CN105435803B - Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of microspheroidal synthesis of gas produced low-carbon hydrocarbon catalyst and preparation method thereof, mainly solves in the prior art because synthesis gas synthesizing low-carbon hydrocarbon reaction is strong exothermal reaction, and during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, catalyst is easily inactivated；Lower carbon number hydrocarbons the problem of especially selectivity of light olefin is relatively low, by using using aluminum oxide as carrier, active component contains with atomic ratio measuring chemical formula following composition the present invention：Fe₁₀₀K_aZn_bCr_cLa_dO_xIron-based fluid catalyst, using synthesis gas as raw material, raw material contacts with the iron-based fluid catalyst in fluid bed, reaction generation lower carbon number hydrocarbons technical scheme preferably solve the problem, in the industrial production available for fluid bed syngas synthesizing low-carbon hydrocarbon.

Description

Catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof

Technical field

The present invention relates to catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon and preparation method thereof.

Background technology

The method that synthesis gas is converted into hydro carbons by catalyst action is nineteen twenty-three by Germany scientist Frans Fischer and Hans Tropsch inventions, heterogeneous catalysis hydrogenation occurs on metallic catalyst for abbreviation F-T synthesis, i.e. CO Reaction, generate the process of the mixture based on linear paraffin and alkene.Germany the twenties in last century just carried out research and Exploitation, and industrialization was realized in 1936, closed after World War II because can not economically be competed with petroleum industry；South Africa possesses Abundant coal resources, but petroleum resources plaque is weary, and limited for a long time by international community's economy and political sanction, force its hair Coal-to-oil industry technology is opened up, and coal base F-T synthesis of the First production capacity for ten thousand tons of product/years of 25-40 has been built up in 1955 Oily factory (Sasol-1).

The world oil crisis twice 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 technologys arouse the interest of industrialized country again.1980 and nineteen eighty-two, south Non- Sasol companies build up in succession again and Liang Zuomeiji artificial oils factory of having gone into operation.But World oil price in 1986 plummets, postpone F-T synthetic technologys are in other national heavy industrialization processes.

Since twentieth century nineties, petroleum resources shortage and in poor quality, while coal and natural gas proved reserves increasingly But it is continuously increased, F-T synthetic technologys cause extensive concern again.At present, the primary raw material of low-carbon alkene is petroleum hydrocarbon in the world Class, wherein naphtha account for major part, also alkane, hydrogenated diesel oil, part mink cell focus etc..It is more with natural gas or lightweight stone both at home and abroad Oil distillate is raw material, produces low-carbon alkene using steam cracking process in Ethylene Complex unit, steam cracking is in petrochemical industry Big power consumption device, and be completely dependent on non-renewable petroleum resources, with the increasingly shortage of petroleum resources, be badly in need of searching and replace For resource.So the research work with other substitution of resources oil producing olefinic hydrocarbons is gradually paid attention to, some are famous in the world Oil company and scientific research institutions all carried out the research of this respect, and achieve good achievement.

By the development of decades, F-T synthetic catalysts have also obtained significant progress, and fischer-tropsch synthetic catalyst generally wraps Include following component：Active metal (the VIIIth group 4 transition metal), oxide carrier or structural promoter (SiO₂,Al₂O₃Deng), chemistry helps Agent (alkali metal oxide, transition metal) and precious metal additive (Ru, Re etc.).Fe largely generates alkene and oxygenatedchemicals, Ru, Co mainly generates long-chain saturated hydrocarbons, and Ni mainly generates methane.Due to easily formed during Ni compressive reactions carbonyls be lost in And methanation is serious, Ru, Rh etc. are expensive, currently used catalyst, from active component for be divided into two major classes：Iron-based Catalyst and cobalt-base catalyst.Co-catalyst influences very big, the raising of selectivity of light olefin for the selectivity of low-carbon alkene Mainly by co-catalyst come what is realized, the selection of co-catalyst and adding technique are the key technologies for developing excellent catalyst One of.

Co-catalyst mainly has two classes：

(1) electron type auxiliary agent：

The interaction between catalyst and reactant can be strengthened or be weakened to electron type auxiliary agent.Electron type auxiliary agent mainly has Alkali metal class and transition metal-type.

Alkali metal：In F-T, methane content increases and reduced Fe base catalyst within the specific limits with surface alkalinty.

