CN107446618A - A kind of method of hydrotreating of Fischer-Tropsch synthesis oil - Google Patents

A kind of method of hydrotreating of Fischer-Tropsch synthesis oil Download PDF

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CN107446618A
CN107446618A CN201610365749.5A CN201610365749A CN107446618A CN 107446618 A CN107446618 A CN 107446618A CN 201610365749 A CN201610365749 A CN 201610365749A CN 107446618 A CN107446618 A CN 107446618A
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molecular sieve
ammonium
oil
sodium
hydrocracking
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CN107446618B (en
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崔哲
于波
王仲义
孙士可
吴子明
曹正凯
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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

Abstract

The present invention discloses a kind of method of hydrotreating of Fischer-Tropsch synthesis oil, including following content：（1）F- T synthesis oil-producing and hydrogen are mixed into hydrocracking reactor, are reacted in the presence of hydrocracking catalyst, and the average pore size of the hydrocracking catalyst is in reduction trend along stream flow direction；（2）Step（1）Hydrogenation effluent be separated into gas phase and liquid phase, gas phase recycles, and liquid phase enters fractionating column；（3）Fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.Light oil yield can be greatly improved in this method, reduce boat coal freezing point and condensation point of diesel oil.

Description

A kind of method of hydrotreating of Fischer-Tropsch synthesis oil
Technical field
The present invention relates to a kind of hydrogenation of Fischer-Tropsch synthesis oil method, and it is excellent to relate in particular to a kind of hydrogenation of Fischer-Tropsch synthesis oil production The method of matter clean fuel.
Background technology
With the fast development of car industry, aircraft industry etc., supply falls short of demand for natural oil, and countries in the world all add coal liquid Change the research ranks of new technology, synthesize coal base（F-T is synthesized）Fuel oil " CTL " gradually puts on industrialization schedule.Switch through by Change technology, Fischer-Tropsch synthesis oil is converted into the chemical products such as gasoline, diesel oil, wax, ethene, propylene, polymer, ammonia, alcohol, aldehyde, ketone. ICL for Indirect Coal Liquefaction（F-T）The oil product of synthesis, it is formed and property has very big difference with natural oil：Without impurity such as sulphur, nitrogen-frees, （Nothing）The features such as cyclic hydrocarbon, high linear paraffin, product condensation point is high, and density is small.Therefore, F-T artificial oils only have hydrofinishing or added Hydrogen cracking could produce qualified automotive fuel.
CN200510028649.5 discloses a kind of method of Fischer-Tropsch synthetic production diesel oil or diesel component, this method The whole or lighter part of Fischer-Tropsch synthetic is subjected to hydrotreating, the Fischer-Tropsch synthetic of hydrotreating is part or all of And/or the heavier part of Fischer-Tropsch synthetic of non-hydrotreating is hydrocracked, product is fractionated into obtained heavy end It is recycled to hydrocracking reactor.This method complex operation, although condensation point of diesel oil can be reduced effectively, reduce limited extent.
CN201310089452.7 discloses one kind and Fischer-Tropsch synthetic is converted into naphtha, diesel oil and liquefied petroleum gas Method, this method separated after Fischer-Tropsch synthetic is entered into hydrofining reactor, obtains refined naphtha, refined bavin Oil, refined heavy diesel fuel and refined tail oil, refine tail oil and enter hydrocracking reactor progress hydrocracking reaction, reaction product point From pressure naphtha, cracking oil-producing, cracking heavy diesel fuel and cracking tail oil is obtained, wherein refined heavy diesel fuel and the mixing of cracking heavy diesel fuel Low freezing point diesel fuel is obtained into pour point depression reactor.Although this method can effectively reduce condensation point of diesel oil, complex process, operation hardly possible Degree is big and plant investment is higher.
It using Fischer-Tropsch synthetic is raw material by being hydrocracked and hydroisomerisation process life that US5378348, which is disclosed a kind of, Produce intermediate oil method, this method by the way that Fischer-Tropsch synthetic is divided into three naphtha, light fraction, heavy distillat cuts, Heavy distillat carries out hydrocracking reaction, and unconverted heavy end is recycled back to hydrocracking reactor and continues cracking.Due to the party Method adds isomerization-visbreaking course of reaction and fractionating column, makes its technological process complex；Add isomerization-visbreaking section, catalyst Dosage is also significantly increased；Unifining process generation water is entered directly into isomerization-visbreaking reactor, is catalyzed for isomerization-visbreaking Agent has certain influence；Midbarrel oil yield is not also high.
