CN101381619A - Fluid catalytic cracking and hydrotreating processes for fabricating diesel fuel from waxes - Google Patents

Fluid catalytic cracking and hydrotreating processes for fabricating diesel fuel from waxes Download PDF

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CN101381619A
CN101381619A CNA2008102127745A CN200810212774A CN101381619A CN 101381619 A CN101381619 A CN 101381619A CN A2008102127745 A CNA2008102127745 A CN A2008102127745A CN 200810212774 A CN200810212774 A CN 200810212774A CN 101381619 A CN101381619 A CN 101381619A
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product
composition
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cracking
metal
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J·A·派特里
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Honeywell UOP LLC
Universal Oil Products Co
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Universal Oil Products Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

A method for obtaining a petroleum distillate product is provided, the method including subjecting a paraffin-based wax, such as a Fisher-Tropsch wax, to the process of cracking at a pressure less than, or equal to, about 7 Kg/cm2 in the presence of a first catalyst to obtain an olefinic intermediate, the cracking being carried out in a fluid catalytic cracking apparatus, followed by hydrogenating the olefinic intermediate at a pressure less than, or equal to, about 35 Kg/cm2, in the presence of a second catalyst, and recovering the petroleum distillate product. An apparatus for carrying out the method is also provided.

Description

Be used for making the fluid catalystic cracking and the hydrogenation technique of diesel oil from wax
Technical field
The present invention relates generally to make the technology of various petroleum based fuels, more specifically, relate to fluid catalystic cracking (FCC) and hydrogenation technique, for example to obtain petroleum distillate, kerosene and diesel oil fischer-tropsch or the slack wax (slack wax) from paraffinic base wax.
Background technology
Fischer-Tropsch synthesis is known to produce the mixture of products widely that mainly comprises paraffinic hydrocarbons and some alkene.The individualized compound of this class mixture can contain maximum 200 carbon atoms, and carbon number typically has 60 mean value between 20～150.The product of the oxidation products of certain limited amount and Trace Sulfur or nitrogen or aromatics also can exist.This class mixture is called as " fischer-tropsch " wax.Inter alia, fischer-tropsch wax is usually as obtaining for example raw material of petroleum distillate, kerosene and diesel oil of various petroleum chemicals.
Cracking is typically when catalyzer exists, the fracture by C-C in the precursor realize with the organic molecule of complexity for example heavy hydrocarbon split into the technology of simple molecules.The characteristic of cleavage rate and final product depends on the condition that technology is carried out, for example the characteristic of temperature, pressure and used any catalyzer.
Catalytic cracking process comprises the existence of an acidic catalyst (being generally solid acid for example silica-alumina and zeolite), and this an acidic catalyst promotes the heterolytic fission of key, produces the ion pair of opposite charges, normally carbonium ion and very unsettled hydride negative ion.Part carbon (carbon-localized) free radical and positive ion all are high unsettled, and the experience chain is reset, the C-C in the β position ruptures (being cracking) and intramolecularly and intermolecular hydrogen transference or hydride transfer.In two class technologies, corresponding reaction intermediate (free radical, ion) is for good and all regenerated, and is undertaken by the self-propagation chain mechanism thus.Reaction chain finally by free radical or ion again in conjunction with and stop.
Fluid catalystic cracking (FCC) is the widely used cracking of a class.This technology typically adopts powdered catalyst, and it has and is suspended in the particle supplied with in the hydrocarbon upwelling to form fluidized-bed.A kind of representative catalyzer is aluminum oxide (aluminum oxide).Usually also use zeolite based catalysts.In representative technology, cracking occurs in the standpipe, and it is vertical or acclivitous pipe.
The charging of preheating (for example, fischer-tropsch wax) can be injected into riser bottom by feed nozzle, and here its fluidized catalyst with heat contacts under 650～800 ℃ temperature.Charging gasification when contacting with catalyzer, and generation changes into high-molecular weight oil the cracking of the lighter composition that comprises liquefied petroleum gas (LPG), gasoline and overhead product.(several seconds) this catalyzer in short period of time-charging mixes upwards flows through standpipe, and this mixture is separated in cyclonic separator then.Isolated hydrocarbon is directed to fractionator to be separated into LPG, gasoline, diesel oil, kerosene, rocket engine fuel etc. from catalyzer thus.