Alkalinous metal auxiliary agent attracts attention as a kind of important electronic auxiliary of Fe base catalyst.Alkali metal is to Fischer-Tropsch Synthesis Fe base catalyst has significant facilitation, and promotes efficiency substantially directly proportional to basicity.After adding alkali metal compound, Fe base catalyst CO heat of adsorption is added, reduces the heat of adsorption and hydrogenation capability of hydrogen, the averagemolecular wt of corresponding F-T products Quality, degree of unsaturation increase, the generation increase of oxygenatedchemicals, methane generation reduce.

Alkali metal cation plays electronq donor to metal Fe, and the chemistry for promoting CO by Fe 3d electronics is inhaled It is attached, weaken C-O keys, strengthen Fe-C keys, help to control the selectivity of catalyst.

To research of the alkali metal as auxiliary agent, mainly for K element.K auxiliary agents to activity improvement mainly due to Its electronic auxiliary effect.K influences the electronic state of Fe catalyst surfaces, makes the increase of Fe electric surface densities, so as to promote CO to solve Suppress H from absorption₂Absorption, so as to catalyst FTS reactivities increase and methane production reduce.K contents have one most preferably Value, during more than optimum value, because CO Dissociatives are greatly promoted, H₂Absorption is suppressed, therefore catalyst FTS reactivities It can not be further enhanced.High K contents lower surface C₁Species are abundant and H species are advantageous to long-chain macromolecule with respect to when lacking Generation, but easily form carbon distribution, accelerate catalyst inactivation.

It is generally believed that K₂Effects of the O to F-T fused iron catalysts be：Reduce catalyst surface area, catalyst activity with K₂O content increase first increases to be reduced afterwards, is suppressed methane generation, is promoted chain to increase, increase the average molecular mass of product, increases Add olefine selective, increase oxygenate selectivity, promote the generation of cementite and carbon deposit, promote water gas shift reaction (WGS)。

The addition of K auxiliary agents contributes to catalyst Fe₂O₃The reduction and carbonization of thing phase, it is easily formed the F-T synthesis masters of small size Want active specy Fe_XC crystalline phases, so as to improve F-T synthetic reactions activity.

Copper auxiliary agent：Under the F-T synthesis reducing conditions of routine, the more difficult reduction of metal oxide in Fe base catalyst, The catalyst of alkaline assistant and carrier is especially with the addition of, because alkaline assistant is to H₂The inhibitory action and metal oxide of absorption Interaction between carrier, cause catalyst to need longer cycle in reduction process, improve catalyst reduction behavior most Effective method is addition reduction auxiliary agent.Conventional reduction auxiliary agent has transition metal Cu, Cu auxiliary agent to promote to reduce, and reduces catalysis Agent reaches the time required for stable state, and Cu auxiliary agents can improve the activity of F-T synthesis and the WGS reactions of catalyst.

The effect that Cu auxiliary agents are added played in Fe catalyst, is to make catalyst be easy to reduce, adds a small amount of Cu auxiliary agents, is promoted The reducing property of catalyst, the initial temperature of the reduction process is reduced, increase Fe reduction degree.As Cu contents increase Add, the chemisorbed of hydrogen first increases to be reduced afterwards.With the increase of Cu contents, the interaction between Cu, Fe gradually strengthens, pressed down on the contrary Made Fe oxides reduction and catalyst to the chemisorbed of hydrogen.

Cu, which is added in Fe-Mn catalyst, makes the increase of carburizing speed, and the stability activity of catalyst is not influenceed significantly, Make the alkalescence increase of catalyst surface, be advantageous to the generation of heavy hydrocarbon, while increase ethylenic alkoxy rate.

CuO plays a driving role in the reduction process of iron oxide, reduces the reduction temperature of catalyst；Cu promotes iron catalyst Chemisorbed, to improve F-T synthesizing activities it is favourable；Double auxiliary agents all in the presence of, promote iron catalyst carbide formation, make Fe catalyst has relatively low pretreatment temperature.

CuO also has certain contribution to promoting chain to increase, and compares K to increase F-T reaction rates₂O is more effective, to secondary response There is certain facilitation.As CuO, K₂O and Fe ratio match, F-T synthesizing activities, selectivity that catalyst had can be made And stability, it is suitable for low H₂, CO coal based synthetic gas F-T building-up processes.

