CN101570698B - Method for catalyzing and transforming naphtha - Google Patents
Method for catalyzing and transforming naphtha Download PDFInfo
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Abstract
The invention relates to a method for catalyzing and transforming naphtha with the boiling range of 40-260 DEG C, comprising the following steps: (1) hydrofining the naphtha under the catalysis of hydrofining catalyst, distilling the hydrofined naphtha and cutting the hydrofined naphtha into the light-weight distillate, the middle-weight distillate and the heavy-weight distillate; (2) dischargingthe light-weight distillate from a device or enabling the light-weight distillate to contact with light-hydrocarbon isomerization catalyst for light-hydrocarbon isomerization reaction; (3) dividing the middle-weight distillate into one or a plurality of distillate for segmental refroming reaction; and (4) enabling the heavy-weight distillate to contact with light-weight catalyst for light-weight reaction. By dividing the hydrofined naphtha into a plurality of distillate and processing the distillate by segments with different catalysts, all components of the naphtha can be effectively utilizedand can be transformed to light-weight aromatic hydrocarbon or high-octane gasoline components, the source of the naphtha is widened, and the distillation range of the applied naphtha is enlarged.
Description
Technical field
The present invention is a kind of catalysis conversion method of petroleum naphtha, specifically, be a kind of be after 40～260 ℃ of petroleum naphthas in the scope are divided into the multiply close-cut fraction by boiling range with ASTM D-86 boiling range, the method for producing aromatic hydrocarbons or producing the stop bracket gasoline blend component with diverse ways respectively.
Background technology
At present, the gasoline product on the China market mainly is catalytically cracked gasoline, and its alkene and sulphur content are higher, and catalytic reforming gasoline has low sulphur content and olefin(e) centent, can remedy this deficiency just.Along with the raising that quality of gasoline requires, need to increase the ratio of catalytic reforming blended gasoline component.Thereby the working ability that increases the catalytic reforming technology becomes urgent task.In addition, market is also growing to the demand of aromatic hydrocarbons, and as the basis of Aromatic Hydrocarbon United Plant, the increase of catalytic reforming working ability is also imperative.
Catalytic reforming is raw material production aromatic hydrocarbons or high octane gasoline component with the petroleum naphtha, and the further increase of its working ability is subjected to the restriction in petroleum naphtha source.Because crude oil in China is generally heavier, the content of virgin naphtha is lower.Simultaneously, petroleum naphtha is again the raw material of producing ethene, and along with greatly developing of ethylene industry, petroleum naphtha problem in short supply is serious day by day.Therefore, further widening the reformer feed source has very important significance.
At present, the main method that addresses this problem is to mix the petroleum naphtha of refining after the secondary processing, as hydrocracking heavy naphtha, coker gasoline, pyrolysis gasoline raffinate oil, catalytic gasoline etc.For taking full advantage of the more aromatic hydrocarbons of existing raw material production or carrying out the upgrading of gasoline component, the method for utilizing combination process to process the petroleum naphtha fraction is developed rapidly.
USP3753891 provides a kind of method that reform to improve the hydro carbons octane value of shunting, this method with boiling range from comprising C
5To the petroleum naphtha of 204.4 ℃ of (400) scopes be that the boundary is divided into the weight fraction and carries out reforming reaction respectively with 70～148.9 ℃ (158～300 °F), separate hydrogen-rich gas and reformate in the heavy fraction reformate, light fraction is contacted with the ZSM-5 zeolite catalyst, the product and the lower boiling aromatic hydrocarbons that form carry out alkylated reaction, reclaim product and obtain the product gasoline that octane value improves.
USP6143166 provides a kind of method of producing aromatic hydrocarbons by reforming reactor arranged side by side, and the life-span that this method can be used in the reforming catalyst of heavy fraction prolongs to greatest extent, and the complicacy of simplification device.This method is fractionated into C with hydrocarbon raw material
5 -, C
6～C
7And C
8 +Fraction is with C
6～C
7Fraction carries out catalytic aromatization reaction generation and contains first reformate stream of benzene and first gas stream of hydrogen in the presence of the hydrogen in first reactor, described catalyzer comprises at least a VIII family's metal and non-acidic zeolite; With C
8 +Fraction is using an acidic catalyst to carry out the C that contains that the catalytic aromatization generation comprises dimethylbenzene in second reactor in the presence of the hydrogen
8Second reformate stream of aromatic hydrocarbons and second gas stream of hydrogen, described an acidic catalyst comprises at least a VIII family's metal and acid carrier, and the part of described first gas stream is sent into second reforming reactor hydrogen is provided.Described non-acidic zeolite is the L zeolite, and an acidic catalyst is conventional dual-function reforming catalyst.
USP5242576 discloses a kind of will the reformation and the synthetic petroleum naphtha method for modifying that combines of selectivity alkane isomerization.This method is separated into petroleum naphtha and contains C
7And C
8The heart cut of hydrocarbon and comprise C
10Heavy fraction, heart cut is contacted and reclaims stable reformate with the reforming catalyst of load platinum metals, the heavy fraction then solid acid catalyst synthetic with having the selectivity isoparaffin contacts, the product that final boiling point that generation contains butane and pentane has reduced, described selectivity isoparaffin building-up reactions is to make the alkylaromatic hydrocarbon in the heavy naphtha take off alkyl in the presence of hydrogen, produce more Trimethylmethane, and make the pentane of generation and butane isomerization to improve octane value.Its catalyzer that uses is the aluminum oxide of load aluminum chloride and VIII family metal component.
USP6900365B2 discloses a kind of method that heavy hydrocarbon feedstocks is changed into stop bracket gasoline, BTX and other valuable aromatic hydrocarbons, the catalyzer that uses contains the borosilicate zeolite that is selected from SSZ series and zeolite component and the hydrogenation/dehydrogenation component of low aluminium boron beta, the acidity of used zeolite is starkly lower than Si-Al zeolite, and the aperture is generally greater than 5
, restricted index (CI) is less than 1.0.This zeolite is used for the process of FCC heavy petrol and the production of LCO upgrading stop bracket gasoline, BTX, EB and naphthalene, shows good catalytic performance.Compare with the Pt/K-L catalyzer with traditional two (many) metal reforming catalysts, handling heavier raw material FCC heavy petrol (boiling range is about 127～200 ℃) and LCO when (boiling range is about 125～250 ℃ or 230～290 ℃), SSZ series borosilicate zeolite catalyzer demonstrates better low pressure stability and sulfur poisoning-resistant.
In recent years, domestic-developed goes out manyly to be applied to reform or the catalytic material with special property of processing treatment heavy arene raw material, but it is less relatively to be applied to widen the research in reformer feed source.A kind of heavy arenes catalytic dealkylation catalyst and preparation method are disclosed as CN1472182A, this catalyzer comprises VIII family metal and the complex carrier of 0.01～2.0 quality %, and complex carrier comprises the ZSM-5 zeolite of 30～70 quality %, the Beta zeolite of 5～30 quality % and the aluminum oxide of 10～65 quality %.This catalyzer can improve C
9 +The productive rate of aromatics conversion rate and benzene and dimethylbenzene, and reduce carbon deposit.
Summary of the invention
The catalysis conversion method that the purpose of this invention is to provide a kind of petroleum naphtha, this method can be handled the wideer petroleum naphtha of boiling range scope, thereby expand the source of reformer feed, and can better control the processing condition of reforming process so that the yield maximization of purpose product.
