CN103361114A - Technique for producing high-octane gasoline from raw material containing rich C4, C5 and C6 alkanes - Google Patents
Technique for producing high-octane gasoline from raw material containing rich C4, C5 and C6 alkanes Download PDFInfo
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- CN103361114A CN103361114A CN2012100977582A CN201210097758A CN103361114A CN 103361114 A CN103361114 A CN 103361114A CN 2012100977582 A CN2012100977582 A CN 2012100977582A CN 201210097758 A CN201210097758 A CN 201210097758A CN 103361114 A CN103361114 A CN 103361114A
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Abstract
The invention relates to a technique for producing high-octane gasoline component, which comprises steps as follows: a raw material containing rich C4, C5 and C6 alkanes and hydrogen are mixed to enter a reactor filled with a dehydrogenation catalyst to perform alkane dehydrogenation reaction; the dehydrogenation product passes through an incondensable gas separation device and is mixed with hydrogen to enter a reactor filled with an aromatization catalyst to perform aromatization; and C4, C5 and C6 alkanes in the separated aromatization product are circulated to a catalytic dehydrogenation unit to continue dehydrogenation and aromatization, thereby enhancing the gasoline component yield. The invention greatly reduces the C1-C4 low-carbon hydrocarbon generation quantity, and enhances the gasoline yield. The produced gasoline component has low alkane content, high nonbenzenoid aromatic content and high octane number, and conforms to the present environmental requirements; and the diesel component can be directly used.
Description
Technical field
The invention provides a kind of tops that is rich in carbon four carbon five carbon six alkane take the refinery, pentane oil, coking light naphthar etc. as raw material, through in dehydrogenation reactor with catalytic dehydrogenation after dehydrogenation catalyst contact, in aromatization reactor, contact with aromatized catalyst and carry out aromatization production stop bracket gasoline and with the method for the carbon four carbon five carbon six alkane circulation catalytic dehydrogenations in the product.
Background technology
Enter " 12 ", propelling along with 2,000 ten thousand ton/years of oil refining of CNPC's Guangdong petrochemical industry, the 1000 ten thousand ton/years of oil refining in Kunming, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, 800,000 ton/years of ethene of Fushun petrochemical industry, 1,200,000 ton/years of projects such as expansion of ethylene of Daqing petrochemical, the oil-refining capacity of CNPC and ethene production capacity also will further enlarge, the C of refinery's by-product
4/ C
5/ C
6Alkane (such as reforming topped oil, hydrogenation coking light naphthar etc.) amount also increases thereupon, however C
4/ C
5/ C
6Alkane is not high because of itself octane value, can not be directly as motor spirit, and cheap, transportation cost is high, in the transportation loss large, concerning this refinery, belong to low-value product.
On the other hand, along with the develop rapidly of Chinese national economy, the continuous increase of automobile pollution, increasing to the demand of vehicle fuel gasoline.Simultaneously, also along with increasingly strict to gasoline quality standard of environmental requirement, the motor spirit quality standard is to low sulfur content, low olefin-content, low-steam pressure and high-octane future development.Market has very big demand to the volume increase premium-type gasoline with to low-sulfur, low olefin-content, high octane value gasoline blending component, and the technological development of this aspect also becomes the hot issue of domestic each research unit and enterprises pay attention.
CN 93102129 discloses inferior patrol catalytic reforming-aromatization method.Thick pressure gasoline is catalytic reforming under conditions of non-hydrogen at first, and then carries out aromizing at Zn-Al or Zn-AL～rare earth HZSM-5, and temperature is 480 ℃～650 ℃, and pressure is 0.05MPa～1.5MPa.The yield of final gasoline is 55m%～75m%.Because aromatized catalyst carbon distribution inactivation is very fast, general aromatized catalyst will be regenerated once in 15 days, therefore, need two aromatization reactor blocked operations.
Publication number is the method that CN 1488724A patent discloses a kind of gasoline hydrofinishing-aromizing.The catalytically cracked gasoline the first step is 220 ℃～300 ℃ in temperature, and pressure is 2.0MPa～10.0MPa, volume space velocity 2.0～10.0h
-1With hydrogen to oil volume ratio 200～800: under 1 the condition, hydrofining removes sulfide and the olefin(e) compound in the gasoline.Second step is 350 ℃～450 ℃ in temperature, and pressure is 1.5MPa～4.5MPa, volume space velocity 0.5～3.0h
-1With hydrogen to oil volume ratio 200～800: under 1 the condition.Adopt the hydrogen type molecular sieve of little grain fineness number, with light-hydrocarbon aromatized be aromatic hydrocarbons, to recover the explosion-proof exponential sum octane value of fs.Although this technology has reached the effect of desulfurating and reducing olefinic hydrocarbon, the explosion-proof index loss of octane number of gasoline is all about 2%, and the gasoline rate of loss is about 10%.