US6656342 discloses a kind of method for being hydrogenated with upgrading Fischer-Tropsch synthetic, and this method produces Fischer-Tropsch synthesis Thing be divided into it is light, weigh two cuts, two cuts of weight carry out hydrogenation reaction in two reaction zones respectively.Heavy distillat enters reactor Upper catalyst bed layer, once by particle diameter different protective agent bed and hydrocracking catalyst bed；Light fraction is being reacted Device middle and lower part enters, and the reactant with carrying out autoreactor top bed layer enters after hydrotreating catalyst bed after mixing and divided System is evaporated, unconverted heavy distillat can be recycled back to reactor and continue to react.In this method, light fraction is without Cracking catalyst Bed, the yield of light oil distillate is improved, but two reaction zones, in same reactor, the reaction condition such as pressure is convergent；If Standby investment is high, complex operation.
US6309432 discloses a kind of method for processing upgrading Fischer-Tropsch synthesis oil, and the method first cuts into Fischer-Tropsch synthesis oil Two cuts of weight, heavy end first pass through and are mixed into fractionating system with light fraction after hydroisomerizing cracker.By Alkene and oxygen content are higher in Fischer-Tropsch synthesis oil, directly contacted with isocraking catalyst the stability that can influence catalyst and Service cycle, and product quality is poor.
CN200510068181.2 provides a kind of method of integrated form hydrogenation of Fischer-Tropsch synthesis oil upgrading, and this method will first take Enter fractionating column, the product of isolated different fractions after support artificial oil whole fraction oil hydrotreating, tail oil, which enters, to be hydrocracked instead Device is answered to be converted into midbarrel product by heavy end is the maximum amount of.Its weak point is to use integrated form flow, and operation is flexible Property is smaller, and diesel product condensation point is higher, and yield is low.
CN200510068183.1 provides a kind of process of Fischer-Tropsch synthetic hydrogenation upgrading, is by F- T synthesis Three components such as high temperature condensate, low temperature cold condensate and the synthetic wax that reaction natural separation obtains are hydrogenated with respectively, and its high temperature is cold Condensate and the mixing of low temperature cold condensate add hydrotreating reactor, and reaction effluent enters the isolated each cut production of fractionating column Thing, wherein bottom of towe heavy end and synthetic wax are mixed into hydroisomerizing cracker.But it is disadvantageous in that Fischer-Tropsch is cold Condensate individually goes hydrofining reactor, the easy coking of catalyst；Synthetic wax does not enter hydrofinishing and directly enters to be hydrocracked, and causes It is hydrocracked investment increase；The condensation point of diesel product can not be ensured simultaneously.
US6863802 discloses a kind of by Fischer-Tropsch synthesis oil and fraction oil of petroleum production gasoline, distillate, crude lube stock The technique of component, this method are to mix Fischer-Tropsch distillate and fraction oil of petroleum to obtain fuel by being hydrogenated with the method for upgrading again Or crude lube stock.But feedstock oil of this method still using petroleum base crude oil as production diesel oil.
CN200710065309 discloses a kind of hydroprocessing technique of Fischer-Tropsch synthesis oil, and the technique is by Fischer-Tropsch synthesis oil Full cut carries out hydrotreating first, the diesel oil distillate of product first is then demultiplex out, tail oil is hydrocracked again, crackate The second diesel oil distillate is isolated again, but this method equipment investment is high, complex operation, and can only production section low-coagulation diesel oil.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of side of Fischer-Tropsch synthetic hydrogenation production high-grade fuel oil Fischer-Tropsch synthetic is directly entered hydrocracking reactor by method, this method, and hydrocracking reactor effluent enters fractionating column and obtained To the product of different fractions.Light oil yield can be greatly improved in this method, reduce boat coal freezing point and condensation point of diesel oil.
