CN107922852A

CN107922852A - The technique for preparing alkane and wax

Info

Publication number: CN107922852A
Application number: CN201680050904.2A
Authority: CN
Inventors: G·L·贝泽梅; H·博里格特; H·M·谭
Original assignee: Shell Internationale Research Maatschappij BV
Current assignee: Shell Internationale Research Maatschappij BV
Priority date: 2015-09-04
Filing date: 2016-09-01
Publication date: 2018-04-17
Anticipated expiration: 2036-09-01
Also published as: ZA201801287B; EP3344730A1; CN107922852B; MY191351A; WO2017037177A1; US20180258354A1

Abstract

The present invention relates to a kind of technique for preparing alkane and wax by the admixture of gas comprising hydrogen and carbon monoxide at least two conversion reactors as first reactor and second reactor, the reactor includes catalyst, and the technique includes at least following steps：(a) admixture of gas is supplied to one or more conversion reactors；(b) under the conditions of initial reaction the admixture of gas of catalytic conversion step (a) to obtain the initial Fischer-Tropsch product for including the alkane with 5 to 300 carbon atoms；(c) the initial Fischer-Tropsch product stream of each at least two reactors from step (b) is merged to obtain the Fischer-Tropsch product stream of combination；(d) the Fischer-Tropsch product stream of the combination of step (c) is made to carry out step of hydrogenation to obtain hydrogenation Fischer-Tropsch product stream；(e) the hydrogenation Fischer-Tropsch product stream of separating step (d), so as at least obtain the cut comprising 5 to 9 carbon atoms, the cut comprising 10 to 17 carbon atoms and the cut for including 18 to 300 carbon atoms；(f) hydrogenated fractions of 18 to 300 carbon atoms are included in separating step (e), so as to obtain lightweight wax and congealing point heavy wax 75 to 120 DEG C in the range of of one or more congealing points in the range of 30 to 75 DEG C, wherein relative concentration, the concentration of lightweight wax and the concentration of heavy wax of the cut then comprising 5 to 9 carbon atoms, the cut comprising 10 to 17 carbon atoms are changed by improving, reducing or keeping reaction temperature at least one in reactor.

Description

The technique for preparing alkane and wax

Technical field

The present invention relates to it is a kind of at least two conversion reactors as first reactor and second reactor by wrapping The gas feed stream of hydrogen and carbon monoxide prepares the technique of alkane and wax, and the reactor includes catalyst.

Background technology

Paraffin and alkane can be obtained by various techniques.US 2,692,835 and EP2655565 disclose it is a kind of from The method that paraffin and alkane are obtained in crude oil.Moreover, paraffin and alkane can be obtained using so-called Fischer-Tropsch process.In WO 2002/102941st, disclosed in EP 1 498 469, WO 2004/009739, WO 2013/064539 and WO 2014095814 One example of this technique.

Fischer-Tropsch process can be used for forming gas being converted into liquid and/or hydrocarbon solid.Forming gas can pass through a kind of technique Obtained from hydrocarbon-containing feedstock, wherein, by raw material for example natural gas, associated gas and/or coal bed methane, heavy and/or residual oil fraction, Coal, biomass are converted into the mixture of hydrogen and carbon monoxide in the first step.This mixture be commonly known as forming gas or Synthesis gas.Then forming gas is fed in reactor, it is passed through to conjunction in one or more steps in the reactor Suitable catalyst changes into paraffin compound and water by actual Fischer-Tropsch process at an elevated temperature and pressure.Obtained The scope of paraffin compound is from methane to high molecular weight module.The high molecular weight module obtained can include at most 200 Carbon atom, or even can include more carbon atoms under specific circumstances.The reactor system of many types is developed System is for progress Fischer-Tropsch reaction.For example, fischer-tropsch reactor system includes fixed bed reactors, particularly multitube fixed bed is anti- Answer device, fluidized-bed reactor, such as entrainment fluidized-bed reactor and fixed fluidized-bed reactor and slurry bed reactor, example Such as three-phase slurry bubble column and fluidized bed reactor.

Catalyst for Fiscber-Tropscb synthesis generally includes in the 8th to 10 race of carrier based support material and the periodic table of elements (special Be not cobalt or iron group) one or more metals, optionally promote with the conduct selected from zirconium, titanium, chromium, vanadium and manganese (particularly manganese) One or more metal oxides of agent and/or metallic combination.Such catalyst is well known in the art and in example As WO 9700231A and US 4595703 specification in have been described above.

One of limitation of Fischer-Tropsch process is that the activity of catalyst is reduced because of Multiple factors with the time.With its initial catalyst Activity is compared, the activity reduction of catalyst.The initial activity of catalyst can be activity when it is just prepared.In Fischer-Tropsch process Show that the catalyst of activity reduction is sometimes referred to as decaying catalyst after use, although it usually still shows activity.Sometimes this The catalyst of sample is referred to as deteriorating catalyst.Sometimes can be with regenerated catalyst.This can for example with one or more oxidation and/or Reduction step carries out.

After regeneration, catalyst usually activity of the display less than the catalyst activity just prepared.Particularly after multiple regeneration, The usual activity level for proving that the activity for being difficult to catalyst of the recovery with just preparing is suitable.In order to for a long time using catalysis Agent, it is thus possible to it is desirable that starting Fischer-Tropsch process with the fresh catalyst with opposite high activity.

