CN87102695A - Improved cobalt catalyst and to be used for methanol conversion be that hydrocarbon and Fischer-Tropsch process are synthetic - Google Patents
Improved cobalt catalyst and to be used for methanol conversion be that hydrocarbon and Fischer-Tropsch process are synthetic Download PDFInfo
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- CN87102695A CN87102695A CN87102695.3A CN87102695A CN87102695A CN 87102695 A CN87102695 A CN 87102695A CN 87102695 A CN87102695 A CN 87102695A CN 87102695 A CN87102695 A CN 87102695A
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Abstract
Be used to transform methyl alcohol or synthetic gas and be hydro carbons, help catalytic cobalt catalyst and method by zirconium, hafnium, cerium or uranium.Make methyl alcohol, the methyl alcohol that preferably is added with hydrogen contacts on said catalyzer, and synthetic gas is contacted on said catalyzer, so that generate C under reaction conditions
10The mixture of+paraffinic hydrocarbons and alkene.These hydro carbons can further be refined into high quality midbarrel fuel and other value product, and for example motor spirit, diesel-fuel and jet fuel, especially carbonatoms are not higher than about C
20Senior midbarrel fuel.
Description
The Fischer-Tropsch process of the invention relates to method improvement that methanol conversion is a hydrocarbon, producing hydrocarbon improves and the improvement of used catalyzer when implementing these methods.Specifically, the invention relates to improved cobalt catalyst, and methanol conversion and Fischer-Tropsch process is synthetic to produce the method for using this catalyzer in hydrocarbon, especially C+ distillate fuel and other valuable product.
At present, need initiative, development and improve to be used for methyl alcohol and synthetic gas are converted into hydrocarbon, especially some Catalyst And Methods of high quality transport fuel.Methane no matter be tail gas as institute's unwanted by product or processing unit, still is that it is very abundant to originate as the waste gas of oil-gas field.A large amount of methane that exist and Sweet natural gas and needs are produced senior transport fuel, especially middle distillate fuel all have important hormesis to developing new solution-air method.Yet, though it is the processing method of methyl alcohol that people have found conversion of natural gas, but in order to utilize this processing method, need but that new or improved to be suitable for methanol conversion be the high quality transport fuel, especially all catalyzer and the method for middle distillate fuel.
It is also fine that to have established Sweet natural gas or methane conversion be the required processing method of synthetic gas.People know that also available Fischer-Tropsch synthesis is converted into hydrocarbon to synthetic gas, but the method that but needs some new or improved catalyzer in a hurry and be suitable for carrying out Fischer-Tropsch reaction.As everyone knows, in technical literature and patent documentation, record Fischer-Tropsch synthesis from carbon monoxide and hydrogen production hydro carbons.Some place has had some industrial equipments to put into operation in the world, also has some to put into operation.What first industrialized Fischer-Tropsch synthesis was used in the world is cobalt catalyst, but active afterwards higher iron catalyst is also by commercialization.An impressive progress in the Fischer-Tropsch catalyst field is at the nickel-Thorotrast of early thirties employing on diatomite support.In thereafter 1 year, just corresponding cobalt catalyst occurs thereupon, promptly counted 100 Co by weight: 18Th O
2: 100 diatomite only it has then occurred through in a few years many time thereafter and have formed suitable 100Co: 18ThO respectively
2: 200 diatomite and 100Co: ThO
2: 8MgO: 200 diatomaceous catalyzer.In Fischer-Tropsch reaction, people use VIII family base metal widely, i.e. iron, cobalt and nickel, and the catalytic activity of these metals is improved with various other metals, with different modes it is carried on the various matrix.The experience of overwhelming majority industrialization aspect is all based on cobalt and iron catalyst; But the activity that cobalt catalyst had is not high usually, need to adopt multiple-stage method, and the synthetic gas productive rate is also low; On the other hand, for iron catalyst, has the water-gas shift activity of height, so in fact it be not suitable for conversion of natural gas owing to it.Therefore, more synthetic gas is by reaction H
2+ 2CO(CH
2) x+CO
2Be converted into CO
2, it is then very few that the reaction of pressing hope is converted into the synthetic gas of hydrocarbon and water:
2H
2+CO（CH
2）x+H
2O
For under high conversion and high yield condition, be suitable for methyl alcohol or synthetic gas are converted into senior transport fuel, especially do not produce excessive CO
2Catalyst composition and the requirement of method aspect, United States Patent (USP) 4,542, those catalyst compositions introduced in 122,4,595,703 and 4,556,752 and method are most of have been satisfied.More wherein said preferred catalyzer are called as granular catalyst composition, and they are by titania support or contain the carrier (preferred those rutile: anatase octahedrite content is than at least 2: 3 titania support) of titanium dioxide and be dispersed with catalytic activity amount cobalt or cobalt and Thorotrast thereon and constituted.These catalyst compositions have good activity and stable, and to be used for for a long time from methanol production hydro carbons or because carbon monoxide and hydrogen synthin.
