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CN105435803A - A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst - Google Patents

A microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst Download PDF

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CN105435803A
CN105435803A CN201410429086.XA CN201410429086A CN105435803A CN 105435803 A CN105435803 A CN 105435803A CN 201410429086 A CN201410429086 A CN 201410429086A CN 105435803 A CN105435803 A CN 105435803A
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catalyst
synthesis
span
microspheroidal
solution
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CN105435803B (en
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陶跃武
庞颖聪
宋卫林
李剑锋
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to a microsphere catalyst for preparing lower hydrocarbons from synthetic gas and a preparing method of the catalyst, and mainly overcomes problems in the prior art that reaction heat dissipation is difficult when fixed beds are used, and temperature runaway can easily arise so that catalysts are liable to deactivate because reactions of synthesizing the lower hydrocarbons from the synthetic gas are strongly exothermal reactions and a problem that selectivity of lower hydrocarbons especially lower olefins is low. According to a technical scheme, an iron-based fluidized bed catalyst adopting aluminium oxide as a carrier and adopting an active component comprising a composition is adopted, with the chemical formula based on an atomic ratio being shown as Fe<100>KaZn<b>Cr<c>La<d>Ox, the synthetic gas is adopted as a raw material, and the raw material is brought into contact with the iron-based fluidized bed catalyst in a fluidized bed and reacts to produce the lower hydrocarbons. The problems are overcome by adoption of the technical scheme. The catalyst can be used for industrial synthesis of the lower hydrocarbons from the synthetic gas in fluidized beds.

Description

The Catalysts and its preparation method of microspheroidal synthesis of gas produced low-carbon hydrocarbon
Technical field
The present invention relates to the Catalysts and its preparation method of microspheroidal synthesis of gas produced low-carbon hydrocarbon.
Background technology
The method that synthesis gas is converted into hydro carbons through catalyst action is invented by Germany scientist FransFischer and HansTropsch nineteen twenty-three, be called for short F-T synthesis, namely there is heterogeneous catalysis hydrogenation in CO on metallic catalyst, generates based on the process of the mixture of linear paraffin and alkene.Germany has just carried out research and development in the twenties in last century, and achieves industrialization in 1936, closes after World War II because competing with petroleum industry economically; South Africa has abundant coal resources, but petroleum resources plaque is weary, and be subject to the restriction of international community's economy and political sanction for a long time, force its Development of Coal oils preparation industry technology, and built up in 1955 the coal-based F-T artificial oil factory (Sasol-1) that First production capacity is ten thousand tons of product/years of 25-40.
Twice world oil crisis of 1973 and 1979, cause world's crude oil price to fall and swing fluctuating, big rise and big fall, based on the consideration of Strategic Technology deposit, F-T synthetic technology arouses the interest of industrialized country again.1980 and nineteen eighty-two, South Africa Sasol company builds up again and two coal-based artificial oil factories of having gone into operation in succession.But plummeting of World oil price in 1986, has postponed the heavy industrialization process of F-T synthetic technology in other country.
Since twentieth century nineties, petroleum resources are shortage and in poor quality increasingly, and coal and natural gas proved reserves but constantly increase simultaneously, and F-T synthetic technology causes extensive concern again.At present, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world, and wherein naphtha accounts for major part, also has alkane, hydrogenated diesel oil, part heavy wet goods.Domestic and international is raw material mainly with natural gas or light petroleum fraction, steam cracking process in Ethylene Complex unit is adopted to produce low-carbon alkene, steam cracking is the large power consumption device in petrochemical industry, and rely on non-renewable petroleum resources completely, along with the day by day shortage of petroleum resources, be badly in need of finding alternate resources.So paid attention to gradually with the research work of other substitution of resources oil producing olefinic hydrocarbons, some famous oil companies and scientific research institutions have all carried out the research of this respect in the world, and achieve good achievement.