Boiling range provided by the invention is the catalysis conversion method of 40～260 ℃ petroleum naphtha, comprises the steps:
(1) petroleum naphtha is carried out hydrofining in the presence of Hydrobon catalyst, again the petroleum naphtha fractionation after the hydrofining is cut into lightweight fraction, middle distillate and heavy fraction,
(2) contact with lightweight fraction discharger or with catalyst for isomerizing light hydrocarbon and carry out light hydrocarbon isomerization reaction,
(3) middle distillate is separated into one to multiple strand of fraction and carries out the segmentation reforming reaction,
(4) heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
The inventive method is divided into lightweight fraction, middle distillate and heavy fraction with petroleum naphtha, thereby can carry out different processing treatment according to the compositing characteristic of isolated fraction, particularly middle distillate can be separated into a plurality of fractions again, reform with different reforming methods, and heavy fraction in the raw material can be changed into light-end products and light aromatics in the presence of lightening catalyst, thereby obtain more benzene,toluene,xylene and C
9Aromatic hydrocarbons.Thereby widened the raw material sources of catalytic reforming, can reach the wideer petroleum naphtha of processing treatment boiling spread.
Description of drawings
Fig. 1～3 are the separation of the used reaction product of the present invention and the schematic flow sheet for the treatment of process.
Embodiment
The inventive method is carried out pre-hydrofining with petroleum naphtha earlier, again the petroleum naphtha behind the hydrogenation is fractionated into lightweight fraction, middle distillate and heavy fraction, again three kinds of fractions are carried out different processing treatment, the lightweight fraction is carried out the light hydrocarbon isomerization reaction, make lighter hydrocarbons generation isomery, selective splitting and alkylated reaction, change into high-octane gasoline blend component; Middle distillate is carried out reforming reaction; Heavy fraction carries out the lighting reaction, makes it that a series of catalyzed reactions such as hydrogenation selectivity cracking, hydro-dealkylation, transalkylation, dehydroaromatizationof and skeletal isomerization take place, to obtain more C
6～C
8Aromatic hydrocarbons.
Described method (1) step is that in the petroleum naphtha in various sources one or more are carried out hydrofining separately or after mixing, and then cuts into different fractions.Hydrofining part generally is made up of separation column, hydrogenation reaction and stripping tower three parts, so that for follow up device provides that boiling range suits, moisture and the qualified raw material of foreign matter content.Adoptable flow process is fractionation-hydrogenation-stripping or hydrogenation-fractionation, preferred hydrogenation-fractionation.
In the hydrofining part, need adopt suitable dechlorinating agent to remove chlorine in the petroleum naphtha toward contact; The employing sweetening agent removes the sulphur in the petroleum naphtha; Adopt suitable dearsenic agent to remove impurity such as arsenic in the petroleum naphtha.Described dechlorinating agent, sweetening agent and dearsenic agent all can use conventional agent, as use the disclosed active ingredient of CN94106413.1 to be the dechlorinating agent of calcium hydroxide (or calcium oxide), use the disclosed sweetening agent of being formed by nickel, diatomite, silicon-dioxide and aluminium sesquioxide of CN86100015B, use the disclosed dearsenic agent of being made by the alumina load metallic nickel of CN1095749A.
Petroleum naphtha fractionation after the hydrofining is cut into lightweight fraction, middle distillate and heavy fraction.Fractionating system can include only a separation column, and difference extraction lightweight fraction and heavy fraction at the bottom of cat head and the tower are extracted middle distillate out from side line; Also can use two or more separation columns, the side line that determines fraction at the bottom of cat head, the tower or in the middle of tower according to the load of system and cut point accuracy requirement obtains.In addition, reformed oil is through after extracting the purpose product and separating in the subsequent step, and raffinating oil of obtaining can be returned the appropriate location of fractionating system, is not limited to first tower of fractionating system or the feed entrance point of initial separating device.
The lightweight fraction that obtains after the fractionation of described process is C
4～C
6Hydro carbons, middle distillate be C
6～C
11Hydro carbons, heavy fraction be C
9～C
11Above hydro carbons.Wherein the ASTM D-86 final boiling point of lightweight fraction is 40～110 ℃, and the ASTM D-86 initial boiling point of heavy fraction is 130～215 ℃, in the described heavy fraction than the low hydrocarbon content of the main ingredient carbon number of fraction less than 20 quality %, preferably less than 15 quality %.Middle distillate can be one or more, preferably be divided into 1～5 fraction, select different reforming reaction modes for use according to the compositing characteristic of each fraction, be segmentation reforming reaction of the present invention, described segmentation reforming reaction comprises any one or a few in aromizing, catalytic reforming, the non-hydrogen upgrading.
The comparatively preferred several petroleum naphtha processing schemes of the present invention are as follows:
First kind of scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
5 -Lightweight fraction, C
6～C
9Middle distillate and C
9 +Heavy fraction, wherein C
9 +In the heavy fraction less than C
9Hydrocarbon content less than 20 quality %, with lightweight fraction discharger, middle distillate contacts with reforming catalyst carries out catalytic reforming reaction, heavy fraction contacts with lightening catalyst and carries out lighting reaction.
Second kind of scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
6Lightweight fraction, C
7～C
9Middle distillate and C
10 +Heavy fraction, wherein C
10 +In the heavy fraction less than C
10Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, middle distillate contacts with reforming catalyst carries out catalytic reforming reaction, heavy fraction contacts with lightening catalyst and carries out lighting and react.
The third scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6～C
7Fraction, C
7～C
11Fraction and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, described lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
7Fraction contacts with aromatized catalyst and faces hydrogen aromatization, C
7～C
11Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
11 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
The 4th kind of scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6～C
7Fraction, C
7～C
8Fraction, C
9～C
11Fraction and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, described lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
7Fraction contacts with aromatized catalyst and carries out non-hydrogen aromatization reaction, C
7～C
8Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
9～C
11Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
11 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
The 5th kind of scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6Fraction, C
7Fraction, C
8Fraction, C
9Fraction and C
10 +Heavy fraction, wherein C
10 +In the heavy fraction less than C
10Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6Fraction and C
7Fraction contacts with aromatized catalyst respectively and faces hydrogen aromatization, C
8Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
9Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
10 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
The 6th kind of scheme is that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5The lightweight fraction, C
6, C
7, C
8, C
9, C
10～C
11Middle distillate and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
9Each fraction contact with reforming catalyst respectively and carry out catalytic reforming reaction, with C
10～C
11Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
11 +Heavy fraction contact with lightening catalyst and carry out lighting reaction.
The temperature of the described hydrofining reaction of the inventive method is 250～460 ℃, preferred 280～400 ℃, and pressure is 0.5～8.0MPa, preferred 1.6～2.5MPa.Suitable charging mass space velocity 0.1～20 hour
-1, preferred 2～8 hours
-1, hydrogen/hydrocarbon volume ratio 1～1000: 1, preferred 50～600: 1.
The used catalyzer of hydrofining should be able to have the hydrogenation saturation of olefins, has the ability of hydrogenating desulfurization, denitrogenation and deoxidation simultaneously.
The used Hydrobon catalyst of the present invention comprises the hydrogenation activity component of 5～50 quality %, the halogen of 0.1～2.0 quality % and the inorganic oxide carrier of 48～94.9 quality %.Described hydrogenation activity component is selected from oxide compound or the sulfide of one or more metals in Co, Ni, Fe, W, Mo, Cr, Bi, Sb, Zn, Cd, Cu, In, Pt, Pd and the rare earth metal.
Above-mentioned Hydrobon catalyst can adopt conventional method preparation, with the aluminium hydroxide moulding, roasting makes gamma-aluminium oxide carrier in air or water vapor again, and then adopts dipping method to introduce the hydrogenation activity component as the described elder generation of CN1169337A.
