CN101497816B - Non-hydrogenation aromatization upgrading method for naphtha - Google Patents
Non-hydrogenation aromatization upgrading method for naphtha Download PDFInfo
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Abstract
The invention relates to a method for reforming naphtha non-hydrogasification aromatization, which comprises the following steps: naphtha contacts with reforming catalyst to perform the aromatization reforming reaction under the condition of non-hydrogasification, the obtained reforming product contacts with sorbent and adsorbs naphthaline series compound therein, and then strippant is used for desorbing the naphthaline series compound adsorbed in the sorbent, the strippant is separated from the naphthaline series compound by fractionation separation, and the sorbent comprises 55-80 percent of lithium by mass and/or sodium modified faujasite and 20-45 percent of caking agent by mass. The method can effectively remove heavy components in the aromatization reforming liquid product, lowers the end point of distillation and can obtain the naphthaline series compound with higher purity.
Description
Technical field
The present invention is the non-hydrogen aromatization modified method of a kind of petroleum naphtha, specifically, is a kind of method of improving the non-hydrogen aromatization modified product liquid character of petroleum naphtha.
Background technology
At present, catalytically cracked gasoline accounts for 80% in China's gasoline product, and conventional FCC content of olefin in gasoline is difficult to reach the fixed sulphur content of live steam fuel oil meter ≯ 0.015% up to 50-55%, olefin(e) centent ≯ 25%, benzene content ≯ 1.0%, the standard of aromaticity content ≯ 35%.Therefore, the clean gasoline blend component of production high-octane rating, low olefin-content becomes pressing for of each refinery.And to produce the method for high-octane rating clean gasoline blend component mainly be CR China present stage, because its insufficient raw material, causes a lot of catalytic reforming units can not running at full capacity.
In the last few years,, can petroleum naphtha and/or low-carbon (LC) hydro carbons be converted into the gasoline blend component that is rich in aromatic hydrocarbons under conditions of non-hydrogen because ZSM-5 selects the discovery of shape zeolite, while by-product high-quality liquefied gas, this technology is called the aromatization modification technology.This technology adaptability to raw material is strong, and is low to raw material impurity content, arene underwater content and boiling range area requirement, and reaction system does not need in the presence of hydrogen, to carry out and can under low pressure operate, and this has opened up an effective way for the utilization of refinery's petroleum naphtha and low-carbon (LC) hydro carbons.But, contain more last running in the aromatization modification gasoline product, do higher.Discover through reducing doing of gasoline and can alleviate the pollution that vehicle exhaust causes.Up to the present, the opinion aromatization modification product of determining is not done high report.
" chemical engineering design " 2003 the 13rd volumes the 6th phase 17-19 page or leaf has been reported " C
10Heavy aromatics comprehensive utilization process technology ", this technology is with C
10Aromatic hydrocarbons is isolated the solvent oil of the different trades mark through rectifying tower; Obtain durol pregnant solution and still Residual oil simultaneously; After wherein the durol pregnant solution is refrigerated to-20 ℃ in mold, send separating unit to dry with whizzer, the naphthalene filter cake gets the naphthalene product again after the squeezing machine squeezing.
CN94105030 discloses a kind of separation method of C+10 heavy aromatic hydrocarbon, with reformation C
10 +Heavy aromatics is a raw material, separates obtaining durol, naphthalene and solvent oil with the crystalline method through rectifying, at C
10 +Adopt the working method of varying reflux ratio in the rectifying of heavy aromatics, promptly when the rich durene cut of cutting, adopt big reflux ratio operation, and when other cut of cutting, adopt little reflux ratio operation, improve the concentration of durol in the rich durene liquid with this.
CN97115776 discloses the method that a kind of coal gas washing oil-diesel oil takes off naphthalene, and this method to-5～5 ℃, is input to quench liquid terepthaloyl moietie the tube side of interchanger with glycol-cooled; The saturated diesel oil that to wait to take off naphthalene again pumps into the shell side of interchanger; Carry out heat exchange, make the naphthalene that dissolves in the saturated diesel oil of naphthalene in the time of 5～10 ℃, be the fine particle shape and separate out, flow in the storage tank with refrigerative diesel oil; Again through the whizzer solid-liquid separation; The diesel oil that takes off behind the naphthalene has 50% separated the going out of naphthalene, becomes to dissolve the naphthalene unsaturated solution, gets back in the coal gas spray column and reuses.