Through the development of decades, F-T synthetic catalyst have also been obtained significant progress, and fischer-tropsch synthetic catalyst generally includes following component: active metal (the VIIIth group 4 transition metal), oxide carrier or structural promoter (SiO 2, Al 2o 3deng), chemical assistant (alkali metal oxide, transition metal) and precious metal additive (Ru, Re etc.).Fe generates alkene and oxygenatedchemicals in a large number, and Ru, Co mainly generate long-chain saturated hydrocarbons, and Ni mainly generates methane.Due to easily formed during Ni compressive reaction carbonyls run off and methanation serious, Ru, Rh etc. are expensive, and catalyst conventional at present, is divided into two large classes: ferrum-based catalyst and cobalt-base catalyst active component.Co-catalyst is very large for the selective impact of low-carbon alkene, and the raising of selectivity of light olefin is mainly realized by co-catalyst, and the selection of co-catalyst and adding technique are one of key technologies of development excellent catalyst.
Co-catalyst mainly contains two classes:
(1) electron type auxiliary agent:
The interaction between catalyst and reactant can be strengthened or weaken to electron type auxiliary agent.Electron type auxiliary agent mainly contains alkali metal class and transition metal-type.
Alkali metal: Fe is catalyst based in F-T, and methane content increases within the specific limits with surface alkalinty and reduces.
Alkalinous metal auxiliary agent receives publicity as the important electronic auxiliary of the one that Fe is catalyst based.Alkali metal has significant facilitation to F-T synthesis Fe is catalyst based, and helps raise efficiency and be roughly directly proportional to basicity.After adding alkali metal compound, add the heat of adsorption of the catalyst based CO of Fe, reduce heat of adsorption and the hydrogenation capability of hydrogen, average molecular mass, the degree of unsaturation of corresponding F-T product increase, and the generation of oxygenatedchemicals increases, and methane generation reduces.
Alkali metal cation plays electronq donor to metal Fe, is promoted the chemisorbed of CO, weakens C-O key, strengthen Fe-C key by the 3d electronics of Fe, contributes to controlling the selective of catalyst.
To the research of alkali metal as auxiliary agent, mainly for K element.K auxiliary agent to the improvement of activity mainly due to its electronic auxiliary effect.K affects the electronic state of Fe catalyst surface, and Fe electric surface density is increased, thus promotes that CO Dissociative suppresses H 2absorption, thus catalyst FTS reactivity increase and methane production minimizing.There is an optimum value in K content, when exceeding optimum value, because CO Dissociative is promoted greatly, and H 2absorption is suppressed, and therefore catalyst FTS reactivity can not be further enhanced.High K content lower surface C 1species are abundant and H species lack relatively time, be conducive to the generation of long-chain macromolecule, but easily form carbon distribution, catalysqt deactivation is accelerated.
It is generally acknowledged, K 2the effect of O to F-T fused iron catalyst is: catalyst surface area is reduced, and the activity of catalyst is with K 2the increase of O content first increases rear reduction, suppresses methane generation, promotes chain growth, increase the average molecular mass of product, increase olefine selective, increase oxygenate selective, promote the generation of cementite and carbon deposit, facilitate water gas shift reaction (WGS).
Adding of K auxiliary agent contributes to catalyst Fe 2o 3the reduction of thing phase and carbonization, be easy to form undersized F-T and synthesize chief active species Fe xc crystalline phase, thus it is active to improve F-T synthetic reaction.
Copper auxiliary agent: under the F-T of routine synthesizes reducing condition, the more difficult reduction of the metal oxide during Fe is catalyst based, especially with the addition of the catalyst of alkaline assistant and carrier, because alkaline assistant is to H 2the inhibitory action of absorption and interaction between metal oxide and carrier, cause catalyst to need longer cycle in reduction process, and improving the most effective method of catalyst reduction behavior is add reduction auxiliary agent.Conventional reduction auxiliary agent has transition metal Cu, and Cu auxiliary agent can promote reduction, and reduction catalyst reaches the time required for stable state, and Cu auxiliary agent can improve the F-T synthesis of catalyst and the activity of WGS reaction.
Cu auxiliary agent adds role in Fe catalyst, is to make catalyst be easy to reduction, adds a small amount of Cu auxiliary agent, facilitates the reducing property of catalyst, reduce the initial temperature of this reduction process, increase the reduction degree of Fe.Along with Cu content increases, the chemisorbed of hydrogen first increases rear reduction.Increase with Cu content, the interaction between Cu, Fe strengthens gradually, inhibits the reduction of Fe oxide and catalyst to the chemisorbed of hydrogen on the contrary.