It is found that these cobalt-titanium deoxide catalysts are wrapped a kind of carbonaceous residue as most of hydrocarbon synthesis catalyst during " turning round in the oil ", promptly during the ongoing operation or the coke that during charging or temperature fluctuation, forms.The high initial activity of this catalyzer reduces owing to coke deposits thereon during operation, therefore must improve service temperature in order to keep transformation efficiency on certain level.At last, the catalyzer deactivation is to such degree, so that cause consuming required C for keeping transformation efficiency required temperature on certain level
10+ hydro carbons forms excessive methane and other light hydrocarbon gases, must make this catalyst regeneration and active again this moment.Yet it is different with many other catalyzer that oil-refinery industry is used usually, under heating up, contact with air (or oxygen) and under oxidizing condition, make said coke settling from this cobalt-titanium deoxide catalyst behind the burning-off, when handling said catalyzer with reducing metal cobalt composition with hydrogen again, the high initial activity of said cobalt-titanium deoxide catalyst can not return to the sort of degree of live catalyst, and cobalt-titanium deoxide catalyst that its specific activity is fresh is much lower.Moreover after said catalyst regeneration and reactivate, deactivation speed does not reduce, and this deactivation will be a starting point from lower initial activity.In the presence of air (oxygen),, not only itself be deleterious owing to burn off coke in these catalyzer causes the loss on the gross activity, but also strictness has limited this catalyst life, threatens its making full use of in industrial operation in heating up down.
Therefore, main purpose of the present invention is to eliminate this problem.
Specifically, the object of the present invention is to provide some novelties and improved cobalt-titanium deoxide catalyst, and utilize this catalyzer that methyl alcohol or synthetic gas are converted into the high quality transport fuel, especially so-called C
10The method that the mixture of+straight-chain paraffin and alkene distillates fuel.
Of the present invention one more specifically purpose to be to provide like this that some are new and improved, to be stated from be cobalt-titanium deoxide catalyst on the carrier, they are not only active high in methanol conversion reaction and F-T synthesis reaction, stable before regeneration and the activation, and after regeneration and reactivate, can recover its high initial activity, can also keep its stability simultaneously.
Another object of the present invention is to provide a kind of use this catalyzer by the raw mix of methyl alcohol or an oxidation and hydrogen by using this catalyzer to prepare hydro carbons, being commonly called the method for middle distillate fuel of the sort of very high-quality of straight-chain paraffin and alkene mixture.
These purposes with other purpose by the present invention reach.Generally speaking, the present invention is summarised as:
(A) a kind of by titania support or contain the pellet type catalyst composition that carrier constituted of titanium dioxide, on said carrier, be dispersed with catalytic activity amount cobalt and capacity metal promoters, said cobalt amount is enough to the methanol production hydro carbons time or provides good active and stable when producing hydro carbons with carbon monoxide-hydrogen synthetic gas, and it [is the periodic table of elements (E.H.Sargent ﹠amp that said metal promoters is selected from by zirconium, hafnium; Company, copyright in 1962, Dyna-Slide company) nucleidic mass is higher than 90 metal in the IV B family], a kind of metal selected in the material group that cerium (a member in the lanthanide series metal) and uranium (a kind of actinide metals) are formed or the mixture of the mixture between these metals or these metals and other metal, with box lunch afterwards at the said cobalt of oxidation under the intensification (what on catalyzer, carry out after the deposition coke between the operation operation), can utilize the method that under heating up, contacts with oxygen or oxygen-containing gas (as air) therefrom the said coke of burn off with the said catalyzer of regenerating, the method that then it is contacted the said cobalt metal composition of reduction with reducing gas (especially hydrogen) makes it reactivate, so as to recovering said activity of such catalysts and stability.According to said catalyst composition gross weight (dry basis), when pressing metallic state metal absolute concentration and calculating, the suitable amount of cobalt is about 25% for about 2%-, and preferred amounts is about 5%-about 15%.The salt or the compound of a certain amount of said promoter metal zirconium, hafnium, cerium or uranium are added to a kind of like this matrix material of formation in said cobalt-titanium deoxide catalyst, its activity and stability level near fresh cobalt-titanium deoxide catalyst (being a kind of catalyzer, the cobalt-titanium deoxide catalyst of never regenerating) after regeneration.Said promoter metal is quite effective under lower concentration, when concentration is higher than when the required numerical value of required reproducibility is provided, has little or no further benefit usually.Efficient that it is generally acknowledged said promoter metal is relevant with the physical condition of its high dispersing on the surface of said titanium dioxide carrier.Utilize in the certainweight ratio metal such as zirconium, hafnium, cerium or uranium and cobalt composite methods in addition, can make reproducible cobalt-titanium deoxide catalyst, the suitable weight ratio of metal and cobalt is approximately greater than 0.010: 1, preferably than about 0.025: about 0.10: 1 of 1-.The cobalt of one or more said promoter metals (being zirconium, hafnium, cerium or uranium) with the catalytic activity amount is dispersed on the titania support, and the rutile especially wherein and the weight ratio of anatase octahedrite are at least about on 2: 3 the sort of titanium dioxide carrier.Said rutile and the ratio of anatase octahedrite are pressed ASTMD3720-78 and are measured (standard method of analysis that the X-ray diffraction method is measured anatase octahedrite and hundred ratios of rutile in the TiO 2 pigment).The absolute concentration of chosen in advance cobalt and promoter metal is so that make the metals such as zirconium, hafnium, cerium or uranium and the ratio of cobalt reach desirable value.From the cost-effectiveness viewpoint, zirconium is an a kind of preferred IV B family metal, and according to the weight ratio of zirconium white and cobalt greater than 0.010: 1(is preferably from about 0.04: the catalyzer that about 0.25: 1 of 1-) zirconium is added cobalt-titanium dioxide it is found that and formed the high catalyzer of a kind of regenerating stability.It is found that, this catalyzer can continuous several times regeneration, and its initial activity is recovered basically fully when catalyzer delivered in the oil operation again, and in methanol conversion reaction or its stable free of losses in hydrocarbon synthesis reaction.When cobalt-titanium deoxide catalyst composition in zirconium, hafnium, cerium or uranium behind any metal or its composition stability, if it is found that the product C that produces
10+ straight-chain paraffin and alkene, few oxidation.With never compare (promptly except not compound therein zirconium, hafnium, cerium or uranium through the regeneration or the catalytic cobalt-titanium deoxide catalyst that do not helped that never experiences those prepared fresh of regeneration condition, the similar catalyzer of others), these helped catalytic catalizer variety in methanol conversion or when carbon monoxide and hydrogen are converted into distillate fuel through after the regeneration, provide essentially identical highly selective, high reactivity and high reactivity hold facility.Therefore, said is that highly efficient regeneration is stable through helping catalytic cobalt-titanium deoxide catalyst, this through helping catalytic catalyst activity and stability after the regeneration, utilize under oxidizing condition in the high temperature air method of burn off coke knot thing to make it to return to never to regenerate without on the level that helps catalytic cobalt-titanium oxide catalyst.