CN99107030 discloses a kind of hydrocarbon adsorption dearylating process, and raw materials used boiling spread is between 45～300 ℃, and wherein the concentration of aromatic substance reaches 0.1～15w%.This method comprises the steps: that charging implements adsorption step and adsorb aromatic substance in containing a plurality of series connection fixed adsorption beds of zeolite adsorbents; Adsorption temp is 30～70 ℃; Be clipped in paraffinic hydrocarbons, isomerization alkanes and the naphthenic hydrocarbon in the sorbent material hole with the discharge of desorb fluid flushing, the aromatic substance of having adsorbed is then carried out desorb with the thermal desorption fluid, cools off bed simultaneously; Make it can be used to restart next round-robin adsorption step, the desorb fluid is gas or steam.
USP5177300 discloses a kind of method of from substituted benzene class hydrocarbon compound, separating naphthalene, and the employing adsorption process makes the absorption of being selected property of naphthalene, and then by desorbing agent naphthalene is desorbed.Raw material is coal tar or petroleum fractions, and boiling range is 200～250 ℃, comprises naphthalene, mononuclear aromatics and alkane; Sorbent material is the LiX zeolite, and desorbing agent is selected from 1,2; 3-Three methyl Benzene, 1, toluene, p-Xylol, m-xylene or benzene; Adsorption temp is 180～250 ℃, and desorption temperature is 20～220 ℃, and pressure is enough to make charging to keep liquid phase to get final product.
It is the method for separating indoles the hydrocarbon compound with X or y-type zeolite from naphthalene that USP4357276 discloses a kind of; This method adopts adsorption process that the indoles in the hydro carbons is optionally adsorbed; The zeolite that will adsorb indoles then contacts with desorbing agent B earlier, contacts with desorbing agent A indoles is wherein desorbed again.Raw material is a coal tar fraction, 220～270 ℃ of boiling range scopes, and sorbent material is X or Y zeolite, and exchange ion is a kind of among Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Cu, Ag, Zn, Cd, Fe, Ni, Co and the La, and desorbing agent A comprises C
2-10Aliphatic ether, C
7-10Aromatic oxide, C
2-10Fatty ester and C
3-10Alkanone, desorbing agent B are korenyl.
CN1600836A discloses the method that a kind of straight-run spirit upgrading prepares gasoline with low olefine content; This method with straight-run spirit with after the C 4 olefin cut mixes; Under 0.2～0.6MPa, 300～500 ℃ of conditions with the catalyzer contact reacts that contains HZSM-5; Dry gas in the separated product, liquefied gas and gasoline component then, but the final boiling point of its gained gasoline component is higher, can't reach the standard of clean gasoline.
Summary of the invention
The purpose of this invention is to provide the non-hydrogen aromatization modified method of a kind of petroleum naphtha, this method can significantly reduce the final boiling point of gained reformulated gasoline behind the aromatization modification, also can obtain the higher naphthalene series compound of purity simultaneously.
The method that petroleum naphtha provided by the invention is non-hydrogen aromatization modified; Comprise petroleum naphtha contacted with modifying catalyst under conditions of non-hydrogen and carry out the aromatization modification reaction; The upgraded product of gained contacts with sorbent material; Absorption naphthalene series compound wherein; With the naphthalene series compound that adsorbs in the strippant desorb sorbent material, through rectifying separation strippant is separated with naphthalene series compound then, described sorbent material comprises the faujusite of 55～80 quality % lithiums and/or sodium modification and the sticker of 20～45 quality %.
The inventive method is a raw material with petroleum naphtha or petroleum naphtha and mixed c 4; It is carried out aromatization modification, then reformulated gasoline is adsorbed with sorbent material of the present invention, remove the high boiling point product in the reformulated gasoline; Thereby significantly reduce doing of aromatization modification gasoline; Especially after in petroleum naphtha, having mixed mixed c 4 and carrying out aromatization modification, it is more and the too high problem of final boiling point that cause had both made full use of C-4-fraction effectively to solve the contained heavy constituent of gained reformulated gasoline; Can improve the reformulated gasoline quality again; Obtain the gasoline products of National standard, thereby alleviate the pollution that vehicle exhaust causes, also can obtain being used to produce the naphthalene series compound of Chemicals such as phthalic anhydride, synthetic resins, plant growth hormones simultaneously through fractionation desorb product.