Cu adds in Fe – Mn catalyst makes carburizing speed increase, and does not significantly affect, the alkalescence of catalyst surface is increased, is conducive to the generation of heavy hydrocarbon, increases ethylenic alkoxy rate simultaneously the stability activity of catalyst.
In the reduction process of iron oxide, CuO plays a driving role, and reduces the reduction temperature of catalyst; Cu promotes the chemisorbed of iron catalyst, favourable to raising F-T synthesizing activity; When two auxiliary agent all exists, promote the formation of iron catalyst carbide, make Fe catalyst have lower pretreatment temperature.
CuO also has certain contribution to promotion chain growth, compares K to increase F-T reaction rate 2o is more effective, should have certain facilitation to secondary counter.As CuO, K 2the ratio match of O and Fe, the F-T synthesizing activity that catalyst can be made to have had, selective and stability, be suitable for low H 2, CO the F-T building-up process of coal based synthetic gas.
Cu auxiliary agent can accelerate Fe 2o 3reduction, when Cu content is lower, little on the selective impact of catalyst.Cu auxiliary agent can improve reduction and the carbonizing degree of catalyst, obviously increases F-T reactivity.Research finds that Cu auxiliary agent can promote Fe/SiO 2the generation of ferrous-carbide nucleus and growth in catalyst reduction and course of reaction.
In iron catalyst, introduce Cu auxiliary agent can play the effect accelerated catalyst reduction speed and strengthen catalyst activity, it obviously can reduce the reduction temperature of catalyst, the activation of promoting catalyst, this may be due to the hydrogenolysis on copper surface from Hydrogen spillover effect.
Zinc auxiliary agent: transition metal Zn is also auxiliary agent important in precipitated iron catalyst.There is structure effect and electronic effect to Fe in him, can add strong interaction, even form Fe with iron simultaneously 3-xm xo 4or (Fe (x<1) 1-xm x) 2o 3solid solution structure.Add auxiliary agent Zn and can suppress the sintering of catalyst in roasting and activation process, improve decentralization and the specific area of catalyst, but it is unfavorable for reduction and the carbonization of catalyst.The interpolation of appropriate Zn can improve activity and the stability of catalyst, but reduces the effective content of active constituent Fe due to the interaction between Zn and Fe, causes the interpolation of excessive Zn can reduce Catalyst for CO conversion ratio.Independent interpolation auxiliary agent Zn is little on selectivity of product impact, and due to Zn and other auxiliary agents, as K, Cu, exists and interact, therefore by regulating the effective content of other auxiliary agent to change product distribution.
Rare earth metal auxiliary agent: rare earth element has certain alkalescence and redox property because of it, therefore the activity and selectivity that can improve catalyst when being used as F-T catalyst promoter.
Research finds at Fe 1-xo catalyst based middle interpolation light rare earth oxide and Eu respectively 2o 3, yield of light olefins and C 5 +yield has the increase of different amplitude.Particularly add CeO 2after, significantly improve Fe 1-xlow-carbon alkene, C that O is catalyst based 5 +selective and the yield of heavy hydrocarbon.After adding rare earth oxide, the Fe of catalyst 5c 2phase content slightly increases, and Fe 5c 2crystal face physically well develop, and occurred new diffraction maximum, the unknown material of its correspondence can belong to RE mutually xfe ything phase.This new thing may be because the redox effect of rare earth oxide formed mutually, and result in rare earth oxide for Fe 1-xthe special promoting catalysis of O base fused iron catalyst.Someone have studied the effect of La auxiliary agent and Ce auxiliary agent on zirconia load ferric oxide catalyst, and research shows that adding La promotes dissociating of CO, improves CO conversion ratio, adds Ce auxiliary agent, significantly improve the decentralization of Fe.
Precious metal additive: precious metal additive not only can make the metal dispersity of catalyst increase, and the reduction of interactional nonactive phase metal oxide species can be had by Hydrogen spillover promoting catalyst surface-active phase and with carrier, thus improve the reducing property of catalyst.Temperature programmed surface reaction (TPSR) result shows, adds precious metal additive rear catalyst and strengthens the absorption dissociation capability of CO, thus the hydrogenation activity of ADSORPTION STATE CO is improved.
Other auxiliary agents: result of study shows, transition metal as Cr to CO affinity higher than Fe, it is catalyst based to be added Fe, and olefine selective can be made to improve.
