CN102212394B - Fluid catalytic cracking (FCC) gasoline modification method comprising light gasoline etherification process - Google Patents
Fluid catalytic cracking (FCC) gasoline modification method comprising light gasoline etherification process Download PDFInfo
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Abstract
The invention relates to a fluid catalytic cracking (FCC) gasoline modification method comprising a light gasoline etherification process. The method comprises the following steps: carrying out selective hydrogenation on FCC gasoline so as to remove diene and mercaptan sulfur in the gasoline; after hydrogenation, cutting full-fraction gasoline into light and heavy components, wherein a large amount of tertiary carbonic olefin is concentrated in the light gasoline; carrying out two-section etherification on the light gasoline and methanol in the presence of an etherification catalyst so as to form an ether compound; carrying out hydrodesulfurization on the heavy gasoline so as to reduce olefin, wherein after sulfide is removed and olefin content is reduced, the hydrogenated heavy gasoline contains a large amount of aromatic hydrocarbon; and extracting the aromatic hydrocarbon, wherein after extraction of aromatic hydrocarbon, the heavy gasoline is a gasoline component enriching alkane, and the gasoline component can be used as a raw material for preparing ethylene by steam thermal cracking and also can be mediated together with etherified light gasoline so as to form a clean gasoline product.
Description
The application is to be on March 23rd, 2007 applying date, and denomination of invention is divided an application for " a kind of Etherification of Light FCC Gasoline technique reaches the modifying catalytically cracked gasoline method containing this technique " patent application.
Technical field
The present invention relates to a kind of containing petroleum naphtha in the modifying catalytically cracked gasoline method, particularly catalytically cracked gasoline of Etherification of Light FCC Gasoline technique through changing into containing the oxygen ether compound with methanol-ethers, the COMBINED PROCESS that heavy petrol is clean gasoline through hydrodesulfurizationmodification modification.
Background technology
At present, the development trend of world's motor spirit is unleaded, high-octane rating, low-steam pressure, low alkene and rich oxygen content.Catalytically cracked gasoline (being called for short FCC gasoline) is one of important sources of motor spirit.Quality of gasoline directly has influence on indices and the environmental requirement of motor spirit.The decline that can bring gasoline octane rating due to the minimizing of gasoline lead tolerance, simultaneously, olefin(e) centent volume fraction in FCC gasoline is up to 40～60%, the raising of content of olefin in gasoline, cause the gasoline discharge not reach the requirement of world's environmental regulation, compared with developed countries, the quality of gasoline gap of China is larger.Therefore, the gasoline upgrading technology of reasonable, the olefin(e) centent in reduction FCC gasoline and don't the octane value of reduction gasoline, be current Technology problem urgently to be resolved hurrily.
Contain a large amount of C in FCC gasoline
4～C
6active olefin, active olefin can carry out etherification reaction with methyl alcohol, can generate low-steam pressure and high-octane containing the oxygen ether compound, when reducing olefin(e) centent, can improve the octane value of motor spirit, reduce the lighter hydrocarbons volatilization that causes smog and low latitude ozone to form, reduce the discharge of CO, CxHy in vehicle exhaust.Therefore, by the COMBINED PROCESS to FCC Etherification of Light FCC Gasoline, heavy petrol hydrogenating desulfurization, by the part conversion of olefines in gasoline, be ether material, improve stability and the octane value of gasoline, also can reduce olefin(e) centent and sulphur content in gasoline.Research and development FCC gasoline upgrading new technology, will improve a new approach for the reasonable upgrading of China's oil refinery gasoline, and with the production stay in grade, excellent property, meet the clean gasoline of environmental regulation.
Petroleum naphtha is subject to the common concern of countries in the world as a kind of new technology of gasoline upgrading, competitively develop the industrial application new technology of gasoline etherification, but both at home and abroad each petro-chemical corporation in the selection cutting of the light gasoline fraction boiling range of raw material of etherification with etherification technology is technical is not quite similar.Reported the method for abroad for reducing FCC sulfur in gasoline and olefin(e) centent in " petrochemical technology and application " the 20th volume third phase (184～189).
Neste technique first cuts out FCC gasoline petroleum naphtha and heavy petrol two portions, and petroleum naphtha enters the fixed bed etherification reactor after caustic wash desulfuration alcohol, under cation exchange resin catalyst exists, and the C in petroleum naphtha
5, C
6active olefin and CH
3oH is reacted into corresponding C
5ether and C
6ether, the CDTech catalytic distillation is processed FCC technique and first FCC gasoline is carried out to diolefin hydrogenation, then FCC gasoline is fractionated into petroleum naphtha and heavy petrol, petroleum naphtha goes etherificate or alkylation, but it adopts catalytic distillation process, therefore reaction and distillation are in same equipment, from catalytic distillation tower top extraction petroleum naphtha, extraction heavy petrol at the bottom of tower, and petroleum naphtha goes to carry out etherificate, again through catalytic distillation tower degree of depth etherificate, at first RIDOS technique cut into FCC gasoline petroleum naphtha and heavy petrol two portions, petroleum naphtha removes mercaptan through alkali cleaning, heavy petrol carries out hydrogenating desulfurization and falls alkene, heavy petrol is first through RGO-2 type guard catalyst layer, the de-diene of hydrogenation under the condition relaxed, and then carry out hydrogenating desulfurization (HDS) and install, at 300 ℃ of lower hydrogenating desulfurizations hydroisomerization.CN1026332C discloses a kind of ether hydro-etherification method of olefine contained gasoline, CN89105065 discloses a kind of olefine contained gasoline etherification method, to make gasoline carry out etherification reaction by the expanded bed reactor that the macropore strong acid cation exchange resin is housed, CN200410003406.1 discloses a kind of containing alkene Etherification of Light FCC Gasoline method, one section takes off diene, dealkalize nitrogen with non-precious metal catalyst, and two sections are carried out ether hydro-etherification.