Description of drawings
Fig. 1 is an aromatization modification method schematic flow sheet provided by the invention.
Fig. 2 is the desorption process synoptic diagram of ADSORPTION IN A FIXED BED separator of the present invention.
Embodiment
The inventive method uses the method for absorption to separate high-boiling hydrocarbons wherein with the product liquid that the mixture of C-4-fraction carries out obtaining behind the aromatization modification petroleum naphtha or its; Thereby reduce the final boiling point of aromatization modification product, make it to reach the national standard of gasoline products.In addition, adsorbent naphthalene series compound comprises naphthalene and verivate thereof, be mainly alkylnaphthalene with the strippant desorb after, go out the higher naphthalene series compound of purity through rectifying is separable, as the raw material of Chemicals, strippant can utilize again.
Active component content should be suitable in the described sorbent material, preferably includes the faujusite of 60～75 quality % lithiums and/or sodium modification and the sticker of 25～40 quality %.
The adsorbent activity component that the inventive method provides is the faujusite of modification, contains a certain amount of sticker in addition.The modified metal of described faujusite is lithium and/or sodium, and faujusite is the mixture of X zeolite, Y zeolite or X and Y zeolite, and the faujusite of modification is the mixture of LiY and LiX in sorbent material, and wherein the mass ratio of LiX and LiY is 50～90: 10～50.The preferred aluminum oxide of sticker in the sorbent material, silicon oxide, wilkinite or kaolin.
The faujusite of described modification can be used conventional ion exchange method preparation.The preparation of adsorbent method is: the faujusite of modification and the precursor of sticker are mixed aftershaping, drying according to the proportioning that each component in the sorbent material requires, in 300～600 ℃ of roastings.
Owing to contain a certain amount of high boiling hydro carbons in the aromizing product of naphtha aromtization upgraded product, particularly petroleum naphtha and mixed c 4, cause doing of aromatization modification product liquid, promptly final boiling point is higher.C in the aromatization modification product in the inventive method
12The content of above hydrocarbon component is 2～10 quality %, preferred 2～7 quality %.
When upgrading liquid product of the present invention passed through adsorption bed, naphthalene series compound wherein was adsorbed agent and optionally adsorbs, and components such as alkane, naphthenic hydrocarbon, alkene and mononuclear aromatics then are not adsorbed.The temperature that the aromatization modification product contacts with sorbent material is 10～100 ℃, preferred 20～80 ℃, and pressure is 0.1～1.0MPa, preferred 0.1～0.6MPa.Charging mass space velocity suitable during fractionation by adsorption is 0.5～5.0 hour
-1, preferred 0.5～3.0 hour
-1
The adsorption separation process of aromatization modification product of the present invention can be intermittently also can be successive.As, sorbent material can be contained in one or more adsorption beds, and liquid stock is with when an adsorption bed contacts, and strippant carries out desorb through other each adsorption bed to sorbent material.Perhaps, sorbent material is contained in the moving-bed, and it is contacted with the liquid stock that contains strippant in a continuous manner, and moving-bed can be also can be mimic really, and the absorption feed stream contacts with sorbent material with perhaps reverse in the same way mode.
For the sorbent material behind the absorption upgraded product, available strippant carries out desorb, and the flow that is rich in naphthalene series compound after the desorb preferably reclaims naphthalene series compound wherein through rectificating method.Described strippant is selected from C
6～C
10Aromatic hydrocarbons, preferred benzene or one or more C is arranged
1～C
3The korenyl of alkyl, perhaps both mixtures, as contain the mixture of korenyl of benzene and 50～80 quality % of 20～50 quality %.The preferred toluene of described korenyl, p-Xylol, 1 or 1,3, the 5-trimethylbenzene.
