor B, C, D of mixing, add second part of metal precursor A after reacting 30-90 minute, add binding agent 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) filtering, use washings filtering stock, regulating slurry solid content is 5～40%, and makes slurry pH value reach 7～7.5；
(6) spray shaping, roasting 6～12 hours at 400～500 DEG C, obtain the catalyst for Oxidative Dehydrogenation of Butene into Butadiene；
Wherein, A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C is Ca, Sr, Ba or Mg；D is W；The mol ratio of A:B:C:D is 1～6:0.01～0.3:0.1～1.0:0.01～0.1.
The preparation method of the 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 55～70% and second part of 30～45% by weight percentage.
The preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said metal precursor A, B, C, D are preferably selected from least one in the group being made up of their nitrate, chloride, sulfate, oxide respectively.
The preparation method of the 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, and the addition of wherein said binding agent is preferably the 0.1～4% of metal precursor gross mass.
The preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the addition of wherein said binding agent is preferably the 1～2% of metal precursor gross mass.
The preparation method of the 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 catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, the concentration of wherein said iron nitrate solution is preferably 0.3～1.0mol/L.
The preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, in wherein said step (2), preferred reaction adds binding agent after 40～60 minutes.
The preparation method of the 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 catalyst for Oxidative Dehydrogenation of Butene into Butadiene of the present invention, wherein said spray shaping preferably employs spray tower and completes, and the feeding temperature of wherein said spray tower is preferably 300～500 DEG C, and discharging opening temperature is preferably 100～150 DEG C.
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 55～70% and 30～45% two part by metal precursor A parts by weights, and substep adds.By metal precursor B, C and D 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 zinc nitrate 892.5g, B cobalt nitrate 29.1g, C magnesium chloride 80.8g, D Tungstic anhydride. 12g used is ground to the microspheroidal of 80 orders；Secondly, zinc nitrate is divided into 491g and 401.5g two parts in the ratio of 55% and 45%, by cobalt nitrate, magnesium chloride, nickel nitrate mix homogeneously；
(2) iron nitrate solution of 10L0.7mol/L is configured, under agitation, first 491g zinc nitrate is added gradually in iron nitrate solution, react 60 minutes, it is slow added into the mixture of cobalt nitrate, magnesium chloride, nickel nitrate, it is slow added into the zinc nitrate of 401.5g after reacting 60 minutes, adds binding agent methylcellulose 48g after reacting 40 minutes, obtain the sedimentary slurry of presoma；
(3) ammonia of dropping 20% in 20 minutes backward slurries of stirring, 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) making slurry pH value reach 7.0 with distilled water wash slurry, solid content reaches 15%；
(6) by slurry by spray shaping tower, controlling inlet temperature is 450 DEG C, and outlet temperature is 220 DEG C.Obtain the catalyst microspheres that particle diameter is 150 μm～210 μm；Then modification by calcination 10 hours at 450 DEG C, obtain finished catalyst.Mainly comprising as Zn of catalyst3Co0.1Mg0.4W0.05·Fe7O14.1。
Embodiment 2
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L0.8mol/L, metal precursor is ground to the microspheroidal of 60 orders, precursor A is divided into 60% and 40% two part, adding respectively 50 minutes and the 40 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: A copper sulfate 996g, B ammonium dimolybdate 8.5g, C calcium chloride 131.4g, D Tungstic anhydride. 17g.Sesbania powder 67g is added after reacting 40 minutes.Stirring the ammonia dripping 15% in 20 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.Using tap water slurry, make slurry pH value reach 7.5, solid content reaches 25%.By slurry by spray shaping tower, controlling inlet temperature is 400 DEG C, and outlet temperature is 100 DEG C.Modification by calcination 12 hours at 420 DEG C again, obtain mainly comprising as Cu4Mo0.05Ca0.0.6W0.07·Fe8O16.8Finished catalyst.
Embodiment 3
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L1.2mol/L, metal precursor is ground to the microspheroidal of 100 orders, precursor A is divided into 65% and 35% two part, adding respectively 40 minutes and the 30 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: A chromic nitrate 2000g, B nickel nitrate 45g, C barium chloride 41.6g, D Tungstic anhydride. 7g.Polyacrylamide powder 125g is added after reacting 60 minutes.Stirring the ammonia dripping 15% in 20 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.Using desalted water filtering stock, make slurry pH value reach 7.2, solid content reaches 20%.By slurry by spray shaping tower, controlling inlet temperature is 350 DEG C, and outlet temperature is 150 DEG C.Modification by calcination 6 hours at 500 DEG C again, obtain mainly comprising as Cr5Ni0.15Ba0.2W0.03·Fe12O23.4Finished catalyst.