It may be had the disadvantage in that with the fresh of relatively high initial activity or the use for restoring catalyst.When in reactor tube The amount of the catalyst used after middle loading catalyst in reactor tube is especially true in the case of fixing.Filled with fixed amount Catalyst reactor tube an example be filled with catalyst granules packed bed reactor tube.

In the Fischer-Tropsch process of the catalyst with relatively high initial activity, the activity of catalyst is special when the technique starts It is not high.Moreover, because the high activity of catalyst, substantial amounts of water is produced in fischer-tropsch hydrocarbon synthesis, causes Fischer-Tropsch process to start When relative humidity it is higher.During starting with the fischer-tropsch reactor of very active catalyst, reaction temperature generally remains in Under relatively low value, such as less than 200 DEG C, to avoid the significantly liter that products collection efficiency is excessive and adjoint due to exothermic reaction Temperature.

Because catalyst is inactivated with the time, the temperature of reactor must raise.The rise of temperature causes in reactor The activity increase of catalyst.By improving temperature, the activity of aging catalyst can obtain part compensation.

The higher operating temperatures of " end of run " (EOR) catalyst cause relatively low C5+ selection rates and lightweight wax.The opposing party Face, incipient (operation starts (SOR)) catalyst operation cause high C5+ selection rates and heavy wax.The operation temperature of catalyst Relation between selection rate for example exists《Fischer-Tropsch and related synthesis (The Fischer-Tropsch and related Synthesis), H.H.Storch；N.Columbic；R.B.Anderson, John ＆ Willie father and son publishing company (John Wiley＆Sons, Inc.), New York, is described on 1951 page 217.Term " lightweight wax " means heavy wax C40+ cuts Seldom trail to longer chain.Term " heavy wax " means hangover to the C40+ cuts of long-chain number.

The hydrocarbon product stream obtained after Fiscber-Tropscb synthesis mainly includes the alkane hydrocarbonylation in the range of from methane to high molecular weight molecules Compound.In the product of this scope, lighter part (namely for methane (C1) to butane (C4)) is the most undesired portion of product stream Point, heavier part is the more desirable part of product stream.Production for alkane and wax, most worthy is from C5 to C41+ Hydrocarbon in the range of (C represents carbon chain lengths).The relatively light part of product stream is recycled usually as tail gas from product stream, and can be with In the upstream of Fischer-Tropsch process, (such as in synthesis gas production) is reused.

It is known there is several methods that can improve comprising the hydrocarbon in the range of the C10 to C40 of product stream obtained from Fischer-Tropsch reaction Alkane and wax yield.For the expectations section of product stream, thus it is possible to vary catalyst formulation is simultaneously selected with raising The catalyst of yield.Relation between catalyst formulation and the yield raising of this catalyst because caused by changing formula is for example 《Applied catalysis A (Applied Catalysis A)》, it is described in 161 the 59-78 pages of (1997).Urged once have selected Agent, distribution is largely fixed.Moreover, even if using identical catalyst, by varying orientating reaction device The concentration of CO, H2 and inert gas in gaseous flow can also realize relatively small change.Partial pressure and H₂/ CO is to activity and first The influence of alkane selectivity for example exists《Industry and engineering chemistry research (Ind.Eng.Chem.Res.)》2005,44,5987- Page 5994 and《Fischer-Tropsch and related synthesis (The Fischer-Tropsch and related synthesis)》, H.H.Storch；N.Columbic；R.B.Anderson, John ＆ Willie father and son publishing company (John Wiley＆Sons, Inc.), New York, is described on page 330 of nineteen fifty-one and the 370-372 pages.Finally, thus it is possible to vary the operation of catalyst Temperature.Temperature for example exists the influence that product is distributed《Fischer-Tropsch and related synthesis (The Fischer-Tropsch and Related synthesis), H.H.Storch；N.Columbic；R.B.Anderson, John ＆ Willie father and son publishing company (John Wiley＆Sons, Inc.), New York, page 217 of nineteen fifty-one are described.It is lasting in this area to wish to improve Fischer-Tropsch Method, particularly adjusts product distribution of the given catalyst during its use.

The content of the invention

It is an object of the present invention to provide a kind of improved Fischer-Tropsch process, wherein using has relatively high initial activity Co catalysts.Particularly improve alkane and the method for wax yield is improved.

According to the present invention, one in above-mentioned or other purposes a kind of can be used as first reactor and the by providing Alkane and wax are prepared by the admixture of gas comprising hydrogen and carbon monoxide at least two conversion reactors of two reactors Technique realize that the reactor includes catalyst, the technique includes at least following steps：

(a) admixture of gas is supplied at least two conversion reactors；

(b) under the conditions of initial reaction catalytic conversion step (a) the admixture of gas with obtain include have 5 to The starting Fischer-Tropsch product of the alkane of 300 carbon atoms；

(c) the starting Fischer-Tropsch product stream of each that will be come from least two reactor of step (b) closes And to obtain the Fischer-Tropsch product stream of combination；

(d) the Fischer-Tropsch product stream of the combination of step (c) is made to carry out step of hydrogenation to obtain Fischer-Tropsch product stream；

(e) the Fischer-Tropsch product stream of separating step (d), so as at least obtain evaporating comprising 5 to 9 carbon atoms Point, the cut comprising 10 to 17 carbon atoms and the cut for including 18 to 300 carbon atoms；

(f) hydrogenated fractions for including 18 to 300 carbon atoms of separating step (e), so as to obtain one or more Lightweight wax and congealing point heavy wax 75 to 120 DEG C in the range of of the congealing point in the range of 30 to 75 DEG C, wherein then including 5 Cut to 9 carbon atoms, the relative concentration of the cut comprising 10 to 17 carbon atoms, the concentration of lightweight wax and heavy wax it is dense Degree is by raising, reducing or keep at least one reaction temperature in the reactor to change.