The inventive method (2) step is lightweight fraction or the discharge system that the refining aftercut of petroleum naphtha hydrogenation is gone out or carries out the light hydrocarbon isomerization reaction, preferably it carried out the light hydrocarbon isomerization reaction.The temperature of light hydrocarbon isomerization reaction is that 130～400 ℃, pressure are 0.1～3.0MPa.Suitable charging mass space velocity is 0.1～20 hour
-1, hydrogen/hydrocarbon volume ratio is 1～2000: 1, preferred 10～1000: 1.
Described catalyst for isomerizing light hydrocarbon is converted into high-octane gasoline blend component after should making a series of catalyzed reactions such as lighter hydrocarbons generation isomery, selective splitting and alkylation.Described catalyst for isomerizing light hydrocarbon is solid super acid catalyst or the catalyzer that contains zeolite.
The described catalyzer that contains zeolite comprises with the carrier being that the content that benchmark calculates is the VIII family metal of 0.01～2.0 quality %, the phosphorus of 0～3.0 quality %, preferred 0.2～1.0 quality %, described carrier comprises the aluminum oxide of 10～90 quality % and the zeolite of 10～90 quality %, described zeolite is selected from mordenite, Beta zeolite or the mixture of the two, and described carrier preferably includes the mordenite of 10～80 quality %, the Beta zeolite of 10～80 quality % and the aluminum oxide of 10～50 quality %.The described VIII preferred Pt of family's metal or Pd.
The above-mentioned catalyzer that contains zeolite can adopt the ordinary method preparation: with h-mordenite, or h-mordenite and Hydrogen Beta zeolite and aluminium hydrate powder or pseudo-boehmite are by required mixed, moulding, drying, roasting make complex carrier, introduce metal active constituent with pickling process again, then dry, roasting.For phosphorous catalyzer, preferred elder generation introduces phosphorus with pickling process, and then introduces metal active constituent.Maturing temperature is 400～650 ℃, preferred 450～600 ℃.
Described solid super acid catalyst comprise complex carrier and load thereon sulfate radical and be that the content that calculates benchmark is the VIII family metal of 0.05～2.0 quality % with the carrier, sulphur content is 1.0～2.5 quality % in the catalyzer, complex carrier by zirconium white, silicon oxide and aluminum oxide by 30～90: 1～30: 9～40, preferred 40～80: 4～24: 16～36 mass ratio is formed.The described VIII preferred Pt of family's metal or Pd.
Above-mentioned solid super acid catalyst can adopt the ordinary method preparation, and step is as follows: 1. earlier the soluble zirconium salts solution is contacted with alkaline solution, form the zirconium hydroxide precipitation, hydrothermal treatment consists is filtered then, with the solid product drying, and the preparation hydrous zirconium oxide; 2. with after aluminium hydroxide and silicon sol mixing, the drying, add ammonium chloride solution, washing, filtration, drying, the mixture of preparation silicon oxide and aluminum oxide; 3. behind the product mixing with first two steps, with the aqueous solution dipping of sulfuric acid, ammonium sulfate or monoammonium sulfate, support of the catalyst is made in solid drying, moulding, roasting; 4. with pickling process active metal component is introduced carrier, dry, roasting makes catalyzer.Maturing temperature is 400～650 ℃, preferred 450～600 ℃.
The inventive method (3) step is middle fraction to be carried out segmentation reform, and is about to middle distillate and is subdivided into a plurality of fractions again, with light constituent wherein, as C
7Following fraction carries out aromatization, C
7～C
10Fraction carry out catalytic reforming, this fraction also can further segment, the C that tells
9～C
10Fraction carries out the non-hydrogen upgrading.Described C
7Following fraction can further be divided into C
6And C
7Fraction faces the reaction of hydrogen or non-hydrogen aromatization respectively under differing temps.Described C
7～C
10Fraction also can further be divided into each fraction of the more single carbon number of a certain carbon number hydrocarbon content again, again each fraction is reformed under differing temps.
Described aromatization temperature is 300～600 ℃, preferred 450～530 ℃, and pressure is 0.1～5.0MPa, preferred 0.2～2.0MPa.
The described VIII family metal that the hydrogen aromatized catalyst comprises 0.1～7.0 quality %, basic metal or alkaline-earth metal, the halogen of 0.1～2.0 quality % and the carrier of 78.0～99.7 quality % of 0.1～13.0 quality % of facing, described carrier comprises the nonacid molecular sieve of 10～90 quality % and the binding agent of 10～90 quality %, the zeolite that described non-acidic zeolite is selected from L zeolite, faujusite or has the MFI structure, binding agent are selected from aluminum oxide or silicon oxide.The preferred platinum of described VIII family's metal, the preferred potassium of basic metal, described halogen is selected from chlorine.
Above-mentionedly face the preparation method that the hydrogen aromatized catalyst adopts and be: with zeolite with after binding agent mixes, be peptizing agent with aqueous acetic acid, mediate the back extruded moulding, dry back was in 500～650 ℃ of roastings 4～6 hours, make carrier, with the method for soaking altogether VIII family metal, basic metal or alkaline-earth metal and halogen are loaded on the carrier after the moulding simultaneously, 50～120 ℃ of dryings 4～12 hours, 200～350 ℃ of roastings 4～6 hours were reduced 1～6 hour in 300～500 ℃ of hydrogen.
Described non-hydrogen aromatization catalyzer comprises the metal oxide that is selected from zinc, molybdenum or gallium of 0.5～5.0 quality %, the rare earth oxide of 0.1～5.0 quality %, the VA family element of 1.0～7.0 quality % and the complex carrier of 83.0～98.4 quality %, and described complex carrier comprises the ZSM series zeolite of 20～70 quality % or the binding agent of MCM series zeolite and 30～80 quality %.The preferred phosphorus of described VA family's element, antimony or bismuth, more preferably phosphorus, the preferred mixed rare-earth oxide of described rare earth oxide contains lanthanum trioxide 20～40 quality %, cerium oxide 40～60 quality %, Praseodymium trioxide 10～18 quality %, Neodymium trioxide 2～10 quality % in the mixed rare-earth oxide.The preferred ZSM-5 of ZSM series zeolite, ZSM-11 or ZSM-12, more preferably ZSM-5, the preferred MCM-22 of MCM series zeolite or MCM-41.Described binding agent is silicon-dioxide or aluminum oxide, preferred aluminum oxide.The mol ratio of the silica of described ZSM-5 zeolite is preferred 10～200, and the mol ratio of the silica of MCM-22 is preferred 30～70, and more preferably 40～60.Described zeolite is h-type zeolite.
Described non-hydrogen aromatization reforming catalyst can adopt conventional preparation method: with the binding agent precursor, add the ZSM series zeolite after with sour peptization or the MCM series zeolite stirs into slurries as pseudo-boehmite, again described slurries are splashed into balling-up in the oil ammonia column, drying, roasting obtain the complex carrier of ball-type then; Or pseudo-boehmite mixed with ZSM series zeolite or MCM series zeolite, be that peptizing agent carries out kneading and compacting with acid, dry, complex carrier that stripe shape is made in roasting then.Described acid is nitric acid, hydrochloric acid or sulfuric acid.Then with step impregnation or the method for soaking altogether reactive metal and VA family element are introduced complex carrier, dry, roasting then.Maturing temperature is 400～650 ℃, preferred 450～600 ℃.