Suitable desorption temperature is 80～200 ℃, preferred 40～180 ℃, and pressure is 0.1～0.6MPa, preferred 0.1～0.3MPa.Charging mass space velocity suitable during desorb is 0.5～5.0 hour
-1, preferred 0.5～3.0 hour
-1
The described aromizing raw material of the inventive method is a petroleum naphtha, also can in petroleum naphtha, mix the mixed c 4 cut as raw material, under conditions of non-hydrogen, contacts with modifying catalyst then to carry out the aromatization modification reaction.Described petroleum naphtha is selected from one or more in normal pressure primary tower overhead oil, reformation tops, white oil, catalytically cracked gasoline, hydrogen cracking gasoline, catalytic cracking gasoline, pyrolysis gasoline, hydrogenation coker gasoline, the straight-run spirit.In the described mixed c 4 cut, C 4 olefin content is 40～90 quality %, and all the other are C
3～C
5Alkane.Contain the butylene of 40～90 quality % in the preferred C-4-fraction, all the other are propane, butane and pentane.The ratio of in petroleum naphtha, mixing the mixed c 4 cut is as the criterion with butene content wherein; Mixing proportion should make that butene content reaches 10～60 quality % in the mixed raw material; Usually, the mixed c 4 cut that in petroleum naphtha, mixes preferably accounts for 30～80 quality % of raw material total amount.
The described aromatization modification catalyzer of the inventive method comprises the modified metal-oxide of 0.1～5.0 quality % and the carrier of 95.0～99.9 quality %; Described modified metal-oxide is the oxide compound of zinc, antimony, mishmetal, bismuth, molybdenum or gallium, and described mixed rare-earth oxide contains the lanthanum trioxide of 20～40 quality %, the cerium oxide of 40～60 quality %, the Praseodymium trioxide of 10～18 quality % and the Neodymium trioxide of 2～10 quality %.Carrier is by the HZSM-5 of 50.0～80.0 quality % and γ-Al of 20.0～50.0 quality %
2O
3Form, the mol ratio of the silica of described HZSM-5 is 30～200, preferred 30～100.
Aromatization modification catalyzer of the present invention can be used conventional extrusion, drip the method moulding of ball or spin, and then introduces metal active constituent with pickling process.The upgrading reaction can be carried out in fixed-bed reactor or moving bed reaction-cyclic regeneration reactor drum, and the number of reactor drum can be one or more.The suitable temperature of reaction of aromatization modification is that 250～480 ℃, pressure are that 0.2～0.7MPa, mass space velocity are 0.1～1.0 hour
-1, upgrading is reflected under the condition of non-hydro and carries out.
Through gas-liquid separator, absorption desorption tower and stabilizer tower, isolate dry gas, liquefied gas and liquid product from the effusive logistics of upgrading reactive system.As qualifying liquid gasification product export, all or part of entering adsorption bed of liquid product is adsorbed heavy constituent wherein to liquefied gas after desulfurization is handled.
Further specify the present invention below in conjunction with accompanying drawing.
Among Fig. 1; The aromizing raw material gets into interchanger 2 through pipeline 1, after reaction effluent heat exchange from pipeline 3, gets into process furnace 5 through pipeline 4 and is heated to temperature of reaction; Get into reforming reactor 7 from the top through pipeline 6; Aromatization reaction products gets into interchanger 2 through pipeline 3, after raw material heat exchange from pipeline 1, gets into water coolers 9 coolings through pipeline 8; Get into HP separator 11 through pipeline 10 again and be divided into gas, liquid two phases; Wherein gas phase gets into through pipeline 12, compressor 13, pipeline 14 and absorbs desorption tower 15 middle parts, and liquid phase material 16 mixes after pipeline 18 gets into stabilizer towers 20 middle parts with absorption desorption tower 15 bottoms discharge material 17, and dry gas is discharged system through pipeline 19 from absorbing desorption tower 15 tops; Liquefied gas is discharged system through pipeline 21 from stabilizer tower 20 tops; Stabilizer tower 20 bottom material parts get into through pipeline 22 and absorb desorption tower 15 tops, and another part gets into ADSORPTION IN A FIXED BED separator 25 or 26 through pipeline 23 or 24, do qualified gasoline blend component and discharge system through pipeline 27 or 28 from ADSORPTION IN A FIXED BED separator 25 or 26 bottoms.Described fixed-bed adsorber 25 and 26 is parallel operation, and one adsorbs, and another carries out desorb simultaneously.
Fig. 2 is the desorption process synoptic diagram of ADSORPTION IN A FIXED BED separator of the present invention.When each other and a fractionation by adsorption device 25 absorption in two ADSORPTION IN A FIXED BED separators that connect saturated after; Strippant gets into ADSORPTION IN A FIXED BED separator 25 through pipeline 29; With the naphthalene series compound desorb that is adsorbed in the sorbent material, material carries out rectifying separation from bottom line 30 entering rectifying tower 31 after the desorb, and naphthalene series compound is discharged from rectifying tower 31 bottoms through pipeline 33; Strippant is discharged from rectifying tower 31 tops through pipeline 32, recycles.