Embodiment 4
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.5mol/L, metal precursor is ground to the microspheroidal of 40 orders, precursor A is divided into 70% and 30% two part, adding respectively 30 minutes and the 50 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 595g, manganese sulfate 33.8g, strontium chloride 212.8g, Tungstic anhydride. 10g.Polyacrylamide powder 30g is added after reacting 50 minutes.Stirring the ammonia dripping 15% in 20 minutes backward slurries, regulating slurry pH value is 9.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Using deionized water wash slurry, make slurry pH value reach 7.4, solid content reaches 35%.By slurry by spray shaping tower, controlling inlet temperature is 450 DEG C, and outlet temperature is 120 DEG C.Modification by calcination 10 hours at 430 DEG C again, obtain mainly comprising as Zn2Mn0.2Sr0.8W0.04·Fe10O18.1Finished catalyst.
Embodiment 5
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.85mol/L, metal precursor is ground to the microspheroidal of 50 orders, precursor A is divided into 60% and 40% two part, adding respectively 70 minutes and the 90 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 1785g, nickel nitrate 90g, calcium chloride 197.1g, Tungstic anhydride. 5g.Polyvinyl alcohol 36g is added after reacting 50 minutes.Stirring the ammonia dripping 25% in 20 minutes backward slurries, regulating slurry pH value is 8.0, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.With tap water and distilled water wash slurry, making slurry pH value reach 7.2, solid content reaches 30%.By slurry by spray shaping tower, controlling inlet temperature is 380 DEG C, and outlet temperature is 280 DEG C.Modification by calcination 10 hours at 450 DEG C again, obtain mainly comprising as Zn6Ni0.3Ca0.9W0.02·Fe17O32.7Finished catalyst.
Embodiment 6
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.3mol/L, metal precursor is ground to the microspheroidal of 90 orders, precursor A is divided into 55% and 45% two part, adding respectively 80 minutes and the 60 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: chromic sulfate 1200g, cobaltous sulfate 44g, magnesium oxide 60.6g, Tungstic anhydride. 19g.Sesbania powder 65g is added after reacting 60 minutes.Stirring the ammonia dripping 22% in 20 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.With desalted water and deionized water wash slurry, making slurry pH value reach 7.2, solid content reaches 32%.By slurry by spray shaping tower, controlling inlet temperature is 420 DEG C, and outlet temperature is 110 DEG C.Modification by calcination 8 hours at 480 DEG C again, obtain mainly comprising as Cr3Co0.15Mg0.3W0.08·Fe6O12.7Finished catalyst.
Embodiment 7
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L0.4mol/L, metal precursor is ground to the microspheroidal of 70 orders, precursor A is divided into 60% and 40% two part, adding respectively 90 minutes and the 80 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: copper sulfate 996g, cobalt nitrate 6g, calcium oxide 109.5g, Tungstic anhydride. 21g.Methylcellulose 59g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 20 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 90 minutes.With distilled water and desalted water filtering stock, making slurry pH value reach 7.0, solid content reaches 28%.By slurry by spray shaping tower, controlling inlet temperature is 430 DEG C, and outlet temperature is 100 DEG C.Modification by calcination 10 hours at 450 DEG C again, obtain mainly comprising as Cu4Co0.02Ca0.5W0.09·Fe4O10.8Finished catalyst.
Embodiment 8
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 20L0.5mol/L, metal precursor is ground to the microspheroidal of 70 orders, precursor A is divided into 65% and 35% two part, adding respectively 60 minutes and the 70 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 1487.5g, ammonium dimolybdate 8.5g, barium chloride 208g, Tungstic anhydride. 2.5g.Polyvinyl alcohol element 120g is added after reacting 50 minutes.Stirring the ammonia dripping 20% in 20 minutes backward slurries, regulating slurry pH value is 8.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 90 minutes.Using tap water slurry, make slurry pH value reach 7.0, solid content reaches 30%.By slurry by spray shaping tower, controlling inlet temperature is 380 DEG C, and outlet temperature is 130 DEG C.Modification by calcination 12 hours at 400 DEG C again, obtain mainly comprising as Zn5Mo0.05Ba1W0.01·Fe10O21.1Finished catalyst.