Reported the Etherification of Light FCC Gasoline technique of Mobil company in " refining of petroleum collected translation " 1987,9 (12-17), this technique is that excessive lower alcohol and petroleum naphtha are mixed, and first carries out etherificate for the first time, then carries out fractionation, contains lower alcohol and C in lighting end
5following hydro carbons, contain ether and C in last running
5above hydro carbons, etherificate is carried out in lighting end again, and process characteristic is to adopt an acidic catalyst when etherificate for the first time, and etherificate adopts metal silicate catalysts for the second time.The another kind of Etherification of Light FCC Gasoline technique of Mobil company is that to take initial boiling point～120 a ℃ FCC light gasoline fraction be raw material of etherification, and mix a certain amount of methyl alcohol and hydrogen, first by the etherification reaction of hydro-refining device of Pd/ beta-zeolite catalyst is housed, make the diolefin hydrogenation in petroleum naphtha saturated, and then carry out etherificate for the second time by strong acid cation exchange resin catalyst, thereby the alkene in reduction gasoline, improve gasoline octane rating.
Summary of the invention
The invention provides a kind of Etherification of Light FCC Gasoline technique, it is characterized in that cation exchange resin catalyst, fill in first paragraph etherificate, second segment etherificate fixed-bed reactor, the light gasoline fraction that will cut out from FCC gasoline before 60 ℃ is raw material, enter in first paragraph etherificate fixed-bed reactor, its temperature of reaction is 50～90 ℃, in petroleum naphtha and methyl alcohol volume ratio (9～12): 1, liquid air speed 1.0～3.0h
-1condition under, tertiary amylene etherificate transformation efficiency reaches more than 65%, the etherificate transformation efficiency of tertiary hexene reaches more than 45%, then the first paragraph etherate is sent into to rectifying tower and is separated, and discharges methyl alcohol and unreacted C from the bottom of tower containing ether compound and heavy hydrocarbon
4, C
5, C
6hydro carbons rises to the top of tower, the charging that enters again second segment etherificate fixed-bed reactor from one material of top lateral line withdrawal function (this amount is preferably 45～60wt% of tower inlet amount) of tower, carry out two sections etherification reactions, its temperature of reaction is 50～90 ℃, in petroleum naphtha and methyl alcohol volume ratio (9～12): 1, liquid air speed 1.0～3.0h
-1condition under, reacted etherification product directly mixes with the material of discharging from rectifier bottoms, after two sections etherificates, the total etherificate transformation efficiency of tertiary amylene reaches more than 90%, the total etherificate transformation efficiency of tertiary hexene reaches more than 54%.
Alkene weight content before etherificate in petroleum naphtha is preferably lower than 50%, and the diolefin weight content is preferably lower than 0.02%, and sulphur content is preferably lower than 100 μ g/g; Alkene weight content in petroleum naphtha after etherificate is lower than 35%.
From the etherificate result, find out, only depend on one section etherification reaction to be subject to thermodynamics equilibrium limit, the etherificate transformation efficiency of etherification reaction is lower, also contains more alkene in petroleum naphtha, does not reach the purpose that alkene falls in etherificate, for making tertiary carbon alkene reach higher etherificate transformation efficiency, the present invention adopts the charging that enters again the second reactor from rectifying tower lateral line withdrawal function thing, carries out two sections etherification reactions, and this technique has been saved a separation column, just reactor is made independently two sections, can press respectively C like this
4, C
5, C
6the concentration of hydrocarbon and the requirement of reaction depth, control reaction conditions slightly different, in two sections etherification reactions because the ether compound after one section etherificate cuts out in separation column, now, the tertiary carbon concentration of olefin improves, the corresponding reduction of product ether compound concentration, thereby broken the restriction of thermodynamic(al)equilibrium, the carrying out that is conducive to etherification reaction, improved the etherification reaction degree of depth, made tertiary carbon alkene after one, two section etherificate, the total etherificate transformation efficiency of tertiary amylene can reach more than 90%, petroleum naphtha alkene weight content drops to below 35%, and the etherification technology schema as shown in Figure 1.The difference of the present invention and Neste side line extraction secondary etherificate is: the Neste process using is at the unreacted C of the top of separation column lateral line withdrawal function
4, C
5tertiary carbon alkene and methanol azeotrope, again introduce fixed bed catalytic reactor and carry out the secondary etherificate, adopt fixed-bed reactor and rectifying tower to carry out the degree of depth etherification reaction of tertiary carbon alkene, and the petroleum naphtha from discharging etherification reaction at the bottom of rectifying tower constantly.The method that the present invention adopts be petroleum naphtha after one section methyltertiarvbutyl ether reactor etherificate, enter rectifying tower, isolate containing ether compound, and unetherified tertiary carbon alkene is from the top lateral line withdrawal function C of rectifying tower
4, C
5, C
6-CH
3the OH component, as the charging of the second reactor, is carried out the secondary etherification reaction, and the product after the secondary etherificate is directly emitted from secondary methyltertiarvbutyl ether reactor bottom, and the mixing of materials of discharging with rectifier bottoms is as the etherified benzine component.Can press respectively C like this
4, C
5and C
6the concentration of active olefin and the requirement of reaction depth, control reaction conditions slightly different, really become two sections methyltertiarvbutyl ether reactors, so not only control well, and each reactor can adopt different processing condition by different characteristics, and advance the tower column plate also can be different, can adjust flexibly as required, to reach best effect.