Following instance is further explained the present invention, but is not therefore limited the present invention.
Instance 1
Prepare sorbent material of the present invention.
(1) preparation LiY molecular sieve: get 100 gram y-type zeolites (Qilu Petrochemical company Zhou village catalyst plant is produced), use concentration to exchange 5 hours as the LiCl solion of 0.1mol/L, being washed till with deionized water does not have Cl again in the washings
-, 110 ℃ of dryings 6 hours, 500 ℃ of roastings 3 hours.Repeat above-mentioned IX three times, make the LiY zeolite.
(2) preparation sorbent material: with (the German Condea company production of LiY zeolite and aluminium hydrate powder; Trade mark SB) press mass ratio mixes at 69: 31; Add and to account for the deionized water of solid masses 45% and 1% nitric acid, mix and pinch the back extruded moulding, 110 ℃ of dryings 10 hours; 500 ℃ of roastings made adsorbent A in 4 hours, wherein contained LiY zeolite quality 75%, gama-alumina 25 quality %.
Instance 2
Method by instance 1 prepares adsorbent B, and different is to use the NaCl solion exchange X type zeolite (Qilu Petrochemical company Zhou village catalyst plant produce) of concentration as 0.1mol/L in (1) step; (2) mass ratio of step preparation added NaX zeolite of sorbent material and aluminium hydrate powder is 60: 40, contains NaX zeolite 67 quality %, gama-alumina 33 quality % in the adsorbent B that makes.
Instance 3
Method by instance 1 prepares sorbent material, counts 75: 25 LiCl and NaCl mixing solutions in order to the mass ratio of Lithium Oxide 98min and sodium oxide in different is (1) step X type zeolite is carried out IX, must the LiNaX zeolite.Get the LiNaX zeolite and mix, mix by the method in 1 (2) step of instance then and pinch back extrusion, drying, roasting, contain LiNaX zeolite 72 quality %, gama-alumina 28 quality % among the sorbent material C that makes with the mass ratio of aluminium hydrate powder by 65: 35.
Instance 4
Method by instance 1 (1) step prepares the LiY zeolite, uses concentration as the LiCl solion of 0.1mol/L X type zeolite to be carried out IX by the method for preparing the LiY zeolite again, makes the LiX zeolite.
's 55: 15: 30 mixed with LiX zeolite, LiY zeolite and aluminium hydrate powder by mass ratio; Mix by the method in 1 (2) step of instance then and pinch back extrusion, drying, roasting, contain LiX zeolite 60 quality %, LiY zeolite 16 quality %, gama-alumina 24 quality % among the sorbent material D that makes.
Instance 5
Method by instance 2 prepares sorbent material, and the mass ratio of different is preparation added NaX zeolite of sorbent material and aluminium hydrate powder is 69: 31, contains NaX zeolite 75 quality %, gama-alumina 25 quality % among the sorbent material E that makes.
Instance 6
Method by instance 3 prepares sorbent material, and the mass ratio of different is preparation added LiNaX zeolite of sorbent material and aluminium hydrate powder is 69: 31, contains LiNaX zeolite 75 quality %, gama-alumina 25 quality % among the sorbent material F that makes.
Instance 7
Method by instance 4 prepares sorbent material; When different is the preparation sorbent material; Is 56: 13: 31 mixed with LiX zeolite, LiY zeolite and aluminium hydrate powder by mass ratio, contains LiX zeolite 61 quality %, LiY zeolite 14 quality %, gama-alumina 25 quality % among the sorbent material G that makes.
Instance 8
The preparation modifying catalyst.
(1) preparation carrier: get 120 gram silica than the HZSM-5 zeolite powder that is 56 (the prosperous chemical plant of Shanghai China produces); 80 gram aluminium hydrate powders (production of Shandong catalyst plant) after stirring, add nitric acid and 100 ml deionized water that 4 ml concns are 40 quality % and fully mediate; Be extruded into diameter and be 2 millimeters bar; 110 ℃ of dryings 8 hours are cut into the particle of 2～3 millimeters of length, again in 570 ℃ of roastings 4 hours.