Embodiment 9
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 10L0.7mol/L, metal precursor is ground to the microspheroidal of 40 orders, precursor A is divided into 70% and 30% two part, adding respectively 30 minutes and the 90 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 297.5g, manganese sulfate 25.4g, strontium chloride 266g, Tungstic anhydride. 13.9g.Sesbania powder 68.6g is added after reacting 40 minutes.Stirring the ammonia dripping 25% in 20 minutes backward slurries, regulating slurry pH value is 10.0, and under 85 DEG C of constant temperature, slurry is carried out heat modification 100 minutes.Using deionized water wash slurry, make slurry pH value reach 7.0, solid content reaches 35%.By slurry by spray shaping tower, controlling inlet temperature is 500 DEG C, and outlet temperature is 150 DEG C.Modification by calcination 10 hours at 450 DEG C again, obtain mainly comprising as Zn1Mn0.15Sr1W0.06·Fe7O12.8Finished catalyst.
Embodiment 10
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 13L1.0mol/L, metal precursor is ground to the microspheroidal of 50 orders, precursor A is divided into 60% and 40% two part, adding respectively 90 minutes and the 30 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 1785g, nickel nitrate 14.9g, calcium chloride 21.9g, Tungstic anhydride. 23.1g.Polyacrylamide 71g is added after reacting 80 minutes.Stirring the ammonia dripping 10% in 60 minutes backward slurries, regulating slurry pH value is 7.5, and under 85 DEG C of constant temperature, slurry is carried out heat modification 120 minutes.With tap water and distilled water wash slurry, making slurry pH value reach 7.5, solid content reaches 30%.By slurry by spray shaping tower, controlling inlet temperature is 300 DEG C, and outlet temperature is 100 DEG C.Modification by calcination 12 hours at 400 DEG C again, obtain mainly comprising as Zn6Ni0.05Ca0.1W0.1·Fe13O26Finished catalyst.
Embodiment 11
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 60L0.3mol/L, metal precursor is ground to the microspheroidal of 90 orders, precursor A is divided into 55% and 45% two part, adding respectively 90 minutes and the 60 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: chromic sulfate 1200g, cobaltous sulfate 87.3g, magnesium oxide 101g, Tungstic anhydride. 2.3g.Polyvinyl alcohol 8.7g is added after reacting 60 minutes.Stirring the ammonia dripping 20% in 20 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.With desalted water and deionized water wash slurry, making slurry pH value reach 7.2, solid content reaches 5%.By slurry by spray shaping tower, controlling inlet temperature is 400 DEG C, and outlet temperature is 125 DEG C.Modification by calcination 6 hours at 500 DEG C again, obtain mainly comprising as Cr3Co0.3Mg0.5W0.01·Fe18O30.8Finished catalyst.
Embodiment 12
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 40L0.1mol/L, metal precursor is ground to the microspheroidal of 70 orders, precursor A is divided into 60% and 40% two part, adding respectively 60 minutes and the 90 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: copper sulfate 1245g, cobalt nitrate 2.9g, calcium oxide 131.4g, Tungstic anhydride. 18.5g.Sesbania powder 120.6g is added after reacting 20 minutes.Stirring the ammonia dripping 15% in 60 minutes backward slurries, regulating slurry pH value is 8.0, and under 85 DEG C of constant temperature, slurry is carried out heat modification 90 minutes.With distilled water and desalted water filtering stock, making slurry pH value reach 7.0, solid content reaches 15%.By slurry by spray shaping tower, controlling inlet temperature is 500 DEG C, and outlet temperature is 150 DEG C.Modification by calcination 10 hours at 450 DEG C again, obtain mainly comprising as Cu5Co0.01Ca0.6W0.08·Fe4O11.9Finished catalyst.
Embodiment 13
Catalyst preparation process presses embodiment 1, the iron nitrate solution of configuration 5L2.0mol/L, metal precursor is ground to the microspheroidal of 70 orders, precursor A is divided into 65% and 35% two part, adding respectively 60 minutes and the 70 minutes response time of metal precursor two minor tick, the consumption of each metal precursor is: zinc nitrate 1190g, ammonium dimolybdate 17g, barium chloride 62.4g, Tungstic anhydride. 9.24g.Methylcellulose 79.8g is added after reacting 50 minutes.Stirring the ammonia dripping 20% 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.Using tap water slurry, make slurry pH value reach 7.3, solid content reaches 40%.By slurry by spray shaping tower, controlling inlet temperature is 380 DEG C, and outlet temperature is 130 DEG C.Modification by calcination 12 hours at 400 DEG C again, obtain mainly comprising as Zn4Mo0.01Ba0.3W0.04·Fe10O19.5Finished catalyst.