Described catalytic reforming is to make raw material that series reaction such as hexa-atomic cycloalkanes dehydrogenation, the dehydrogenation of five-ring alkane isomery, dehydrating alkanes cyclisation, alkane isomerization, hydrocracking take place, and is converted into the reformate or the high-octane gasoline blend component that are rich in aromatic hydrocarbons.The temperature of reaction of catalytic reforming is 400～600 ℃, preferred 430～530 ℃, and pressure is 0.1～8.0MPa, preferred 0.1～2.5MPa, and suitable charging mass space velocity is 0.1～20 hour
-1, hydrogen/hydrocarbon volume ratio is 1～2000: 1, preferred 10～1500: 1.Carry out the mode that segmentation is reformed again for being divided into several fractions, as the described scheme of the 6th scheme, the temperature of reforming reaction should the corresponding adjustment along with the difference (mainly considering the content of different carbon number naphthenic hydrocarbon) of each fractional composition.
Above-mentioned catalytic reforming reaction can adopt moving-bed CONTINUOUS REFORMER, fixed bed half generative reforming, fixed bed cyclic regeneration to reform and the low pressure combined bed reformer mode.
Described catalytic reforming catalyst comprises inorganic oxide carrier and is that the content that benchmark calculates is the VIII family metal of 0.1～5.0 quality % and the halogen of 1.0～5.0 quality % with the carrier.Described reforming catalyst also can comprise a kind of metal or the multiple metal that are selected from IVA family metal, VIIB family metal, basic metal, alkaline-earth metal, rare earth element, In, W, Y, Mo, Cr, P, Bi, Sb, Zn, Cd or Cu of 0.1～5.0 quality %.Described inorganic oxide carrier comprises aluminum oxide, magnesium oxide, chromic oxide, B
2O
3, TiO
2, ThO
2, ZnO, ZrO
2, silica-alumina, silicon oxide-magnesium oxide, chromic oxide-aluminum oxide, Al
2O
3-B
2O
3, SiO
2-ZrO
2, various potteries, alumina, bauxite, SiO
2, silicon carbide, synthetic or naturally occurring various silicate or clay, preferred aluminum oxide.
Described catalytic reforming catalyst adopts the ordinary method preparation, the carrier that namely prepares moulding earlier, support shapes can be ball-type or stripe shape, and then dipping is introduced metal constituent element and halogen, the method that can adopt step impregnation or flood is altogether introduced metal component, and the dipping back is dry, 450～650 ℃ of roastings namely get catalyzer, as if adopting step impregnation method, then a kind of component of every immersion all needs dry, roasting, and noble metal component step introducing in the end.
The temperature of described non-hydrogen upgrading reaction is 300～600 ℃, preferred 350～530 ℃, and pressure is 0.1～4.0MPa, preferred 0.2～2.0MPa.
Described non-hydrogen modifying catalyst comprises with the carrier being that the content that benchmark calculates is mixed rare-earth oxide or the weisspiessglanz of 0.1～5.0 quality %, 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 %, the Neodymium trioxide of 2～10 quality %, and carrier comprises the HZSM-5 zeolite of 50～80 quality % and the gama-alumina of 20～50 quality %.
The preparation method of above-mentioned non-hydrogen modifying catalyst is: the HZSM-5 zeolite is mixed with pseudo-boehmite, the adding acid solution mixes as peptizing agent and pinches even, extruded moulding, make carrier after drying, the roasting, carrier is flooded with mixed rare earth chlorides or antimony chloride solution, and dipping back solid drying, roasting make catalyzer.Described maturing temperature is 400～650 ℃, preferred 450～600 ℃.Peptizing agent is hydrochloric acid or nitric acid.
The inventive method (4) step is the lighting reaction of heavy fraction, and described lighting temperature of reaction is 400～650 ℃, preferred 420～600 ℃, and pressure is 0.1～8.0MPa, preferred 0.3～2.5MPa.Mass space velocity is 0.1～20 hour
-1, hydrogen/hydrocarbon volume ratio is 1～2000: 1, preferred 10～1500: 1.
Described lightening catalyst comprises carrier and is that the content that benchmark calculates is the VIII family metal of 0.01～5.0 quality % with the carrier, 0.1 the IVA family metal of～5.0 quality %, described carrier comprises the molecular sieve of 1～90 quality % and the binding agent of 10～99 quality %, described molecular screening is from the boracic Beta of low-aluminum-content molecular sieve, the SSZ borosilicate zeolite, crystalline phase is the compound borosilicate zeolite of the low-aluminum-content of Beta/ZSM-5, CIT-5, UTD-1, have in the molecular sieve of MFI structure one or more, described binding agent is selected from silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, vanadium oxide, in chromic oxide and the zirconium white one or more.The preferred platinum of described VIII family's metal, the preferred rhenium of IVA family metal, the compound borosilicate zeolite of the preferred Beta/ZSM-5 low-aluminum-content of the molecular sieve in the carrier.
Above-mentioned lightening catalyst adopts the ordinary method preparation: earlier described zeolite and binding agent mixing moulding are made carrier, carrier can be ball-type or stripe shape, and then introduces required metal component with pickling process, and dry, roasting namely gets catalyzer.Described maturing temperature is 400～650 ℃, preferred 450～600 ℃.
Petroleum naphtha of the present invention is C
4～C
14Hydro carbons, can be selected from that virgin naphtha, hydrocracking petroleum naphtha, catalytic naphtha, thermal naphtha, cracking of ethylene are raffinated oil, in raffinating oil one or more of coal tar, alkylate oil, liquefied coal coil, F-T synthetic oil and aromatic hydrocarbons.
The product of the inventive method segmentation reaction back gained mix or optionally partially mixed after, can adopt the refining of fractionation again, aromatic hydrocarbons extracting, benzene extracting, toluene disproportionation process, xylene isomerization, p-Xylol fractionation by adsorption, purpose aromatic hydrocarbon product and method such as separate and obtain benzene,toluene,xylene and C
9Purpose aromatic hydrocarbon product or production high octane gasoline components such as aromatic hydrocarbons, and by-product hydrogen, dry gas and liquefied gas etc.
The separation method of the reaction product that accompanying drawing is selected for use for the present invention describes in detail below in conjunction with accompanying drawing.
Fig. 1 is for being the separation process synoptic diagram of purpose aromatic hydrocarbon product with benzene and p-Xylol, and mixed reaction product is sent into separation column 1 carries out fractionation, isolates C successively at the bottom of from cat head to tower
5 -, C
6～C
7, C
8, C
9And C
9 +Fraction, wherein C
5 -Can further isolate liquefied gas and C
5Fraction is as the byproduct pentane oil; C
6～C
7Fraction enters aromatic hydrocarbons extracting unit 2 and carries out the aromatic hydrocarbons extracting, and non-aromatics is then discharged by cat head, the C that extracting goes out
6～C
7Aromatic hydrocarbons enters benzene-toluene knockout tower 3, and benzene is discharged from cat head as product, and toluene is discharged from tower bottom tube line.The C that discharges from separation column 1 middle part
8Fraction enters adsorption separation unit 4, and isolated p-Xylol is discharged system as product, the remaining C that contains aromatic hydrocarbons 〉=90 quality %
8BTX aromatics product part discharge system, a part enters xylene isomerization reaction device 5, under the xylene isomerization catalyst of routine and reaction conditions with C
8O-Xylol in the BTX aromatics, m-xylene and ethylbenzene conversion are p-Xylol, and isomerization product returns adsorption separation device.The C that discharge separation column 1 bottom
9Fraction is mixed into toluene disproportionation and transalkylation reactor 6 with the toluene of discharging at the bottom of benzene-toluene knockout tower, changes into benzene and C under the toluene disproportionation catalyst of routine and reaction conditions
8Aromatic hydrocarbons, disproportionation products then return initial separation column 1.The C that separation column 1 bottom tube line is discharged
9 +Fraction is discharger then.