Cu auxiliary agents can accelerate Fe₂O₃Reduction, when Cu contents are relatively low, the selectivity of catalyst is influenceed little.Cu auxiliary agent energy Improve reduction and the carbonizing degree of catalyst, hence it is evident that increase F-T reactivities.Research finds that Cu auxiliary agents can promote Fe/SiO₂Urge Agent reduces the generation and growth with ferrous-carbide nucleus in course of reaction.

Cu auxiliary agents are introduced in iron catalyst can play the work accelerated catalyst reduction speed and strengthen catalyst activity With it can substantially reduce the reduction temperature of catalyst, promote the activation of catalyst, and this is probably due to the hydrogenolysis on copper surface Acted on from Hydrogen spillover.

Zinc auxiliary agent：Transition metal Zn is also auxiliary agent important in precipitated iron catalyst.Structure effect be present simultaneously to Fe in him And electronic effect, it can occur to strengthen strong interaction with iron, or even form Fe_3-xM_xO₄(x<Or (Fe 1)_1-xM_x)₂O₃Solid solution Structure.Addition auxiliary agent Zn can suppress sintering of the catalyst in roasting and activation process, improve the decentralization and Bi Biao of catalyst Area, but it is unfavorable for the reduction and carbonization of catalyst.Appropriate Zn addition can improve the activity and stability of catalyst, But because the interaction between Zn and Fe reduces active constituent Fe effective content, cause excessive Zn addition to reduce and urge Agent CO conversion ratios.Individually addition auxiliary agent Zn influences little on selectivity of product, and due to Zn and other auxiliary agents, such as K, Cu, deposit Interacting, therefore can be distributed by adjusting the effective content of other auxiliary agents to change product.

Rare earth metal auxiliary agent：Rare earth element is used as F-T catalyst because it has certain alkalescence and redox property The activity and selectivity of catalyst can be improved during auxiliary agent.

Research is found in Fe_1-xLight rare earth oxide and Eu are added respectively in O base catalyst₂O₃, yield of light olefins and C₅ ⁺ Yield has the increase of different amplitudes.Particularly add CeO₂Afterwards, hence it is evident that improve Fe_1-xLow-carbon alkene, the C of O base catalyst₅ ⁺ The selectivity and yield of heavy hydrocarbon.After adding rare earth oxide, the Fe of catalyst₅C₂Phase content is increased slightly, and Fe₅C₂'s Crystal face physically well develops, and new diffraction maximum occurs, and its corresponding unknown material mutually can belong to RE_xFe_yThing phase.This new thing phase It is probably by the redox effect of rare earth oxide is formed, and result in rare earth oxide for Fe_1-xO base molten irons The special promoting catalysis of catalyst.Someone have studied the work of La auxiliary agents and Ce auxiliary agents on zirconium oxide load ferric oxide catalyst With research shows to add the dissociation that La promotes CO, improves CO conversion ratios, adds Ce auxiliary agents, hence it is evident that improve Fe decentralization.

Precious metal additive：Precious metal additive not only can increase the metal dispersity of catalyst, and can pass through hydrogen Overflow promotes catalyst surface active phase and has the reduction of the nonactive phase metal oxide species of interaction with carrier, from And improve the reducing property of catalyst.Temperature programmed surface reaction (TPSR) result shows, adds precious metal additive rear catalyst Absorption dissociation capability enhancing to CO, so that ADSORPTION STATE CO hydrogenation activity improves.

Other auxiliary agents：Result of study shows that transition metal such as Cr is higher than Fe to CO affinity, is added into the catalysis of Fe bases Agent, olefine selective can be improved.

(2) Structure promoter

The decentralization of active phase in catalyst can be improved, the aggregation velocity of catalyst surface active component is reduced, strengthens it Anti- caking power, the aggregation of blocked catalysts surface active composition, increase its stability, while can also significantly increase catalyst Mechanical strength, so as to a certain extent improve catalyst F-T synthetic reaction performances.The typically difficult reduction of Structure promoter Inorganic oxide, such as SiO₂、Al₂O₃、MgO、ThO₂And TiO₂Deng.