It has been found that in the case of carrying out hydrocarbon synthesis in two or more reactors, production can be managed and include C5 The alkane of hydrocarbon in the range of to C41 and the more flexible mode of wax.

This means that this method allows to adjust the reaction temperature in different reactor so that from including at least two reactors The product stream that system obtains can be optimized for desired product.

Yet another advantage of the present invention is that in the case where hydrocarbon synthesis carries out in two or more reactors, Fischer-Tropsch Catalyst can be managed with the inactivation of time by varying the reaction temperatures of at least two reactors.

Another advantage is that, by controlling the technological temperature in different reactor, the beginning of catalyst running temperature is with urging Difference between the end of agent running temperature is less than operation, and can not possibly change the reaction temperature of different reactor.Therefore, exist In whole service life, therefore the product distribution difference of each reactor is reduced.

Embodiment

Process according to the invention is a kind of for being mixed in fischer-tropsch reactor by the gas comprising hydrogen and carbon monoxide The technique that compound prepares alkane and wax.Admixture of gas comprising hydrogen and carbon monoxide is also referred to as synthesis gas or synthesis gas Body.At least two conversion reactors, i.e. first reactor and second reactor are operated, the reactor includes reduction Fischer-Tropsch and urges The fixed bed of agent.The catalyst includes cobalt as catalytically-active metals.

Catalyst can be fresh catalyst or restore catalyst.The fresh catalyst being mentioned herein be just prepared without Cross the catalyst of Fischer-Tropsch process.The recovery catalyst being mentioned herein refers to typically via its of several reduction and/or oxidation step The regenerated catalyst that initial activity has recovered at least in part.Catalyst is preferably fresh catalyst, because particularly new Fresh catalyst has very high initial activity.

Fischer-Tropsch catalyst comprising cobalt as catalytically-active metals is well known in the art.This area can be used Known any suitable Fischer-Tropsch catalyst containing cobalt.Typically, such catalyst wraps on the carrier material based on carrier Containing cobalt, optionally with as one or more metal oxygens as accelerating agent selected from zirconium, titanium, chromium, vanadium and manganese (particularly manganese) Compound and/or metallic combination.Most suitable catalyst includes the cobalt as catalytically-active metals and the dioxy as carrier material Change titanium.

Catalyst can further include one or more accelerating agents.One or more metals or metal oxide can be made Exist for accelerating agent, more particularly one or more d- metals or d- metal oxides.Suitable metal oxide promoter can With the 2-7 races selected from the periodic table of elements, or actinides and lanthanide series.Especially, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanum, Cerium, titanium, zirconium, hafnium, thorium, uranium, vanadium, the oxide of chromium and manganese are suitable accelerating agents.Suitable metallic promoter agent can be selected from member The 7-10 races of plain periodic table.Manganese, iron, rhenium and 8-10 races noble metal are particularly suitable as accelerating agent, and preferably with salt Or the form of hydroxide provides.

If present in catalyst, the amount of accelerating agent is usually every 100 parts by weight 0.001 to 100 Parts by weight, preferably 0.05 to 20, more preferably 0.1 to 15.It should be appreciated, however, that for the respective member as accelerating agent For element, the optimised quantity of accelerating agent can be different.

Suitable catalyst includes the cobalt as catalytically-active metals and the zirconium as accelerating agent.Another kind is most suitable to urge Agent includes the cobalt as catalytically-active metals and the manganese and/or vanadium as accelerating agent.Live if catalyst is included as catalysis The cobalt of property metal and manganese and/or vanadium as accelerating agent, then cobalt:(manganese+vanadium) atomic ratio is advantageously at least 12:1.

" race " that is mentioned herein and the periodic table of elements are related to the new IUPAC versions of the periodic table of elements, such as《Chemistry and thing Manage handbook (Handbook of Chemistry and Physics)》Those described in 87th edition (CRC publishing houses).

In at least two conversion reactors according to the present invention are operated, catalyst is reducing catalyst.In reduction catalysts In agent, cobalt lies substantially in its metallic state.At least two reactors can be by the fixed bed of in-situ reducing catalyst precarsor, i.e., In the same reactor of fischer-tropsch hydrocarbon synthesis wherein occurs, or by making reactor be mounted with reducing catalyst, the reduction catalysts Agent for example by before reducing catalyst is loaded into reactor in separated container or reactor before reducing catalyst Prepared by body, and the fixed bed with reducing catalyst.Preferably, at least two reactors pass through in-situ reducing catalyst precarsor Fixed bed and with reducing catalyst fixed bed.

The catalyst precarsor being mentioned herein refers to can be by being reduced precursor, before usually being made by using reducing condition Body is subjected to hydrogen or hydrogen-containing gas and is converted into the precursor of catalytic activity catalyst.This reduction step is many institutes in the art Known.

The process according to the invention the step of in (a), admixture of gas is supplied at least two conversion reactors.

The process according to the invention the step of in (b), the admixture of gas of step (a) occurs under the conditions of initial reaction Catalyzed conversion includes the starting Fischer-Tropsch product of the alkane with 5 to 300 carbon atoms to obtain.

" the Fischer-Tropsch product stream for including the alkane with 5 to 300 carbon atoms " partly means 5 to 300 carbon of per molecule Atom.