A kind of method of hydrotreating of Fischer-Tropsch synthesis oil, including following content：
（1）F- T synthesis oil-producing is mixed into hydrocracking reactor with hydrogen, is carried out in the presence of hydrocracking catalyst Reaction, the average pore size of the hydrocracking catalyst are in reduction trend along stream flow direction；
（2）Step（1）Hydrogenation effluent be separated into gas phase and liquid phase, gas phase recycles, and liquid phase enters fractionating column；
（3）Fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.
In the inventive method, the Fischer-Tropsch synthesis oil includes high temperature fischer-tropsch artificial oil or Low Temperature Fischer Tropsch artificial oil, high temperature take Support artificial oil preferably first passes through the oxygen in hydrofinishing removing raw material.Described F- T synthesis oil-producing property is as follows：Density 0.8g/ cm3~1.0 g/cm3, preferably 0.5g/cm3~0.95 g/cm3；Oxygen content is 0 ~ 2m%, preferably 0.2 ~ 0.5 m%；650 DEG C of the end point of distillation ~750 DEG C, preferably 680 DEG C~720 DEG C.
In the inventive method, hydrocracking operation condition is as follows：5.0~35.0MPa of reaction pressure, preferably 6.0~ 19.0MPa；Reaction temperature is 200 DEG C~480 DEG C, preferably 270 DEG C~450 DEG C；Volume space velocity is 0.1~15.0h-1, preferably 0.2 ~3.0h-1；Hydrogen to oil volume ratio is 100：1~2500：1, preferably 400：1~2000：1.
In the inventive method, hydrocracking catalyst sets at least to more than two layers.About being arranged to point during two layers of filling Admission space ratio is 1:5~5:1, preferably 1:2~2:1；The average pore size of upper strata hydrocracking catalyst is hydrocracked compared to lower floor High 0.5 ~ the 5nm of average pore size of catalyst, preferably 1 ~ 2 nm.The average pore size of upper strata hydrocracking catalyst is 7-11nm.
In the inventive method, the hydrocracking catalyst by weight, including following component：Carrier 55% ~ 85%, with oxygen The group VIII and/or vib metals 15% ~ 45% of compound meter；Wherein described carrier is Y molecular sieve, amorphous silicon aluminium, oxygen Change the one or more in aluminium.During if carrier containing Y molecular sieve, the mass percent of molecular sieve in the carrier is 30% ~ 70%, Surplus is amorphous silica-alumina and/or aluminum oxide.The group VIII metal can be Ni and/or Co, and vib active metal can To be W and/or Mo, in terms of metal oxide, group VIII tenor be 3% ~ 15%, vib metals content be 10% ~ 40%。
In the inventive method, the hydrocracking catalyst is prepared using commercial goods or by prior art.Such as Y molecular sieve, amorphous silicon aluminium and/or aluminum oxide are well mixed, dust technology is added into extruded moulding after slurry, through drying, roasting Obtain the carrier containing Y molecular sieve.The carrier containing Y molecular sieve is entered using the maceration extract containing group VIII and/or vib metals Row impregnates, and the carrier after dipping obtains hydrocracking catalyst through drying, roasting.Containing group VIII and/or vib metals The liquid-solid ratio that impregnates when being impregnated to carrier of maceration extract be 1.5：1~3：1.The content of group vib metallic compound in maceration extract 20 ~ 60g/100ml is calculated as by corresponding oxide, the content of group VIII metallic compound is calculated as 3 ~ 20g/ by corresponding oxide 100ml, the concentration of metallic compound can need adjust accordingly according to product in maceration extract.Described dried strip after dipping Part is：Dried 2 ~ 8 hours at 90 ~ 150 DEG C；Roasting condition is：It is calcined 1 ~ 5 hour at 400 ~ 700 DEG C.
In the inventive method, modified Y molecular sieve is contained in the hydrocracking catalyst of upper strata, the modified Y molecular sieve property is such as Under, 500 ~ 800m of specific surface area2/ g, 0.4 ~ 0.6ml/g of pore volume, wherein 2 ~ 7nm secondary pore volume accounting more than 40%, meleic acid Measure 0.6 ~ 1.2mmol/g, Na2O mass contents are less than 0.15%, SiO2/Al2O3Mol ratio 8 ~ 40, lattice constant 2.430 ~ The product of 2.445,2 ~ 7nm secondary pore volume accounting syncrystallization degree is 38% ~ 60%.