When through standpipe, can exhaust cracking catalyst, because this technology is accompanied by the formation of sedimentation of coke on granules of catalyst.So contaminated catalyzer is separated from the cracked hydrocarbon vapour, again with steam treatment to remove the hydrocarbon in the hole that remains in catalyzer.Then this catalyzer is imported in the revivifier that the coke on granules of catalyst surface is burnt, thereby recover activity of such catalysts and be provided for the necessary heat of next reaction cycle.Cracking technology is absorbed heat.The regenerated catalyzer is used in the new circulation then.
FCC technology exists some defective and deficiency.For example, this technology causes the generation and the obvious lower chemical stability of most relatively various alkene.The alkene polymer deposits that formation is not expected in storage tank, fuel conductor etc. again.
The another kind of technology that is used for high molecular weight component is changed into the non-refinable crude overhead product is catalytic hydrocracking, and it is included in hydrogen and the catalyzer hydrogenation under existing and the technology of the carbon-to-carbon rupture of fischer-tropsch wax.In this technology, can remove the compound of most nitrogenous, oxygen and/or sulphur at least, if their exist, and alkene typically by saturated to produce paraffinic hydrocarbons.This technology needs very high pressure (for example up to 75) usually and is higher than 400 ℃ temperature.
Although many advantages are arranged, traditional catalytic hydrocracking also exists many defectives and deficiency.For example, using high-pressure energy consumption big, is dangerous sometimes, and needs to use special machine.Hydrocracking catalyst is subjected to the passivation of dirt and poisonous substance, must take special measure to prevent this class passivation.
For fear of or reduce the above-mentioned insufficient influence of FCC and catalytic hydrocracking, and, need better technology and fischer-tropsch wax to use together for the purpose of improving overhead product selectivity and overall process efficient.
Summary of the invention
The invention provides the method that obtains the petroleum distillate product.A kind of method comprises makes paraffinic base wax experience following technology: be less than or equal to 7Kg/cm 2The pressure and first catalyzer exist and to carry out cracking down with acquisition alkene class intermediate product, in fluidized bed catalytic cracker, carry out cracking, then be less than or equal to 35Kg/cm 2The pressure and second catalyzer have hydrogenation alkene class intermediate product down, and reclaim the petroleum distillate product.
Experience cracked wax can be any wax that comprises fischer-tropsch wax.Experience cracked wax also can be that slack wax or other mainly are the materials of normal paraffin.First catalyzer promptly is used for the catalyzer of cracking technology, can be to be embedded in zeolite matrix, typically to be the metal composites in the [amorphous.This metal composites can comprise for example scandium, yttrium or lanthanide series metal-typically be called " rare earth " type catalyzer of rare earth metal.Second catalyzer promptly is used for the catalyzer of hydrogenation technique, can be the underlying metal composition, and for example nickel-molybdenum compositions, cobalt-molybdenum composition etc. perhaps alternatively, comprise for example precious metal composition of platinum, palladium etc.
The present invention also provides to use and comprises that the method for fluid catalystic cracking and hydrogenation obtains the system of overhead product boiling range product from paraffinic base wax.This system comprises, the fluid catalystic cracking reactor is used for being less than or equal to 7Kg/cm 2Pressure under cracking paraffinic base wax to obtain alkene class intermediate product; With the fractionator that the fluid catalystic cracking reactor fluid is connected, be used for reclaiming overhead product from alkene class intermediate product; With the hydrogenation unit that is connected with the fractionator fluid, be used for the hydrogenation overhead product to obtain to comprise the clean reactor effluent (net reactor effluent) of at least 50 quality % overhead product boiling range products.
Description of drawings
This accompanying drawing is used for the device of illustrative according to the FCC that is used for fischer-tropsch wax of one embodiment of the present invention.
Embodiment
Next except as otherwise noted, otherwise the definition below using:
Term " fischer-tropsch wax " refers to mainly the mixture of being made up of the n-paraffin with carbonatoms of 20～150, and this mixture also randomly contains some oxide compound, and randomly trace naphthenic hydrocarbon and/or aromatics.
Term " slack wax " refers to the waxy stone that makes by cooling and solvent filter pressed wax overhead product.
Term " catalytic cracking " refers to and utilize high temperature and relative low pressure refining alkyl charging in the presence of catalyzer, and the hydrocarbon that the result will be present in weight in the charging and relative complex splits into the technology of fairly simple and lighter hydrocarbon.