The Fischer-Tropsch product stream provided in step (b) comes from Fischer-Tropsch process.Fischer-Tropsch product stream is known in the art 's.Term " Fischer-Tropsch product " means the synthetic product of Fischer-Tropsch process.In Fischer-Tropsch process, forming gas is converted into synthetic product. Forming gas or synthesis gas are obtained by the conversion of hydrocarbon-containing feedstock.Suitable raw material include natural gas, crude oil, heavy oil fraction, coal, Biomass and lignite.The Fischer-Tropsch product obtained from the hydrocarbon-containing feedstock for being generally in gas phase is referred to as GTL (gas-liquids) Product.The preparation of Fischer-Tropsch product is described in such as WO2003/070857.

It is known to those skilled in the art that the pressure and temperature effect forming gas for carrying out Fischer-Tropsch process is converted into hydrocarbon Degree and the branching level (therefore amount of isoparaffin) for influencing alkane.Typically, the technique for preparing Fisher-Tropsch derived wax can be with Carried out under the pressure higher than 25 bars.Preferably, Fischer-Tropsch process is more preferably above 45 bars higher than 35 bars, and most preferably Carried out under pressure higher than 55 bars.Fischer-Tropsch process is actually limited to 200 bars, and preferably this method is less than 120 bars, more preferably Ground carries out under the pressure less than 100 bars.

Fischer-Tropsch process is suitably at a temperature of 170 to 290 DEG C, preferably at a temperature of 180 to 270 DEG C, more preferably The low temperature process that ground carries out at a temperature of 200 to 250 DEG C.

Preferably, fischer-tropsch reactor operates under the conditions of the initial reaction of step (b), including 200 to 250 DEG C, Yi Jiyou Initial temperature in the range of 205 to 230 DEG C of selection of land.

Carbon monoxide and hydrogen, which change into hydrocarbon, in the process according to the present invention to be suitable for what fischer-tropsch hydrocarbon synthesized known Carried out under any reaction pressure and gas hourly space velocity.Preferably, reaction pressure is in the range of 10 to 100 bars (absolute), more preferably Ground is in the range of 20 to 80 bars (absolute).Gas hourly space velocity preferably in 500 to 25,000h-1, more preferably 900 to 15, 000h-1, even more preferably still 1, in the range of 300 to 8,000h-1.Preferably, reaction pressure and gas hourly space velocity are kept constant.

Based on the total amount of the alkane with 9 to 24 carbon atoms, the amount of isoparaffin is suitably less than 20 weight %, excellent Selection of land is less than 10 weight %, even more preferably less than 7 weight %, and more preferably less than 4 weight %.

Suitably, Fisher-Tropsch derived paraffin according to the present invention comprises more than the normal paraffin hydrocarbons of 75 weight %, preferably super Cross the normal paraffin hydrocarbons of 80 weight %.In addition, paraffin can include isoparaffin, cycloalkane and alkylbenzene.

The Fischer-Tropsch process for being used to prepare Fisher-Tropsch derived wax according to the present invention can be slurry Fischer Tropsch method, fluidized bed process or Fixed bed Fischer-Tropsch process, particularly multitube fixed bed.

The product stream of Fischer-Tropsch process generally fall into current, comprising unconverted forming gas, carbon dioxide, inert gas and Gaseous flow and the C5+ stream of C1 to C4.

Whole Fischer-Tropsch is containing hydrocarbon products suitably comprising C1 to C300 cuts.

The lighter fraction for suitably including C1 to the Fischer-Tropsch product of C 4 fraction is separated by distilling from Fischer-Tropsch product, So as to obtain Fischer-Tropsch product stream, it is suitably comprising C5 to C300 cuts.

Compound with least 60 or more carbon atoms in Fischer-Tropsch product with least 30 carbon atoms The above-mentioned weight ratio of compound is preferably at least 0.2, and more preferably 0.3.

Suitably, in the case where preparing Fisher-Tropsch derived wax fraction of the congealing point higher than 90 DEG C, above-mentioned weight ratio is at least 0.5。

Weight ratio in Fischer-Tropsch product can cause the Fisher-Tropsch derived paraffin with low oil content.

, will be from the initial Fischer-Tropsch of each at least two reactors of step b) in the step (c) of the present invention Product stream merges to obtain the Fischer-Tropsch product stream of combination.Typically, the Fischer-Tropsch product stream of combination, which includes, has 5 to 300 carbon The alkane of atom.

In the step (d) of the present invention, the Fischer-Tropsch product stream of the combination of step (c) is set to carry out step of hydrogenation to obtain hydrogen Change Fischer-Tropsch product stream.

Hydrogenation suitably carries out at 200 to 275 DEG C of temperature and 20 to 70 bars of pressure.Typically, hydrogenate from hydrogen Change and alkene and oxygenatedchemicals are removed in cut.Oxygenatedchemicals is preferably that per molecule contains one or more oxygen atoms Hydrocarbon.Typically, oxygenatedchemicals is alcohol, aldehyde, ketone, ester and carboxylic acid.

In the step (e) of the present invention, the Fischer-Tropsch product stream of separating step (d) is at least to obtain comprising 5 to 9 The cut of carbon atom, the cut comprising 10 to 17 carbon atoms and the cut for including 18 to 300 carbon atoms.

The hydrocarbonaceous thing of whole Fischer-Tropsch to C300 cuts comprising C1 is preferably based on, 5 to 9 carbon originals are included in step (e) The amount of the cut of son is in the range of 3 to 14 weight %.