Fig. 2 is main separation and the rectification flow synoptic diagram of producing the stop bracket gasoline blend component.The mix products that obtains after the reaction is sent into separation column 1, isolate C successively at the bottom of from cat head to tower
5 -, C
6And C
7 +Fraction is with C
5 -Fraction is introduced separation column 7 and is further isolated liquefied gas and C
5Fraction.The C that discharges from separation column 1 middle part
6Fraction enters benzene extraction tower unit 8, and the benzene that extracting goes out is discharged system as product, C
6Non-aromatic raffinating oil and C
5Fraction and the C that discharges from separation column 1 bottom
7 +Fraction mixes the back and discharges system as the gasoline blend component.
Fig. 3 is for being the separation process synoptic diagram of purpose aromatic hydrocarbon product coproduction stop bracket gasoline blend component with BTX.Mix products is sent into separation column 1, isolate C from top to bottom successively
5 -, C
6～C
8And C
9 +Fraction, wherein C
5 -Fraction can further be isolated liquefied gas and C
5Fraction; C
6～C
8Fraction is then sent into aromatic hydrocarbons extracting unit 2, the BTX that extracting goes out through separate simply again and make with extra care after directly discharge system, the C that obtains as product
6～C
8Non-aromatic raffinating oil then and C
5Cut and C
9 +Fraction mixes the back and discharges system or return the raw material fractionating system as the gasoline blend component.
Gaseous media circuit in Fig. 1～3 and some utility appliance such as compressor, separating tank, pump, various cold exchange devices etc. do not mark, but this is known to those of ordinary skills.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
This examples preparation hydrofining petroleum naphtha.
With ASTM D-86 boiling range be 95～258 ℃ hydrocrackates, 50～166 ℃ coking oil, 42～163 ℃ cycle oil, 58～89 ℃ normal pressure just push up oil and 91～182 ℃ virgin naphtha according to 50: 20: 5: 5: 20 mass ratio is made into mixing raw material oil.
Be that 2.0MPa, hydrogen/hydrocarbon volume ratio are that 200: 1, feed volume air speed are 8.0 hours with above-mentioned mixing raw material oil at 290 ℃, hydrogen dividing potential drop
-1Condition under in the presence of hydrogenation catalyst A, carry out hydrofining.Reaction product is sent into watercooler, be separated into gas-liquid two-phase, measure respectively and carry out compositional analysis.Described hydrogenation catalyst A contains the NiO of CoO, the 2.0 quality % of 0.03 quality %, the WO of 19.0 quality %
3Al with 78.97 quality %
2O
3Stock oil character sees Table 1 before and after the hydrofining.
Example 2
Preparation heavy fraction lighting catalyst for reaction.
(1) the Beta molecular sieve of preparation low-aluminum-content boracic.
With 0.5g pseudo-boehmite powder (German Condea company, trade mark SB), 2.0g borax, 2.2gNaOH and 209.4g concentration are that the tetraethyl-oxyammonia solution of 25 quality % mixes, (Cabot company produces to add the 40g superfine SiO 2 again, trade mark CAB-O-SILM-5), back immigration reactor stirs, 140 ℃ of crystallization 10 days, crystallization is cooled to 40 ℃ rapidly after finishing, product is after the centrifugation washing, with 120 ℃ of dryings of gained solid 10 hours, obtain the Beta molecular screen primary powder a of low-aluminum-content boracic.
(2) the compound borosilicate zeolite of preparation Beta/ZSM-5 low-aluminum-content.
Be that tetraethyl-oxyammonia solution and the 52ml deionized water of 25 quality % mixes with 3.7g borax, 0.4gNaOH, 4.88g concentration, stir down and add the Beta molecular screen primary powder a of the above-mentioned low-aluminum-content boracic of 2g as crystal seed, back adding 10g solid silicone stirs, violent stirring is even, 25 ℃ of aging 2h, move into reactor then, 150 ℃ of crystallization are cooled to 30 ℃ rapidly after 5 days, product through centrifugation, wash to the pH value be 8～9, the gained solid was in 100 ℃ of dryings 12 hours, and obtaining crystalline phase is the compound borosilicate zeolite b of the low-aluminum-content of Beta/ZSM-5.The Beta molecular sieve accounts for 6.5 quality % in the described composite molecular screen, the ZSM-5 molecular sieve accounts for 93.5 quality %.
(3) preparation heavy fraction lightening catalyst.
With above-mentioned compound borosilicate zeolite b and pseudo-boehmite powder (German Condea company, trade mark SB) mixes by 3: 7 weight ratios, add then with mixing the Glacial acetic acid of 2～6 quality % that the back dry powder quality is the calculating benchmark and the water of 30 quality %, fully mediate the back extrusion, 110 ℃ of dryings 24 hours, 550 ℃ of roastings 3 hours.With containing Pt (NH
3)
2Cl
2And HReO
4Solution impregnation, Pt, Re content are respectively 2.1 quality %, 2.6 quality % (all with respect to the butt carrier) in the steeping fluid, liquid during dipping/solid volume ratio is 3: 1, dipping back solid was in 120 ℃ of dryings 12 hours, 400 ℃ of roastings 4 hours, get catalyzer C, wherein containing with the carrier is that the Pt content that benchmark calculates is that 2.0 quality %, Re content are 2.5 quality %.
Example 3
Following example transforms petroleum naphtha by the inventive method.
Stock oil after the hydrofining is sent into separation column, and to be fractionated into boiling point be 40～99 ℃ C
4～C
6Lightweight fraction, C wherein
7Content is 13.6 quality %, and boiling point is 99～172 ℃ C
7～C
9Fraction, C wherein
10Content is no more than 20 quality %, and the C of boiling point 〉=172 ℃
10 +Heavy fraction, in the heavy fraction less than C
10Hydrocarbon content less than 20 quality %.
With C
4～C
6The lightweight fraction is 1.2 hours at 170 ℃, 1.6MPa, mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 600: 1 the condition, carries out the light hydrocarbon isomerization reaction under the effect of catalyzer Z.Catalyzer Z is made up of the mixed oxide of the sulfur loaded acid group of the Pt of 0.3 quality % and 99.7 quality %, and described mixed oxide is mixed by 60: 24: 16 mass ratio by zirconium white, aluminum oxide and silicon oxide and forms, and sulphur content is 1.95 quality % in the catalyzer.
The preparation method of catalyzer Z is as follows:
1. preparation mixes the hydrous zirconium oxide of crystalline phase: with zirconium oxychloride (ZrOCl
28H
2O) be made into the aqueous solution of 5 quality %, slowly add the ammoniacal liquor that concentration is 25 quality %, regulate pH value to 10, gained zirconium hydroxide precipitation is moved to autoclave together with solution seal, 130 ℃ of following hydrothermal treatment consists 24 hours.Solids with deionized water washing and filtration, there is not Cl in filtrate
-, 110 ℃ of dryings 24 hours make the hydrous zirconium oxide powder, and wherein monocline crystalline phase proportion is 25 quality %.
2. the mixture for preparing silicon oxide and aluminum oxide: get 49 gram silicon sol (SiO
2Content is 41 quality %), join in 40 gram pseudo-boehmites (German Condea company, the trade mark SB) pressed powders, to grind evenly, 110 ℃ of dryings 24 hours add 10% NH
4200 milliliters of Cl solution refluxed under 80 ℃ of stirrings 3 hours, and with deionized water wash, filtration, triplicate, 110 ℃ of dryings 24 hours are made the mixture of silicon oxide and aluminum oxide.