(B) a kind of method, wherein make above and saidly in (A) to be helped catalytic particulate state cobalt-titanium deoxide catalyst composition to form a bed or catalyst bed by zirconium, hafnium, cerium or uranium, under reaction conditions, make said bed catalyst bed or contact with methanol feeding or with charging of forming by the mixture of carbon monoxide and hydrogen or the compound that can decomposition in situ in said bed generates carbon monoxide and hydrogen, so that produce mainly by straight-chain paraffin and alkene, especially C
10The middle distillate fuel product that+straight-chain paraffin and alkene are formed.
When (ⅰ) making the methyl alcohol reaction, the methyl alcohol dividing potential drop in reaction mixture is maintained at about usually and is higher than 100(pounds per square inch absolute (psia) pound/inch
2) (Psia), preferred value is approximately higher than 200 Psia.Usually in methyl alcohol, add hydrogen for well.In order to increase C in the product
10The concentration of+alkane, the mol ratio CH of used methyl alcohol and hydrogen
3OH: H
2To be advisable greater than 4: 1 approximately, preferred value was greater than 8: 1.Under the condition of using hydrogen, CH
3OH: H
2Mol ratio is to be advisable from about 4: 1 to about 60: 1, and the mol ratio of preferentially using methyl alcohol and hydrogen is from about 8: 1 to about 30: 1.The dividing potential drop preferred value of inlet hydrogen is lower than about 80Psia and more preferably is worth about 40Psia; Inlet hydrogen dividing potential drop scope is preferably from about 5 Psia to about 80Psia, and more preferably from about 10Psia about 40Psia extremely.The condition that this reaction is carried out is: the liquid hourly space velocity rate was from about 0.1 to about 10 hours
-1, preferred value was from about 0.2 to about 2 hours
-1; Temperature is from about 150 ℃ to about 350 ℃, preferably from about 180 ℃ to about 250 ℃.The preferable range of methyl alcohol dividing potential drop is from about 100 to about 1000Psia, more preferably from about 200 to about 700 Psia.
(ⅱ) condition of carrying out of said building-up reactions is:
H
2: the CO mol ratio is generally approximately greater than 0.5, and preferable range is from about 0.1 to about 10, preferred scope from about 0.5 to about 4; The gas hourly space velocity scope is generally from about 100 to about 5000V/ hours/V, and preferred value was from about 300 to about 1500V/ hours/V; Temperature range is generally from about 160 to being about 290 ℃, and preferred value is from about 190 to about 260 ℃; Pressure generally is approximately higher than 80 pounds/inch
2(gauge pressure) (Psia), preferable range is from about 80 to about 600 Psia, more preferably from about 140 to about 400 Psia.
No matter be methanol conversion reaction product or building-up reactions product, select for use usually and preferentially and contain 45% or more be higher than (320) ebullient C under 160 ℃
10+ liquid hydrocarbon more preferably contains 60% or more said hydrocarbon.
When making said shaping of catalyst, adopt titanium dioxide, perhaps titanium dioxide is made carrier with other material as carrier.But, in transforming, methanol conversion or synthetic gas be used as the titanium dioxide of said carrier, and the preferential ratio of measuring (ASTM D3720-78) rutile anatase octahedrite through the X-ray diffraction method that uses is at least about such a kind of carrier of 2: 3.Transform with the catalyst carrier for synthetic gas,, preferentially be at least about 3: 2 the sort of with the ratio of rutile and anatase octahedrite as the titanium dioxide of support of the catalyst.Used titanium dioxide in synthetic gas transforms, the ratio of the rutile that wherein contains and anatase octahedrite from 3: 2 to about 100: 1 or higher being advisable, preferentially uses this ratio by about 4: 1 to about 100: 1 or higher the sort of titanium dioxide with approximately.Preferred and the stronger catalyzer of selectivity that uses in methanol conversion reaction is a rutile and the ratio of anatase octahedrite is about 2: 3 to about 3: 2 titanium dioxide.The surface-area of these form titanium dioxide is approximately less than 50 meters
2/ gram.The rutile of this weight provides best activity and C usually
10+ hydrocarbon-selective and do not have a large amount of gases and CO
2Generate.