Zeo-karb of the present invention can be general catalyst for etherification, as strong-acid cation-exchange resin, by vinylbenzene and divinyl benzene crosslinked thing, be normally matrix, sulfonation obtains, but the existing cation resin catalyzing agent of all using particle diameter 0.2～1.3mm both at home and abroad, the present invention is recommendation macrobead cation exchange resin catalyst more, the macrobead cation exchange resin catalyst refers to that with vinylbenzene and divinyl benzene crosslinked thing be matrix, sulfonation machine-shaping are the macrobead cation exchange resin catalyst with regular shape, its particle diameter is 2～10mm, as the method for being reported in " Gansu chemical industry " 2005.19 (2) 21-25 makes, the macrobead cation exchange resin catalyst has convenient filling, bed resistance falls little, do not need the complicated advantages such as reactor internal components, therefore recommend preferably to use the macrobead cation exchange resin catalyst, one section etherification reaction can adopt identical or different cation exchange resin catalysts from two sections etherification reactions.
The present invention also provides a kind of modifying catalytically cracked gasoline method containing this technique, mainly heavy petrol arene extracting process after FCC gasoline selective hydrogenation, petroleum naphtha cutting, Etherification of Light FCC Gasoline, heavy petrol hydrogenating desulfurization, hydrogenation, consists of, and it is characterized in that:
(1) catalytic cracking (FCC) gasoline selective hydrogenation takes off the diene mercaptan removal
By the alkene weight content lower than 45%, the diene weight content is lower than 1.5%, sulphur content joins in the pre-hydrogenation fixed-bed reactor 1 that are filled with the de-diene of selective hydrogenation, mercaptan-eliminating catalyst lower than the FCC gasoline fraction of 800 μ g/g, 50～90 ℃ of temperature of reaction, and charging air speed 2～6h
-1operational condition under reacted, reacted material A diene weight content is lower than 0.02%, sulphur content is lower than 650 μ g/g.Selective hydrogenation catalyst is precious metals pd/Al normally
2o
3catalyzer, its shortcoming is that sulfur poisoning-resistant ability, arseniasis are more obvious, and expensive.The de-diene of recommendation Ni based selective hydrogenation, mercaptan-eliminating catalyst in the present invention, price is approximately Pd catalyst based (1/4)～(1/3), the sulfur poisoning-resistant ability is strong, the transformation efficiency that the isomery of its 3-methyl-1-butene turns to 2-methyl-1-butene alkene is greater than 70%, and monoene hydrogenation saturation exponent is less than 10%.
(2) material A is cut into light, weigh two components
Material A is through catch pot 2, enter petroleum naphtha Cutting Tap 3 after isolating the hydrogen more than needed added, the petroleum naphtha B component cut out before 60 ℃ through petroleum naphtha Cutting Tap 3 enters in first paragraph etherificate fixed-bed reactor 4, and heavy petrol component C enters the heavy petrol hydrogenating desulfurization and falls alkene reaction device 7.
(3) Etherification of Light FCC Gasoline
The petroleum naphtha B component enters in first paragraph etherificate fixed-bed reactor 4, its temperature of reaction is 50～90 ℃, in petroleum naphtha and methyl alcohol volume ratio (9～12): 1, under the condition of liquid air speed 1.0～3.0h-1, tertiary amylene etherificate transformation efficiency is more than 65%, and the etherificate transformation efficiency of tertiary hexene is more than 45%; The first paragraph etherate is sent into to rectifying tower 5 and separate, discharge methyl alcohol and unreacted C containing ether compound and heavier hydro carbons from the bottom of tower
4, C
5, C
6hydro carbons rises to the top of tower, the charging that enters again second segment etherificate fixed-bed reactor 6 from tower top one material of lateral line withdrawal function (this amount is preferably 45～60wt% of tower inlet amount), carry out two sections etherification reactions, its temperature of reaction is 50～90 ℃, in petroleum naphtha and methyl alcohol volume ratio (9～12): 1, under the condition of liquid air speed 1.0～3.0h-1, reacted etherification product and the mixing of materials of discharging from rectifying tower 5 tops and bottom as the blend component of clean gasoline.
Alkene weight content before etherificate in petroleum naphtha B is lower than 50%, and the diolefin weight content is lower than 0.02%, and sulphur content is lower than 100 μ g/g; Alkene weight content in petroleum naphtha after etherificate is lower than 35%.After two sections etherificates, in the present invention, total etherificate transformation efficiency of tertiary amylene preferably reaches more than 90%, and total etherificate transformation efficiency of tertiary hexene preferably reaches more than 54%.