3. prepare catalyzer: get 75 gram aqua oxidation zirconium powders, the mixture that adds 50.9 gram silicon oxide and aluminum oxide, after mixing, the sulfuric acid that adds 150 milliliter of 0.5 mol flooded 1 hour, 110 ℃ of dryings 24 hours add nitric acid and 130 ml deionized water of 4 gram sesbania powder and 9 milliliter of 40 quality % concentration, mix fully that to be extruded into diameter after pinching be 1.8 millimeters, long 3～4 millimeters bar, 110 ℃ of dryings 24 hours, 650 ℃ of roastings 3 hours.With 79 milliliters of dippings of the platinum acid chloride solution of 0.8 quality % 4 hours, 110 ℃ of dryings 24 hours, catalyzer Z is made in 550 ℃ of roastings 3 hours.
C
7～C
9Fraction be 2.0 hours at 498 ℃, 1.2MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, to carry out reforming reaction under the effect of catalyzer D.Contain Pt 0.25 quality %, Re 0.48 quality % among the described catalyzer D, Cl1.30 quality %, surplus is γ-Al
2O
3
C
10 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, carries out the lighting reaction under the effect of lightening catalyst C.
The product of above-mentioned three-step reaction is mixed the back adopt ordinary method shown in Figure 2 to separate and refining, the results are shown in Table 2.
Example 4
Stock oil after example 1 hydrofining is sent into the C that separation column is fractionated into boiling point≤50 ℃
5 -Lightweight fraction, wherein C
6Content is no more than 8 quality %, and boiling point is 50～130 ℃ C
6～C
9Fraction, wherein C
9Content 18.5 quality %, and boiling point is greater than 130 ℃ C
9 +Heavy fraction, in the heavy fraction less than C
9Hydrocarbon content less than 20 quality %.
With C
5 -The lightweight fraction is as the direct discharger of tops.
C
6～C
9Fraction be 2.0 hours at 520 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.Contain Pt 0.35 quality %, Sn 0.30 quality % in the described catalyst B, surplus is γ-Al
2O
3
C
9 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, to react under the effect of lightening catalyst C.
The two-step reaction product is mixed, adopt ordinary method shown in Figure 1 to separate with refining, the results are shown in Table 3.
Example 5
It is 40～75 ℃ C that stock oil after example 1 hydrofining is fractionated into boiling point
4～C
5Lightweight fraction, C wherein
6Content is 15.4 quality %, and boiling point is 75～99 ℃ C
6～C
7Fraction, C wherein
7Content is 27.4 quality %, and boiling point is 99～185 ℃ C
7～C
11Fraction, C wherein
11Content is no more than 20 quality %, and boiling point is greater than 185 ℃ C
11 +Heavy fraction, in the heavy fraction less than C
11Hydrocarbon content less than 20 quality %.
Be 1.5 hours with the lightweight fraction at 150 ℃, 1.6MPa, mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 500: 1 the condition, under the effect of catalyzer E, carries out the light hydrocarbon isomerization reaction.Contain the phosphorus of Pd, 0.2 quality % of 0.42 quality % and the complex carrier of surplus among the described catalyzer E, described complex carrier comprises the mordenite of 20 quality %, the Beta zeolite of 35 quality % and the aluminum oxide of 45 quality %.
C
6～C
7Fraction is 2.0 hours at 480 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, under the effect of aromatized catalyst F, to carry out aromatization.
The preparation method of catalyzer F: with L zeolite (SiO
2/ Al
2O
3=6) with pseudo-boehmite powder (German Condea company, trade mark SB) mixes by 7: 3 weight ratios, add then with mixing the Glacial acetic acid of 2～6 quality % that the back dry powder quality is the calculating benchmark and the water of 30 quality %, mediate extrusion, 120 ℃ of dryings 2 hours, 550 ℃ of roastings 4 hours make carrier.Be the Pt (NH that benchmark contains Pt 0.6 quality % in order to the carrier quality then
3)
2Cl
2(by H
2PtCl
4Reduction makes) and the aqueous solution that contains KCl5 quality % 25 ℃ of dippings 24 hours, admittedly liquid/be 2 milliliters/gram carrier wherein.Filter, the gained solid reduces in 400 ℃ of hydrogen gas stream in 85 ℃ of dryings, 300 ℃ of roastings, is crushed to 40～60 sieve meshes after the cooling, obtains catalyzer F.
C
7～C
11Fraction is 2.0 hours at 520 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, to carry out reforming reaction under the effect of reforming catalyst B.
C
11 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, carries out the lighting reaction under the effect of lightening catalyst C.
To separate with the method for Fig. 1 after the product mixing of above-mentioned four-step reaction and make with extra care, that different be the C that discharges
6～C
7Non-aromatic raffinating oil reacted by the aromatization method in this example more again, the results are shown in Table 3.
Example 6
It is 40～75 ℃ C that petroleum naphtha after example 1 hydrofining is fractionated into boiling point
4～C
5Lightweight fraction, C wherein
6Content is 15.4 quality %, and boiling point is 75～99 ℃ C
6～C
7Fraction, C wherein
7Content is 27.4 quality %, and boiling point is 99～125 ℃ C
7～C
8Fraction, C wherein
9Content is 17.5 quality %, and boiling point is 125～185 ℃ C
9～C
11Fraction, wherein C
11Content is 2.8 quality %, and boiling point is greater than 185 ℃ C
11 +Heavy fraction, in the heavy fraction less than C
11Hydrocarbon content less than 20 quality %.
Be 1.2 hours with the lightweight fraction at 150 ℃, 1.8MPa, mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 500: 1 the condition, under the effect of catalyzer E, carries out the light hydrocarbon isomerization reaction.
C
6～C
7Fraction is 2.0 hours at 480 ℃, 0.35MPa, charging mass space velocity
-1Conditions of non-hydrogen under, under the effect of aromatized catalyst H, carry out non-hydrogen aromatization reaction.
Contain oxidation mishmetal, the P of 2.0 quality % and the complex carrier of surplus of ZnO, the 0.5 quality % of 2.0 quality % among the catalyzer H, described complex carrier is made up of the ZSM-5 zeolite of 30 quality % and the gama-alumina of 70 quality %.
The preparation method of catalyzer H is as follows:
1. prepare complex carrier: (Sasol company produces, PURAL to get 94.6 gram pseudo-boehmite powder
SB, alumina content 74 quality %), under the agitation condition, joining 300 gram concentration is in the aqueous nitric acid of 1.1 quality %, after stirring 2 hours peptizations, add 33.0 gram silica and be 60 HZSM-5 zeolite powder (zeolite content 91%), high-speed stirring 3 hours.The slurries of making are splashed in the oil ammonia column that 8 quality % ammoniacal liquor are housed, the wet bulb that forms in the oil ammonia column is taken out, 60 ℃ of dryings 10 hours, 550 ℃ of roastings 3 hours obtain complex carrier, for containing the alumina globule of HZSM-5 zeolite 30 quality %.
2. prepare catalyzer: get 50 gram complex carriers, with 50 the gram contain zinc nitrate 4.7 quality %, (wherein lanthanum trioxide accounts for 31% to chlorination mishmetal 1.5 quality %, cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%), the mixing solutions of phosphoric acid 6.6 quality % dipping is 30 minutes, 110 ℃ of dryings 24 hours, 550 ℃ of roastings 5 hours are handled in 550 ℃ with water vapor then and were obtained catalyzer H in 4 hours.
C
7～C
8Fraction is 2.0 hours at 500 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, to carry out reforming reaction under the effect of reforming catalyst B.
C
9～C
11Fraction is 2.5 hours at 480 ℃, 1.0MPa, charging mass space velocity
-1Condition under under the effect of catalyzer G, carry out non-hydrogen upgrading reaction.Contain with the carrier among the described catalyzer G is that the content that calculates benchmark is the mixed rare-earth oxide of 0.45 quality %, described mixed rare-earth oxide contains the lanthanum trioxide of 31 quality %, the cerium oxide of 51 quality %, the Praseodymium trioxide of 14 quality %, the Neodymium trioxide of 4 quality %, and described carrier is made up of the HZSM-5 zeolite of 65 quality % and the gama-alumina of 35 quality %.