It is found that, help catalytic cobalt-titanium deoxide catalyst through zirconium, hafnium, cerium or uranium, the activity that has before the regeneration is basically together accordingly without helping catalytic cobalt-titanium deoxide catalyst high like that.Therefore, utilize the methanol conversion effect or utilize carbon monoxide and during the synthetic hydrocarbon of hydrogen, between working run, perhaps producing between the on-stream period of hydrocarbon with raw catalyst in starting from oil, the activity of these two kinds of different catalysts does not have difference in essence.But with without help catalytic cobalt-titanium deoxide catalyst or except not containing zirconium, hafnium, cerium or uranium all the other similar catalyzer different, initial high reactivity through helping catalytic cobalt-titanium deoxide catalyst will be kept, utilize even under the temperature that improves and in oxygen containing gas (for example air), burn the coke settling, and then utilize and make catalyzer contact step such as reducing catalyst that the catalyst regeneration of coke structure also can be kept afterwards with hydrogen or hydrogenous gas.And, said stability through helping catalytic cobalt catalyst also will be kept, this catalyzer under the corresponding condition in oil the deactivation speed in when running be not higher than any regeneration never and without helping catalytic cobalt-titanium deoxide catalyst, be not higher than except not containing zirconium, hafnium, cerium or uranium all the other similar any catalyzer of regenerated that never pass through yet.It is found that, though have high initial activity when helping catalytic fresh cobalt-titanium deoxide catalyst in oil, to operate, but this activity of such catalysts is not recovered fully after promptly finding regeneration subsequently, and the activity that this catalyzer recovers only is equivalent to said live catalyst former activated about 50%.And, in oil after the operation, through regenerated by zirconium, hafnium, cerium or uranium help catalytic cobalt-titanium deoxide catalyst activity will with fresh, without helping the identical speed of catalytic cobalt-titanium deoxide catalyst to reduce.Therefore, by this activity and stability through helping catalytic cobalt-titanium oxide catalyst to keep, overcome original effectively because use, and can in industrial operation, make full use of cobalt-titanium deoxide catalyst without the shortcoming that helps catalytic cobalt-titanium deoxide catalyst to cause.
As most hydrocarbon synthesis catalysts, cobalt-titanium deoxide catalyst is operating period in oil, the deactivation mainly due to depositing certain carbonaceous residue thereon, this carbonaceous residue for example coke form during the ongoing operation or in charging or temperature fluctuation the time.It is believed that this coked catalyzer can obtain regeneration with the method for burn off close-burning thing in this catalyzer certainly, and recovers its initial activity.Utilization is as 400-500 ℃ of calcining method in air, thereby can from catalyzer, remove whole carbon effectively basically usually, this just provides a kind of quite simple, method of being easy to industrial enforcement for the cobalt-titanium deoxide catalyst of regeneration deactivation.Yet, recover active for air regenesis, the cobalt metal of said catalyzer in oil, operate and regeneration condition under must remain under the dispersion state.It is found that though what fully be dispersed with cobalt thereon is stable without helping catalytic cobalt catalyst operating period in oil, cobalt will lump during high temperature air is handled.Yet it is found that, even the zirconium of lower concentration, hafnium, cerium or uranium or its mixture, all can be as the additive of stablizing said cobalt-titanium deoxide catalyst, operating period in oil not only, and all can keep the dispersion state of cobalt on titanium dioxide, thereby provide a kind of easy regenerated catalyzer at this additive during the air calcination.
Though the applicant does not wish to be subjected to any specific mechanisms to fetter, believe and can explain, at least partial interpretation with air calcination during, metals such as zirconium, hafnium, cerium or uranium improve the effect of cobalt-titanium deoxide catalyst reproducibility aspect.That is, during air calcination, the oxidized generation of cobalt metal crystal grain in cobalt-titanium deoxide catalyst is as the Co of temperature is higher than about 350 ℃ time cakings
3C
4Make after the said reactivation of catalyst by contacting, form and contain the grains cobalt metal caking bigger than the original metal crystallite size of cobalt metal with hydrogen.The catalyzer that is formed by big caking cobalt is than by disperseing to such an extent that better the catalyst activity that forms of cobalt is little.In helping catalytic cobalt-titanium deoxide catalyst, zirconium, hafnium, cerium or uranium promoter metal are present in TiO with the oxide form of high dispersing said
2On the carrier surface, and all have the isometric system crystalline structure (can be with isometric system CeO except promptly
2Again can be with hexagonal system Ce
2O
3Outside the Ce that form exists).According to these oxide compounds of proof and the Co that also has cubic crystal structure
3O
4Form a kind of strong surface interaction effect.Thereby it is believed that this cubic oxide promotor forms a kind of matrix, at Co
3O
4And TiO
2" binding agent " effect that plays, and cobalt is remained on the carrier surface with the high dispersing form.