(4) alkene falls in the heavy petrol hydrogenating desulfurization
Heavy petrol C after cutting is joined to the heavy petrol hydrogenating desulfurization that the hydrogenating desulfurization olefine lowering catalyst is housed to fall in alkene reaction device 7,280～300 ℃ of service temperatures, working pressure 1.6～3.0MPa carries out the reaction of desulfurating and reducing olefinic hydrocarbon hydrogenation reaction, reacted product enters catch pot 8, isolated H
2, H
2s enters soda-wash tower 9, obtains dry gas after alkali cleaning; Isolate H
2, H
2the heavy petrol D of S, its sulphur content is down to below 100 μ g/g, and the weight content of alkene can drop to 0.1～10% as required, enters Aromatics Extractive Project tower 10.
(5) heavy petrol Aromatics Extractive Project
Heavy petrol D enters Aromatics Extractive Project tower 10 use solvents and carries out Aromatics Extractive Project, its service temperature is 130～170 ℃, working pressure 0.3～0.7MPa, agent-oil ratio (weight) is (5～8): 1, tower top is for raffinating oil, for the heavy naphtha that the alkane weight content is greater than 70%, rich solvent-laden extraction aromatic hydrocarbon oil is discharged in the tower bottom.
In petroleum naphtha, the existence of diene makes gasoline perishable, and affects the further processing of back, because very easily polymerization of diene, if do not added and remove, Hydrobon catalyst or the very fast inactivation of catalyst for etherification of back will be made, and the existence of mercaptan will have a strong impact on smell and the color of gasoline, must first remove.Prime-G
+technique, CDTech and RIDOS technique, have first de-diene technique.By the diene weight content lower than 1.5%, the de-diene mercaptan-eliminating catalyst of the hydrogenation that sulphur content is used lower than the FCC gasoline of 800 μ g/g adopts Ni catalyst based more, desulfurization degree is preferably arranged, Ni based selective hydrodesulfurizationcatalyst catalyst as Chinese Petroleum Univ., fill in pre-hydrogenation fixed-bed reactor, 50～90 ℃ of temperature of reaction, charging air speed 2～6h
-1operational condition under, in gasoline, the decreasing ratio of various pentadienes can reach 100%, the transformation efficiency that the isomery of 3-methyl-1-butene turns to 2-methyl-1-butene alkene is greater than 70%, monoene hydrogenation saturation exponent is less than 10%, the mercaptan decreasing ratio can reach more than 70%.Ni is catalyst based to be generally with Al
2o
3for carrier, the metal constituent elements such as NiO are active ingredient.
For ease of processing, FCC gasoline is cut into to weight two components.Needs according to this technique, cut out the petroleum naphtha component before 60 ℃ from FCC gasoline, because olefin(e) centent in the petroleum naphtha component is high, and sulphur content is lower, and mostly is mercaptan, therefore after the first step removes, sulphur content is very low, and the active olefin content in alkene is very high, but only need to process just decrease alkene with methanol etherification, and heavy petrol is the main body of sulfur-bearing, need process through hydrogenating desulfurization.
Be raw material by the light gasoline fraction before 60 ℃, FCC gasoline, adopt cation exchange resin catalyst, particularly macrobead Zeo-karb, fill in two sections fixed-bed reactor, 50～90 ℃ of temperature of reaction, petroleum naphtha and methyl alcohol volume ratio 9～12: 1, liquid air speed 1.0～3.0h
-1condition under, the total etherificate transformation efficiency of tertiary amylene reaches more than 90%, total etherificate transformation efficiency of tertiary hexene reaches more than 54%.
Petroleum naphtha olefin(e) centent decrease after etherificate, owing to having increased in etherified gasoline containing the oxygen ether compound, make the petroleum naphtha octane value improve 2 units.
Through the cutting after heavy petrol in enrichment sulfocompound, sulphur content wherein accounts for 95% of FCC gasoline sulfur-bearing total amount, therefore the heavy petrol hydrogenating desulfurization is the key of FCC gasoline desulfur.The heavy petrol hydrogenation is under the effect of catalyzer and hydrogen, makes sulfur-bearing in heavy petrol, nitrogenous, oxygenatedchemicals carry out the hydrogenation decomposition, generates H
2s, NH
3and H
2o removes.
It is catalyst based that the heavy petrol hydrogenation catalyst is generally Ni, and the Ni catalyzer is used in special recommendation of the present invention, and such catalyzer has the characteristics such as high desulfurization rate, denitrification percent and olefin saturated rate, and it forms generally with Al
2o
3for carrier sub-dip WO
3, the metal constituent element such as NiO or Mo makes.
The catalyzer RS-1A that the present invention can adopt the Research Institute of Petro-Chemical Engineering of domestic industrial application to develop is as the hydrogenating desulfurization olefine lowering catalyst, in fixed bed hydrogenation reactor, 280～300 ℃ of service temperatures, working pressure 1.6～3.0MPa, sulphur content can be down to below 100 μ g/g, large isomerization of alkene and alkylation, thus reach the purpose of heavy petrol desulfurating and reducing olefinic hydrocarbon.Reach the gasoline products of low sulfur, low olefin, yield of gasoline is high, can directly carry out oil product mediation or further processing and utilization.