Publication number is that the patent of CN 1580199A discloses a kind of technique by etherificate and aromatization reformulated gasoline.This technology is cut into gasoline first weight two portions, contains 1～20% carbon four, 60～80% carbon five, no more than 20% carbon in the light constituent more than six, carbon six following components no more than 30% in the restructuring minute.Alkene in the light constituent and alcohols carry out etherification reaction, and restructuring minute is advanced reactor with hydrogen and carried out aromatization, and then with the component blending, octane value that can Effective Raise gasoline.
EP256604A2 discloses a kind of C
5～C
7The isomerized method of straight-chain paraffin is containing C
5～C
7Raw material be divided into two cuts of weight, lighting end enters isomerization reactor from a segmentation after mixing with hydrogen, last running mixes with hydrogen afterwards from the middle part of isomerization reactor and enters reaction, temperature of reaction is low on the reactor, the lower end temperature of reaction is high.The catalyzer that this method is used is the catalyzer that contains mordenite or y-type zeolite.
CN200410004475 discloses a kind of C
5, C
6Isomerized method.The method is with the raw material rectifying separation, with C
5Light constituent and C
6Restructuring is the aromizing oil ingredient that steams next life under different processing condition minute respectively.
CN 1073198A discloses a kind of dehydroaromatizationof dual-function catalyst preparation method who utilizes macropore L alkali type zeolite and a kind of butter binding agent mixing moulding.The active ingredient of this catalyzer is precious metals pt.US4104320, US4435283, US4458075, US4619906, EP184451A, US4780223 and CN 86107521A introduce the Pt-L zeolite to introduce Ba, sylvite, basic metal and come modification L zeolite, to overcome this weakness of less stable in the dehydroaromatizationof of alkane reaction.
As mentioned above, the modification technology of existing carbon five carbon six alkane, by isomerization, aromizing, etherificate be combined with aromizing, hydrogenating desulfurization is combined with aromizing etc., and technology realizes.Isomerization technique produces a large amount of diluted acids, serious environment pollution owing to adopting hydrofluoric acid and the vitriol oil to make catalyzer.Because the direct technology of aromatization temperature of reaction of carbon five carbon six alkane is high, yield of gasoline is low, and the aromatized catalyst life-span is short.No matter and hydrogenating desulfurization is combined with aromatization technology or etherification technology is combined with aromatization technology, the just loss of octane value in remedying hydrogenation, etherification procedure of aromatization technology.
Think C more than contriver's process
4/ C
5/ C
6In the alkane transformation of the way technology, mainly undertaken by isomerization of paraffins and aromizing, but owing to severe reaction conditions, liquid are received the lower economic benefit that had a strong impact on.The alkene octane value is high than alkane in the gasoline, but poor stability, and environmental protection standard is more and more stricter to its requirement, and is low but it compares the alkane reaction temperature in the reactions such as polymerization, cyclisation, alkylation, aromizing.Aromatization mainly by cracking, oligomerisation, dehydrogenation, cyclisation, alkylation, take off that many reactions steps such as alkyl realize.In the alkene aromatization, temperature of reaction is hanged down the generation that well suppresses cracking, dehydrogenation when guaranteeing olefin conversion, take off the reactions such as alkyl, will significantly lower C
1～C
4Deng the lower carbon number hydrocarbons growing amount, improve gasoline yield.
Summary of the invention
The object of the present invention is to provide a kind of can be with refinery's low octane rating, the low value-added raw material that is rich in carbon four carbon five carbon six alkane, through the method for dehydrogenation, aromizing production high octane gasoline component.
The present invention relates to a kind of technique take the alkane that is rich in carbon four carbon five carbon six as raw material production gasoline, enter to the catalytic dehydrogenating reaction device after it is characterized in that being rich in carbon four carbon five carbon six paraffinic feedstocks and hydrogen mixing, contact with dehydrogenation catalyst and to carry out catalytic dehydrogenating reaction, after dehydrogenation product is isolated noncondensable gas through the noncondensable gas tripping device, be mixed into aromatization reactor with hydrogen, contact with aromatized catalyst and to carry out aromatization, reacted product is divided into dry gas by separating, carbon three, carbon four carbon five carbon six alkane, high-octane gasoline component, diesel component; Will be wherein in the product carbon four carbon five carbon, six paraffin sections or all be circulated to dehydrogenation reactor before participate in catalytic dehydrogenating reaction.