Catalyzer of the present invention can be prepared with the currently known methods of other catalyzer of preparation in the ability.This catalyzer for example can or be total to the gelling process preparation with gelling process.But, metals such as zirconium, hafnium, cerium or uranium, or these intermetallic mixtures, perhaps mixtures of a little and other metal of these gold can suitably be deposited on the carrier substance of making spherical, ball shape, pearl, extruding or screening in advance with pickling process.Preparation makes these metals be deposited on from solution on the carrier according to the amount of selecting in advance during catalyzer, makes the absolute magnitude and the weight ratio of respective metal (for example cobalt and zirconium or hafnium, or the mixture of cobalt and zirconium and hafnium) reach desirable value.Metals such as cobalt and zirconium, hafnium, cerium or uranium and carrier is suitably compound, and concrete grammar is to make carrier and compound that contains cobalt or salt (for example Xiao Suangu, cobaltous acetate, acetylacetone cobalt, cobalt naphthenate, cobalt-carbonyl or the like) and contain the compound of promoter metal or the solution of salt contacts.Can make a kind of metal and carrier compound, and then make another kind of metal composite.For example, at first promoter metal is immersed on the carrier, and then the dipping cobalt, or opposite.Promoter metal and cobalt are immersed on the carrier selectively altogether.The cobalt that in said dip operation, uses and the metallic compound of promotor, can be any organometallic compound or the inorganic metal compound that when calcining, can decompose the oxide compound that generates cobalt and zirconium, hafnium, cerium or uranium, for example nitrate of cobalt, zirconium or hafnium, acetate, acetylacetonate compound, naphthenate, carbonyl compound or the like.Employed dipping solution amount should be enough the said carrier of submergence fully, the 1-20 that is about carrier usually according to volumometer doubly, concrete multiple is decided on one or more metal concentrations in the dipping solution.Said dip operation can be carried out in room temperature or so very wide condition and range that heats up.Multiple metallic compound or metal except that cobalt and promoter metal also can add.Can use any method, in any time of the said catalyzer of preparation, for example before the metal ingredients such as carrier impregnation cobalt and zirconium, hafnium, cerium or uranium, afterwards or simultaneously, in said catalyzer, add one or more additional metals.In operating usually, said supplementary component adds simultaneously with compositions such as cobalt and zirconium, hafnium, cerium or uranium.
Preferably at first on carrier, flood metals such as zirconium, hafnium, cerium or uranium, make perhaps that one or more metals and cobalt are impregnated on the titania support altogether in zirconium, hafnium, cerium or the uranium, and then drying and calcined catalyst.Therefore, a kind of method for preparing catalyzer is that the carrier that makes titania support or contain titanium dioxide at first floods metal-salt or compounds such as zirconium, hafnium, cerium or uranium, then under conventional conditions and calcining.One or more metals and through disperseing cobalt on the burnt said carrier in advance in being dispersed with zirconium, hafnium, cerium or uranium then are then again to the in addition dry and calcining of this catalyzer.Perhaps one or more metals in zirconium, hafnium, cerium or the uranium can be immersed on the said carrier altogether, and then dry and this catalyzer of calcining.It is believed that zirconium, hafnium, cerium or uranium metal exist with oxide form in newly formed incinerating catalyzer, compare with cobalt and combine closelyr between this oxide compound and the titania support.
After the carrier impregnation, nitrogen or oxygen or the two simultaneously in the presence of or in the presence of air, in air-flow or vacuum, in being approximately higher than under 30 ℃ (between preferred 30-125 ℃ under the temperature) heat drying through helping catalytic cobalt-titanium deoxide catalyst.Before using, must activate the catalyzer of making.Being preferably in the first step makes said catalyzer and oxygen, air or other oxygen-containing gas be enough to make cobalt oxidation be transformed into Co
3O
4Temperature under contact.When temperature is approximately higher than 150 ℃ greatly, when preferably approximately is higher than 200 ℃, be enough to cobalt is converted into said oxide compound, also do not allow but temperature is not higher than 500 ℃ (for example temperature that may adopt) approximately when the catalyzer of the serious deactivation of regeneration.Temperature from about 150 ℃ to about 300 ℃ of scopes, cobalt is suitable oxidized.Contained cobalt/cobalt oxide is a cobalt metal so that activate this catalyzer in the reducing catalyst then.Be approximately higher than under 250 ℃,, contacting with reducing gas, preferably contacting, finishing reductive action with hydrogen or hydrogenous air-flow by making said catalyzer (no matter whether in advance through oxidation) preferably approximately greater than under 300 ℃.At normal pressure to about 40 normal atmosphere, usually under from about 250 ℃ to 500 ℃, preferably from about 300 ℃ to about 450 ℃ of temperature, reduce said catalyzer about 0.5 to about 24 hours.Use hydrogen or hydrogeneous all satisfactory when reducing with mixture rare gas element.
In regeneration step, burn off coke knot thing from catalyzer.Catalyzer is contacted with hypoxic gas, be lower than under the sintering of catalyst temperature burn off coke knot thing from catalyzer at controlled temperature.By controlling oxygen concn and going into implication concentration and keep maturing temperature on desired level, this need consider the close-burning thing amount of desiring to remove and finish the required time of roasting.Usually use oxygen partial pressure greater than 0.1 pound/inch
2(Psi) gas about, preferably use the gas (purpose is that temperature is in the 300-500 ℃ of left and right sides scope) about oxygen partial pressure 0.3-2.0Psi, under static state or dynamic condition, preferably under dynamic condition, handle said catalyzer till removing the coke settling.Can finish the work of burn off close-burning thing with following method: feed during beginning and only enough light required oxygen, make temperature remain on a low side of this temperature range simultaneously, utilize the method that sprays into additional content oxygen that flamjne front is increased then, till this moment, temperature improved gradually when temperature reaches desirable value.Generally can remove most close-burning things in this way.As handling raw catalyst, this catalyzer is reactivated then with hydrogen or hydrogen-containing gas.Present invention will become more fully understood with embodiment with reference to the following describes, and some comparative datas wherein are provided, and the characteristics that it is outstanding more are described.Except indicating specially, all umber all refers to parts by weight, and feed composition is represented by the mol ratio of each composition.