(2) Structure promoter
The decentralization of active phase in catalyst can be improved, reduce the aggregation velocity of catalyst surface active component, strengthen its anti-caking power, the gathering of blocked catalysts surface active composition, increase its stability, also can improve the mechanical strength of catalyst simultaneously significantly, thus improve the F-T synthetic reaction performance of catalyst to a certain extent.The inorganic oxide of the general difficult reduction of Structure promoter, as SiO 2, Al 2o 3, MgO, ThO 2and TiO 2deng.
Carrier: be divided active component on the one hand, prevent clinkering and recrystallization, increase specific area, improve mechanical strength; Be the secondary response changing F-T synthesis on the other hand, and be elected to be with improving selective by shape.The oxide carrier that can be used as ferrum-based catalyst has a lot, as MnO, MnO 2, MgO, Al 2o 3, ThO 2, ZrO 2, TiO 2, ZnO, SiO 2deng.More typical carrier is SiO 2, Al 2o 3.
Al 2o 3have relatively weak acidity, have lower light hydrocarbon selective, it can disperse and the active phase of stable metal, produces stronger metal and auxiliary agent interphase interaction, thus exerts one's influence to the activity and selectivity of catalyst.Al 2o 3the dispersion of Cr, K auxiliary agent in ferrum-based catalyst can be promoted, and then improve the reactivity of catalyst.Al 2o 3stronger to the inhibitory action of the surface alkalinty of catalyst, Al 2o 3the catalyst of load can be formed larger ferriferous oxide crystal grain, be unfavorable for the dispersion of iron oxygen phase.
According to the difference of adopted catalyst and the difference of target product, F-T synthesis reactor is divided into again fixed bed reactors, fluidized-bed reactor and paste state bed reactor.Fixed bed reactors complex structure, expensive, remove heat difficulty, the production capacity of whole device is lower.The feature of slurry bed system is that reaction temperature is lower, is easy to control, but conversion ratio is lower, product mostly be high-carbon hydrocarbon and in reactor the solid-liquor separation of slurries comparatively difficult.The feature of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, and there is not the difficulty of solid-liquor separation, product mostly is lower carbon number hydrocarbons; Build and operating cost lower, and low pressure reduction in turn saves a large amount of compression expenses, and is more conducive to the heat of releasing in dereaction, and simultaneously because gas linear velocity is low, wear problem is less, and this makes to operate for a long time to become possibility.
Iron catalyst has a lot of advantages, as highly selective obtains low-carbon alkene, prepares high-octane gasoline etc., and ferrum-based catalyst also has the feature that operating condition is wide, product adjustability is large in addition.The preparation method of Fe-series catalyst mainly contains three kinds: the precipitation method (precipitated catalyst), and its composition, except Fe, also has the auxiliary agents such as Cu, Mn, K, it is made into mixed solution by a certain percentage, after being heated to boiling, adding precipitating reagent and stir, then filter, wash.Add water gained filter cake pulp again, adds quantitative potassium silicate, drying, extruded, then, grinds, sieves; Sintering process (sintered catalyst); Oxide mixing method (fused iron catalyst), makes raw material with the mill scale of steel rolling mill or magnetite powder, adds auxiliary agent A l 2o 3, MgO, MnO and CuO etc., send into 1500 DEG C of electric arc furnaces meltings, the fused mass of outflow is through mold, cooling, multiple stage crushing.
Current ferrum-based catalyst direct F-T synthesizing low-carbon alkene is many to carry out in fixed bed, and as being just referred to a kind of ferrum-based catalyst for F-T synthesis low-carbon alkene in patent CN1040397C, the selective of low-carbon alkene can up to 69%.But fixed bed reactors complex structure, expensive, remove heat difficulty, the production capacity of whole device is lower.The feature of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, and there is not the difficulty of solid-liquor separation, product mostly is lower carbon number hydrocarbons; Build and operating cost lower, and low pressure reduction in turn saves a large amount of compression expenses, and is more conducive to the heat of releasing in dereaction, and simultaneously because gas linear velocity is low, wear problem is less, and this makes to operate for a long time to become possibility.The currently reported molten iron type that the mostly is catalyst being applied to fluid bed F-T synthesis, as being referred to a kind of molten iron type catalyst for F-T synthesis in patent CN1704161A; But it is concentrated not to there is product in fluid bed F-T synthesis at present, the selective not high enough problem of low-carbon alkene.