The preparation of above-mentioned modified Y molecular sieve, comprises the following steps：
（1）Ammonium Salt Ionic is carried out using NaY zeolite in ammonium salt solution as former powder to exchange to Na2O weight contents are less than 3.5%；
（2）To step（1）In obtained ammonium exchange after Y molecular sieve in temperature be 500 ~ 620 DEG C, pressure is 0.01 ~ 0.3MPa, Processing time is 1.0 ~ 4.0 hours；
（3）Step（2）Obtained hydro-thermal process Y molecular sieve carries out sodium ion exchange in sodium salt solution；
（4）By step（3）After obtained Y molecular sieve carries out ammonium fluosilicate dealumination complement silicon processing, after filtered, dry, roasting To final Modified Zeolite Y.
The preparation of above-mentioned modified Y molecular sieve, step（1）Described in Ammonium Salt Ionic exchange process it is as follows：Using NaY zeolite as original Material is in ammonium salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchange times are 1 ~ 2 time, are handed over NaY zeolite after changing, Na2O content 1.3 ~ 2.8%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, and sodium oxide molybdena quality percentage contains Amount 6% ~ 7%；Ammonium salt is the one or more in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, and ammonium salt aqueous solution is dense Spend 0.3 ~ 6.0mol/L, preferably 1.0 ~ 3.0 mol/L.
The preparation of above-mentioned modified Y molecular sieve, step（3）Described in sodium salt ion exchange process it is as follows：With step（2）Reclaimed water Hot Y molecular sieve be raw material in sodium-salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchange 1 ~ 3 hour, exchange times are 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass contents are not less than 3.0%；Sodium salt be sodium chloride, sodium nitrate, sodium sulphate, One or more in sodium citrate, sodium oxalate, preferably sodium-salt aqueous solution 0.3 ~ 6.0mol/L of concentration, 1.0 ~ 3.0 mol/L.It is excellent It is selected in the removing that the non-framework aluminum that glycerine promotes hydrothermal treatment process to generate is added in sodium salt solution and improves sodium salt and exchanges effect Rate, glycerol concentration is 0.1 ~ 2.0 in sodium salt solution, preferably 0.1-0.5 mol/L.
The preparation of above-mentioned modified Y molecular sieve, step（4）Described in dealumination complement silicon handle for known to those skilled in the art Method, conventional ammonium fluosilicate dealumination complement silicon method can be used, by step（3）Obtained Y molecular sieve is according to the solid mass ratio of liquid 3：1~20：1, preferably 5:1~10:1 mixes with the ammonium fluosilicate aqueous solution, and wherein ammonium fluosilicate concentration is in ammonium fluosilicate solution 0.01 ~ 1.0mol/L, preferably 0.1 ~ 0.8 mol/L, handled 0.5 ~ 6 hour in 50 ~ 100 DEG C.
The preparation of above-mentioned modified Y molecular sieve, step（4）In ammonium fluosilicate dealumination complement silicon during, ammonium fluosilicate solution In can to add the inorganic acids such as nitric acid, hydrochloric acid, acetic acid, citric acid, oxalic acid or organic acid non-in molecular sieve preferably to remove The concentration of framework aluminum, inorganic acid and/or organic acid is with H+It is calculated as 0.1 ~ 0.7mol/L, preferably 0.2 ~ 0.5mol/L.
The preparation process of above-mentioned modified Y molecular sieve by exchanging NaY original powder ammonia to reduce molecular sieve Na contents, carries first High hydro-thermal process efficiency, and reduce hydrothermal treatment process skeleton destructiveness.Y molecular sieve after hydro-thermal process by supplement Na from Son, promote the dealumination complement silicon of follow-up ammonium fluosilicate processing procedure to react and carry out.Therefore, hydro-thermal process and fluosilicic acid are improved while The reaction efficiency of ammonium, modified Y molecular sieve remains the secondary pore volume of hydrothermal treatment process greatly and ammonium fluosilicate processing procedure is in depth The characteristics of spending dealuminzation and high skeleton crystal degree.