Be rich in carbon four carbon five carbon six paraffinic feedstocks among the present invention and refer to the in process of production hydro carbons take carbon four carbon five carbon six alkane as main ingredient of institute's by-product of refinery, carbon four carbon five carbon six hydro carbons that reclaim such as tops, oil field light hydrocarbon, coking light naphthar, pentane oil and other device etc., the content of general paraffinic hydrocarbons is more than 90%, be preferably in more than 95%, the boiling range of raw material 95% is in 70 ℃, in 60 ℃, can be the same raw material preferably, also can be that different material mixes.The content of alkene is preferably below 10%, is preferably below 5%.Above content all is weight percentage.
Be not particularly limited dehydrogenation catalyst among the present invention, require that olefin(e) centent is not less than 35% in the catalytic dehydrogenation product, preferably so that olefin(e) centent more than 45%.Dehydrogenation catalyst preferably is comprised of carrier and active ingredient, and catalyzer is preferably take high-temperature inorganic oxide as carrier, as being TiO
2, Al
2O
3, SiO
2, one or several the mixing among the ZnO, also can be molecular sieve or molecular sieve and the mixing of above several high-temperature inorganic oxides.Contain preferably that at least a metal is active ingredient in VIB, VIII, IA, the IIA family, as being Na, Zn, Rb, Cs, Mg, Sr, Ba, Pt, Mo, Cl, F, Br etc., preferably Pt, Cl, Mo, Cr; The content of active ingredient is 0.1%～20% of catalyst weight.It can also be the compound multi-metal-oxide catalyst that above-mentioned active ingredient obtains with co-precipitation; Molecular sieve can be one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve equimolecular sieve, and two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.The shape of catalyzer can be bead, also can be bar shaped.The per-cent that the present invention does not specify is % by weight.
Entering hydrogen in the dehydrogenation reactor among the present invention is 0.01: 1～1: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane, is preferably 0.1: 1～0.5: 1.
Enter the mass ratio of hydrogen and hydro carbons in the aromatization reactor among the present invention
Be 0.01: 1～1: 1, be preferably 0.1: 1～0.5: 1.
The reaction conditions of catalytic dehydrogenating reaction is preferably among the present invention: 480～700 ℃, and pressure 0.01～3MPa, the liquid volume air speed is 0.1～10h
-1The air speed that the present invention does not specify is the liquid volume air speed.
Be not particularly limited aromatized catalyst among the present invention, catalyzer preferably contains molecular sieve and one or more active ingredients.Molecular sieve specifically can be the molecular sieve of the mesopores such as ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, aluminium silicophosphate molecular sieve, mesoporous and micropore, can be one or more in the molecular sieve, two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.Large pore molecular sieve also is not suitable for aromatization of the present invention, and this is that the characteristics of raw material cause, the dehydrogenation intermediate product receive through liquid behind this catalytic unit and aromatics yield very undesirable.Aromatized catalyst can contain high-temperature inorganic oxide and molecular sieve, one or more active ingredients, and wherein high-temperature inorganic oxide can be TiO
2, Al
2O
3, SiO
2, one or several the mixing among the ZnO.The active ingredient that supports can be in rare earth element, IIIB, VIB, VIIB, VIII, the IIB family element one or several, as being La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, Pt etc., preferably La, Pr, Ni, Co, Cr; The active ingredient weight that supports is 0.01～8%.Catalyst shape can be bead, also can be strip.
The reaction conditions of aromatization is preferably among the present invention: 260～560 ℃, pressure 0.5～5.0MPa, volume space velocity are 0.1～10h
-1
Naphthene content should be less than 10%, preferably less than 5% in the raw material.Such substances content surpasses 10% raw material, and to be not suitable for reason of the present invention be that the conversion of such raw material aromizing unit after dehydrogenation is limited, affects the quality of gasoline component among the present invention.
The flow process of petroleum naphtha etc. 95% more than 75 ℃ not within raw material range of the present invention, above and the aromatics yield owing to the C5 of aromizing product after the overweight component dehydrogenation, also greatly shorten simultaneously the work-ing life of aromatized catalyst, can increase cost of the present invention undoubtedly.
Olefin(e) centent in the dehydrogenation product is generally greater than 35%, more preferably greater than 45%.Olefin(e) centent is crossed and low will be caused in the aromizing unit product aromaticity content to cross low and C5 liquid is received not highly, will affect the economic performance of technique of the present invention.
In addition, for variation and the realization mass transfer that adapts to pressure between technique dehydrogenation unit of the present invention and the aromizing unit, should between two districts, add tripping device and the pressure changing device of noncondensable gas.The tripping device of noncondensable gas can be flash tank, absorption/Analytic Tower, refrigerating unit and compression set etc.The pressure changing device can be pump, compressor etc.