Summary of the invention
Technical problem to be solved by this invention be exist in prior art because the reaction of synthesis gas synthesis light hydrocarbon is for strong exothermal reaction, when using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway, makes the easy inactivation of catalyst; When using fluid bed, product is concentrated not, and the selective not high enough problem of lower carbon number hydrocarbons especially low-carbon alkene, provides a kind of method of new synthesis of gas produced low-carbon hydrocarbon.The method fluidized-bed reactor, have and remove heat soon, lower carbon number hydrocarbons is the selective high advantage of lower carbon number hydrocarbons especially.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon.This catalyst take aluminium oxide as carrier, and active component contains with atomic ratio measuring, the composition that chemical formula is following:
Fe 100K aZn bCr cLa dO x
In formula, the span of a is 0.1 ~ 10.0;
The span of b is 5.0 ~ 60.0;
The span of c is 0.1 ~ 15.0;
The span of d is 0.1 ~ 10.0;
X is for meeting the oxygen atom sum in catalyst needed for each element valence;
Carrier consumption is 30 ~ 70% of catalyst weight by weight percentage.
In technique scheme, the value preferable range of a is 1.0 ~ 8.0, the value preferable range of b is 10.0 ~ 50.0, the value preferable range of c is the value preferable range of 1.0 ~ 10.0, d is 1.0 ~ 8.0, and carrier consumption preferable range is 40 ~ 60% of catalyst weight by weight percentage.
In technique scheme, the span of a is more preferably 2 ~ 8; The span of b is more preferably 20 ~ 50; The span of c is more preferably 5 ~ 10; The span of d is more preferably 1 ~ 5.
In technique scheme, the span of the preferred version of catalyst to be atomic ratio also containing Ru, Ru and iron in catalyst be e:100, e is 0.01 ~ 0.2; The span of e is preferably 0.05 ~ 0.1; The most preferably scheme of catalyst is also comprise Pd in catalyst, and the atomic ratio of Pd and iron is the span of f:100, f is 0.01 ~ 0.2; The span of f is preferably 0.05 ~ 0.1.
The reducing condition of the catalyst that the present invention obtains: pressure is 0.05 ~ 5MPa, is preferably 0.1 ~ 4MPa; Reducing gas can use hydrogen, carbon monoxide or synthesis gas, when using synthesis gas, and its H 2/ CO mol ratio is 0.1 ~ 6.0, is preferably 0.2 ~ 6.0; The volume space velocity of reducing gases is 100 ~ 8000 hours -1, be preferably 500 ~ 6000 hours -1; Reduction temperature is 200 ~ 600 DEG C, is preferably 220 ~ 500 DEG C; Recovery time is 1 ~ 100 hour, is preferably 6 ~ 72 hours.
The reaction condition of the catalyst that the present invention obtains: pressure is 0.5 ~ 10MPa, is preferably 1 ~ 8MPa; Reaction temperature is 200 ~ 600 DEG C, is preferably 220 ~ 500 DEG C; Volume space velocity is 100 ~ 8000 hours -1, be preferably 500 ~ 6000 hours -1; H in unstripped gas 2/ CO mol ratio is 0.1 ~ 5.0, is preferably 0.5 ~ 3.0.
The preparation method of the ferrum-based catalyst of synthesis of gas produced low-carbon hydrocarbon is as follows:
(1) solution I is made by soluble in water for aequum soluble ferric iron salt,
(2) aequum solubility La salt be dissolved in hot water water make solution II,
(3) solution III is made by soluble in water for the soluble-salt of aequum Cr and Zn,
(4) solution I solution, II solution, III solution mixing system are become mixed solution IV,
(5) join in solution IV by aequum alumina sol in 70-100 DEG C of water-bath, mixing making beating, add acid-base modifier simultaneously and regulate the pH value of slurry to be 1 ~ 5, obtaining solid content is 15 ~ 45wt% slurry V,
(6) send into spray dryer spray shaping after slurry V being cooled to 20 ~ 60 DEG C, then 400 ~ 750 DEG C of roasting temperatures 0.15 ~ 6 hour, obtain microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst.