Fischer-Tropsch synthetic is by being hydrocracked or hydro-upgrading can produce high smoke point and navigate coal and high cetane number diesel oil Component, but because Fischer-Tropsch synthetic boiling range span is larger, wherein rich in midbarrel and heavy end, in hydrocracking process In, because macromolecular substances polarity is big, it is easier to which in catalyst surface cracking reaction occurs for absorption, and midbarrel is inhaled by competition It is attached influence and in the larger catalyst duct of catalyst molecule mesh size the residence time it is shorter, cause to react insufficient, and The midbarrel that this part is mainly made up of direct-connected alkane is enriched in boat coal and the diesel oil distillate in isocrackate, thus Boat coal freezing point and condensation point can not effectively be reduced.Upper strata hydrocracking catalyst changes rich in the high silicon of meso-hole structure, high-crystallinity Property Y molecular sieve, the secondary pore formed between Y molecular sieve is that being hydrocracked for macromolecular alkane provides place, makes it in Y The outer surface of/sieve is cracked, while the microcellular structure of Y molecular sieve can be such that the small-molecule substance in raw material fully occurs Reaction, is translated into isoparaffin, the effective freezing point and condensation point of diesel oil for improving product Air China coal.
Embodiment
The technical characterstic of the inventive method is further described by embodiment in next step, but following examples can not limit this Invention.% is weight/mass percentage composition such as without special marking in embodiment and comparative example.Wherein embodiment 1-3 is that upper strata hydrogenation splits Change the preparation of catalyst.
Embodiment 1
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, with the ammonium nitrate that concentration is 2.0mol/L according to liquid-solid ratio 4:1 Mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 1.8%；
（2）To step（1）550 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.3Mpa；
（3）To step（2）Obtained Y molecular sieve is with the sodium chloride solution that concentration is 1.7mol/L according to liquid-solid ratio 5:1 mixing, 65 DEG C exchange 1 hour, repeat this process 3 times, Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 3.8%；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 5:1 and 0.5mol/L ammonium fluosilicate and 0.3mol/L citric acids （With H+Meter）Solution be mixed with beating, 85 DEG C handle 2 hours；
（5）Through step（4）Y molecular sieve after processing, 120 DEG C of dryings 2 hours obtain molecular sieve, numbering Y-1, and property is shown in Table 1。
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml dippings after being dissolved in water molten Liquid, active metal is with WO in gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, solution is compiled Number RY-1；
（2）Take Y-1 60g to be mixed with 40g macroporous aluminium oxides, add 4g/100ml dust technologies and mix in a mixer and roll to can Shape is extruded, extruded moulding obtains carrier T-1 on banded extruder；
（3）Take T-1 60g to add 120ml RY-1 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C to be calcined 3 small When, obtain hydrocracking catalyst, numbering Cat-1, average pore size 10.7nm.
Embodiment 2
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, with the ammonium chloride that concentration is 2.5mol/L according to liquid-solid ratio 5:1 Mixing, 85 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 1.3%；
（2）To step（1）530 DEG C of obtained Y molecular sieve, hydro-thermal process 1.5 hours under 0.15Mpa；
（3）To step（2）Obtained Y molecular sieve is with the sodium nitrate that concentration is 1.5mol/L according to liquid-solid ratio 5:1 mixing, 80 DEG C of friendships Change 1 hour, repeat this process 2 times, Na contents are calculated as 3.6% with Na2O in the Y molecular sieve after exchange；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 5:1 mix dozen with the ammonium fluosilicate solution that concentration is 0.5mol/L Slurry, 95 DEG C are handled 2 hours；
（5）Through step（6）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of dryings, 2 hours acquisition molecular sieves, numbering Y-2, property Matter is shown in Table 1.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml dippings after being dissolved in water molten Liquid, active metal is with WO in gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, solution is compiled Number RY-2；
（2）Take Y-2 40g to be mixed with 60g macroporous aluminium oxides, add 4g/100ml dust technologies and mix in a mixer and roll to can Shape is extruded, extruded moulding obtains carrier T-2 on banded extruder；
（3）Take T-2 60g to add 120ml RY-2 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C to be calcined 3 small When, obtain hydrocracking catalyst, numbering Cat-2, average pore size 8.5nm.