Contain a large amount of aromatic hydrocarbons in heavy petrol after hydrogenation, can adopt existing Aromatics Extractive Project industrial technology, utilize aromatic hydrocarbons and the significant difference of non-aromatics solubleness in solvent (as tetramethylene sulfone) that both are separated, typical technique is that hydrogenating desulfurization heavy petrol is sent into to the extraction tower bottom, because the density ratio solvent of stock oil is little, stock oil is bottom-up to flow, solvent from up to down flow inverse to contact, the dispersed solvent small droplets of aromatic hydrocarbons in raw material extracts, during to the extracting tower top, aromatic hydrocarbons in raw material is almost by the whole extractings of solvent, now tower top is for raffinating oil, the tower bottom goes out rich solvent-laden extraction aromatic hydrocarbon oil, the aromatic hydrocarbons separated is separable goes out triphen and gasoline blend component.And tower top obtains, be mainly containing the heavy naphtha of alkane, can be used as the raw material of steam heat cracking ethylene preparation, because heavy naphtha mainly contains alkane, again through hydrogenation and Aromatics Extractive Project, therefore do not contain alkene and aromatic hydrocarbons in heavy naphtha, thereby be the cracking ethylene preparation raw material of high-quality, also can be in harmonious proportion as the high-quality clean gasoline with etherified benzine, whole technique is as shown in Figure 2.
The accompanying drawing explanation
Fig. 1 is Etherification of Light FCC Gasoline process flow diagram of the present invention
Fig. 2 is the modifying catalytically cracked gasoline process flow diagram containing Etherification of Light FCC Gasoline of the present invention.
Fig. 3 is Neste Etherification of Light FCC Gasoline process flow diagram.
In figure: the pre-hydrogenation fixed-bed reactor of 1-; The 2-catch pot; 3-petroleum naphtha Cutting Tap; 4-first paragraph etherificate fixed-bed reactor; The 5-rectifying tower; 6-second segment etherificate fixed-bed reactor; The alkene reaction device falls in the hydrogenating desulfurization of 7-heavy petrol; The 8-catch pot; The 9-soda-wash tower; 10-Aromatics Extractive Project tower; The 11-pre-reactor; 12-side line reactor; The 13-distillation tower.
Embodiment:
Ni is catalyst based: Chinese Petroleum Univ.'s development, model are SYH-8
Pd is catalyst based: Research Institute of Petro-Chemical Engineering's development, model are RGO-2
Cation exchange resin catalyst 1: Nankai University's development, model are D72, particle diameter: 0.315～1.25mm, specific surface: 45～50m
2/ g, exchanging equivalent: 4.39mmol/g (doing).
Macrobead cation exchange resin catalyst 2: the development of Lanzhou Petrochemical research institute, model are LY-98A, particle diameter: Φ 5 * 5mm cylindricality, specific surface: 44～50m
2/ g, exchanging equivalent: 4.0～4.5mmol/g (doing).
Hydrogenating desulfurization olefine lowering catalyst 1: Research Institute of Petro-Chemical Engineering's development, model are RS-1A
Hydrogenating desulfurization olefine lowering catalyst 2: the development of Lanzhou Petrochemical research institute, model are LY-9802 (Co/Mo/Ni)
The character of the catalytic gasoline of whole fraction used in embodiment is in Table 1.
The character of the full cut catalytically cracked material of table 1
| Catalytically cracked gasoline | Raw material 1 | Raw material 2 |
| Density/g.cm -3 | 0.7132 | 0.7205 |
| Sulphur content/μ g.g -1 | 530.4 | 784.6 |
| Boiling range/℃ | 32.1～169.2 | 36.7～172.9 |
| Diolefin content/w% | 1.43 | 1.15 |
| Group composition/w% | ||
| Alkane | 35.01 | 34.39 |
| Naphthenic hydrocarbon | 8.46 | 7.08 |
| Alkene | 38.24 | 37.89 |
| Aromatic hydrocarbons | 18.27 | 20.64 |
Embodiment 1:
The pre-hydrogenation fixed-bed reactor 1 of the catalyst based SYH-8 of Ni by raw material 1 through the de-diene of selective hydrogenation, mercaptan removal are housed, remove diolefin and mercaptan sulfur.Because the diolefin weight content approximately 1.43% in petroleum naphtha; these diolefine are very active; under certain temperature of reaction, except polymerization own, also together with other hydro carbons in FCC gasoline, react; generate colloid and other coking precursor; thereby reduce the active of catalyzer and can increase reactor pressure decrease, therefore need to, at FCC gasoline before the contact etherificate, under the mitigation condition, remove diolefine; remove the mercaptan sulfur easily removed simultaneously, thereby reduce the gasoline stink caused therefrom.All conditions is in Table 1.