Comparative example 1
Preparing catalyst by the preparation process of embodiment 1, but metal precursor is not ground, precursor A zinc nitrate is not drawn to points two parts.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
Catalyst packing embodiment prepared is in small-sized fluidized bed reactor, with butylene for raw material, is 380 DEG C in reaction temperature, and butylene volume space velocity is 800h-1, oxygen/alkene ratio is 0.7, and water/alkene ratio carries out catalyst when being 12 and evaluates continuously, and butadiene productivity (%) and the butadiene selective (%) of each catalyst are still higher, and detailed results is 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 92～95%.The poor catalyst stability of comparative example 1 preparation, after 500h, the productivity of butadiene is only 27.8%, and the catalyst activity of comparative example 2 preparation is poor, and the productivity of initial reaction stage butadiene is only 60.2%.Metal precursor used is ground by the present invention, and is 55～70% and 30～45% two part by metal precursor A parts by weights, and substep adds.By metal precursor B, C and D 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 greater than 77.0%.It addition, catalyst preparation process adds pro-oxidant tungsten, it is effectively increased the activity of catalyst.The butadiene productivity of embodiment is more than 78.8%, and activity is good.Comparative example 1 and 2 productivity and selectivity are decreased obviously, poor stability, and activity is low.
Claims (13)
1. the catalyst for Oxidative Dehydrogenation of Butene into Butadiene, it is characterised in that described catalyst is represented by formula (I):
AaBbCcDd·FexOe(I)
Wherein: A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C is Ca, Sr, Ba or Mg；D is W；A is 1～6, and b is 0.01～0.3, and c is 0.1～1.0, and d is 0.01～0.1, and x is 4～18, and e takes any number meeting valency requirements.
2. the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 1, it is characterised in that: a is 3～5, and b is 0.05～0.15, and c is 0.3～0.6, and d is 0.04～0.08, and x is 7～13.
3., for a preparation method for the catalyst of Oxidative Dehydrogenation of Butene into Butadiene, it is the preparation method of catalyst described in claim 1 or 2, it is characterised in that comprise the steps:
(1) metal precursor A, B, C, D are ground to respectively the microspheroidal of 40～100 orders, by ground metal precursor B, C, D 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 metal precursor B, C, D of mixing, add second part of metal precursor A after reacting 30-90 minute, add binding agent 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) filtering, use washings filtering stock, regulating slurry solid content is 5～40%, and makes slurry pH value reach 7～7.5；
(6) spray shaping, roasting 6～12 hours at 400～500 DEG C, obtain the catalyst for Oxidative Dehydrogenation of Butene into Butadiene；
Wherein, A is Cu, Zn or Cr；B is Co, Mn, Ni or Mo；C is Ca, Sr, Ba or Mg；D is W；The mol ratio of A:B:C:D is 1～6:0.01～0.3:0.1～1.0:0.01～0.1.
4. 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 (1), metal precursor A is divided into first part of 55～70% and second part of 30～45% by weight percentage.
5. the preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterised in that described metal precursor A, B, C, D are respectively selected from least one in the group being made up of their nitrate, chloride, sulfate, oxide.
6. the preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterized in that described binding agent is at least one in the group selecting free sesbania powder, polyacrylamide, methylcellulose, polyvinyl alcohol to form, the addition of wherein said binding agent is the 0.1～4% of metal precursor gross mass.
7. the preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 6, it is characterised in that the addition of described binding agent is the 1～2% of metal precursor gross mass.
8. the preparation method of the 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.
9. the preparation method of the 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 0.3～1.0mol/L.
10. 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 (2), reaction added binding agent after 40～60 minutes.
11. 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 (4), modification time is 90～120 minutes.
12. the preparation method of the catalyst for Oxidative Dehydrogenation of Butene into Butadiene according to claim 3, it is characterized in that described spray shaping adopts spray tower to complete, the feeding temperature of wherein said spray tower is 300～500 DEG C, and discharging opening temperature is 100～150 DEG C.
13. 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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