Embodiment 3
（1）The NaY molecular sieve original powder 200g for taking laboratory to prepare, with the ammonium nitrate that concentration is 1.6mol/L according to liquid-solid ratio 3:1 Mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na contents are with Na in the Y molecular sieve after exchange2O is calculated as 2.0%；
（2）To step（1）550 DEG C of obtained Y molecular sieve, hydro-thermal process 2 hours under 0.2Mpa；
（3）To step（2）Obtained Y molecular sieve is with the mixing for containing sodium nitrate and glycerine being respectively 3.0mol/L and 0.2mol/L Solution is according to liquid-solid ratio 5:1 mixing, 80 DEG C exchange 1 hour, repeat this process 2 times, in the Y molecular sieve after exchange Na contents with Na2O is calculated as 5.3%；
（4）Step（3）The molecular sieve of gained is according to liquid-solid ratio 10:1 mix dozen with the ammonium fluosilicate solution that concentration is 0.7mol/L Slurry, 85 DEG C are handled 2 hours；
（5）Through step（4）Y molecular sieve after ammonium fluosilicate processing, 120 DEG C of drying 2 hours, acquisition molecular sieve, numbering Y-3, Property is shown in Table 1.
Hydrocracking catalyst preparation process：
（1）Configure W-Ni dipping solutions：Ammonium metatungstate 480g and nickel nitrate 480g is taken to configure 1000ml dippings after being dissolved in water molten Liquid, active metal is with WO in gained dipping solution3It is respectively 40g/100ml and 12g/100ml with NiO cubages, solution is compiled Number RY-3；
（2）Take Y-3 50g to be mixed with 50g macroporous aluminium oxides, add 4g/100ml dust technologies and mix in a mixer and roll to can Shape is extruded, extruded moulding obtains carrier T-3 on banded extruder；
（3）Take T-3 60g to add 120ml RY-3 maceration extracts and impregnate 2 hours, then 120 DEG C of drying 4 hours, 500 DEG C to be calcined 3 small When, obtain hydrocracking catalyst, numbering Cat-3, average pore size 7.4nm.
Table 1
Embodiment 4-8
Raw material oil nature is shown in Table 2, and commercially available hydrocracking catalyst is the FC-14 series that Fushun Petrochemical Research Institute develops Catalyst hydrogenation Cracking catalyst, property are shown in Table 3, and the filling of catalyst and process conditions are shown in Table 4, evaluation result be shown in Table 5, table 6, Table 7.
The raw material main character of table 2
The main physico-chemical property of the catalyst of table 3
Embodiment 4
Hydrocracking reactor from top to bottom descending FC-14A, FC-14B, FC-14C tri- in loading catalyst aperture successively Kind catalyst.
Comparative example 1
Hydrocracking reactor only loads a kind of FC-14A catalyst of large aperture.
The technological condition of table 4
The main character of the scheelite of table 5
The main character of the boat coal of table 6
The product diesel oil main character of table 7
Embodiment 5
Hydrocracking reactor descending bis- kinds of catalyst of Cat-1, FC-14A in loading catalyst aperture successively from top to bottom, Admission space ratio is 1:2, operating condition is constant, and evaluation result is shown in Table 8, table 9, table 10.
The main character of the scheelite of table 8
The main character of the boat coal of table 9
The product diesel oil main character of table 10
Embodiment 6
Hydrocracking reactor descending bis- kinds of catalyst of Cat-2, FC-14B in loading catalyst aperture successively from top to bottom, Admission space ratio is 2:1, operating condition is constant, and evaluation result is shown in Table 11, table 12, table 13.
The main character of the scheelite of table 11
The main character of the boat coal of table 12
The product diesel oil main character of table 13
Embodiment 7
Hydrocracking reactor descending bis- kinds of catalyst of Cat-3, FC-14C in loading catalyst aperture successively from top to bottom, Admission space ratio is 3:1, operating condition is constant, and evaluation result is shown in Table 14, table 15, table 16.
The main character of the scheelite of table 14
The main character of the boat coal of table 15
The product diesel oil main character of table 16
Fischer-Tropsch synthetic can obtain high-quality boat coal by this technology it can be seen from embodiment and comparative example, diesel oil is adjusted And component, and plant investment cost is low, and it is simple to operate.