The manufacture method of the catalyst in the inventive method there is no particular/special requirement, can be undertaken by well-established law.First catalyst each component is made solution, then be mixed and made into slurry with carrier, be spray-driedly shaped to microspheroidal, finally within 0.5 ~ 5 hour, make catalyst 450 ~ 700 DEG C of roastings.The preparation of slurry is preferably undertaken by CN1005248C method.
The raw material manufacturing catalyst of the present invention is:
Iron component ferric nitrate in catalyst or ferric sulfate.
All the other components its nitrate the most handy, hydroxide or can be analyzed to the salt of oxide.
As carrier A l 2o 3raw material can use colloidal sol.
Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but with better centrifugal, can ensure that the catalyst made has good size distribution.
The roasting of catalyst can be divided into two stages to carry out: the decomposition of each element salt and high-temperature roasting in catalyst.Catabolic phase temperature is preferably 200 ~ 300 DEG C, and the time is 0.5 ~ 2 hour.Sintering temperature is 500 ~ 800 DEG C, is preferably 550 ~ 700 DEG C; Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be divided into two regions in a stove, in continous way rotary roasting furnace, also can complete decomposition and roasting simultaneously.Appropriate air to be passed into, to generate Catalytic active phase in catalyst decomposes and roasting process.
Because the present invention adopts fluidized-bed process, therefore solve because the reaction of synthesis gas synthesis light hydrocarbon is strong exothermal reaction in prior art, when using fixed bed, heat difficulty is removed in reaction, and easy temperature runaway, makes the problem of the easy inactivation of catalyst; In addition due to introduce in the catalyst lanthanum, zinc is as catalyst promoter, facilitate the dispersion of catalyst activity component at catalyst surface, thus be conducive to the activity improving catalyst, solve when using fluid bed, lower carbon number hydrocarbons is low-carbon alkene (ethene, propylene and butylene) selective low problem especially, when introducing Ru or Pd in the catalyst, catalyst has more excellent catalytic effect.Use method of the present invention, reaction temperature 200 ~ 600 DEG C, reaction pressure 0.5 ~ 10MPa, catalyst loading 100 ~ 8000 hours -1, pulp furnish (mole) H 2carry out synthetic reaction under the condition of/CO=0.1 ~ 5.0:1, CO conversion ratio can reach 91.5%, and in product, the weight selectivities of low-carbon alkene can reach 71.1%, achieves good technique effect.
Below by embodiment, the invention will be further elaborated.
Detailed description of the invention
[embodiment 1]
Get 612.0 grams of ferric nitrates and 22.53 grams of zinc nitrates in same container, add the water-soluble solution of 1000g, obtain material I, get 0.4 gram of lanthanum nitrate and add 10g water heating for dissolving, obtain material II, get 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation add the Alumina gel material of 312.5 gram 40 % by weight, then the solution 50g containing 0.1 gram of KOH is added, the pH value of above-mentioned slurry is regulated to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length is that the catalyst made consists of in 500 DEG C of roastings 2.0 hours in the rotary roasting furnace of 1700 millimeters (φ 89 × 1700 millimeters):
50 % by weight Fe 100cr 0.1zn 5.0k 0.1la 0.1o x+ 50 % by weight Al 2o 3
[embodiment 2]
Get 611.9 grams of ferric nitrates and 22.53 grams of zinc nitrates in same container, add the water-soluble solution of 1000g, obtain material I, get 0.4 gram of lanthanum nitrate and add 10g water heating for dissolving, obtain material II, get 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 312.5 gram 40 % by weight, then add containing 0.1 gram of KOH and 0.06 gram RuCl 3solution 50g, the pH value of above-mentioned slurry is regulated to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length is that the catalyst made consists of in 500 DEG C of roastings 2.0 hours in the rotary roasting furnace of 1700 millimeters (φ 89 × 1700 millimeters):
50 % by weight Fe 100cr 0.1zn 5.0k 0.1la 0.1ru 0.01o x+ 50 % by weight Al 2o 3
[embodiment 3]