C
11 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, carries out the lighting reaction under the effect of lightening catalyst C.
To convert the gasoline except the direct accent of light hydrocarbon isomerization product in the above-mentioned five steps reaction, remaining product carries out the aromatic hydrocarbons extracting earlier, the C that extracting goes out after mixing
6～C
8Aromatic hydrocarbons obtains benzene, toluene and dimethylbenzene (BTX) by the rectificating method separation of routine, and non-aromatics is raffinated oil and returned the feed naphtha fractionating system, the results are shown in Table 4.
Example 7
It is 40～61 ℃ C that petroleum naphtha after example 1 hydrofining is fractionated into boiling point
4～C
5Lightweight fraction, C wherein
5Content is 55.4 quality %, and boiling point is 61～81 ℃ C
6Fraction, C wherein
6Content is 87.4 quality %, and boiling point is 81～110 ℃ C
7Fraction, C wherein
7Content is 84.5 quality %, and boiling point is 110～125 ℃ C
8Fraction, wherein C
8Content is 80.8 quality %, and boiling point is 125～172 ℃ C
9Fraction, C wherein
10Content is no more than 20 quality %, and boiling point is greater than 172 ℃ C
10 +Heavy fraction, in the heavy fraction less than C
10Hydrocarbon content less than 20 quality %.
With C
4～C
5The lightweight fraction is 1.5 hours at 150 ℃, 1.8MPa, mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 500: 1 the condition, carries out the light hydrocarbon isomerization reaction under the effect of catalyzer E.
C
6Fraction is 1.5 hours at 470 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 700: 1 the condition, under the effect of aromatized catalyst F, to carry out aromatization.
C
7Fraction is 1.6 hours at 490 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, under the effect of aromatized catalyst F, to carry out aromatization.
C
8Fraction is 2.0 hours at 500 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.
C
9Fraction is 0.5 hour at 480 ℃, 1.0MPa, charging mass space velocity
-1Condition under, under the effect of catalyzer G, carry out non-hydrogen upgrading reaction.
C
10 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, carries out the lighting reaction under the effect of lightening catalyst C.
The product mixing back of above-mentioned six-step process is handled with separation shown in Figure 3 and process for purification, the results are shown in Table 4.
Example 8
Petroleum naphtha after example 1 hydrofining is fractionated into the C of boiling point≤61 ℃
4～C
5Lightweight fraction, C wherein
5Content is 55.4 quality %, and boiling point is 61～81 ℃ C
6Fraction, C wherein
6Content is 87.4 quality %, and boiling point is 81～110 ℃ C
7Fraction, C wherein
7Content is 84.5 quality %, and boiling point is 110～125 ℃ C
8Fraction, C wherein
8Content is 80.8 quality %, and boiling point is 125～152 ℃ C
9Fraction, C wherein
9Content is 82.3 quality %, and boiling point is 152～185 ℃ C
10～C
11Fraction, C wherein
11Content is no more than 20 quality %, and the C of boiling point 〉=185 ℃
11 +Heavy fraction, in the heavy fraction less than C
11Hydrocarbon content less than 20 quality %.
With C
4～C
5The lightweight fraction be 1.5 hours at 150 ℃, 1.6MPa, mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 500: 1 the condition, under the effect of catalyzer E, carries out the light hydrocarbon isomerization reaction.
C
6Fraction is 1.5 hours at 450 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 500: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.
C
7Fraction is 1.6 hours at 470 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 700: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.
C
8Fraction is 1.8 hours at 490 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 800: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.
C
9Fraction is 2.0 hours at 510 ℃, 0.35MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, under the effect of reforming catalyst B, to carry out reforming reaction.
C
10～C
11Fraction is 0.5 hour at 510 ℃, 1.0MPa, charging mass space velocity
-1Condition under, under the effect of catalyzer G, carry out non-hydrogen upgrading reaction.
C
11 +Heavy fraction is 2.0 hours at 510 ℃, 1.0MPa, charging mass space velocity
-1, hydrogen/hydrocarbon volume ratio is under 1000: 1 the condition, under the effect of lightening catalyst C, carries out the lighting reaction.
The product liquid that above-mentioned lightweight fraction isomerization product is isolated behind the liquefied gas is discharged, can be directly used in to transfer and convert gasoline; C
6Mainly be benzene in the fraction reformate, through solvent extraction, benzene is discharged system as product; C
7And C
9The fraction reformate reacts under the toluene disproportionation of routine and transalkylation catalyst effect; C
8The fraction reformate is through fractionation by adsorption, and isolated p-Xylol (PX) is discharged system as product, and all the other products make C through xylene isomerization reaction
8PX in the aromatic hydrocarbons reaches balance again.Carry out fractionation with extracting again after resultant product behind benzene and the p-Xylol is mixed, tell C
5 -, C
6～C
8Non-aromatics, C
8Aromatic hydrocarbons, C
9 +, C wherein
5 -Mix with the light hydrocarbon isomerization product; C
8The aromatic hydrocarbons part is discharged system as the BTX aromatics product, and part is returned aforementioned adsorption separation unit; C
6～C
8Non-aromatic and C
9 +In a part return the raw material fractionating system again, the results are shown in Table 3.
Table 1
| Boiling range, ℃ | 42～258℃ |
| Stock oil character before refining | |
| Alkene, volume % | 5.20 |
| Alkane, quality % | 47.17 |
| Naphthenic hydrocarbon, quality % | 39.30 |
| Aromatic hydrocarbons, quality % | 8.33 |
| Refining back stock oil character | |
| Alkane, quality % | 51.93 |
| Naphthenic hydrocarbon, quality % | 39.62 |
| Aromatic hydrocarbons, quality % | 8.45 |
| Sulphur, ppm | ＜0.5 |
| Nitrogen, ppm | ＜0.5 |
| Bromine number, gBr/100g | ＜0.1 |
Table 2
Table 3
Table 4
Claims (25)
1. the catalysis conversion method that boiling range is 40～260 ℃ petroleum naphtha comprises the steps:
(1) petroleum naphtha is carried out hydrofining in the presence of Hydrobon catalyst, again the petroleum naphtha fractionation after the hydrofining is cut into lightweight fraction, middle distillate and heavy fraction, described lightweight fraction is C
4～C
6Hydro carbons, middle distillate be C
6～C
11Hydro carbons, heavy fraction be C
9～C
11Above hydro carbons, in the described heavy fraction than the low hydrocarbon content of the main ingredient carbon number of fraction less than 20 quality %,
(2) contact with lightweight fraction discharger or with catalyst for isomerizing light hydrocarbon and carry out light hydrocarbon isomerization reaction,
(3) middle distillate is separated into one to multiple strand of fraction and carries out the segmentation reforming reaction,
(4) heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
2. in accordance with the method for claim 1, it is characterized in that described segmentation reforming reaction of (3) step comprises any one or a few in aromizing, catalytic reforming, the non-hydrogen upgrading.
3. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
5 -Lightweight fraction, C
6～C
9Middle distillate and C
9 +Heavy fraction, wherein C
9 +In the heavy fraction less than C
9Hydrocarbon content less than 20 quality %, with lightweight fraction discharger, middle distillate contacts with reforming catalyst carries out catalytic reforming reaction, heavy fraction contacts with lightening catalyst and carries out lighting reaction.
4. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
6Lightweight fraction, C
7～C
9Middle distillate and C
10 +Heavy fraction, wherein C
10 +In the heavy fraction less than C
10Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, middle distillate contacts with reforming catalyst carries out catalytic reforming reaction, heavy fraction contacts with lightening catalyst and carries out lighting and react.
5. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6～C
7Fraction, C
7～C
11Fraction and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, described lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
7Fraction contacts with aromatized catalyst and faces hydrogen aromatization, C
7～C
11Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
11 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
6. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6～C
7Fraction, C
7～C
8Fraction, C
9～C
11Fraction and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, described lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
7Fraction contacts with aromatized catalyst and carries out non-hydrogen aromatization reaction, C
7～C
8Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
9～C
11Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
11 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
7. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5Lightweight fraction, C
6Fraction, C
7Fraction, C
8Fraction, C
9Fraction and C
10 +Heavy fraction, wherein C
10 +In the heavy fraction less than C
10Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6Fraction and C
7Fraction contacts with aromatized catalyst respectively and faces hydrogen aromatization, C
8Fraction contacts with reforming catalyst and carries out catalytic reforming reaction, C
9Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
10 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
8. in accordance with the method for claim 1, it is characterized in that the petroleum naphtha fractionation after the hydrofining is cut into C
4～C
5The lightweight fraction, C
6, C
7, C
8, C
9, C
10～C
11Middle distillate and C
11 +Heavy fraction, wherein C
11 +In the heavy fraction less than C
11Hydrocarbon content less than 20 quality %, the lightweight fraction contacted with catalyst for isomerizing light hydrocarbon carries out light hydrocarbon isomerization reaction, C
6～C
9Each fraction contact with reforming catalyst respectively and carry out catalytic reforming reaction, C
10～C
11Fraction contacts with the non-hydrogen modifying catalyst and carries out the reaction of non-hydrogen upgrading, C
11 +Heavy fraction contacts with lightening catalyst and carries out the lighting reaction.
9. in accordance with the method for claim 1, the temperature that it is characterized in that described hydrofining reaction of (1) step is that 250～460 ℃, pressure are 0.5～8.0MPa.
10. in accordance with the method for claim 1, the temperature that it is characterized in that the described light hydrocarbon isomerization reaction of (2) step is that 130～400 ℃, pressure are 0.1～3.0MPa.
11. it is characterized in that in accordance with the method for claim 1, described catalyst for isomerizing light hydrocarbon of (2) step is solid super acid catalyst or the catalyzer that contains zeolite.
12. in accordance with the method for claim 11, it is characterized in that described solid super acid catalyst comprise complex carrier and load thereon sulfate radical and be that the content that calculates benchmark is the VIII family metal of 0.05～2.0 quality % with the carrier, sulphur content is 1.0～2.5 quality % in the catalyzer, complex carrier by zirconium white, silicon oxide and aluminum oxide by 30～90: 1～30: 9～40 butt mass ratio is formed.
13. in accordance with the method for claim 11, it is characterized in that it is that the content that calculates benchmark is the VIII family metal of 0.01～2.0 quality %, the phosphorus of 0～3.0 quality % that the described catalyzer that contains zeolite comprises with the carrier, described carrier comprises the aluminum oxide of 10～90 quality % and the zeolite of 10～90 quality %.
14. in accordance with the method for claim 13, it is characterized in that it is that the content that calculates benchmark is the phosphorus of the platinum of 0.01～2.0 quality % or palladium, 0.2～1.0 quality % that the described catalyzer that contains zeolite comprises with the carrier, described carrier comprises the mordenite of 10～80 quality %, the Beta zeolite of 10～80 quality % and the aluminum oxide of 10～50 quality %.
15. according to claim 5 or 7 described any one methods, it is characterized in that described aromatized catalyst comprises the VIII family metal of 0.1～7.0 quality %, basic metal or alkaline-earth metal, the halogen of 0.1～2.0 quality % and the carrier of 78.0～99.7 quality % of 0.1～13.0 quality %, described carrier comprises the nonacid molecular sieve of 10～90 quality % and the binding agent of 10～90 quality %, and described nonacid molecular screening is from L zeolite, faujusite or zeolite with MFI structure.
16. in accordance with the method for claim 6, it is characterized in that the used non-hydrogen aromatization catalyzer of non-hydrogen aromatization reaction comprises the metal oxide that is selected from zinc, molybdenum or gallium of 0.5～5.0 quality %, the rare earth oxide of 0.1～5.0 quality %, the VA family element of 1.0～7.0 quality % and the complex carrier of 83.0～98.4 quality %, described complex carrier comprises the ZSM series zeolite of 20～70 quality % or the binding agent of MCM series zeolite and 30～80 quality %.
17. in accordance with the method for claim 16, it is characterized in that described VA family element is phosphorus, described rare earth oxide is mixed rare-earth oxide, contain lanthanum trioxide 20～40 quality %, cerium oxide 40～60 quality %, Praseodymium trioxide 10～18 quality %, Neodymium trioxide 2～10 quality % in the mixed rare-earth oxide, the ZSM series zeolite is ZSM-5, the MCM series zeolite is MCM-22 or MCM-41, and binding agent is aluminum oxide.
18. according to described any one method of claim 3～8, the temperature that it is characterized in that described catalytic reforming reaction is that 400～600 ℃, pressure are 0.1～8.0MPa.
19. in accordance with the method for claim 18, it is characterized in that the used reforming catalyst of catalytic reforming reaction comprises inorganic oxide carrier and be that the content that benchmark calculates is the VIII family metal of 0.1～5.0 quality % and the halogen of 1.0～5.0 quality % with the carrier.
20. in accordance with the method for claim 19, it is characterized in that described reforming catalyst comprises that also 0.1～5.0 quality %'s is selected from one or more of IVA family metal, VIIB family metal, basic metal, alkaline-earth metal, rare earth element, In, W, Mo, Cr, P, Bi, Sb, Zn, Cd or Cu.
21. in accordance with the method for claim 19, it is characterized in that described inorganic oxide carrier is aluminum oxide.
22. according to described any one method of claim 6～8, it is characterized in that it is that the content that calculates benchmark is mixed rare-earth oxide or the weisspiessglanz of 0.1～5.0 quality % that described non-hydrogen modifying catalyst comprises with the carrier, 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 %, the Neodymium trioxide of 2～10 quality %, and carrier comprises the HZSM-5 zeolite of 50～80 quality % and the gama-alumina of 20～50 quality %.
23. it is characterized in that in accordance with the method for claim 1, the temperature of (4) step described lighting reaction is that 400～650 ℃, pressure are 0.1～8.0MPa.
24. in accordance with the method for claim 1, it is characterized in that described lightening catalyst of (4) step comprises carrier and be that the content that benchmark calculates is the VIII family metal of 0.01～5.0 quality % with the carrier, 0.1 the IVA family metal of～5.0 quality %, described carrier comprises the molecular sieve of 1～90 quality % and the binding agent of 10～99 quality %, described molecular screening is from the boracic Beta of low-aluminum-content molecular sieve, the SSZ borosilicate zeolite, crystalline phase is the compound borosilicate zeolite of the low-aluminum-content of Beta/ZSM-5, CIT-5, UTD-1 and have in the molecular sieve of MFI structure one or more, described binding agent is selected from silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, vanadium oxide, in chromic oxide and the zirconium white one or more.
25. in accordance with the method for claim 1, it is characterized in that described petroleum naphtha is selected from that virgin naphtha, hydrocracking petroleum naphtha, catalytic naphtha, thermal naphtha, cracking of ethylene are raffinated oil, in raffinating oil one or more of coal tar, alkylate oil, liquefied coal coil, F-T synthetic oil and aromatic hydrocarbons.
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