The catalytic dehydrogenating reaction device, the aromatization reactor that relate among the present invention are fixed-bed reactor, can be that a reactor uses separately, intermittently realize by two processes of reaction-catalyst regeneration, also can in parallel use of two or more reactors carry out cyclical operation, can also divide a plurality of reactors parallel connections and series combination to use.Catalyzer in one or several reactor is because the serious inactivation of carbon distribution by switching material import and export, recycles the continuous operation of realization response, regeneration system rapidly after the decaying catalyst regeneration.
Among the present invention, carbon four carbon five carbon six alkane are circulated to the catalytic dehydrogenation unit in the product behind the aromatization, the mass ratio that cyclic part accounts for carbon four carbon five carbon six alkane in the product is 0.01 quality %～100 quality %, and circulation ratio is preferably 25 quality %～70 quality %.
Method of the present invention can be more specifically: make first hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane after the ratio of amount of substance is to mix in 0.01: 1～1: 1, at 480～700 ℃, pressure 0.01～3MPa, volume space velocity are 0.1～10h
-1Under carry out catalytic dehydrogenating reaction mix with hydrogen again at 260～560 ℃ so that carbon four carbon five C 6 olefin content more than 45%, then remove behind the noncondensable gas, pressure 0.5～5.0MPa, volume space velocity are 0.1～8h
-1Under carry out aromizing, after isolate in the aromizing product carbon four carbon five carbon six alkane and be circulated to the catalytic dehydrogenation unit and recycle, can make in the aromizing product liquid product yield more than 83%, the high octane gasoline component yield is more than 75%, non-benzene aromaticity content is more than 30% in the gasoline component, and benzene content is lower than 2% in the gasoline component.
Aromizing, dehydrogenation etherificate dual-function catalyst technology are different respectively for utilize aromizing after technology such as the first etherificate, the weight component of the present invention and existing carbon four carbon five carbon six alkane, because this technology adopts aromizing after the dehydrogenation of raw material elder generation, then isolate the processing method that carbon four carbon five carbon six alkane in the product are circulated to dehydrogenation unit, independently dehydrogenation unit is guaranteeing higher olefins yield, receives to increase the higher aromatics yield in aromizing unit and liquid.Aromizing unit process temperature is lower, and low, the non-benzene aromaticity content of the gasoline component olefin(e) centent of production is high, octane value is high and meet present environmental requirement; Diesel component can directly use, and carbon four carbon five carbon six alkane recycle and significantly improved utilization of materials.
Description of drawings
Fig. 1 is for using process flow diagram of the present invention.
Among the figure: 1-catalytic dehydrogenating reaction device, the 2-aromatization reactor, 3-stabilizer tower, 4-take off the liquefied gas tower, 5-carbon three knockout towers, 6-gasoline Cutting Tap, 7-noncondensable gas tripping device.
Tops, oil field light hydrocarbon, the pentane wet goods that uses method of the present invention can be produced from the refinery is rich in carbon four carbon five carbon six alkane, itself can not be as the hydro carbons of gasoline use, upgrading is the gasoline component of low alkene, high non-benzene aromatic hydrocarbons and directly uses diesel component, well improved the added value of raw material.
Embodiment
Below by embodiment in detail the present invention is described in detail.Table 1～table 4 adopts the group composition of raw material for embodiment, wherein raw material A is the circulating water plant of Dushanzi Refinery reforming topped oil, raw material B is circulating water plant of Dushanzi Refinery hydrocracking light naphthar, and raw material C is circulating water plant of Dushanzi Refinery aromatic hydrocarbons pentane oil, and raw material D is Lanzhou Petrochemical ethylene plant petroleum naphtha.Table 5 is that the reaction product of embodiment forms.
Embodiment all adopts as shown in Figure 1 technique, reactor all adopts the 200ml fixed bed reactor, the noncondensable gas tripping device adopts flash tank, embodiment 1～3 is single reactor periodical operation for catalytic dehydrogenating reaction device and aromatization reactor, among the embodiment 4～6, catalytic dehydrogenating reaction device and aromatization reactor are two reactor parallel circulatings and use.Analytic sample is the instantaneous sample of reaction after 10 hours.