Get 611.8 grams of ferric nitrates and 22.52 grams of zinc nitrates in same container, add the water-soluble solution of 1000g, obtain material I, get 0.4 gram of lanthanum nitrate and add 10g water heating for dissolving, obtain material II, get 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 312.5 gram 40 % by weight, then add containing 0.1 gram of KOH, containing 0.04 gram of PdCl 2and 0.06 gram of RuCl 3solution 50g, the pH value of above-mentioned slurry is regulated to make the pH=6.0 of mixed slurry with ammoniacal liquor, slurry is obtained after fully stirring, the slurry made carried out in spray dryer framboid according to well-established law shaping, last is 89 millimeters at internal diameter, length is that the catalyst made consists of in 500 DEG C of roastings 2.0 hours in the rotary roasting furnace of 1700 millimeters (φ 89 × 1700 millimeters):
50 % by weight Fe 100cr 0.1zn 5.0k 0.1la 0.1ru 0.01pd 0.01o x+ 50 % by weight Al 2o 3
[embodiment 4]
Get 358.2 grams of ferric nitrates and 105.49 grams of zinc nitrates in same container, add the water-soluble solution of 1000g, obtain material I, get 25.5 grams of lanthanum nitrates and add 100g water heating for dissolving, obtain material II, get 8.87 grams of chromium trioxides, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 312.5 gram 40 % by weight, then add 8.92 grams of KOH, containing 0.52 gram of PdCl 2and 0.74 gram of RuCl 3solution 200g, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring slurry, it is shaping the slurry made to be carried out in spray dryer framboid, and the catalyst that last roasting is made consists of:
50 % by weight Fe 100cr 10.0zn 60.0k 15.0la 10.0ru 0.2pd 0.2o x+ 50 % by weight Al 2o 3
[embodiment 5]
Get 622.3 grams of ferric nitrates and 114.5 grams of zinc nitrates in same container, add the water-soluble solution of 1000g, obtain material I, get 22.2 grams of lanthanum nitrates and add 100g water heating for dissolving, obtain material II, get 7.7 grams of chromium trioxides, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 187.5 gram 40 % by weight, then add 7.75 grams of KOH, containing 0.45 gram of PdCl 2and 0.64 gram of RuCl 3solution 200g, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring slurry, it is shaping the slurry made to be carried out in spray dryer framboid, and the catalyst that last roasting is made consists of:
70 % by weight Fe 100cr 5.0zn 25.0k 7.5la 5.0ru 0.1pd 0.1o x+ 30 % by weight Al 2o 3
[embodiment 6]
266.7 grams of ferric nitrates and 49.09 grams of zinc nitrates, in same container, add the water-soluble solution of 1000g, obtain material I, and get 9.5 grams of lanthanum nitrates and add 100g water heating for dissolving, obtain material II, get 3.3 grams of chromium trioxides, add 50g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 437.5 gram 40 % by weight, then add 3.32 grams of KOH, containing 0.19 gram of PdCl 2and 0.27 gram of RuCl 3solution 200g, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring slurry, it is shaping the slurry made to be carried out in spray dryer framboid, and the catalyst that last roasting is made consists of:
30 % by weight Fe 100cr 5.0zn 25.0k 7.5la 5.0ru 0.1pd 0.1o x+ 70 % by weight Al 2o 3
[comparative example 1]
Get 889.0 grams of ferric nitrates and 163.65 grams of zinc nitrates in same container, add the water-soluble solution of 1500g, obtain material I, get 31.7 grams of lanthanum nitrates and add 100g water heating for dissolving, obtain material II, get 11.0 grams of chromium trioxides, add 100g water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds 11.07 grams of KOH, containing 0.64 gram of PdCl 2and 0.91 gram of RuCl 3solution 200g, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring slurry, it is shaping the slurry made to be carried out in spray dryer framboid, and the catalyst that last roasting is made consists of:
Fe 100Cr 5.0Zn 25.0K 7.5La 5.0Ru 0.1Pd 0.1O x
[comparative example 2]
Get 177.8 grams of ferric nitrates and 32.73 grams of zinc nitrates in same container, add the water-soluble solution of 600g, obtain material I, get 6.3 grams of lanthanum nitrates and add 50g water heating for dissolving, obtain material II, get 2.2 grams of chromium trioxides, add 50) water, stirring and dissolving obtains material III.