Moreover, based on the hydrocarbonaceous thing of whole Fischer-Tropsch comprising C1 to C300 cuts, 10 to 17 carbon originals are included in step (e) The amount of the cut of son is in the range of 7-21 weight %.

The cut is preferably divided into the cut comprising 10 to 13 carbon atoms and includes the cut of 14 to 17 carbon atoms. In addition, containing hydrocarbon products based on the whole Fischer-Tropsch comprising C1 to C300 cuts, the amount of the cut comprising 10 to 13 carbon atoms is 3 To 11 weight %, and the amount of the cut comprising 14 to 17 carbon atoms is in the range of 4 to 10 weight %.

In the step (f) of the present invention, the hydrogenated fractions of 18 to 300 carbon atoms are included in separating step (e), so as to obtain Lightweight wax and congealing point heavy wax 75 to 120 DEG C in the range of of one or more congealing points in the range of 30 to 75 DEG C is obtained, Wherein then the cut comprising 5 to 9 carbon atoms, the relative concentration of cut comprising 10 to 17 carbon atoms, lightweight wax it is dense The concentration of degree and heavy wax is changed by improving, reducing or keeping the reaction temperature of at least one reactor.

Preferably, relative concentration, the lightweight of the cut comprising 5 to 9 carbon atoms, the cut comprising 10 to 17 carbon atoms The concentration of wax and the concentration of heavy wax are changed by adding nitrogenous compound at least one reactor.

Preferably, by nitrogenous compound add step (a) admixture of gas in so that nitrogenous compound with 0.05 to Concentration in the range of 10ppmV is present in admixture of gas.

The example of suitable nitrogenous compound is ammonia, HCN, NO, amine, organic cyanide (nitrile) or former containing at least one nitrogen Heterocyclic compound of the son as heterocycle ring members.

Suitably, nitrogenous compound is selected from by ammonia, HCN, NO, amine and combinations thereof or two or more groups formed Compound.

Preferable amine includes the amine with alkyl of the one or more with most five carbon atoms or alcohol radical.More preferably Ground, amine are monoamines.The example of particularly preferred amine includes trimethylamine, di-n-propylamine, diethanol amine and methyl diethanolamine.

Particularly preferred nitrogenous compound is ammonia.

Lightweight wax means wax of the congealing point in the range of 30 to 75 DEG C.Heavy wax means congealing point in 75 to 120 DEG C of scopes Interior wax.

The congealing point of paraffin according to the present invention is measured according to ASTM D938.

Suitably, by the hydrogenated fractions that 18 to 300 carbon atoms are included in step (d) by being evaporated in vacuo in 5 to 20 millis Bar, preferably 5 to 15 millibars, and separated under more preferably 10 to 15 millibars of pressure.Distillation is also preferably 300 to 350 Carried out at a temperature of DEG C.

Preferably, the first lightweight one or more wax is used as distillate and/or acquisition of sideing stream, example in vacuum distillation Such as, first lightweight wax fraction of the congealing point in the range of 30 to 35 DEG C, second lightweight wax of the congealing point in the range of 50 to 60 DEG C Cut, and threeth lightweight wax fraction of the congealing point in the range of 65 to 75 DEG C.

Suitably, the first lightweight wax fraction is obtained as the overhead fraction of vacuum distillation, and the second lightweight wax fraction is as true The acquisition of sideing stream of sky distillation, and heavier side stream acquisition of the 3rd lightweight wax fraction as vacuum distillation.

Preferably, one or more wax fractions of the congealing point in step (f) in the range of 30 to 75 DEG C are subjected to hydrogenation essence Make to obtain the wax fraction of hydrofinishing of one or more congealing points in the range of 30 to 75 DEG C.Suitably, congealing point is existed Wax fraction hydrofinishing in the range of 30 to 75 DEG C, so that the wax for obtaining hydrofinishing of the congealing point in the range of 30 to 75 DEG C evaporates Point.

Optionally, the first lightweight wax fraction and the second lightweight wax fraction are subjected to hydrofinishing, existed so as to obtain congealing point Second lightweight of the wax fraction and congealing point of the first lightweight hydrofinishing in the range of 30 to 35 DEG C in the range of 50 to 60 DEG C adds The wax fraction that hydrogen refines.

It is preferably based on the whole Fischer-Tropsch comprising C1 to C300 cuts and contains hydrocarbon products, the hydrogenation with 30 DEG C of congealing point The amount of refined wax fraction is in the range of 3 to 7 weight %.It is moreover, hydrocarbonaceous based on the whole Fischer-Tropsch comprising C1 to C300 cuts Product, the amount of the wax fraction of the hydrofinishing with 50 DEG C of congealing point is preferably in the range of 5 to 13 weight %.

In addition, hydrocarbon products are contained based on the whole Fischer-Tropsch comprising C1 to C300 cuts, the hydrogenation essence with 70 DEG C of congealing point The amount of the wax fraction of system is in the range of 7 to 16 weight %.

Preferably, at least by the 3rd lightweight wax, that is, the most heavy side cut that step (f) is evaporated in vacuo carries out hydrofinishing, from And obtain the wax fraction of hydrofinishing of the congealing point in the range of 65 to 75 DEG C.

The typical Hydrofinishing conditions of the hydrofinishing of above cut are described in such as WO2007/082589.

Suitably, the second heavy wax of separating step (f), so as to obtain at least one congealing point in the range of 75 to 85 DEG C Remaining wax fraction in the range of 95 to 120 DEG C of distillation wax fraction and at least one congealing point.