Term " fluid catalystic cracking " or " FCC " refer to a class catalytic cracking, its adopt be typically powder type, have and be suspended in the upwelling of supplying with hydrocarbon to form the particulate catalyzer of fluidized-bed.Be called for short " FCC " and also refer to such device, promptly carry out the fluid catalystic cracking reactor of fluid catalytic cracking process in suitable place.
Term " hydrogenation " refers to typically in the presence of the catalyzer that is fit to, and to unsaturated organic compound such as alkene (alkene) interpolation hydrogen, the result obtains the technology of saturated organic compound such as paraffinic hydrocarbons.
Term " catalyzer " refers to the speed or the productive rate that can change chemical reaction in technology, and self does not have substantially to consume or the material of other chemical transformation.
Term " precious metal " relate to most of underlying metal form correlated, highly corrosion or oxidation resistant, and be not easy the dissolved metal.Example includes, but not limited to platinum, palladium, gold and silver, tantalum etc.
Term " underlying metal " refer to can be easily oxidized any base metal.Example includes, but not limited to nickel, molybdenum, tungsten, cobalt etc.
Term " lanthanide series metal " refers to a kind of in 14 kinds of rare earth metals that have 58～71 atomicity (from the cerium to the lutetium) on the periodic table of elements.
Term " hydrocarbon " refers to the organic compound that molecule only is made of carbon and hydrogen.
Term " paraffinic hydrocarbons " refers to the hydrocarbon that is limited by saturated carbochain, and it is positive structure (straight chain), branching or ring (" naphthenic hydrocarbon "), and by general formula C nH 2n+2(for straight chain or branched paraffin) or general formula C nH 2n(for naphthenic hydrocarbon) expression, wherein n is an integer.
Term " alkene " is also referred to as " alkene ", refers to the hydrocarbon that contains at least one carbon-to-carbon double bond (C=C), and by general formula C nH 2nExpression, wherein n is an integer.
Term " carbonium ion " refer to than corresponding free radical lack an electronics and have can but be not organic positive ion that must be positioned at the positive charge on the carbon atom.
Term " overhead product " refers to contain with the boiling range of illustrating among the ASTM D-975 and comes kerosene, rocket engine fuel and the diesel oil of characterizing definition and the petroleum product of domestic fuel oil." second overhead product " relates to the overhead product at the requirement of second overhead product that satisfies ASTM D-975 standard.
Term " diesel oil " refers to the technological standard that technological standard D975 limited according to ASTM (ASTM), and refers to and have 280～340 ℃ distillation temperature in 90% recovery point and mainly contain C 10～C 24Hydrocarbon, and burning-point is greater than 38 ℃ petroleum fractions.
Term " rocket engine fuel " refers to the technological standard that is limited according to ASTM technological standard D 1655, and relates to and have 300 ℃ of final maximum boiling points and greater than the keryl product of 38 ℃ flash-point.
Term " kerosene " refers to and contain the petroleum fractions heavier a little than such hydrocarbon, i.e. its hydrocarbon for being found, for example C in gasoline and petroleum naphtha 9～C 16Hydrocarbon, and under environmental stress, have 150～300 ℃ of boiling points.
Term " petroleum naphtha " refers to the petroleum fractions with about 25～200 ℃ of boiling points.
Term " liquefied petroleum gas " or " LPG " refer under suitable pressure, exist with liquid state at ambient temperature less than 1.5MPa, mainly contain the mixture of the low boiling hydrocarbon of propane, propylene and butane.
The overhead product product can pass through, and catalytic cracking paraffinic base wax is fischer-tropsch wax or slack wax alternatively for example, and then hydrogenation obtains.The fs of method of the present invention comprises, use wax for example fischer-tropsch wax makes its experience catalytic cracking process as charging, this technology comprises wax is exposed in the temperature of rising, as discussed below, under the situation that catalyzer exists, to form alkene class intermediate product.Catalytic cracking process can carry out in fluidized bed catalytic cracker, under mild conditions, still is as discussed below.