Carrier：On the one hand it is divided active component, prevents clinkering and recrystallization, increase specific surface area, improves mechanical strength； On the other hand it is the secondary response for changing F-T synthesis, and is elected to be by shape with raising selectivity.Can be as the oxygen of ferrum-based catalyst Compound carrier has a lot, such as MnO, MnO₂、MgO、Al₂O₃、ThO₂、ZrO₂、TiO₂、ZnO、SiO₂Deng.It is than more typical carrier SiO₂、Al₂O₃。

Al₂O₃With relatively weak acidity, there is relatively low lightweight hydrocarbon-selective, it can disperse and stable metal activity Phase, stronger metal and auxiliary agent interphase interaction are produced, so as to be exerted one's influence to the activity and selectivity of catalyst.Al₂O₃It can promote Enter the scattered of Cr, K auxiliary agent in ferrum-based catalyst, and then improve the reactivity of catalyst.Al₂O₃To the surface alkalinty of catalyst Inhibitory action it is stronger, Al₂O₃Larger ferriferous oxide crystal grain can be formed on the catalyst of load, is unfavorable for the scattered of iron oxygen phase.

According to the difference of used catalyst and the difference of target product, it is anti-that F-T synthesis reactor is divided into fixed bed again Answer device, fluidized-bed reactor and paste state bed reactor.Fixed bed reactors are complicated, expensive, remove hot difficulty, whole dress The production capacity put is relatively low.The characteristics of slurry bed system is that reaction temperature is relatively low, easily controllable, but conversion ratio is relatively low, and product is mostly high-carbon hydrocarbon And in reactor slurries solid-liquor separation it is more difficult.The characteristics of fluidized-bed reactor is that temperature is higher, and conversion ratio is higher, does not deposit In the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；Build and operating cost is relatively low, and low pressure difference saves substantial amounts of pressure Contracting expense, and be more conducive to remove the heat released in dereaction, simultaneously because gas linear velocity is low, wear problem is smaller, and this makes length Phase operating is possibly realized.

Iron catalyst has the advantages of a lot, such as obtains low-carbon alkene with high selectivity, prepares high-octane gasoline etc., Other ferrum-based catalyst also has the characteristics of operating condition is wide, product adjustability is big.The preparation method of Fe-series catalyst mainly has Three kinds：The precipitation method (precipitated catalyst), its composition is in addition to Fe, and it is made into mixed by the also auxiliary agent such as Cu, Mn, K by a certain percentage Solution is closed, after being heated to boiling, precipitating reagent stirring is added, then filters, washs.Gained filter cake is added into water pulp again, added Quantitative potassium silicate, through drying, extrusion forming, then, grind, sieve；Sintering process (sintered catalyst)；Oxide mixing method (fused iron catalyst), raw material, addition auxiliary agent A l are made with the mill scale or magnetite powder of steel rolling mill₂O₃, MgO, MnO and CuO etc., be sent into 1500 DEG C of electric arc furnaces meltings, the fused mass of outflow is through mold, cooling, multiple stage crushing.

The direct F-T synthesizing low-carbons alkene of ferrum-based catalyst is more at present is carried out in fixed bed, in patent CN1040397C A kind of ferrum-based catalyst for F- T synthesis low-carbon alkene is just referred to, the selectivity of low-carbon alkene can be up to 69%.But It is that fixed bed reactors are complicated, it is expensive, hot difficulty is removed, the production capacity of whole device is relatively low.The spy of fluidized-bed reactor Point is that temperature is higher, and conversion ratio is higher, and in the absence of the difficulty of solid-liquor separation, product is mostly lower carbon number hydrocarbons；Build and operating cost compared with It is low, and low pressure difference saves substantial amounts of compression expense, and be more conducive to remove the heat released in dereaction, simultaneously because gas Linear velocity is low, and wear problem is smaller, and this makes it possible to operate for a long time.The currently reported fluid bed F-T that is applied to is synthesized Be mostly molten iron type catalyst, as be referred in patent CN1704161A it is a kind of for F-T synthesize molten iron type catalyst；But mesh The problem of there is product and not enough concentrate in preceding fluid bed F-T synthesis, the selectivity of low-carbon alkene is not high enough.

The content of the invention

The technical problems to be solved by the invention are because synthesis gas synthesis lightweight hydrocarbon reaction is present in prior art Strong exothermal reaction, during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, catalyst is easily inactivated；During using fluid bed, production A kind of the problem of thing is not enough concentrated, and the selectivity of lower carbon number hydrocarbons especially low-carbon alkene is not high enough, there is provided new synthesis of gas produced low-carbon The method of hydrocarbon.This method fluidized-bed reactor, have and remove hot fast, lower carbon number hydrocarbons the advantages of especially low-carbon hydrocarbon-selective is high.