FCC gasoline A after the de-diene of hydrogenation, through gas-oil separation gas tank 2, after isolating remaining hydrogen, sends FCC gasoline A into petroleum naphtha Cutting Tap 3, by FCC gasoline cut into light, weigh two components.Petroleum naphtha Cutting Tap 3 is the knockout tower that the ф 150 * 4500mm of Cy700 silk net metal filler is housed, knockout tower cuts out the petroleum naphtha B component before 60 ℃, petroleum naphtha Cutting Tap working pressure 0.2MPa (absolute pressure), under the operational condition of operating reflux ratio 1.5, cut, tower top cuts out the petroleum naphtha B before 60 ℃, discharge heavy petrol and trace impurity at the bottom of tower, the petroleum naphtha total recovery cut out is 38.86% (weight), wherein C
4cut accounts for 2.16% (weight), C
5cut accounts for 65.52% (weight), C
6cut accounts for 30.99% (weight), C
7cut accounts for 1.35% (weight), and petroleum naphtha density is 0.64g/cm
3, olefin(e) centent is 42% (weight), sulphur content is 62.80 μ g.g
-1.The petroleum naphtha B cut out from petroleum naphtha Cutting Tap 3 and methyl alcohol enter first paragraph etherificate fixed-bed reactor 4, reactor charge macrobead cation exchange resin catalyst 2 (LY-98A), and 62 ℃ of temperature of reaction, reaction pressure 1.5MPa, feed liquid air speed 2.0h
-1, under the operational condition that petroleum naphtha and methyl alcohol volume ratio are 10: 1, tertiary amylene etherificate transformation efficiency can reach 69.34%, and tertiary hexene etherificate transformation efficiency can reach 48.09%.After one section etherificate, due to the restriction that is subject to thermodynamic(al)equilibrium, the tertiary carbon etherification of olefine transformation efficiency in petroleum naphtha is about 2/3,1/3 active olefin not by etherificate, does not reach the purpose that alkene falls in etherificate.For further improving the etherification reaction degree of depth and the etherification reaction yield of tertiary carbon alkene in petroleum naphtha, the present invention adopts etherification product to separate through rectifying tower 5, through two sections etherificate coupling process, one section etherified benzine is sent into to rectifying tower 5 again, tower side line (the 4th block of column plate) is extracted unreacted C out
4, C
5, C
6hydro carbons and methyl alcohol, advance second segment etherificate fixed-bed reactor 6, discharges etherification product and heavier hydro carbons at the bottom of tower.Enter second segment etherificate fixed-bed reactor from the not etherificate tertiary carbon alkene of knockout tower lateral line withdrawal function, second segment etherificate fixed-bed reactor still load macrobead cation exchange resin catalyst 2 (LY-98A), at 65 ℃ of temperature of reaction, reaction pressure 1.5MPa, liquid feeding air speed 1.2h
-1condition under carry out two sections etherificates.In petroleum naphtha after one section etherificate rectifying tower 5 isolate containing ether compound, broken the thermodynamical restriction of etherification reaction, active olefin is reacted with methyl alcohol, speed of response is accelerated, and has improved the degree of depth of etherification reaction and the yield of etherate.Petroleum naphtha is after one, two section etherification reaction, the etherification reaction degree of depth and total amount have been improved, make the total etherificate transformation efficiency of active tertiary amylene in petroleum naphtha reach 91.01%, the total etherificate transformation efficiency of tertiary hexene reaches 60.50%, and in petroleum naphtha, olefin(e) centent is reduced to 30.06% (weight).And the heavy petrol C from discharging at the bottom of petroleum naphtha Cutting Tap 3 towers, most of sulfocompound and trace metal impurities have been concentrated, deliver to the heavy petrol hydrogenating desulfurization of the RS-1A type desulfurization catalyst that is filled with Beijing petroleum science research institute industrial application and fall alkene reaction device 7, adopt this hydrogenating desulfurization olefine lowering catalyst, 295 ℃ of service temperatures, under working pressure 2.0MPa, can be by the sulphur content decrease in heavy petrol, the most of isomerization of alkene and alkylation, thus reach the purpose of heavy petrol desulfurating and reducing olefinic hydrocarbon.Heavy petrol after hydrogenating desulfurization, through catch pot 8, separates H
2and H
2s hydrogen, wash H off through soda-wash tower 9
2s, the fuel gas pipe network is sent in all the other dry gas emptying.Emit desulfurization from catch pot 8 bottoms and fall alkene heavy petrol D (sulphur content is reduced to 52.36 μ g/g), send the Aromatics Extractive Project tower 10 extracting aromatic hydrocarbons.Be rich in sulfolane solvent in extracting aromatic hydrocarbons, need be through washing to reclaim solvent, and in heavy naphtha containing alkene and aromatic hydrocarbons, be the cracking ethylene preparation raw material of high-quality, also can be in harmonious proportion as the clean gasoline product with etherified benzine.
Embodiment 2:
The present embodiment technological process and embodiment 1 are identical, and process parameter and embodiment's 1 is more as shown in table 2, and what in table, do not illustrate is substantially the same manner as Example 1.
Use the macrobead cation exchange resin catalyst except thering is convenient filling, not needing complicated reactor internal components, can reduce plant investment.From the contrast of embodiment 1 and embodiment 2, can find out, the reactor bed pressure decreased that uses the agent of macrobead cation resin catalyzing when using the agent of small-particle cation resin catalyzing approximately 20%, and in the situation that temperature of reaction is low approximately 10 ℃, can reach the reaction result of small-particle cation resin catalyzing agent, therefore from above two aspects, use the agent of macrobead cation resin catalyzing more energy-conservation.