Claims (15)

  1. A kind of 1. method of hydrotreating of Fischer-Tropsch synthesis oil, it is characterised in that：Including following content：
    （1）F- T synthesis oil-producing is mixed into hydrocracking reactor with hydrogen, is carried out in the presence of hydrocracking catalyst Reaction, the average pore size of the hydrocracking catalyst are in reduction trend along stream flow direction；
    （2）Step（1）Hydrogenation effluent be separated into gas phase and liquid phase, gas phase recycles, and liquid phase enters fractionating column；
    （3）Fractionation obtains naphtha, boat coal, diesel oil and tail oil in fractionating column；Tail oil is recycled to hydrocracking reactor.
  2. 2. according to the method for claim 1, it is characterised in that：Described F- T synthesis oil-producing property is as follows：Density 0.8g/cm3~1.0 g/cm3, preferably 0.5g/cm3~0.95 g/cm3；Oxygen content is 0 ~ 2m%, preferably 0.2 ~ 0.5 m%；The end point of distillation 650 DEG C~750 DEG C, preferably 680 DEG C~720 DEG C.
  3. 3. according to the method for claim 1, it is characterised in that：Hydrocracking operation condition is as follows：Reaction pressure 5.0~ 35.0MPa, preferably 6.0~19.0MPa；Reaction temperature is 200 DEG C~480 DEG C, preferably 270 DEG C~450 DEG C；Volume space velocity is 0.1~15.0h-1, preferably 0.2~3.0h-1；Hydrogen to oil volume ratio is 100：1~2500：1, preferably 400：1~2000：1.
  4. 4. according to the method for claim 1, it is characterised in that：Hydrocracking catalyst sets at least to more than two layers.
  5. 5. according to the method for claim 1, it is characterised in that：When hydrocracking catalyst is arranged to two layers of filling up and down Admission space ratio is 1:5~5:1, preferably 1:2~2:1；The average pore size of upper strata hydrocracking catalyst is hydrocracked compared to lower floor High 0.5 ~ the 5nm of average pore size of catalyst, preferably 1 ~ 2 nm, the average pore size of upper strata hydrocracking catalyst is 7-11nm.
  6. 6. according to the method for claim 1, it is characterised in that：The hydrocracking catalyst is by weight, including as follows Component：Carrier 55% ~ 85%, group VIII and/or vib metals 15% ~ 45% in terms of oxide；Wherein described carrier is One or more in Y molecular sieve, amorphous silicon aluminium, aluminum oxide.
  7. 7. according to the method for claim 6, it is characterised in that：During if carrier containing Y molecular sieve, molecular sieve is in the carrier Mass percent be 30% ~ 70%, surplus is amorphous silica-alumina and/or aluminum oxide.
  8. 8. according to the method for claim 1, it is characterised in that：The group VIII metal is Ni and/or Co, vib Active metal is W and/or Mo, and in terms of metal oxide, group VIII tenor is 3% ~ 15%, and vib metals content is 10%~40%。
  9. 9. according to the method for claim 5, it is characterised in that：Contain modified Y molecular sieve in the hydrocracking catalyst of upper strata, The modified Y molecular sieve property is as follows, 500 ~ 800m of specific surface area2/ g, 0.4 ~ 0.6ml/g of pore volume, wherein 2 ~ 7nm secondary pore Hold accounting more than 40%, meleic acid amount 0.6 ~ 1.2mmol/g, Na2O mass contents are less than 0.15%, SiO2/Al2O3Mol ratio 8 ~ 40, lattice constant 2.430 ~ 2.445, the product of 2 ~ 7nm secondary pore volume accounting syncrystallization degree is 38% ~ 60%.
  10. 10. according to the method for claim 9, it is characterised in that：The preparation of modified Y molecular sieve, comprises the following steps：
    （1）Ammonium Salt Ionic is carried out using NaY zeolite in ammonium salt solution as former powder to exchange to Na2O weight contents are less than 3.5%；
    （2）To step（1）In obtained ammonium exchange after Y molecular sieve in temperature be 500 ~ 620 DEG C, pressure is 0.01 ~ 0.3MPa, Processing time is 1.0 ~ 4.0 hours；
    （3）Step（2）Obtained hydro-thermal process Y molecular sieve carries out sodium ion exchange in sodium salt solution；
    （4）By step（3）After obtained Y molecular sieve carries out ammonium fluosilicate dealumination complement silicon processing, after filtered, dry, roasting To final Modified Zeolite Y.