At Co-TiO
2Add a small amount of hafnium, zirconium, cerium or uranium in the catalyzer respectively cobalt is remained under the high dispersing state, and make said catalyzer stabilization when high temperature air is handled.The zirconium, hafnium, cerium or the uranium that add, thereby make said catalyzer after regeneration period and regeneration, keep very high intrinsic activity, this activity is that cobalt is well dispersed in TiO
2On the feature of live catalyst.By the Co-TiO of promotor
2This high intrinsic activity, can after regeneration, operate with same high transformation efficiency in low temperature, as the use raw catalyst, be converted into C by methyl alcohol or synthetic gas
10Obtained high selectivity in the process of+hydrocarbon.
Provided the result of a series of tests in the following embodiments, wherein, at several parts of freshly prepd Co-TiO
2Respectively added different metals in the catalyzer respectively, comprising zirconium, hafnium, cerium or uranium, with these catalyst samples and a Co-TiO that does not add promoter metal
2Catalyzer is compared.These catalyzer are utilized the method calcining that contacts with air under simulation close-burning thing roasting condition,, be used for Fischer-Tropsch reaction then under the temperature that improves by contacting with hydrogen to activate.To be impregnated with the catalyzer and the comparative catalyst of metal, promptly with wherein except that not adding promoter metal others all similarly catalyzer compared.After simulation regeneration, utilize the CO inversion quantity proof that obtains by every kind of catalyzer at Co-TiO
2Add the effect behind the metal (or metal promoters) in the catalyzer.
Embodiment 1
With titanium dioxide (Degussa p-25 Ti O
2) as the carrier for preparing various catalyzer.With Degussa p-25 TiO
2With a kind of stearic vegetables oil of Sterotex(as lubricant, a kind of product of capital city Products Co., Ltd) mixes, granulation then, grind, filter out 80-150 order (Tyler) part, in 650 ℃ of following air calcination 16 hours, the TiO that obtains having following character
2Carrier:
Rutile and anatase octahedrite surface-area pore volume
Weight ratio
(1)m
2/ g ml/g
97∶3 14 0.16
（1）ASTM D3720-78
According to following method, use rotatory evaporator, dipping TiO
2Carrier has prepared a series of catalytic 11%Co-TiO that helped
2Catalyzer, in carrying out hydrocarbon synthetic operation process with these through help catalytic catalyzer with without helping catalytic 11%Co-TiO
2Catalyzer is compared.
Promoter metal and cobalt are imposed on TiO simultaneously
2On the carrier, used immersion solvent is acetone, acetone-15-20% water or water (preparation example A, B or C); Perhaps use pickling process successively, at first in promoter metal solution, flood, under 140-500 ℃ of temperature, carry out intermediate air then and handle, flood the TiO that contains promotor of drying at last with salpeter solution
2Mixture (preparation D, E, F, G and H).These Preparation of catalysts steps are recorded in the following table I.
The table I
Catalyst preparation step
The while immersion solvent
A acetone
B acetone-15-20% water
C water
The dipping dipping first time floods for the second time with the solvated mesophase air handling and uses solvent successively
(promotor dipping) temperature (℃) (Xiao Suangu)
D Virahol 140 acetone
E acetone-15% water 140 acetone
F acetone-15% water 500 acetone
G water 140 acetone
H water 500 water
In 140 ℃ of vacuum drying ovens with dry about 20 hours of the impregnated catalyzer of this quadrat method.In all temps, carry out air handling in 3 hours in the blast furnace.With 80-150 order TiO
2This catalyzer by volume is diluted to 1: 1(is so that reduce thermograde), pack in 1/4 inch internal diameter reaction tubes, 450 ℃ down and 5000 volumes/hour/hydrogen stream of volume of catalyst in reduction 1 hour, be that 1500(is on catalyzer at 200 ℃, 280psig, gas hourly space velocity then) and H
2At least reacted 16 hours with synthetic gas under the conditions such as/CO=2.Use neon to make interior mark (accounting for 4% in the charging), with the performance of every kind of catalyzer of conventional gas-phase red, orange, green, blue, yellow (ROGBY) monitoring.Activity the results are shown in the table II and is shown among Fig. 1 and 2 with curve.Using these Co-TiO
2In the catalyzer during any one catalyzer, all obtained the high selectivity that counterweight burns hydrocarbon, irrelevant with the promotor that exists.In each test, the selectivity of methane is about 3-5mol.%, and the CO selectivity is less than about 0.2mol.%.Rest part is C in the product
2+ hydrocarbon.