In subordinate phase, make the alkene class intermediate product experience hydrogenation of above-mentioned acquisition, it comprises makes intermediate product and hydrogen under the temperature and pressure that raises, and it also can be in high level down, in the presence of catalyzer, reacts.One when finishing hydrogenation technique, just can reclaim final petroleum distillate, and this overhead product mainly contains the combination of rocket engine fuel and diesel oil, and the petroleum naphtha and/or the liquefied petroleum gas (LPG) that may contain a tittle in addition.
More specifically, about the fs, catalytic cracking process adopts the catalyzer that can comprise metal.Those of ordinary skills can select various catalyzer.Yet the catalyzer that can use comprises the metal that is embedded in unbodied matrix preferably in the present invention.The metal that exists in the catalyzer can be a kind of in the lanthanide series metal in scandium, yttrium or the periodic table of elements.
As above mentioned, catalytic cracking process can be in fluidized bed catalytic cracker, and under mild conditions, for example temperature is less than or equal to 7Kg/cm usually less than 500 ℃, pressure 23～5Kg/cm for example 2, carry out.Because come from than low activity catalyst with than the mild conditions of low reaction temperatures, the transformation efficiency of wax per pass fluidized bed catalytic cracker is restricted.Limited transformation efficiency requires the unconverted wax of recirculation 0～500 quality % on the fresh feed basis to fluidized bed catalytic cracker.In the application of typical fluidized bed catalytic cracker, the condition of catalytic cracking is strict more.For example, typical reaction ℃ can be greater than 535 ℃, can be greater than 80 quality % by the transformation efficiency of middle wax at single.Therefore, in typical cracking was used, wax can mainly be cracked into petroleum naphtha and LPG product.Among the present invention, use gentle more condition to realize the production of overhead product rather than gasoline and LPG.
Catalytic cracking process can be undertaken by various mechanism.Be not limited to a kind of concrete mechanism or principle, believe that usually one group of detailed chemical conversion of generation comprises that ion as described below transforms.
The first step causes, and can be paraffinic hydrocarbons or be taken place by the formed alkene of of the same race or another kind of paraffinic hydrocarbons in advance by alkane.Initiation reaction is schematically shown by following reaction formula (1) and (2).From reaction formula (1) as can be seen, the catalyzer K of paraffinic hydrocarbons and cationic form reaction, from reaction formula (2) as can be seen, and alkene and acid catalyzer K reaction, every kind all produces carbonium ion R 1-(CH 2)-CH + -R 2:
R 1-CH 2-CH 2-R 2+K +＝＝>R 1-CH 2-CH +-R 2+HL (1)
R 1-CH＝CH-R 2+KZ＝＝>R 1-CH 2-CH +-R 2+K - (2)
Wherein K is the matrix element of alumina base or silicate-base catalyzer, and L is Lewis acid or alkali, each R 1, R 2, R 3It all is alkyl.
Next, react, wherein the carbonium ion R that forms in the step formerly by growth steps (3) 1-CH 2-CH +-R 2Fracture forms another alkene and continues main chain thus:
R 1-CH 2-C H +-R 2＝＝>R 1 ++CH 2＝CH-R 2 (3)
React by shown in reaction formula (4A), forming light alkene, wherein the R of reaction formula (4A) 3Be R 1A part, or form light alkene shown in the reaction formula (4B) and stop.
R 1 ++K -＝＝>R 3-CH＝CH 2+KH (4A)
R 1 ++KH＝＝>R 1-H+K + (4B)
Further an example explaining the mechanism that catalytic cracking is possible can adopt concrete alkene, 2,4,4-2,4,4-Trimethyl-1-pentene-1 wherein causes step (5), growth steps (6 and 7), and stop step (8) and cause simple olefins, promptly the 2-methacrylic is the formation of iso-butylene:
(CH 3) 3C-CH 2-C(CH 3)＝CH 2+HK＝＝>(CH 3) 3C-CH 2-C +-(CH 3) 2+K - (5)
(CH 3) 3C-CH 2-C +-(CH 3) 2＝＝>(CH 3) 3C ++CH 2＝C(CH 3) 2 (6)
(CH 3) 3C-CH 2-C(CH 3)＝CH 2+(CH 3) 3C +＝＝>
＝＝>(CH 3) 3C-CH 2-C +-(CH 3) 2+CH 2＝C(CH 3) 2 (7)
(CH 3) 3C ++K -＝＝>CH 2＝C(CH 3) 2+HK (8)
As can be seen, be (CH from initial alkene 3) 3C-CH 2-C (CH 3)=CH 2, and carbonium ion (CH 3) 3C-CH 2-C +-(CH 3) 2, form the molecule that another final product is an iso-butylene, and also produce the i.e. (CH of carbonium ion 3) 3C +, allow ion chain such as reaction formula (6) and (7) to increase thus.In step (8), the iso-butylene of another molecule is by carbonium ion (CH 3) 3C +Deprotonation form, catalyzer HK produces and prepares once more catalytic step (5) again.