Embodiment 1
Dehydrogenation catalyst adopts the Hai Tai HTPB-DH of company dehydrogenation catalyst, wherein with Al
2O
3For carrier take Pt and Cl as active ingredient, wherein the mass content of Pt is 1%, the chlorine mass content is 2%, specific surface area is 200m
2/ g, pore volume 0.5ml/g, diameter are 1.59mm, bulk density 0.6g/cm
3
Aromatized catalyst adopts the method for CN 1586721A catalyzer Preparation Example 3 and adds active ingredient Ni, its concrete preparation process is as follows: adopt Hydrothermal Synthesis to go out grain fineness number less than the former powder of the supersiliceous zeolite of 500nm, 110 ℃ lower dry 3 hours, 550 ℃ of dryings 24 hours.Then according to the Ni (NO of the drying of 80g zeolite 20g aluminum oxide butt and 3.66g
3)
2The powder hand mix is even, uses rare nitric acid kneading of 10% again, then with behind the twin screw extruder extruded moulding 110 ℃ lower dry 3 hours, afterwards 550 ℃ of constant temperature 3 hours.Then with 0.6mo1/L, the liquid-solid volume ratio of exchange be 10, each 1 hour swap time, exchange 5 times, liquid is changed in the centre.Exchange use deionized water wash after finishing, and 110 ℃ lower dry 3 hours, at 550 ℃ of lower constant temperature after 5 hours, the cooling use.
Adopt raw material A, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.1: 1 in the aromatization reactor.So that the reaction conditions of catalytic dehydrogenation is 480 ℃ of temperature of reaction, volume space velocity 0.1h
-1, reaction pressure 3MPa, reaction obtains that olefin(e) centent is 37.1% in the dehydrogenation product.The reaction conditions of aromizing is: 260 ℃ of temperature of reaction, volume space velocity 1.1h
-1, reaction pressure 1.5MPa.0.01% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Embodiment 2
The load 10%MoO that dehydrogenation catalyst adopts fine chemistry industry key lab of Xinjiang University to provide
3γ-Al
2O
3Catalyzer, its preparation process are to take by weighing a certain amount of (NH
4)
6Mo
7O
244H
2Dipping γ-Al after O is dissolved in the hot water
2O
3, stirring is evaporated to dried, and 120 ℃ of lower dry 10h at last at 550 ℃ of lower roasting 4h, make catalyzer.
Aromatized catalyst adopts that Dalian University of Technology provides contains chromium ZSM-5 zeolite molecular sieve catalyst, and its carrier is Al
3O
2, wherein chromium content is 4%, ZSM-5 zeolite molecular sieve content 25%, profile are the cylindrical bars of the long 3mm of diameter 1.5mm, bulk density 0.65g/ml, specific surface area 340m
2/ g, pore volume are 0.25ml/g.
Adopt raw material B, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.5: 1 in the aromatization reactor.The reaction conditions that changes catalytic dehydrogenation is: 520 ℃ of temperature of reaction, volume space velocity 1.0h
-1, reaction pressure 1.5MPa, reaction obtains that olefin(e) centent is 51.6% in the dehydrogenation product.The reaction conditions that changes aromizing is: 380 ℃ of temperature of reaction, volume space velocity 3h
-1, reaction pressure 2.2MPa.50% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Embodiment 3
Dehydrogenation catalyst adopts the method preparation of embodiment 1 among the patent CN 101618319.2.24 gram calcium oxide and 3.1 gram polyoxyethylene glycol are dissolved in the 120ml deionized water, 240 ℃ of hydrothermal treatment consists 24 hours, 600 ℃ of calcinations are after 5 hours, it is mixed with an amount of dehydrated alcohol and 7.2 gram chromium nitrates, 6 gram aluminium sesquioxides, grind after dry 12 hours evenly, for subsequent use after 3 hours 550 ℃ of lower calcinations.
Aromatized catalyst adopts the prosperous grand chemical industry OCTC-02 of the company limited aromatization of gas catalyzer in Zibo.Its main component is the cobalt of 40%ZSM-5 molecular sieve and 6%, and all the other are Al
2O
3, its profile is the cylindrical bars of the long 3mm of diameter 2.5mm, bulk density 0.70g/ml, and ultimate compression strength is 90N/cm.
Adopt raw material C, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.2: 1 in the aromatization reactor.The reaction conditions that changes catalytic dehydrogenation is: 570 ℃ of temperature of reaction, volume space velocity 3.0h
-1, reaction pressure 0.01MPa, reaction obtains that olefin(e) centent is 54.9% in the dehydrogenation product.The reaction conditions that changes aromizing is: 340 ℃ of temperature of reaction, volume space velocity 6h
-1, reaction pressure 5MPa.100% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Embodiment 4
Dehydrogenation catalyst adopts the method preparation of embodiment 4 among the CN101940922A.Its concrete steps are: take by weighing first the chromic oxide of 117.5 grams, be dissolved in the deionized water and fully stir, being mixed with weight concentration is 47% chromic oxide solution.Be 3.86% Alkitrate in the configuration weight concentration.Then with the wilkinite of 55.0 gram pseudo-boehmites, 2.2 grams, the chromic oxide solution for preparing with 7.59 grams fully mixes, and mediates, is extruded into bead.And then 120 ℃ lower dry 3 hours, and then 500 ℃ of constant temperature 3 hours, 620 ℃ of constant temperature 2 hours, at last 760 ℃ of roastings 4 hours under 20% water and 80% air.Get again chromic oxide solution 11.39 gram for preparing, will join burned sample dipping 20 minutes, 120 ℃ of dryings 3 hours, 550 ℃ of constant temperature calcinings 5 hours.Get again the Alkitrate dipping for preparing, 120 ℃ of dryings 3 hours, for subsequent use 620 ℃ of constant temperature calcinings 6 hours.