Preferably, the second wax of heavy of separating step (f), so as to obtain at least one congealing point at 70 to 90 DEG C, preferably Distillation wax fraction in the range of 70 to 85 DEG C of ground and more preferably 75 to 85 DEG C.

Suitably, heavy distillation wax fraction of the congealing point in the range of 75 to 85 DEG C is subjected to hydrofinishing, so as to obtain The heavy distillation wax fraction of hydrofinishing of the congealing point in the range of 75 to 85 DEG C.

In addition, by congealing point in the range of 70 to 90 DEG C, preferably in the range of 70 to 85 DEG C and more preferably 75 Heavy distillation wax fraction in the range of to 85 DEG C carries out hydrofinishing, so as to obtain congealing point in the range of 70 to 90 DEG C, preferably The heavy distillation wax fraction of hydrofinishing of the ground in the range of 70 to 85 DEG C and more preferably in the range of 75 to 85 DEG C.

Preferably, heavy residual wax fraction of the congealing point in the range of 95 to 120 DEG C is subjected to hydrofinishing, so as to obtain The heavy residual wax fraction of hydrofinishing of the congealing point in the range of 95 to 120 DEG C.

The second wax of heavy of step (f) is preferably distilled at preferably 0.05 to 0.5 millibar by short path, and more Separated under preferably 0.1 to 0.3 millibar of pressure.Distillation is preferably at 200 to 350 DEG C, more preferably 250 to 300 DEG C of temperature Degree is lower to carry out.

Typically, residual heavy wax of the congealing point in the range of 95 to 120 DEG C is obtained as the residual fraction that short path distills .Term remnants mean that it is residual bottom cut by distilling the cut obtained, neither overhead fraction is nor side evaporates Point.

Short path distillation (also referred to as molecular distillation) is well known in the art, therefore is not described in here.One The example of kind short path distillation form is luwa evaporator.Typical short path distillation for example exists《Distillation：Operation and application (Distillation,operations and applications)》,Andrzej Górak and Hartmut Schoenmakers, Elsevier Inc, Oxford, is described in the 9.1st chapter of 2014.

It is therefore preferred that heavy residual wax fraction of the congealing point in the range of 95 to 120 DEG C is subjected to hydrofinishing, from And obtain the heavy residual wax fraction of hydrofinishing of the congealing point in the range of 95 to 120 DEG C.

Preferably, Fisher-Tropsch derived wax of one or more congealing points in the range of 30 to 120 DEG C is obtained.It is highly preferred that freeze Condensation point in the range of 30 to 35 DEG C or in the range of 50 to 60 DEG C or in the range of 60 to 70 DEG C, or in the range of 75 to 85 DEG C or In the range of 95 to 100 DEG C, or Fisher-Tropsch derived wax in the range of 100 to 106 DEG C or in the range of 106 to 120 DEG C passes through root Obtained according to the technique of the present invention.

Suitably, hydrocarbon products are contained based on the whole Fischer-Tropsch comprising C1 to C300 cuts, congealing point is in 100 to 105 DEG C of scopes The amount of the wax fraction of interior hydrofinishing is in the range of 15 to 70 weight %.

Measuring content of the whole Fischer-Tropsch containing every kind of final product cut in hydrocarbon products can be by using such as high temperature gas phase Chromatography or the chromatographic process of distillation analyze the sample of the logistics to realize.Advantageously, gas phase, liquid phase and solid phase are quantified, Analyzed using respective chromatographic process and be combined to produce the distribution of Fischer-Tropsch product, it is contemplated that alkene and oxygenatedchemicals quilt It is hydrogenated to respective alkane.

Suitably, reaction temperature passes through following raising：

- the synthesis gas scale of construction provided to reactor is provided；

- improve to reactor provide cooling water temperature；And/or

- preferably by step a) and b) before by nitrogenous compound addition admixture of gas, being provided to reactor Nitrogenous compound, preferably nitrogenous compound are selected from by ammonia, HCN, NO, amine and its combination or two or more groups formed Group.

Suitably, reactor operating point passes through following raising：

- the synthesis gas scale of construction provided to reactor is provided；

- improve to reactor provide cooling water temperature；And/or

Reactor operating point means to realize the operation temperature of the target conversion of CO and H2.

In one embodiment of the invention, reaction temperature and/or reactor operating point are provided by increase to reactor The amount of forming gas improve.Because Fischer-Tropsch reaction is exothermic reaction, providing more hydrogen and carbon monoxide will cause More heats produce.The increase of heat will cause the selectivity to heavier hydrocarbon products to reduce.

In one embodiment of the invention, reaction temperature and/or reactor operating point are carried by improving to the reactor The temperature of the cooling water of confession improves.Reaction temperature and/or reactor operating point can be by providing nitrogenous chemical combination to reactor Thing improves.By supplying nitrogenous compound to the firm reducing catalyst for preparing or restoring, catalyst activity reduces and temperature It can raise.The condition that this higher temperature and activity reduce causes relatively low relative humidity and less catalyst inactivation.And And because influence of this nitrogenous compound to catalyst activity seems to be reversible, catalyst activity can pass through tune The concentration for saving nitrogenous compound is adjusted.Particularly, gradual reduce of catalyst activity can be by gradually reducing to catalyst The concentration of nitrogenous compound compensates in the flow of feed gas of offer.Therefore, in the long period after reactor start-up, reaction temperature Degree and reactor productivity (yield) can be controlled and kept constant, and cause the raising of catalyst stability.