Usually be in and above-mentioned graphic (1), (3) and (4A) typical process of the catalytic cracking in the scope of relevant technology, on reaction scheme (9)～(12), schematically show below, be used for basically the conversion process of the fischer-tropsch wax formed by n-paraffin.The catalytic cracking mechanism of n-paraffin comprises the formation of unsettled carbonium ion intermediate product.
More specifically, beginning, at initiating stage, dehydrogenation causes the formation of alkene to n-paraffin (that is, octane as follows) in the presence of the metal of catalyzer, is schematically shown by reaction scheme (9):
Figure A200810212774D00111
As shown above the alkene of Xing Chenging then apace with the alpha proton reaction that exists at the acid point place of catalyzer, be rearranged subsequently forming carbonium ion, shown in following reaction scheme (10):
As can be seen, top reaction scheme (1) also shows the formation of same carbonium ion, but the process combination shown in reaction scheme (9) and (10) provides more detailed explanation.The carbonium ion that forms shown in reaction scheme (10) is very unstable, and can be isomerizated into different carbonium ions to obtain more stability.
Growth technology shown in the reaction scheme (11), usually corresponding to top reaction formula (3) but more detailed, the cracking of the original carbonium ion by occurring in the β position is carried out, to form another positively charged ion and alkene.Cracking for the second time, it also is a part that increases, and takes place when continuous isomerization of carbonium ion and cracking.These increase technology, comprise cracking and isomerization reaction, are schematically shown by reaction scheme (11):
Figure A200810212774D00121
Shown in above reaction scheme (4A), catalytic cracking process also passes through the conversion of the product of stage acquisition formerly, and for example the formation of alkene stops.In the detailed diagram by the technology of reaction formula (9) beginning, the termination phase that is in the point that catalyzer produces again is by shown in the reaction scheme (12), and can be begun once more by the technology of reaction formula (9) beginning:
The wax that is used to transform can comprise, except straight chain and/or branched paraffin, and at least one quantitative naphthenic hydrocarbon, oxide compound and possible aromatics.Like this, as implied above except the conversion process of n-paraffin, catalytic cracking process also comprises the conversion of naphthenic hydrocarbon, oxide compound and possible aromatics.The transformation mechanism of naphthenic hydrocarbon is schematically shown by following reaction scheme (13)～(15).The catalytic cracking mechanism of naphthenic hydrocarbon comprises the formation of unsettled carbonium ion intermediate product.As a result, unsaturated cyclic cpds forms, to be used for the hydrogenation technique of back.
As can be seen, the naphthenic hydrocarbon cracking typically comprises cleavage reaction from reaction scheme (13)～(15), and wherein specific alkyl is removed by selectivity, and the integrity of saturated rings itself is kept.The cracked mechanism that comprises naphthenic hydrocarbon is consistent with aforementioned normal paraffin cracked mechanism.For purposes of illustration, reaction scheme (13)～(15) use 1,2,3, and 4-tetramethyl-ring hexane is as original naphthenic hydrocarbon.
As shown below, at first, alkene (promptly 1,2,3,6-tetramethyl-ring hexene) forms, and forms carbonium ion subsequently, and isomerization, shown in reaction scheme (13) and (14):
Figure A200810212774D00131
Formed carbonium ion passes through a series of isomerization steps subsequently, with generation cycloolefin and another carbonium ion, shown in reaction scheme (15):
Figure A200810212774D00132
After the above-mentioned catalytic cracking process is hydrogenation technique known in the art.During hydrogenation, the alkene that forms in the cracking stage in the presence of catalyzer with H-H reaction, with saturated formation alkane.If original wax comprises cycloolefin, then naphthenic hydrocarbon also can form in addition.