Aromatized catalyst adopts the method for CN 1586721A catalyzer Preparation Example 3 also to add active ingredient Pr, and its concrete preparation process is as follows: adopt Hydrothermal Synthesis to go out the ZSM-11 zeolite powder, 110 ℃ lower dry 3 hours, 550 ℃ of dryings 24 hours.Then according to the Pr (NO of the drying of 70g zeolite 30g aluminum oxide butt and 20g
3)
2The powder hand mix is even, uses rare nitric acid kneading of 10% again, then with behind the twin screw extruder extruded moulding 110 ℃ lower dry 3 hours, afterwards 550 ℃ of constant temperature 3 hours.Then with 1mol/L, the liquid-solid volume ratio of exchange be 5, each 2 hours swap times, exchange 3 times, liquid is changed in the centre.Exchange use deionized water wash after finishing, and 110 ℃ lower dry 3 hours, at 550 ℃ of lower constant temperature after 5 hours, the cooling use.
Adopt raw material A, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.4: 1 in the aromatization reactor.The reaction conditions that changes catalytic dehydrogenation is: 700 ℃ of temperature of reaction, volume space velocity 5.0h
-1, reaction pressure 0.15MPa, reaction obtains that olefin(e) centent is 64.0% in the dehydrogenation product.The reaction conditions that changes aromizing is: 440 ℃ of temperature of reaction, volume space velocity 0.5h
-1, reaction pressure 5MPa.20% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Embodiment 5
Dehydrogenation catalyst adopts the method preparation of embodiment 9 among the patent CN96121452.X.Take by weighing 17 gram Cr (NO
3)
39H
2O, 1.1 gram Cu (NO
3)
23H
2O, 80.8 gram Al (NO
3)
39H
2O uses the coprecipitation method Kaolinite Preparation of Catalyst, and precipitation agent is selected 10% KOH (or NaOH) solution, nitrate is dissolved in the distilled water, add while stirring precipitation agent, make it be completed into gel, and pH value is 8.5-9, aging 3 hours, filter, under 110 ℃, dry 20 hours, 650 ℃ of roastings 7 hours, for subsequent use behind crushing and screening.
The preparation method of catalyzer C1 among the embodiment 1 among the aromatized catalyst employing patent CN101898150A.Concrete steps are as follows: get 100 gram SiO
2/ Al
2O
3The molecule mol ratio is 65 HZSM-5 molecular sieve, is 6.32 mg/ml phosphoric acid solutions dipping 8 hours with 100 ml concns first, and 110 ℃ of dryings are the LaCl of 3.04 mg/ml with 100 ml concns again after 4 hours
36H
2O solution impregnation 8 hours, so that the content of La in catalyzer is 8wt%, then 110 ℃ of dryings are 4 hours, 550 ℃ of roastings 4 hours are for subsequent use.
Adopt raw material B, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.35: 1 in the aromatization reactor.The reaction conditions that changes catalytic dehydrogenation is: 500 ℃ of temperature of reaction, volume space velocity 8.0h
-1, reaction pressure 0.1MPa, reaction obtains that olefin(e) centent is 35.6% in the dehydrogenation product.The reaction conditions that changes aromizing is: 600 ℃ of temperature of reaction, volume space velocity 4.5h
-1, reaction pressure 3MPa.71% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Embodiment 6
Dehydrogenation catalyst adopts the step Kaolinite Preparation of Catalyst that catalyzer prepares among the embodiment 1 among the patent CN 101623633A.At first the former powder of ZSM-5 molecular sieve is at the SnCl of 0.16M
22H
2In the O solution in 80 ℃ of dipping 10hr, so that the charge capacity of the Sn in the catalyzer reaches 4wt%, and then 120 ℃ of lower dry 6hr.Dried sample is roasting 4hr under 550 ℃ of air atmosphere.Powder after the roasting is at the H of 0.03M
2PtCl
66H
2At 80 ℃ of lower dipping 4hr, make and finally make the catalyzer that Pt content is 20wt% in the O solution, then at 120 ℃ of lower dry 6hr, at 550 ℃ of lower roasting 4hr.For subsequent use at 550 ℃ of hydrogen reducing 12hr afterwards.