  11. 11. according to the method for claim 10, it is characterised in that：Step（1）Described in Ammonium Salt Ionic exchange process such as Under：It is raw material in ammonium salt aqueous solution using NaY zeolite, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, exchanges time Number is 1 ~ 2 time, the NaY zeolite after being exchanged, Na2O content 1.3 ~ 2.8%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, Sodium oxide molybdena weight/mass percentage composition 6% ~ 7%；Ammonium salt is one kind or several in ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate Kind, ammonium salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.
  12. 12. according to the method for claim 10, it is characterised in that：Step（3）Described in sodium salt ion exchange process such as Under：With step（2）Middle hydro-thermal Y molecular sieve be raw material in sodium-salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchange 1 ~ 3 hours, exchange times were 1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass contents are not less than 3.0%；Sodium salt is chlorination One or more in sodium, sodium nitrate, sodium sulphate, sodium citrate, sodium oxalate, sodium-salt aqueous solution concentration 0.3 ~ 6.0mol/L are excellent Select 1.0 ~ 3.0 mol/L.
  13. 13. according to the method for claim 12, it is characterised in that：Glycerine is added in sodium-salt aqueous solution, glycerine is dense Spend for 0.1 ~ 2.0, preferably 0.1-0.5 mol/L.
  14. 14. according to the method for claim 10, it is characterised in that：Step（4）Described in dealumination complement silicon processing be ability Method known to field technique personnel, by step（3）Obtained Y molecular sieve is according to the solid mass ratio 3 of liquid：1~20：1, preferably 5:1~10: 1 mixes with the ammonium fluosilicate aqueous solution, and ammonium fluosilicate concentration is 0.01 ~ 1.0mol/L wherein in ammonium fluosilicate solution, preferably 0.1 ~ 0.8 mol/L, handled 0.5 ~ 6 hour in 50 ~ 100 DEG C.
  15. 15. according to the method for claim 10, it is characterised in that：Step（4）In ammonium fluosilicate dealumination complement silicon during, The concentration of addition inorganic acid or organic acid in ammonium fluosilicate solution, inorganic acid and/or organic acid is with H+0.1 ~ 0.7mol/L is calculated as, It is preferred that 0.2 ~ 0.5mol/L.
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US6589415B2 (en) * 2001-04-04 2003-07-08 Chevron U.S.A., Inc. Liquid or two-phase quenching fluid for multi-bed hydroprocessing reactor
US20060011512A1 (en) * 2004-07-16 2006-01-19 Conocophillips Company Combination of amorphous materials for hydrocracking catalysts
CN1854264A (en) * 2005-04-29 2006-11-01 中国石油化工股份有限公司 Integrated Fischer-Tropsch synthetic oil hydrogenation purification
CN101177619A (en) * 2007-04-13 2008-05-14 中科合成油技术有限公司 Method for producing diesel oil and chemical materials by f-t synthetic wax
CN101177623A (en) * 2007-03-26 2008-05-14 中科合成油技术有限公司 Hydro-cracking method for Fisher-Tropsch synthesis fuels

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6589415B2 (en) * 2001-04-04 2003-07-08 Chevron U.S.A., Inc. Liquid or two-phase quenching fluid for multi-bed hydroprocessing reactor
US20060011512A1 (en) * 2004-07-16 2006-01-19 Conocophillips Company Combination of amorphous materials for hydrocracking catalysts
CN1854264A (en) * 2005-04-29 2006-11-01 中国石油化工股份有限公司 Integrated Fischer-Tropsch synthetic oil hydrogenation purification
CN101177623A (en) * 2007-03-26 2008-05-14 中科合成油技术有限公司 Hydro-cracking method for Fisher-Tropsch synthesis fuels
CN101177619A (en) * 2007-04-13 2008-05-14 中科合成油技术有限公司 Method for producing diesel oil and chemical materials by f-t synthetic wax

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