(2) introduce active ingredient: get above-mentioned carrier 100 grams; (Baotou rare earth industrial in the Inner Mongol produces to contain 1.0 gram mixed chlorinated rare earths with 100 milliliters; Wherein contain the lanthanum trioxide of 31 quality %, the cerium oxide of 51 quality %, the Praseodymium trioxide of 14 quality % and the Neodymium trioxide of 4 quality %) the aqueous solution 80 ℃ the dipping 2 hours; 120 ℃ of dryings 8 hours, 550 ℃ of roastings 4 hours.
(3) steam-treated: the catalyzer that makes is packed in the tubular reactor, in airflow, be warming up to 580 ℃ under the normal pressure, under this temperature, change water flowing VT 5 hours then, total inflow is 400 grams, feeds dry air again and purges cooling.
The catalyzer that aforesaid method makes contains the mixed rare earth oxide (x-ray fluorescence method analysis) of 0.43 quality %, the HZSM-5 of 64.33 quality %, γ-Al of 35.24 quality %
2O
3, the α value is 30.
Instance 9
Following instance carries out the aromatization modification reaction.
The prepared modifying catalyst of filling 100 gram instances 8 on 100 milliliters of fixed-bed pilot plants was a raw material with the C-4-fraction of 60 quality % straight-run spirit and 40 quality %, 380 ℃, 0.3MPa, mass space velocity 0.4 hour
-1Condition under carry out upgrading reaction, the character and the composition of straight-run spirit are seen table 1, the composition of C-4-fraction is seen table 2, the group composition and the boiling range of upgrading product liquid are seen table 3.
Instance 10
Method by instance 9 is that reaction raw materials carries out the upgrading reaction with the straight-run spirit shown in the table 1, and the group composition and the boiling range of gained upgrading product liquid are seen table 3.
Following instance carries out adsorption experiment.
Filling 50 gram adsorbent B are carried out adsorption test to instance 9 upgrading reaction liquid products on 100 milliliters of fixed-bed pilot plants, and adsorption conditions is: 60 ℃ of temperature, pressure 0.1MPa, mass space velocity 1.2 hours
-1, adsorption time is 120 hours.The boiling range of adsorbent bed outflow product is seen table 4.
Instance 12
Filling 50 gram sorbent material C carry out adsorption test to instance 9 upgrading reaction liquid products on 100 milliliters of fixed-bed pilot plants, and adsorption conditions is: 20 ℃ of temperature, pressure 0.1MPa, mass space velocity 2.5 hours
-1, adsorption time is 120 hours.The boiling range of adsorbent bed outflow product is seen table 4.
Filling 50 gram sorbent materials carry out adsorption test to instance 9 upgrading reaction liquid products on 100 milliliters of fixed-bed pilot plants, and adsorption conditions is: 20 ℃ of temperature, pressure 0.1MPa, mass space velocity 2.0 hours
-1, adsorption time is 120 hours.The boiling range of sorbent material that each instance uses and adsorption bed outflow product is seen table 5.
Filling 50 gram adsorbent A are that raw material carries out adsorption test with the upgrading reaction liquid product of instance 10 on 100 milliliters of fixed-bed pilot plants, and adsorption conditions is: 60 ℃ of temperature, pressure 0.2MPa, mass space velocity 1.5 hours
-1, adsorption time is 120 hours.The boiling range of adsorbent bed outflow product is seen table 6.
Instance 18
Filling 50 gram sorbent material D on 100 milliliters of fixed-bed pilot plants are that raw material carries out adsorption test with the upgrading reaction liquid product of instance 10, and adsorption conditions is: 70 ℃ of temperature, pressure 0.1MPa, mass space velocity 1.8 hours
-1, adsorption time is 120 hours.The boiling range of adsorbent bed outflow product is seen table 6.
Table 4～6 data presentation, the upgrading product liquid final boiling point of products therefrom after adsorbing significantly reduces, and all reduces to below 200 ℃, meets the gasoline products standard of national regulation.
Instance 19
Following instance carries out desorption experiment.
The sorbent material C that 12 pairs of instance 9 upgraded products of instance are adsorbed carries out desorb, and strippant is a benzene, and desorption condition is: 150 ℃ of temperature, pressure 0.1MPa, mass space velocity 2.0 hours
-1, desorption time 48 hours.Logistics after the desorb reclaims wherein naphthalene series compound and strippant with rectificating method, and the content of other material is 0.78 quality % in the naphthalene series compound that obtains after the rectifying separation.