Aromatized catalyst adopts the method preparation of aromatized catalyst preparation among the embodiment 1 among the patent CN98101358.9.Concrete preparation process is: with 10gHZSM-5 and Al
2O
3Than being to pour the Zn (NH that concentration is 54 mg/ml in 65: 35 the carrier
3)
4(NO
3)
212 milliliters of the aqueous solution flooded 2 hours.Then use twice, 120 ℃ of drying of deionized water rinsing 6 hours.Then use 8 milliliters of chloride containing mishmetal (industrial goods, packet header, Inner Mongol industrial produces, wherein lanthanum trioxide 31%, oxygen cerium oxide 51%, Praseodymium trioxide 14%, Neodymium trioxide 4%) the aqueous solution at room temperature flooded two hours, 110 ℃ of dryings 16 hours, 540 ℃ of roastings are after 6 hours, 540 ℃ of steam treatment 2 hours.Make rare earth oxide content 0.34wt% in the catalyzer, zinc content 2.1wt%.
Adopt raw material B, the mass ratio that enters hydrogen and the raw material that is rich in carbon four carbon five carbon six alkane in the dehydrogenation reactor with enter that the mass ratio of hydrogen and hydro carbons is 0.13: 1 in the aromatization reactor.The reaction conditions that changes catalytic dehydrogenation is 600 ℃ of temperature of reaction, volume space velocity 10.0h
-1, reaction pressure 1.0MPa, reaction obtains that olefin(e) centent is 44.7% in the dehydrogenation product.The reaction conditions that changes aromizing is: 520 ℃ of temperature of reaction, volume space velocity 8h
-1, reaction pressure 4MPa.3% of carbon four carbon five carbon six alkane recycles in the product.Products therefrom character is listed in table 5.
Comparative Examples 1
Repeat embodiment 1, change in its technological process dehydrogenation unit and do not use, raw material A is directly carried out aromizing, product separation.Products therefrom character is listed in table 5.
Comparative Examples 2:
Repeat embodiment 1, feed change A is raw material D, and products therefrom character is listed in table 5.
Table 1 raw material A forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 3.19 | 5.20 | |||
| C 5 | 14.85 | 15.88 | 9.11 | 0.03 | |
| C 6 | 4.19 | 41.20 | 3.93 | 1.90 | |
| C 7 | 0.05 | 0.09 | 0.06 | ||
| C 8 | 0.16 |
Table 2 raw material B forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Aromatic hydrocarbons |
| C 4 | 5.81 | 8.82 | ||
| C 5 | 0.92 | 50.87 | 14.47 | |
| C 6 | 1.75 | 15.47 | 1.38 | 0.11 |
| C 7 | 0.12 | 0.22 | 0.01 | |
| C 8 | 0.05 |
Table 3 raw material C forms (W%)
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene |
| C 4 | 0.24 | 11.73 | 0.07 | |
| C 5 | 0.32 | 53.16 | 32.36 | 0.86 |
The composition of table 4 raw material D
| Component | Naphthenic hydrocarbon | Branched paraffin | Straight-chain paraffin | Alkene | Aromatic hydrocarbons |
| C 4 | 1.40 | 3.61 | 0.03 | ||
| C 5 | 1.01 | 4.07 | 5.24 | 0.15 | |
| C 6 | 4.91 | 6.86 | 5.96 | 0.29 | 2.57 |
| C 7 | 10.16 | 5.45 | 5.41 | 0.32 | 2.06 |
| C 8 | 9.21 | 5.54 | 4.48 | 0.28 | 2.28 |
| C 9 | 1.18 | 8.38 | 2.63 | 0.13 | 1.29 |
| C 10 | 0.93 | 2.63 | 1.37 | 0.09 |
Reaction effect after the six alkane catalytic dehydrogenations of table 5 carbon four carbon five carbon, the aromizing
Claims (28)
1. technique take the alkane that is rich in carbon four carbon five carbon six as raw material production gasoline, enter to the catalytic dehydrogenating reaction device after it is characterized in that being rich in carbon four carbon five carbon six paraffinic feedstocks and hydrogen mixing, contact with dehydrogenation catalyst and to carry out catalytic dehydrogenating reaction, after dehydrogenation product is isolated noncondensable gas through the noncondensable gas tripping device, be mixed into aromatization reactor with hydrogen, contact with aromatized catalyst and to carry out aromatization, reacted product is divided into dry gas, carbon three, carbon four carbon five carbon six alkane, gasoline component, diesel component by separating; Will be wherein in the product carbon four carbon five carbon, six paraffin sections or all be circulated to dehydrogenation reactor before participate in catalytic dehydrogenating reaction.