Hydrogenation technique carries out in the hydrotreatment unit, under mild conditions, and 250～315 ℃ temperature and be less than or equal to 35Kg/cm usually for example 2, 10～20Kg/cm for example 2Pressure.The hydrogen delivery rate of expectation can be selected.For example, for every m 3The overhead product boiling range in alkene class intermediate product, can be with 170～840m 3The speed hydrogen supply.
Hydrogenation technique can graphic by exemplary reaction (16) (being used for for example methyl butene of normal olefine) and (17) (being used for for example cyclopentenes of cycloolefin) describe:
Figure A200810212774D00141
From reaction scheme (16) and (17) as can be seen, hydrogenation technique carries out in the presence of catalyzer.The catalyzer that is fit to can be selected from the known available selection of various prior aries.For example, the available catalyzer is the underlying metal composition, nickel-molybdenum compositions for example, cobalt-molybdenum composition etc.Alternatively, can use and contain for example precious metal composition of platinum, palladium etc.
Any fischer-tropsch wax and/or slack wax all can be as the chargings in the above-mentioned technology, to form overhead product.As discussed above, this class overhead product typically contains the hydrocarbon of the middle boiling range of the combination (being composition) that comprises rocket engine fuel and diesel oil.
The concrete composition of the reactor effluent that obtains from fluidized bed catalytic cracker, and each wherein contained component ratio between LPG, petroleum naphtha and the overhead product for example except other factors, depend on the characteristic and concrete composition the thereof of used wax.For example, the reactor effluent of the combination that contains rocket engine fuel and diesel oil, petroleum naphtha and LPG that obtains from FCC can comprise, surpasses the composition that is made of rocket engine fuel and diesel oil of 50 quality %.
The various waxes that can be used in the technology are described here.The acceptable fischer-tropsch wax that can use is optional not to have oxide compound basically, and the hydrocarbon composition is made of the paraffinic hydrocarbons composition of 100 quality % basically.The paraffinic hydrocarbons composition can comprise one or more linear paraffins, and can comprise at least a branched paraffin in addition.This class straight chain and branched paraffin are the main ingredients of paraffinic hydrocarbons composition.Except linear paraffins and branched paraffin, the paraffinic hydrocarbons composition can also contain the naphthenic hydrocarbon of at least one tittle.In some embodiments, the alkyl aromatic compound of trace and many alkyl-aromatic compounds also may reside in the fischer-tropsch wax.
Multiple FCC system and device can be used to implement technology of the present invention.Next a specific examples of the system that this class can be used and can be described as shown in drawings.
System 100 comprises heat exchanger network 1, in order to before wax 11 is introduced fluid catalystic cracking reactors 2, wax is heated to above-mentioned desired temperatures, promptly is lower than 500 ℃ temperature, thus cracking.Fluid catalystic cracking reactor 2 is devices of implementing the catalytic cracking process of wax when the fluidized catalyst (not shown) exists.
The pressure of expectation keeps by fractionator 5 the higher authorities' stream 14 in reactor 2, and it also is communicated with reactor 2.Reactor pressure remains on the level of above-mentioned expectation, promptly is in to be less than or equal to 7Kg/cm 2, 3～5Kg/cm for example 2Level.Heated wax 11 and any unconverted wax 12 that is recovered are introduced in the reactor 2, and catalytic cracking process carries out as described above when wax contacts with catalyzer.Being suitable as any catalyzer of the cracking catalyst that is used for FCC technology uses as can be as previously mentioned.
In catalytic cracking process, alkene class intermediate product produces in reactor 2.Alkene class intermediate product 4 experiences further technology then.More specifically, the stream of alkene class intermediate product 4 is introduced into fractionator 5, and here alkene class intermediate product is separated into cut, and it is obtained with as overhead product 6 to satisfy the cut of alkene class intermediate product of expectation of fuel technology standard.There are various fuel technology standards.Some can adopt among them, classifies by for example specified burning-point of ASTM T90 or T95 and distillation temperature.Except overhead product, fractionator 5 also produces the stream of unconverted product 13 and the stream of refiltered oil 12, and it is unconverted wax.The latter can make up with the maximum 500 quality %s amounts of wax 11 with the wax charging, reduces the logical out of date transformation efficiency of each wax in the reactor 2 thus.Fractionation process is implemented according to standard procedure and rules, and can change as required or regulate.For example, other cut can be collected, for example naphtha fraction 15 and/or LPG cut 16.