In one embodiment, when reaction temperature and/or reactor operating point raise, carried to one or more reactors For nitrogenous compound.

Moreover, reaction temperature passes through following reduction：

- reduce to reactor provide forming gas amount；

- reduce to reactor provide cooling water temperature；And/or

Moreover, reactor operating point passes through following reduction：

- reduce to reactor provide forming gas amount；

- reduce to reactor provide cooling water temperature；And/or

In one embodiment, the reaction temperature in one or more reactors and/or reactor operating point pass through reduction Reduced to the amount of the forming gas of reactor offer.By reducing the amount of the synthesis gas provided to reactor, synthesize less Hydrocarbon.Because FT reactions are exothermic reactions, if the hydrocarbon that synthesis is less, will discharge less energy.

In one embodiment, the reaction temperature in one or more reactors and/or reactor operating point pass through reduction Reduced to the temperature of the cooling water of reactor offer.Moreover, caused pair to reduce temperature by the temperature for reducing cooling medium The selectivity increase of heavy end.

In one embodiment, the reaction temperature in one or more reactors and/or reactor operating point are by anti- Device is answered to provide nitrogenous compound to reduce.

In one embodiment of the invention, one during method comprises the following steps：

- in the case where first reactor includes the minimum catalyst of activity, provide nitrogenous compound to first reactor；

- in the case where second reactor includes the minimum catalyst of activity, provide nitrogenous compound to second reactor.This Completed in the case of temperature that can be in the reactor is elevated, cause the activity increase of catalyst, but to the selection of heavy hydrocarbon Property reduce.

- in the case where first reactor includes active maximum catalyst, provide nitrogenous compound to first reactor；

- in the case where second reactor includes active maximum catalyst, provide nitrogenous compound to second reactor.

It is added to increase or decrease the nitrogenous chemical combination of reaction temperature and/or operation point in one or more reactors Thing is similar with above-mentioned nitrogenous compound.

In another aspect, the present invention provides the Fisher-Tropsch derived alkane that can be obtained by process according to the invention And wax.

The present invention is illustrated by following non-limiting examples.

Example

In present example, two fischer-tropsch reactor are connected in series.Cobalt Fischer-Tropsch catalyst is loaded in two instead Answer in device and reduce.Upstream reactor (being named as R1) supply synthesis gas, it is anti-that downstream reactor (being named as R2) receives upstream Answer the exhaust gas of device.

Exhaust gas includes unreacted hydrogen and carbon monoxide.In each example, a reactor just starts, another is anti- Answer device activity deterioration.Under base case, two reactors are all operated with identical productivity, but operation temperature is different.Table 1 arranges The amount of gas, solvent, LDF, HDF, SX-30, SX-50, SX-70, SX-100/105 are gone out.

In table 1, first three rows provide reaction condition.With (no) addition for representing ammonia of Y (YES) or N.Based on Fischer-Tropsch product Stream, product gas, solvent, LDF, HDF, SX-30, SX-50, SX-70, SX-100/105 are represented with weight %.

In the first example according to the present invention, the productivity of first reactor raises simultaneously temperature by adding ammonia Reduce.The productivity increase of second reactor at the same time.The distribution of product is given in table.It can be seen that solvent, LDF, HDF, SX- 30th, the total amount of SX-50 and SX-70 increases to 41% from 36%.

In the second example according to the present invention, increased by the load of first reactor and pass through second reactor Load reduction, so as to keep always producing constant.As can be seen that the amount of SX-30, SX-50, SX-70, SX-100/105 increase from 54% It is added to 60%.

In the 3rd example, increased by the production of first reactor and add N compounds.Pass through second reactor Production is reduced by adding N compounds in charging.As can be seen that the amount of solvent, LDF and HDF increases to 41% from 36%.

Table 1

Discuss

1 example 1 of table clearly illustrates the increase of gas, solvent, LDF, HDF, SX-30, SX-50, SX-70, but SX-100/ 105 reduction.These observation indicate that, to synthesis air-flow in add ammonia cause Fischer-Tropsch catalyst C41+ selectively reduce.

Example 2 clearly demonstrates the reduction of gas, solvent, LDF, but the increase of SX-100/105.HDF、SX-30、 The amount of SX-50, Sx-70 remain unchanged.These observation indicate that, improve two reactors temperature cause Fischer-Tropsch catalyst C41+ selectively increase.

Example 3 clearly demonstrates the increase of gas, solvent, LDF, HDF, SX-30, SX-50, SX-70, but SX-100/ 105 reduction.

These observation indicate that, to synthesis air-flow in add ammonia and raise a reactor in temperature, reduce at the same time Temperature in another reactor causes the C41+ of Fischer-Tropsch catalyst selectively to reduce.

Therefore, these examples clearly illustrate, by considering to urge present in each reactor in fischer-tropsch reactor system The state of agent, can control the content of product stream well." race " that is mentioned herein and the periodic table of elements are related to period of element The new IUPAC versions of table, such as《Handbook of Chemistry and Physics (Handbook of Chemistry and Physics)》(CRC Publishing house) the 87th edition described in those.

Although according to the most practical and preferred embodiment are presently believed to be, the invention has been described, should manage Solution, the disclosure are not necessarily limited to the disclosed embodiments.Be intended to include in the spirit and scope of the claims various repaiies Change, combine and similar arrangement, its scope should be shown with broadest explanation one and cover all such modifications and similar structures.This The open any and whole embodiments for including following claims.