2. technique according to claim 1 is characterized in that being rich in the boiling range of raw material 95 % by weight of carbon four carbon five carbon six alkane in 70 ℃.
3. technique according to claim 2 is characterized in that being rich in the boiling range of raw material 95 % by weight of carbon four carbon five carbon six alkane in 60 ℃.
4. technique according to claim 1 is characterized in that being rich in the raw material paraffinicity of carbon four carbon five carbon six alkane more than 90 % by weight.
5. technique according to claim 4 is characterized in that being rich in the raw material paraffinicity of carbon four carbon five carbon six alkane more than 95 % by weight.
6. technique according to claim 1, it is characterized in that the catalytic dehydrogenating reaction condition is: 480～700 ℃, pressure 0.01～3MPa, volume space velocity are 0.1～10h
-1, entering hydrogen in the dehydrogenation reactor is 0.01: 1～1: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane.
7. technique according to claim 6 is characterized in that entering that hydrogen is 0.1: 1～0.5: 1 with the mass ratio that is rich in the raw material of carbon four carbon five carbon six alkane in the dehydrogenation reactor.
8. technique according to claim 1, it is characterized in that the aromatization condition is: 260～600 ℃, pressure 0.5～5.0MPa, volume space velocity are 0.1～10h
-1, enter that the mass ratio of hydrogen and hydro carbons is 0.01: 1～1: 1 in the aromatization reactor.
9. technique according to claim 8 is characterized in that entering that the mass ratio of hydrogen and hydro carbons is 0.1: 1～0.5: 1 in the aromatization reactor.
10. technique according to claim 1 is characterized in that catalytic dehydrogenating reaction device and aromatization reactor are fixed-bed reactor, is respectively the parallel connection of a reactor or a plurality of reactor or series connection.
11. technique according to claim 1 is characterized in that the tripping device with noncondensable gas is connected between catalytic dehydrogenating reaction device and the aromatization reactor.
12. technique according to claim 1 is characterized in that tripping device comprises flash tank, absorption/Analytic Tower, refrigerating unit and/or compression set.
13. technique according to claim 1 is characterized in that dehydrogenation catalyst is comprised of carrier and active ingredient, active ingredient contains in VIB, VIII, IA, the IIA element at least a, and the content of active ingredient is 0.1%～20% of catalyst weight.
14. technique according to claim 1 is characterized in that dehydrogenation catalyst is the multi-metal-oxide catalyst that coprecipitation method makes, active metal component contains in VIIB, VIII, IA, the IIA family at least a.
15. technique according to claim 13, the carrier that it is characterized in that dehydrogenation catalyst is TiO
2, Al
2O
3, SiO
2, one or several the mixture among the ZnO.
16. technique according to claim 13, the carrier that it is characterized in that dehydrogenation catalyst is the mixture of molecular sieve or molecular sieve and high-temperature inorganic oxide.
17. technique according to claim 13 is characterized in that active ingredient is one or several among Na, Zn, Rb, Cs, Mg, Sr, Pt, Ba, Re, Mn, Cl, F, the Br.
18. technique according to claim 16, it is characterized in that molecular sieve is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve, two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
19. technique according to claim 1 is characterized in that aromatized catalyst contains molecular sieve and one or more active ingredients, active ingredient weight is 0.01～8%.
20. technique according to claim 1 is characterized in that aromatized catalyst contains high-temperature inorganic oxide and molecular sieve supported one or more active ingredients.
21. technique according to claim 20 is characterized in that high-temperature inorganic oxide is TiO in the aromatized catalyst
2, Al
2O
3, SiO
2, one or several the mixture among the ZnO.
22. according to claim 19 or 20 described techniques, it is characterized in that the molecular sieve in the aromatized catalyst is micropore, mesoporous or/and the mixing of one or several in the mesoporous molecular sieve.
23. technique according to claim 22, it is characterized in that molecular sieve in the aromatized catalyst is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, the aluminium silicophosphate molecular sieve, two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
24. according to claim 19 or 20 described techniques, it is characterized in that active ingredient in the aromatized catalyst is one or several in rare earth element, IIIB, VIB, VIIB, VIII, the IIB family element.
25. technique according to claim 24 is characterized in that active ingredient in the aromatized catalyst is one or more among La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, the Pt.
26. technique according to claim 25 is characterized in that active ingredient in the aromatized catalyst is one or more among La, Pr, Ni, Co, the Cr.
27. technique according to claim 1 is characterized in that the ratio that cyclic part accounts for carbon four carbon five alkane carbon six hydrocarbon product is 0.01 quality %～100 quality %.
28. technique according to claim 1 is characterized in that the ratio that cyclic part accounts for carbon four carbon five alkane carbon six hydrocarbon product is 25 quality %～85 quality %.
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