The table II
Catalyst test result
The air place
Promotor Li Wendu CO transformation efficiency on 11%Co-TiO
Element compound Wt.% preparation process ℃-3 hours (%)
Do not have--A-78
″ 250 73
″ 400 63
″ 500 48
″ 550 32
″ 600 28
Hf HfO（NO
3）
20.06 A 500 48
″ 0.31 ″ 400 78
″ 0.31 ″ 500 73
″ 0.50 ″ 500 70
″ 0.50 ″ 600 58
″ 0.63 ″ 500 71
″ 1.89 ″ 500 78
″ 3.0 ″ 500 81
Ce （NH
42Ce（NO
3）
60.5 B - 79
″ 0.5 B 500 81
″ 0.5 E 500 78
″ 0.5 F 500 76
″ 0.5 B 600 63
″ 2.0 B 500 64
″ 2.0 H 500 61
Zr Zr（OC
3H
7）
40.5 D - 85
″ 0.5 D 500 31
ZrO（O
2CCH
3）
20.3 C - 75
″ 0.3 C - 75
″ 0.3 C 500 63
″ 0.6 C 500 68
″ 0.9 C - 80
″ 0.9 C 500 70
″ 1.1 C 500 74
U UO
2（NO
3）
21.0 A 500 79
As reference Fig. 1 described, these results obviously find out from table: zirconium, hafnium, cerium or uranium promote also to have kept 11%Co-TiO after calcining
2Activity of such catalysts.Therefore, through helping catalytic 11%Co-TiO
2Catalyzer is still high up to the activity behind 500 ℃ of temperature lower calcinations and be actually constant, otherwise, without helping catalytic 11%Co-TiO
2Activity of such catalysts but promptly and sharp descends, and active lowering speed is relevant with calcining temperature.
The data of describing among Fig. 2 illustrate that clearly a small amount of zirconium, hafnium, cerium or uranium are improving 11%Co-TiO
2The effect of catalyst regeneration aspect, approximately the promotor of 0.5Wt.% concentration is enough to make static stabilization near maximum value.As if the promotor that concentration is higher (if present) do not produce any great effect.
Use 11.2%Co-0.5%Hf-TiO at one
2In the test of catalyzer, further investigated thoroughly the distribution situation of hydrocarbon product.This catalyzer (150cc) is used 110cc TiO
2After the dilution, put into the reactor of 1/2 English internal diameter, use H under 450 ℃
2Reduced 4 hours, and be used for the reaction that synthetic gas is converted into hydrocarbon then.Operational condition and products distribution situation are listed among the table III, and these results confirm, at Co-Hf-TiO
2Various heavy hydrocarbons have been generated on the catalyzer.
The table III
Use Co-Hf-TiO
2The time hydrocarbon product distribution situation
Temperature, ℃
Sand bath 204
Average reactor temperature 206
Gas hourly space velocity 1000 on the catalyzer
Pressure, Psig 280
H
2/ CO inlet is than 2.090
The CO transformation efficiency, % 89
The distribution situation of hydrocarbon product, Wt.%
C
15.6
C
2-C
43.4
C
5-550°F 15.1
550-700°F 10.0
700-1050°F 29.2
1050°F+ 36.7
It is the catalyzer of the present invention that uses in the hydro carbons that the following examples are described in detail in methanol conversion.
Embodiment 2
Ball shape titanium dioxide is supplied with by catalyzer manufactory, and is used to make catalyzer.This titanium dioxide coarseness is 14-20 order (Tyler), is characterized in: rutile: anatase octahedrite=86: 14, surface-area are 17m
2/ g, pore volume are 0.11ml/g.Several parts of titanium dioxide are flooded simultaneously contain Xiao Suangu and contain ZrO(O respectively
2CCH
3)
2, HfO(NO
3)
2, (NH
4)
2Ce(NO
3)
6And VO
2(NO
3)
2The aqueous solution, prepare catalyzer in this way.Behind the dipping, with every kind of catalyzer drying, 500 ℃ of following air handlings 3 hours.In these catalyst compositions, the concentration expressed in percentage by weight (1Wt.%) that every kind of catalyzer contains the concentration expressed in percentage by weight of cobalt and contains promotor is listed among the table IV.
In several tests of separately carrying out, each test all will be through helping catalytic CoTiO
2It is in 3/8 inch reaction tubes that catalyzer adds internal diameter, reduction 1 hour in hydrogen under 450 ℃, 1000 gas hourly space velocities and Opsig.Then, (wherein the mol ratio of three materials is 20CH to make the incoming mixture of hydrogen, argon and methyl alcohol
3OH: 1H
2: 4Ar), at CH
3Pass through from every kind of catalyzer under the conditions such as OH liquid hourly space velocity=0.67,230 ℃ and 400psig.Utilization is carried out the performance that the conventional gas-phase red, orange, green, blue, yellow (ROGBY) is monitored every kind of catalyzer to product, the results are shown in the table IV.
The table IV
By methanol conversion is the test-results of hydrocarbon
(230 ℃, 400psig, liquid hourly space velocity=0.67,20CH
3OH: 1H
2: 4Ar)
At TiO
2On catalyst composition
Weight %Co 5.00 4.34 4.65 4.55 4.73
The no Zr Hf of promotor (1Wt.%) Ce U
CH
3The OH transformation efficiency, % 31 37 34 49 46
Speed,
The methyl alcohol that transforms/hour/gram Co 1.6 2.3 1.9 2.8 2.6
Carbonaceous products distributes, Wt, %
CO 16 13 16 10 9
CO
28 9 7 9 13
CH
48 8 8 7 9
C
2+ 68 70 69 74 69
These presentation of results are calcined after help catalytic catalyzer ratio without helping catalytic Co-TiO through 500 ℃
2Catalyzer is more active; This point is proved best by the conversion rate of methyl alcohol.As observed, cerium is a kind of good especially promotor for the methanol conversion effect, helps catalytic Co-TiO through cerium
2Catalyzer has the highest active and to C
2+ hydro carbons best choice.Co-TiO
2Selectivity of catalyst, usually the utilization method that adds corresponding promotor therein remains on very high numerical value, and owing to existing said promotor to obtain in a way improvement.