In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of microspheroidal synthesis of gas produced low-carbon hydrocarbon Ferrum-based catalyst.Using aluminum oxide as carrier, active component contains with atomic ratio measuring, chemical formula following combination the catalyst Thing：

Fe₁₀₀K_aZn_bCr_cLa_dO_x

A span is 0.1~10.0 in formula；

B span is 5.0~60.0；

C span is 0.1~15.0；

D span is 0.1~10.0；

X is to meet the oxygen atom sum in catalyst needed for each element chemical valence；

Carrier dosage is the 30~70% of catalyst weight by weight percentage.

The value preferred scope that a value preferred scope is 1.0~8.0, b in above-mentioned technical proposal is 10.0~50.0, c Value preferred scope be 1.0~10.0, d value preferred scope be 1.0~8.0, carrier dosage preferred scope is with weight hundred Ratio is divided to be calculated as the 40~60% of catalyst weight.

In above-mentioned technical proposal, a span is more preferably 2~8；B span is more preferably 20~50；C's Span is more preferably 5~10；D span is more preferably 1~5.

In above-mentioned technical proposal, the preferred scheme of catalyst is also to contain Ru in catalyst, and the atomic ratio of Ru and iron is e: 100, e span is 0.01~0.2；E span is preferably 0.05~0.1；The most preferably scheme of catalyst is to urge Also include Pd in agent, the atomic ratio of Pd and iron is f:100, f span is 0.01~0.2；F span is preferably 0.05~0.1.

The reducing condition of catalyst produced by the present invention：Pressure is 0.05~5MPa, preferably 0.1~4MPa；Also Primordial Qi Body can use hydrogen, carbon monoxide or synthesis gas, during with synthesis gas, its H₂/ CO mol ratios be 0.1~6.0, preferably 0.2~ 6.0；Also the volume space velocity of Primordial Qi is 100~8000 hours^-1, preferably 500~6000 hours^-1；Reduction temperature is 200~600 DEG C, preferably 220~500 DEG C；Recovery time is 1~100 hour, preferably 6~72 hours.

The reaction condition of catalyst produced by the present invention：Pressure is 0.5~10MPa, preferably 1~8MPa；Reaction temperature For 200~600 DEG C, preferably 220~500 DEG C；Volume space velocity is 100~8000 hours^-1, preferably 500~6000 hours^-1； H in unstripped gas₂/ CO mol ratios are 0.1~5.0, 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 aequum soluble ferric iron salt is soluble in water,

(2) aequum solubility La salt is dissolved in hot water water and solution II is made,

(3) solution III is made by aequum Cr and Zn soluble-salt are soluble in water,

(4) by the solution of solution I, II solution, III solution mixing system into mixed solution IV,

(5) aequum alumina sol is added in solution IV in 70-100 DEG C of water-bath, be mixed with beating, added simultaneously The pH value of acid-base modifier regulation slurry is 1~5, and it is 15~45wt% slurries V to obtain solid content,

(6) spray dryer spray shaping is sent into after slurry V being cooled into 20~60 DEG C, then in 400~750 DEG C of temperature The lower roasting of degree 0.15~6 hour, obtains microspheroidal fluid bed iron-base fischer-tropsch synthesis catalyst.

The manufacture method of catalyst in the inventive method has no particular/special requirement, can be carried out by well-established law.First by catalyst Solution is made in each component, then is mixed and made into slurry with carrier, spray-dried to be shaped to microspheroidal, finally in 450~700 DEG C of roastings Burn 0.5~5 hour and catalyst is made.The preparation of slurry is preferably carried out by CN1005248C methods.

The raw material for manufacturing catalyst of the present invention is：

Iron component ferric nitrate or ferric sulfate in catalyst.

Remaining component most handy its nitrate, hydroxide or the salt that can be analyzed to oxide.

As carrier Al₂O₃Raw material can use colloidal sol.

Spray dryer available pressure formula, two streamings or centrifugal turntable formula, but with it is centrifugal preferably, can guarantee that manufactured urge Agent has good size distribution.

The roasting of catalyst can be divided into two stages progress：The decomposition and high-temperature roasting of each element salt in catalyst.Point It is preferably 200~300 DEG C to solve phase temperature, and the time is 0.5~2 hour.Sintering temperature be 500~800 DEG C, preferably 550~ 700℃；Roasting time is 20 minutes to 2 hours.Above-mentioned decomposition and roasting are carried out respectively in two roasters, also can be at one It is divided into two regions in stove, also can completes to decompose and be calcined simultaneously in continous way rotary roasting furnace.Decompose and roast in catalyst Appropriate air is passed through during burning, to generate catalytic activity phase.