It should also be understood that various changes can be being made without departing from the essence of the present invention.Also implied in explanation Include these changes.They still fall within the scope of the present invention.It should be understood that the disclosure is intended to produce independently and make Cover the patent of many aspects of the present invention for whole system and under method and apparatus pattern.

Any patent, publication or the other bibliography referred in present patent application is all incorporated by reference into text.Separately Outside, for used each term, it should be appreciated that unless its use in this application and this explanation are inconsistent, Otherwise for each term and it is defined, alternative terms and synonym are construed as general dictionary definition, such as comprising In those at least one by the standard technique dictionary of technical staff's accreditation.

Claims

1. by including hydrogen and carbon monoxide at least two conversion reactors as first reactor and second reactor Admixture of gas prepare the technique of alkane and wax, the reactor includes catalyst, and the technique includes at least following step Suddenly：

(a) admixture of gas is supplied at least two conversion reactors；

(b) admixture of gas of catalytic conversion step (a) has 5 to 300 to obtain to include under the conditions of initial reaction The starting Fischer-Tropsch product of the alkane of carbon atom；

(c) will come from step (b) at least two reactor in the starting Fischer-Tropsch product stream of each merge with Obtain the Fischer-Tropsch product stream of combination；

(e) the Fischer-Tropsch product stream of separating step (d), so as at least obtain the cut comprising 5 to 9 carbon atoms, bag Cut containing 10 to 17 carbon atoms and the cut for including 18 to 300 carbon atoms；

(f) hydrogenated fractions of 18 to 300 carbon atoms are included in separating step (e), are congealed so as to obtain one or more The heavy wax of lightweight wax and congealing point in the range of 75 to 120 DEG C o'clock in the range of 30 to 75 DEG C, wherein then including 5 to 9 The cut of a carbon atom, the relative concentration of cut comprising 10 to 17 carbon atoms, the concentration of the lightweight wax and the heavy The concentration of wax is changed by improving, reducing or keeping the reaction temperature at least one in the reactor.

2. technique according to claim 1, wherein the fischer-tropsch reactor is grasped under the conditions of the initial reaction of step (b) Make, the initial reaction condition includes 200 to 250 DEG C, and the temperature in the range of preferably 205 to 230 DEG C.

3. technique according to claim 1 or 2, wherein hydrocarbonaceous based on the whole Fischer-Tropsch comprising C1 to C300 cuts Thing, the amount of the cut comprising 5 to 9 carbon atoms in step (e) is in the range of 3 to 14 weight %.

4. technique according to any one of claim 1 to 3, wherein based on described whole comprising C1 to C300 cuts The hydrocarbonaceous thing of Fischer-Tropsch, the scope of the amount of the cut comprising 10 to 17 carbon atoms in step (e) in 7 to 21 weight % It is interior.

5. technique according to any one of claim 1 to 4, wherein by the congealing point of step (f) in 30 to 75 DEG C of scopes Interior one or more wax fractions carry out hydrofinishing to obtain hydrogenation of one or more congealing points in the range of 30 to 75 DEG C Refined wax fraction.

6. technique according to any one of claim 1 to 5, wherein based on described whole comprising C1 to C300 cuts The hydrocarbonaceous thing of Fischer-Tropsch, congealing point are the amount of the wax fraction of 30 DEG C of the hydrofinishing in the range of 3 to 7 weight %.

7. technique according to any one of claim 1 to 6, wherein based on described whole comprising C1 to C300 cuts The hydrocarbonaceous thing of Fischer-Tropsch, congealing point are the amount of the wax fraction of 50 DEG C of the hydrofinishing in the scope from 5 to 13 weight % It is interior.

8. technique according to any one of claim 1 to 7, wherein based on described whole comprising C1 to C300 cuts The hydrocarbonaceous thing of Fischer-Tropsch, congealing point are the amount of the wax fraction of 70 DEG C of the hydrofinishing in the range of 7 to 16 weight %.

9. technique according to any one of claim 1 to 8, the heavy wax of separating step (f), are derived from least A kind of distillation wax fraction and at least one congealing point remnants 95 to 120 DEG C in the range of of congealing point in the range of 75 to 85 DEG C Wax fraction.

10. technique according to claim 9, by the heavy of the congealing point in the range of 75 to 85 DEG C distill wax fraction into Row hydrofinishing, to obtain the heavy of hydrofinishing of the congealing point in the range of 75 to 85 DEG C distillation wax fraction.

11. technique according to claim 9, wherein the heavy residual wax fraction by congealing point in the range of 95 to 120 DEG C Hydrofinishing is carried out, to obtain the heavy residual wax fraction of hydrofinishing of the congealing point in the range of 95 to 120 DEG C.

12. technique according to any one of claim 1 to 11, wherein based on described whole comprising C1 to C300 cuts The hydrocarbonaceous thing of Fischer-Tropsch, congealing point are scope of the amount in 15 to 70 weight % of the wax fraction of 100 to 105 DEG C of hydrofinishing It is interior.

13. technique according to any one of claim 1 to 12, wherein the reactor operating point passes through following raising：

The synthesis gas scale of construction provided to the reactor is provided；

The temperature of the cooling water provided to the reactor is provided；And/or

Preferably by adding the nitrogenous compound in the admixture of gas before in step a) and b), to the reaction Device provides nitrogenous compound, and preferably described nitrogenous compound is selected from by ammonia, HCN, NO, amine and it is combined or two or more The group of composition.

14. technique according to any one of claim 1 to 13, wherein the reactor operating point passes through following reduction：

The amount of the forming gas provided to the reactor is provided；