Obviously, under the preceding topic of spirit and scope of the invention, can make various changes and variation.
Claims (10)
1, a kind of regeneration stable catalyst, said catalyzer is used for being translated into hydro carbons under methyl alcohol or synthesis gas reaction condition, comprising will by cobalt and the titania support of the about 2%-of said catalyst composition weight about 25% or to contain the carrier of titanium dioxide compound, add zirconium, hafnium, cerium or uranium promotor therein, the weight ratio of wherein said zirconium, hafnium, cerium or uranium metal and cobalt is approximately greater than 0.010: 1.
2, the composition of claim 1, the weight ratio of wherein said zirconium, hafnium, cerium or uranium metal and cobalt are approximately from 0.04: 1 to about 0.25: 1.
3, the composition of claim 1, wherein said catalyzer contains 5% to about 15% the cobalt of having an appointment by the weight of said catalyst composition.
4, the composition of claim 1, rutile is at least about 3: 2 with the content ratio of anatase octahedrite in the wherein said titanium dioxide.
5, a kind of regeneration stable catalyst, said catalyzer is used for being translated into hydro carbons under methyl alcohol or synthesis gas reaction condition, comprising with catalytic activity amount cobalt and titania support or to contain the carrier of titanium dioxide compound, the zirconium that adds capacity therein, hafnium, cerium or uranium promotor, so that when making methyl alcohol or synthetic gas be converted into hydro carbons, because of the close-burning thing deposits on said catalyzer, and with the said catalyzer of regenerating of the method for burn off close-burning thing therefrom, contact with reducing gas then after the reduction cobalt, obtain active and activity is remained on except said cobalt-titanium dioxide to urge agent not contain on the level of the catalyzer that others were not similarly regenerated as yet the said promotor that adds.
6, a kind of being applicable to transforms methyl alcohol or raw material of synthetic gas is the method for hydro carbons, comprising said raw material is contacted with catalyzer, said catalyzer comprises with titania support or contains the carrier compound cobalt of titanium dioxide, contain cobalt about 2% to about 25% by said catalyst composition weight, add zirconium, hafnium, cerium or uranium promotor therein, said zirconium, hafnium, cerium or uranium metal compare approximately greater than 0.010: 1 with weight of cobalt.
7, the method for claim 6, the weight ratio scope of wherein said zirconium, hafnium, cerium or uranium metal and cobalt are approximately from 0.04: 1 to about 0.25: 1.
8, the method for claim 6, wherein said catalyzer contain and are about 5% to about 15% cobalt by said catalyst composition weight.
9, the method for claim 6, wherein the said raw material that contacts with said catalyzer is the mixture of carbon monoxide and hydrogen, said reaction conditions is defined as within following scope:
H
2: CO mol ratio about 0.5: 1-4: 1
Gas hourly space velocity (V/ hour/V) about 100-5000
Temperature (℃) about 160-290
Total pressure (pound/inch
2, gauge pressure) and about 80-600
10, the method for claim 6, wherein the said raw material that contacts with said catalyzer is made up of the mixture of methyl alcohol and hydrogen, and said reaction conditions is defined within the following scope:
The ratio of methyl alcohol and hydrogen is approximately greater than 4: 1
Space velocity (hour
-1) about 0.1-10
Temperature (℃) about 150-350
Methyl alcohol dividing potential drop (pound/inch
2, gauge pressure) and about 100-1000.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN90102061A CN1018917B (en) | 1987-04-11 | 1987-04-11 | Process for conversion of methanol or synthetic gas into hydrocarbons |
| CN87102695A CN1010283B (en) | 1985-12-27 | 1987-04-11 | Improved cobalt catalysts and use thereof for conversion of methanol to hydrocarbons, and for ficher-tropsch synthesis |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/813,918 US4663305A (en) | 1984-06-29 | 1985-12-27 | Cobalt catalysts for the conversion of methanol and for Fischer-Tropsch synthesis to produce hydrocarbons |
| CN87102695A CN1010283B (en) | 1985-12-27 | 1987-04-11 | Improved cobalt catalysts and use thereof for conversion of methanol to hydrocarbons, and for ficher-tropsch synthesis |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90102061A Division CN1018917B (en) | 1987-04-11 | 1987-04-11 | Process for conversion of methanol or synthetic gas into hydrocarbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87102695A true CN87102695A (en) | 1988-11-02 |
| CN1010283B CN1010283B (en) | 1990-11-07 |
Family
ID=25742306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87102695A Expired CN1010283B (en) | 1985-12-27 | 1987-04-11 | Improved cobalt catalysts and use thereof for conversion of methanol to hydrocarbons, and for ficher-tropsch synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1010283B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718783A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of stable ultra-fine FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718773A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
-
1987
- 1987-04-11 CN CN87102695A patent/CN1010283B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109718783A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of stable ultra-fine FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718773A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of FT synthetic catalyst and its preparation method and application and Fischer-Tropsch synthesis method |
| CN109718783B (en) * | 2017-10-27 | 2022-03-11 | 中国石油化工股份有限公司 | Stable superfine FT synthesis catalyst, preparation method and application thereof, and Fischer-Tropsch synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1010283B (en) | 1990-11-07 |
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