Respectively adsorbent A, E, F, the G through the absorption of instance 9 upgraded products in the instance 13～16 carried out desorb, strippant is a benzene, and desorption condition is: 150 ℃ of temperature, pressure 0.1MPa, mass space velocity 2.0 hours
-1, desorption time 48 hours.Logistics after the desorb reclaims wherein naphthalene series compound and strippant with rectificating method, and the content of other material is respectively 0.76 quality %, 0.82 quality %, 0.58 quality %, 0.62 quality % in the naphthalene series compound that obtains after the rectifying separation.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Claims (10)
1. method that petroleum naphtha is non-hydrogen aromatization modified; Comprise petroleum naphtha contacted with modifying catalyst under conditions of non-hydrogen and carry out the aromatization modification reaction, the upgraded product of gained contacts with sorbent material, adsorbs naphthalene series compound wherein; Then with the naphthalene series compound that adsorbs in the strippant desorb sorbent material; Through rectifying separation strippant is separated with naphthalene series compound, described sorbent material comprises the faujusite of 55～80 quality % lithiums and/or sodium modification and the sticker of 20～45 quality %, and the temperature of described aromatization modification reaction is that 250～480 ℃, pressure are 0.2～0.7MPa; The temperature that described upgraded product contacts with sorbent material is 10～100 ℃; Pressure is 0.1～1.0MPa, and described desorption temperature is 80～200 ℃, and pressure is 0.1～0.6MPa.
2. according to the described method of claim 1, it is characterized in that described sorbent material comprises the faujusite of 60～75 quality % lithiums and/or sodium modification and the sticker of 25～40 quality %.
3. according to claim 1 or 2 described methods, it is characterized in that described sticker is selected from aluminum oxide, silicon oxide, wilkinite or kaolin.
4. according to the described method of claim 1, it is characterized in that C in the described upgraded product
12The content of above hydrocarbon component is 2～10 quality %.
5. according to the described method of claim 1, it is characterized in that described faujusite is the mixture of X zeolite or Y zeolite or X and Y zeolite.
6. according to the described method of claim 5, the faujusite that it is characterized in that described lithium and/or sodium modification is the mixture of LiY and LiX, and wherein the mass ratio of LiX and LiY is 50～90: 10～50.
7. according to the described method of claim 1; It is characterized in that in petroleum naphtha, mixing the mixed c 4 cut; Under conditions of non-hydrogen, contact with modifying catalyst then and carry out the aromatization modification reaction, the mixed c 4 cut that mixes accounts for 30～80 quality % of raw material total amount.
8. according to the described method of claim 1; It is characterized in that described aromatization modification catalyzer comprises the modified metal-oxide of 0.1～5.0 quality % and the carrier of 95.0～99.9 quality %; Described modified metal-oxide is the oxide compound of zinc, antimony, mishmetal, bismuth, molybdenum or gallium, and carrier is by the HZSM-5 of 50.0～80.0 quality % and γ-A1 of 20.0～50.0 quality %
2O
3Form.
9. according to the described method of claim 1, it is characterized in that described strippant is selected from C
6～C
10Aromatic hydrocarbons.
10. according to the described method of claim 9, it is characterized in that described C
6～C
10Aromatic hydrocarbons be benzene or one or more C arranged
1～C
3The korenyl of alkyl.
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| CN107573966A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | A kind of method that high octane gasoline component is produced by F- T synthesis naphtha |
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| CN115785999A (en) * | 2022-11-21 | 2023-03-14 | 北方国际合作股份有限公司 | Method and system for producing gasoline and diesel oil from condensate oil |
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| US4357276A (en) * | 1979-11-02 | 1982-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for separation of indole using X and Y type zeolites |
| CN1600836A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for preparing gasoline with low content of olefin by modifying direct distillation gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4357276A (en) * | 1979-11-02 | 1982-11-02 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for separation of indole using X and Y type zeolites |
| CN1600836A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Method for preparing gasoline with low content of olefin by modifying direct distillation gasoline |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107573966A (en) * | 2016-07-05 | 2018-01-12 | 中国石油化工股份有限公司 | A kind of method that high octane gasoline component is produced by F- T synthesis naphtha |
| CN107573966B (en) * | 2016-07-05 | 2020-03-24 | 中国石油化工股份有限公司 | Method for producing high-octane gasoline component from Fischer-Tropsch synthesis naphtha |
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| CN101497816A (en) | 2009-08-05 |
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