Table 2 embodiment 2 process parameter and results
| Project | Embodiment 1 | Embodiment 2 |
| Raw material | Raw material 1 | Raw material 2 |
| The selectivity catalyst for pre-hydrogenation | SYH-8 | RGO-2 |
| Selectivity pre-hydrotreating reaction temperature/℃ | 86 | 55 |
| The pre-hydrogenation charging of selectivity air speed/h -1 | 3.0 | 5.5 |
| The pre-hydrogenation monoene of selectivity saturation exponent/% | 3.47 | 8.62 |
| Material A diene weight content/% | 0.004 | 0.01 |
| Material A sulphur content/μ g.g -1 | 424.3 | 634.7 |
| Material B sulphur content/μ g.g -1 | 62.80 | 83.41 |
| Material C sulphur content/μ g.g -1 | 654.1 | 972.6 |
| One, two sections catalyst for etherification | LY-98A | D72 |
| One section etherification reaction temperature/℃ | 62 | 73 |
| Two sections etherification reaction temperatures/℃ | 65 | 75 |
| Petroleum naphtha and methyl alcohol volume ratio | 10∶1 | 11∶1 |
| One section methyltertiarvbutyl ether reactor pressure drop of column/MPa | 0.024 | 0.030 |
| Two sections methyltertiarvbutyl ether reactor pressure drop of column/MPa | 0.019 | 0.025 |
| The one section tertiary amylene etherificate of etherificate transformation efficiency/% | 69.34 | 68.23 |
| The one section tertiary hexene etherificate of etherificate transformation efficiency/% | 48.09 | 47.11 |
| The total etherificate transformation efficiency/% of tertiary amylene | 91.01 | 90.28 |
| The total etherificate transformation efficiency/% of tertiary hexene | 60.50 | 59.86 |
| Olefin(e) centent/w% after material B etherificate | 30.06 | 29.75 |
| The heavy petrol hydrogenation catalyst | RS-1A | LY-9802 |
| Heavy petrol hydrogenation reaction temperature/℃ | 295 | 280 |
| Heavy petrol hydrogenation reaction pressure/MPa | 2.0 | 2.8 |
| Material D sulphur content/μ g.g -1 | 52.36 | 82.00 |
| Material D olefin(e) centent/w% | 0.47 | 1.61 |
Comparative Examples 1:
This Comparative Examples only illustrates the difference with Neste side line extraction secondary etherificate, and advantage and the importance of the present invention's existence.
Neste Etherification of Light FCC Gasoline technique mainly comprises a pre-reactor and a distillation tower with the side line reactor, and the technical process of Neste Etherification of Light FCC Gasoline as shown in Figure 3.Technological process is containing C through pretreated
4～C
7the petroleum naphtha of cut enters with pre-reactor and is reacted with methyl alcohol, then sends into the distillation tower fractionation, discharges methyl alcohol and unreacted C from the bottom of tower containing ether compound and heavier hydro carbons
4, C
5hydro carbons rises to top and discharges, be to improve the etherificate transformation efficiency, from a side of tower by unreacted C
4, C
5introduce the second reactor etherificate with methyl alcohol, product returns to the distillation tower fractionation again, and one, second stage reactor uses is all the storng-acid cation exchange resin of general small particle size.Overhead product and bottom product are mixed into etherified benzine, wherein TAME accounts for 16%, heavier ethers accounts for 7%, methyl alcohol accounts for 0.1%, and the etherificate transformation efficiency of tertiary amylene is 90%, the etherificate transformation efficiency of tertiary hexene is 40～60%, the etherificate transformation efficiency of C7 active olefin is 20～40%.
This Etherification of Light FCC Gasoline technique is to adopt first paragraph methyltertiarvbutyl ether reactor and a rectifying tower with the side line reactor, and technological process is by the C that contains before 60 ℃
4, C
5, C
6the distillate of tertiary carbon alkene and methyl alcohol enter pre-reactor and carry out etherification reaction, then send into rectifying tower and separate, and the hydro carbons that contains ether compound is discharged from the bottom of rectifying tower, methyl alcohol and C
4, C
5, C
6hydro carbons rises to top and discharges, enter two sections methyltertiarvbutyl ether reactors of side line, carry out the degree of depth etherificate of active olefin, ether compound after two sections etherificates, directly with the ether compound of discharge at the bottom of rectifying tower, be mixed into etherified benzine, wherein TAME accounts for 18～20%, heavier ethers accounts for 7%, methyl alcohol accounts for 0.1%, the etherificate transformation efficiency of tertiary amylene is more than 90%, the etherificate transformation efficiency of tertiary hexene is more than 54%, petroleum naphtha octane value after etherificate improves 1～2 unit, and one, second stage reactor uses general strong acidic ion resin catalyzer.Etherification of Light FCC Gasoline process distinction of the present invention is in the difference of Neste technique, one is that two sections methyltertiarvbutyl ether reactors are not the combinations in when series connection, the 2nd, the ether compound that the extraction of rectifying tower side line enters two sections methyltertiarvbutyl ether reactors no longer returns to the rectifying tower separation, the ether compound of directly discharging with rectifier bottoms mixes, thereby reduced thermal load and the calorific loss of rectifying tower, more reasonable economically.