Because the present invention uses fluidized-bed process, therefore solve in the prior art because synthesis gas synthesizes lightweight hydrocarbon reaction For strong exothermal reaction, during using fixed bed, hot difficulty is removed in reaction, easy temperature runaway, the problem of making catalyst easily inactivate；Additionally, due to The lanthanum that introduces in the catalyst, zinc promote catalyst activity component in the scattered of catalyst surface as catalyst promoter, from And be advantageous to improve the activity of catalyst, solve when using fluid bed, lower carbon number hydrocarbons especially low-carbon alkene (ethene, propylene And butylene) selectivity it is low the problem of, when in the catalyst introduce Ru or Pd when, catalyst has more excellent catalytic effect.Use The method of the present invention, in 200~600 DEG C, 0.5~10MPa of reaction pressure of reaction temperature, catalyst loading 100~8000 is small When^-1, raw material proportioning (mole) H₂/ CO=0.1~5.0:Carry out synthetic reaction under conditions of 1, CO conversion ratios are up to 91.5%, instead The weight selectivities of low-carbon alkene in product are answered to achieve preferable technique effect up to 71.1%.

Below by embodiment, the invention will be further elaborated.

Embodiment

【Embodiment 1】

612.0 grams of ferric nitrates and 22.53 grams of zinc nitrates are taken to obtain material I in same container, adding 1000g water to dissolve, take 0.4 gram of lanthanum nitrate adds 10g water to dissolve by heating, and obtains material II, takes 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains thing Material III.

Material I, II, III is mixed, adds 312.5 gram of 40 weight % Alumina gel material under agitation, then adds and contains 0.1 gram of KOH solution 50g, the pH=6.0 of mixed slurry is caused with the pH value of the above-mentioned slurry of ammoniacal liquor regulation, after being sufficiently stirred Manufactured slurry is subjected to framboid shaping in spray dryer according to well-established law, is finally 89 millimeters in internal diameter, length 1700 It is calcined 2.0 hours in 500 DEG C in the rotary roasting furnace of millimeter (89 × 1700 millimeters of φ), manufactured catalyst composition is：

50 weight %Fe₁₀₀Cr_0.1Zn_5.0K_0.1La_0.1O_x+ 50 weight %Al₂O₃

【Embodiment 2】

611.9 grams of ferric nitrates and 22.53 grams of zinc nitrates are taken to obtain material I in same container, adding 1000g water to dissolve, take 0.4 gram of lanthanum nitrate adds 10g water to dissolve by heating, and obtains material II, takes 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains thing Material III.

Material I, II, III is mixed, adds 312.5 gram of 40 weight % Alumina gel material under agitation, then adds and contains 0.1 gram of KOH and 0.06 gram of RuCl₃Solution 50g, the pH value that above-mentioned slurry is adjusted with ammoniacal liquor causes the pH=6.0 of mixed slurry, Manufactured slurry is subjected to framboid shaping in spray dryer according to well-established law after being sufficiently stirred, is finally 89 millis in internal diameter Rice, length is is calcined 2.0 hours in 500 DEG C in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ), manufactured catalysis Agent forms：

50 weight %Fe₁₀₀Cr_0.1Zn_5.0K_0.1La_0.1Ru_0.01O_x+ 50 weight %Al₂O₃

【Embodiment 3】

611.8 grams of ferric nitrates and 22.52 grams of zinc nitrates are taken to obtain material I in same container, adding 1000g water to dissolve, take 0.4 gram of lanthanum nitrate adds 10g water to dissolve by heating, and obtains material II, takes 0.15 gram of chromium trioxide, add 100g water, stirring and dissolving obtains thing Material III.