After fractionation process, the cut of the expectation of alkene class intermediate product can be guided hydrotreatment unit 7 into as distillating logistics 6, experiences hydrogenation here.Distillate logistics 6 and can in heat exchanger network 8, be preheating to desired temperatures.The technology of hydrogenation comprises makes overhead product and hydrogen 9 for example react on the fixed bed (not shown) at the bed of catalyzer.
Hydrogen can be used as stream 9 and is incorporated in the hydrotreatment unit 7, and can use any catalyzer that is suitable as hydrogenation catalyst.For example, above-mentioned underlying metal composition can be used as nickel-molybdenum compositions or cobalt-molybdenum composition.Alternatively, precious metal composition, as the composition that contains platinum or palladium also can use.Hydrogen is heated before can be randomly in being introduced into hydrotreatment unit 7.Be introduced into for example every 1m in the above under the speed that hydrogen is discussed 3The alkene class intermediate product in the overhead product boiling range 170～840m is provided 3Hydrogen.Above-mentioned hydroprocessing technique produces final product, i.e. hydrogenant overhead product, and it can be removed as stream 10 then, and it comprises the clean reactor effluent that contains at least 50 quality % overhead product boiling range products.
Although method and system of the present invention is described with reference to reaction discussed above and structure, be understood that improvement and distortion within the category of the present invention that also comprises claims qualification.

Claims (10)

1, a kind of method that obtains the petroleum distillate product comprises:
(a) in fluidized bed catalytic cracker, in the presence of first catalyzer, be less than or equal to 7Kg/cm 2Pressure under cracking paraffinic base wax, obtain alkene class intermediate product;
(b) this alkene class intermediate product of hydrogenation in the presence of second catalyzer; And
(c) recovery contains the clean reactor effluent of the overhead product boiling range product of at least 50 quality %, obtains the overhead product product thus.
2, method according to claim 1 is characterized in that, the step of described hydrogenation is being less than or equal to 35Kg/cm 2Pressure implement down.
3, method according to claim 1 is characterized in that, described cracking is at 3～5Kg/cm 2Pressure under carry out.
4, method according to claim 1, it is characterized in that, described first catalyzer contains first metal composites, and said composition contains scandium, yttrium or is selected from metal in the group of the lanthanides of the periodic table of elements, and wherein this first metal composites is embedded in amorphous or zeolite matrix.
5, method according to claim 4 is characterized in that, the metal in described first metal composites is selected from the group of scandium and yttrium composition.
6, method according to claim 1, it is characterized in that, described second catalyzer contains the [amorphous with second metal composites, and said composition contains underlying metal composition or precious metal composition, and wherein this second metal composites is impregnated in [amorphous.
7, method according to claim 6 is characterized in that, described underlying metal composition is selected from the group of nickel-molybdenum compositions and cobalt-molybdenum composition composition.
8, method according to claim 6 is characterized in that, described precious metal composition contains the precious metal of the group that is selected from platinum and palladium composition.
9, method according to claim 1 is characterized in that, described overhead product boiling range product contains the combination of rocket engine fuel and diesel oil.
10, a kind of system (100) that obtains petroleum distillate boiling range product from paraffinic base wax comprising:
(a) fluid catalystic cracking reactor (2) is used for being less than or equal to 7Kg/cm 2Pressure under cracking paraffinic base wax to obtain alkene class intermediate product (4);
(b) fractionator (5) that is communicated with fluid catalystic cracking reactor (2) fluid is used for reclaiming overhead product (6) from alkene class intermediate product (4); And
(c) hydrogenation unit (7) that is communicated with fractionator (5) fluid is used for hydrogenation overhead product (6) contains the petroleum distillate boiling range product of at least 50 quality % with acquisition clean reactor effluent (10).
CNA2008102127745A 2007-09-07 2008-09-08 Fluid catalytic cracking and hydrotreating processes for fabricating diesel fuel from waxes Pending CN101381619A (en)

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US20100297749A1 (en) * 2009-04-21 2010-11-25 Sapphire Energy, Inc. Methods and systems for biofuel production
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US20160168486A1 (en) * 2013-08-21 2016-06-16 Gi-Gasification International (Luxembourg), S.A. Methods, systems, and apparatuses for low-temperature, fischer-tropsch wax hydrogenation
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