Material I, II, III is mixed, under agitation adds the Alumina gel material of 500.0 gram 40%, then add 2.21 grams of KOH, containing 0.13 gram of PdCl 2and 0.18 gram of RuCl 3solution 200g, regulate the acidity of above-mentioned slurry to make the pH=6.0 of mixed slurry with ammoniacal liquor, after fully stirring slurry, it is shaping the slurry made to be carried out in spray dryer framboid, and the catalyst that last roasting is made consists of:
20 % by weight Fe 100cr 5.0zn 25.0k 7.5la 5.0ru 0.1pd 0.1o x+ 80 % by weight Al 2o 3
Obtained catalyst carries out at reducing condition:
Reduce, then carry out Fischer-Tropsch synthesis under the following conditions:
The experimental result of synthetic reaction lists in table 1.
Table 1
*C 2 0～C 4 0：C 2H 6、C 3H 8、iso-C 4H 10、n-C 4H 10
C 2 ＝～C 4 ＝：C 2H 4、C 3H 6、iso-C 4H 8、n-C 4H 8、tra-2-C 4H 8、cis-C 4H 8。

Claims (10)

1. microspheroidal synthesis of gas produced low-carbon hydrocarbon catalyst and preparation method thereof, this catalyst take aluminium oxide as carrier, and active component contains with atomic ratio measuring, the composition that chemical formula is following:
Fe 100K aZn bCr cLa dO x
In formula, the span of a is 0.1 ~ 10.0;
The span of b is 5.0 ~ 60.0;
The span of c is 0.1 ~ 15.0;
The span of d is 0.1 ~ 10.0;
X is for meeting the oxygen atom sum in catalyst needed for each element valence;
Carrier consumption is 30 ~ 70% of catalyst weight by weight percentage.
2. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 1, is characterized in that the span of a is 2 ~ 8; The span of b is 20 ~ 50; The span of c is 5 ~ 10; The span of d is 1 ~ 5.
3. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 1 and 2, is characterized in that the atomic ratio of catalyst also containing Ru, Ru and iron be the span of e:100, e is 0.01 ~ 0.2.
4. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 3, is characterized in that the span of e is 0.05 ~ 0.1.
5. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 3, is characterized in that catalyst also comprises Pd, and the atomic ratio of Pd and iron is the span of f:100, f is 0.01 ~ 0.2.
6. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 5, is characterized in that the span of f is 0.05 ~ 0.1.
7. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 1, it is characterized in that catalyst reduces before reactions, reducing condition is as follows: reaction pressure is 0.05 ~ 5MPa, and the volume space velocity of reducing gases is 100 ~ 8000 hours -1, reduction temperature is 200 ~ 600 DEG C, and the recovery time is 1 ~ 100 hour, and described reducing gases is hydrogen, carbon monoxide or synthesis gas.
8. ferrum-based catalyst described in any one of claim 1 ~ 7 is for the synthesis of the reaction of gas preparing low carbon hydrocarbons, it is characterized in that the reaction condition of synthesis of gas produced low-carbon hydrocarbon: reaction pressure is 0.5 ~ 10MPa, reaction temperature is 200 ~ 600 DEG C, and volume space velocity is 100 ~ 8000 hours -1, H in unstripped gas 2/ CO mol ratio is 0.1 ~ 5.0.
9. the preparation method of the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 1, comprises following processing step:
(1) solution I is made by soluble in water for soluble ferric iron salt,
(2) solubility La salt be dissolved in hot water water make solution II,
(3) solution III is made by soluble in water for the soluble-salt of Cr and Zn,
(4) solution I solution, II solution, III solution mixing system are become mixed solution IV,
(5) in 70-100 DEG C of water-bath by aequum Al 2o 3colloidal sol join in solution IV, mixing making beating, add acid-base modifier simultaneously and regulate the pH value of slurry to be 1 ~ 5, obtaining solid content is 15 ~ 45wt% slurry V,
(6) send into spray dryer spray shaping after slurry V being cooled to 20 ~ 60 DEG C, then 400 ~ 1000 DEG C of roasting temperatures 0.15 ~ 10 hour, obtain microspheroidal Fluidized Multicomponent Metallic Oxides Catalysts.
10. the preparation method of the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 9, it is characterized in that sintering temperature is 450 ~ 800 DEG C, roasting time is 0.5 ~ 8 hour.
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