Material I, II, III is mixed, adds 312.5 gram of 40 weight % Alumina gel material under agitation, then adds and contains 0.1 gram of KOH, containing 0.04 gram of PdCl₂And 0.06 gram of RuCl₃Solution 50g, the pH value that above-mentioned slurry is adjusted with ammoniacal liquor to mix The pH=6.0 of slurry, after being sufficiently stirred slurry, manufactured slurry carried out in spray dryer according to well-established law framboid into Type, it is finally 89 millimeters in internal diameter, length is to be calcined in the rotary roasting furnace of 1700 millimeters (89 × 1700 millimeters of φ) in 500 DEG C 2.0 hours, manufactured catalyst, which forms, was：

50 weight %Fe₁₀₀Cr_0.1Zn_5.0K_0.1La_0.1Ru_0.01Pd_0.01O_x+ 50 weight %Al₂O₃

【Embodiment 4】

358.2 grams of ferric nitrates and 105.49 grams of zinc nitrates are taken to obtain material I in same container, adding 1000g water to dissolve, Take 25.5 grams of lanthanum nitrates to add 100g water to dissolve by heating, obtain material II, take 8.87 grams of chromium trioxides, add 100g water, stirring and dissolving Obtain material III.

Material I, II, III is mixed, 312.5 gram of 40 weight % Alumina gel material is added under agitation, then adds 8.92 grams of KOH, containing 0.52 gram of PdCl₂And 0.74 gram of RuCl₃Solution 200g, the acidity that above-mentioned slurry is adjusted with ammoniacal liquor to mix The pH=6.0 of slurry is closed, slurry is obtained after being sufficiently stirred, manufactured slurry is subjected to framboid shaping in spray dryer, Finally catalyst composition is made of roasting：

50 weight %Fe₁₀₀Cr_10.0Zn_60.0K_15.0La_10.0Ru_0.2Pd_0.2O_x+ 50 weight %Al₂O₃

【Embodiment 5】

622.3 grams of ferric nitrates and 114.5 grams of zinc nitrates are taken to obtain material I in same container, adding 1000g water to dissolve, take 22.2 grams of lanthanum nitrates add 100g water to dissolve by heating, and obtain material II, take 7.7 grams of chromium trioxides, add 100g water, stirring and dissolving obtains thing Material III.

Material I, II, III is mixed, 187.5 gram of 40 weight % Alumina gel material is added under agitation, then adds 7.75 grams of KOH, containing 0.45 gram of PdCl₂And 0.64 gram of RuCl₃Solution 200g, the acidity that above-mentioned slurry is adjusted with ammoniacal liquor to mix The pH=6.0 of slurry is closed, slurry is obtained after being sufficiently stirred, manufactured slurry is subjected to framboid shaping in spray dryer, Finally catalyst composition is made of roasting：

70 weight %Fe₁₀₀Cr_5.0Zn_25.0K_7.5La_5.0Ru_0.1Pd_0.1O_x+ 30 weight %Al₂O₃

【Embodiment 6】

266.7 grams of ferric nitrates and 49.09 grams of zinc nitrates obtain material I, taken in same container, adding 1000g water to dissolve 9.5 grams of lanthanum nitrates add 100g water to dissolve by heating, and obtain material II, take 3.3 grams of chromium trioxides, add 50g water, stirring and dissolving obtains material Ⅲ。

Material I, II, III is mixed, 437.5 gram of 40 weight % Alumina gel material is added under agitation, then adds 3.32 grams of KOH, containing 0.19 gram of PdCl₂And 0.27 gram of RuCl₃Solution 200g, the acidity that above-mentioned slurry is adjusted with ammoniacal liquor to mix The pH=6.0 of slurry is closed, slurry is obtained after being sufficiently stirred, manufactured slurry is subjected to framboid shaping in spray dryer, Finally catalyst composition is made of roasting：

30 weight %Fe₁₀₀Cr_5.0Zn_25.0K_7.5La_5.0Ru_0.1Pd_0.1O_x+ 70 weight %Al₂O₃

【Comparative example 1】

889.0 grams of ferric nitrates and 163.65 grams of zinc nitrates are taken to obtain material I in same container, adding 1500g water to dissolve, Take 31.7 grams of lanthanum nitrates to add 100g water to dissolve by heating, obtain material II, take 11.0 grams of chromium trioxides, add 100g water, stirring and dissolving Obtain material III.