Claims (5)
1. the modifying catalytically cracked gasoline method containing Etherification of Light FCC Gasoline technique, mainly be comprised of heavy petrol arene extracting process after catalytic gasoline selective hydrogenation, petroleum naphtha cutting, Etherification of Light FCC Gasoline, heavy petrol hydrogenating desulfurization, hydrogenation, it is characterized in that:
1. the catalytic gasoline selective hydrogenation takes off the diene mercaptan removal
By diene content, lower than 1.5%, sulphur content takes off the pre-hydrogenation fixed-bed reactor (1) of diene mercaptan-eliminating catalyst lower than the catalytically cracked gasoline cut of 800 μ g/g through being filled with selective hydrogenation, 50～90 ℃ of temperature of reaction, and charging air speed 2～6h
-1operational condition under reacted, reacted material A diene content is lower than 0.02%, sulphur content is lower than 650 μ g/g;
2. material A is cut into light, weigh two components
Material A is through catch pot (2), enter petroleum naphtha Cutting Tap (3) after isolating the hydrogen more than needed added, the petroleum naphtha B component cut out before 60 ℃ through petroleum naphtha Cutting Tap (3) enters in first paragraph etherificate fixed-bed reactor (4), and heavy petrol component C enters the heavy petrol hydrogenating desulfurization and falls alkene reaction device (7);
3. Etherification of Light FCC Gasoline
The petroleum naphtha B component enters in first paragraph etherificate fixed-bed reactor (4), and its temperature of reaction is 50～90 ℃, at petroleum naphtha and methyl alcohol volume ratio 9～12:1, liquid air speed 1.0～3.0h
-1condition under, tertiary amylene etherificate transformation efficiency reaches more than 65%, uncle's etherificate transformation efficiency of alkene reaches more than 45%, then the first paragraph etherate is sent into to rectifying tower (5) and is separated, and discharges methyl alcohol and unreacted C from the bottom of tower containing ether compound and heavy hydrocarbon
4, C
5, C
6hydro carbons rises to the top of tower, enter the charging of second segment etherificate fixed-bed reactor (6) from one material of top lateral line withdrawal function of tower again, carry out two sections etherification reactions, its temperature of reaction is 50～90 ℃, at petroleum naphtha and methyl alcohol volume ratio 9～12:1, liquid air speed 1.0～3.0h
-1condition under, reacted etherification product and the mixing of materials of discharging from rectifying tower (5) top and bottom; Alkene weight content before etherificate in petroleum naphtha is lower than 50%, and the diolefin weight content is lower than 0.02%, and sulphur content is lower than 100 μ g/g; After two sections etherificates, the total etherificate transformation efficiency of tertiary amylene reaches more than 90%, and the total etherificate transformation efficiency of tertiary hexene reaches more than 54%, and the alkene weight content in petroleum naphtha is lower than 35%;
4. alkene falls in the heavy petrol hydrogenating desulfurization
Heavy petrol C after cutting is joined to the heavy petrol hydrogenating desulfurization that the hydrogenating desulfurization olefine lowering catalyst is housed to fall in alkene reaction device (7), 280～300 ℃ of service temperatures, working pressure 1.6～3.0MPa, be down to sulphur content below 100 μ g/g alkene weight content 0.1～10% through reaction; Reacted product enters catch pot (8), isolated H
2, H
2s enters soda-wash tower (9), obtains dry gas after alkali cleaning; Isolate H
2, H
2the heavy petrol D of S enters Aromatics Extractive Project tower (10);
5. heavy petrol Aromatics Extractive Project
Heavy petrol D enters Aromatics Extractive Project tower (10) and carries out Aromatics Extractive Project with solvent, its service temperature is 130～170 ℃, working pressure 0.3～0.7MPa, the agent weight of oil is than being (5～8): 1, tower top is for raffinating oil, for the heavy naphtha that alkane is greater than 70%, rich solvent-laden extraction aromatic hydrocarbon oil is discharged in the tower bottom.
2. modifying catalytically cracked gasoline method according to claim 1, is characterized in that the de-diene mercaptan-eliminating catalyst of hydrogenation is that Ni is catalyst based.
3. modifying catalytically cracked gasoline method according to claim 1, is characterized in that the hydrogenating desulfurization olefine lowering catalyst refers to that Ni is catalyst based.
4. modifying catalytically cracked gasoline method according to claim 1, is characterized in that the Aromatics Extractive Project solvent for use is tetramethylene sulfone.
5. processing method according to claim 1, is characterized in that referring to the macrobead cation exchange resin catalyst for the catalyzer of Etherification of Light FCC Gasoline, and particle diameter is 2～10mm.
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| EP3017028B1 (en) * | 2013-07-02 | 2018-03-21 | Saudi Basic Industries Corporation | Process for the production of light olefins and aromatics from a hydrocarbon feedstock. |
| CN103525460B (en) * | 2013-10-11 | 2015-09-02 | 宁夏宝塔石化科技实业发展有限公司 | A kind of catalytic gasoline selective hydrodesulfurizationmodification and Etherification of Light FCC Gasoline process integration |
| CN105562019B (en) * | 2014-10-14 | 2018-09-14 | 中国石油化工股份有限公司 | The catalyst of mercaptan thioetherification |
| CN104845671A (en) * | 2015-04-27 | 2015-08-19 | 宁夏宝塔石化科技实业发展有限公司 | Novel process technology using combined operation mode |
| CN105623735B (en) * | 2016-01-13 | 2018-10-12 | 山东联星能源集团有限公司 | A kind of method that Etherification of Light FCC Gasoline improves gasoline quality |
| CN108949229B (en) * | 2017-05-19 | 2020-10-27 | 中国石油化工股份有限公司 | Method and system for producing clean gasoline |
| CN109722308B (en) * | 2017-10-31 | 2021-03-12 | 中国石油化工股份有限公司 | Method for producing low-sulfur low-olefin gasoline |
| CN108456552B (en) * | 2018-02-08 | 2020-03-31 | 中国石油大学(北京) | Method for producing chemical products by using catalytic cracking gasoline |
| CN108424787B (en) * | 2018-02-08 | 2020-02-14 | 中国石油大学(北京) | Method for upgrading quality of high-olefin catalytic cracking gasoline |
| CN108485702B (en) * | 2018-02-08 | 2020-02-14 | 中国石油大学(北京) | Method for maximizing aromatic hydrocarbon production by utilizing catalytic cracking gasoline |
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| CN108315049B (en) * | 2018-02-08 | 2020-02-14 | 中国石油大学(北京) | Method for producing aromatic hydrocarbon by using catalytic cracking gasoline |
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