Material I, II, III is mixed, 11.07 grams of KOH are added under agitation, containing 0.64 gram of PdCl₂And 0.91 gram of RuCl₃'s Solution 200g, the pH=6.0 of mixed slurry is caused with the acidity of the above-mentioned slurry of ammoniacal liquor regulation, slurry is obtained after being sufficiently stirred, will Manufactured slurry carries out framboid shaping in spray dryer, and finally catalyst composition is made of roasting：

Fe₁₀₀Cr_5.0Zn_25.0K_7.5La_5.0Ru_0.1Pd_0.1O_x

【Comparative example 2】

177.8 grams of ferric nitrates and 32.73 grams of zinc nitrates are taken to obtain material I in same container, adding 600g water to dissolve, take 6.3 grams of lanthanum nitrates add 50g water to dissolve by heating, and obtain material II, take 2.2 grams of chromium trioxides, add 50) water, stirring and dissolving obtains material Ⅲ。

Material I, II, III is mixed, 500.0 gram 40% of Alumina gel material is added under agitation, then adds 2.21 grams KOH, containing 0.13 gram of PdCl₂And 0.18 gram of RuCl₃Solution 200g, the acidity that above-mentioned slurry is adjusted with ammoniacal liquor causes mixed slurry PH=6.0, after being sufficiently stirred slurry, manufactured slurry is subjected to framboid shaping in spray dryer, finally roasted The catalyst being fired into forms：

20 weight %Fe₁₀₀Cr_5.0Zn_25.0K_7.5La_5.0Ru_0.1Pd_0.1O_x+ 80 weight %Al₂O₃

Obtained catalyst is carried out in reducing condition：

Reduced, then carry out Fischer-Tropsch synthesis under the following conditions：

The experimental result of synthetic reaction is listed in table 1.

Table 1

*C₂ ⁰~C₄ ⁰：C₂H₆、C₃H₈、iso-C₄H₁₀、n-C₄H₁₀

C₂ ⁼~C₄ ⁼：C₂H₄、C₃H₆、iso-C₄H₈、n-C₄H₈、tra-2-C₄H₈、cis-C₄H₈ 。

Claims (6)

1. a kind of microspheroidal synthesis of gas produced low-carbon hydrocarbon catalyst, the catalyst is using aluminum oxide as carrier, and active component is with atomic ratio Meter, the following composition of chemical formula：

Fe₁₀₀K_aZn_bCr_cLa_dO_x

A span is 0.1~10.0 in formula；

B span is 5.0~60.0；

C span is 0.1~15.0；

D span is 0.1~10.0；

X is to meet the oxygen atom sum in catalyst needed for each element chemical valence；

Carrier dosage is the 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, it is characterised in that a value model Enclose for 2~8；B span is 20~50；C span is 5~10；D span is 1~5.

3. the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 1, it is characterised in that catalyst exists Reduced before reaction, reducing condition is as follows：Reaction pressure is 0.05~5MPa, also the volume space velocity of Primordial Qi for 100~ 8000 hours^-1, reduction temperature is 200~600 DEG C, and the recovery time is 1~100 hour, and the also Primordial Qi is hydrogen, carbon monoxide Or synthesis gas.

4. any one of claims 1 to 3 ferrum-based catalyst is used for the reaction of synthesis of gas produced low-carbon hydrocarbon, it is characterised in that synthesis The reaction condition of gas preparing low carbon hydrocarbons：Reaction pressure is 0.5~10MPa, and reaction temperature is 200~600 DEG C, volume space velocity 100 ~8000 hours^-1, H in unstripped gas₂/ CO mol ratios are 0.1~5.0.

5. the preparation method of the ferrum-based catalyst of the microspheroidal synthesis of gas produced low-carbon hydrocarbon described in claim 1, including following technique Step：

(1) solution I is made by soluble ferric iron salt is soluble in water,

(2) soluble La salt is dissolved in hot water water and solution II is made,

(3) solution III is made by Cr and Zn soluble-salt is soluble in water,

(4) by the solution of solution I, II solution, III solution mixing system into mixed solution IV,

(5) by aequum Al in 70-100 DEG C of water-bath₂O₃Colloidal sol be added in solution IV, be mixed with beating, while add soda acid The pH value of conditioning agent regulation slurry is 1~5, and it is 15~45wt% slurries V to obtain solid content,

(6) spray dryer spray shaping is sent into after slurry V being cooled into 20~60 DEG C, then at a temperature of 400~1000 DEG C Roasting 0.15~10 hour, obtains microspheroidal Fluidized Multicomponent Metallic Oxides Catalysts.

6. the preparation method of the ferrum-based catalyst of microspheroidal synthesis of gas produced low-carbon hydrocarbon according to claim 5, its feature exist It it is 450~800 DEG C in sintering temperature, roasting time is 0.5~8 hour.