CN103361113B - A kind of technique with being rich in carbon four carbon five carbon six paraffinic feedstock production stop bracket gasoline - Google Patents
A kind of technique with being rich in carbon four carbon five carbon six paraffinic feedstock production stop bracket gasoline Download PDFInfo
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Abstract
A kind of technique of producing high octane gasoline component, be rich in carbon four carbon five carbon six alkane to mix with hydrogen and be introduced into after the reactor that dehydrogenation catalyst is housed carries out dehydrating alkanes reaction, after dehydrogenation product mixes with the raw material being rich in alkene after noncondensable gas tripping device, enter aromatized catalyst is housed reactor in carry out aromizing, generate the high octane gasoline component that low benzene is rich in aromatic hydrocarbons.In gasoline after upgrading, non-benzene aromaticity content is high, and benzene content is very low, and olefin(e) centent is low.
Description
Technical field
The invention provides a kind of can by refinery C four carbon five carbon six alkanes through catalytic dehydrogenation, mix with the raw material being rich in alkene the technique that the steps such as aromizing produce stop bracket gasoline.
Background technology
Along with the develop rapidly of Chinese national economy, the continuous increase of automobile pollution, increasing to the demand of vehicle fuel gasoline.Meanwhile, also along with increasingly strict to gasoline quality standard of environmental requirement, motor spirit quality standard is to low sulfur content, low olefin-content, low-steam pressure and high-octane future development.Market is to volume increase premium-type gasoline and have very big demand 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.
Enter 12, along with the propelling of the projects such as CNPC's Guangdong petrochemical industry 2,000 ten thousand tons/year oil refining, the oil refining of 1,000 ten thousand tons/year, Kunming, Sichuan petrochemical industry Integrated Refinery And Petrochemical engineering, Fushun petrochemical industry 800,000 tons/year of ethene, Daqing petrochemical 1,200,000 tons/year of expansion of ethylene, oil-refining capacity and the ethene production capacity of CNPC also will expand further, the C of refinery's by-product
4/ C
5/ C
6alkane (as reforming topped oil, oil field light hydrocarbon, pentane wet goods), catalytic cracking C
4with cracking C
4the output of resource is also significantly increasing.C
4/ C
5/ C
6alkane is not high because of itself octane value, can not, directly as motor spirit, need to process upgrading further.C
4resource is except part is for the production of except MTBE, alkylate oil, polymerization single polymerization monomer, and major part is burnt as domestic fuel.And C
4hydrocarbon and tops are not only cheap, and transportation cost is high, in transportation loss large, concerning this refinery, belong to low-value product.
CN93102129 discloses inferior patrol catalytic reforming-aromatization method.Thick pressure gasoline is catalytic reforming under conditions of non-hydrogen first, and then carries out aromizing on Zn-Al or Zn-AL ~ rare earth HZSM-5, and temperature is 480 DEG C ~ 650 DEG C, 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 regenerate once for 15 days, therefore, need two aromatization reactor blocked operations.
Publication number is a kind of method that CN1488724A patent discloses gasoline hydrofinishing-aromizing.The catalytically cracked gasoline the first step is 220 DEG C ~ 300 DEG C in temperature, and pressure is 2.0MPa ~ 10.0MPa, volume space velocity 2.0 ~ 10.0h
-1with under the condition of hydrogen to oil volume ratio 200 ~ 800: 1, hydrofining removes sulfide in gasoline and olefin(e) compound.Second step is 350 DEG C ~ 450 DEG C in temperature, and pressure is 1.5MPa ~ 4.5MPa, volume space velocity 0.5 ~ 3.0h
-1with under the condition of hydrogen to oil volume ratio 200 ~ 800: 1.Adopt the hydrogen type molecular sieve of little grain fineness number, by light-hydrocarbon aromatized be aromatic hydrocarbons, to recover the explosion-proof exponential sum octane value of first stage.Although this technology reaches the effect of desulfurating and reducing olefinic hydrocarbon, the explosion-proof index loss of octane number of gasoline is all about 2%, and gasoline loss rate is about 10%.
Publication number be CN1580199A patent discloses a kind of technique by etherificate and aromatization reformulated gasoline.Gasoline is first cut into weight two portions by this technology, in light constituent containing 1 ~ 20% carbon four, 60 ~ 80% carbon five, no more than 20% carbon more than six, carbon less than six component no more than 30% in heavy constituent.Alkene in light constituent and alcohols carry out etherification reaction, and heavy constituent is entered reactor and carried out aromatization together with hydrogen, and then by component blending, effectively can improve the octane value of gasoline.
EP256604A2 discloses a kind of C
5~ C
7the method of straight chain alkane isomerization, containing C
5~ C
7raw material be divided into weight two cuts, enter isomerization reactor from a segmentation after lighting end mixes with hydrogen, the middle part from isomerization reactor after last running mixes with hydrogen enters reaction, and reactor upper end temperature of reaction is low, and lower end temperature of reaction is high.The catalyzer that this method uses is the catalyzer containing mordenite or y-type zeolite.
CN200410004475 discloses a kind of C
5, C
6isomerized method.The method by raw material rectifying separation, by C
5light constituent and C
6heavy constituent is aromizing under different processing condition respectively.
CN1073198A discloses a kind of dehydroaromatizationof dual-function catalyst preparation method utilizing macropore L alkaline 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 CN86107521A introduce that Pt-L zeolite introduces Ba, sylvite, basic metal carry out modification L zeolite, to overcome this weakness of less stable in dehydroaromatizationof of alkane reaction.
CN101993320A discloses a kind of method of producing light aromatics, comprises with mixed c 4 and C
9+ heavy arene is raw material, under conditions of non-hydrogen with aromatized catalyst 400 ~ 600 DEG C of abundant contact reactss.The method except except raising light aromatics yield by a relatively large margin, can reducing dry gas yield, for refinery provides the approach of cost-effective processing residue lighter hydrocarbons and heavy arene resource.
CN101747933A discloses a kind of petroleum naphtha and light-hydrocarbon aromatized method for modifying, comprises petroleum naphtha and C
3~ C
5lighter hydrocarbons contact with aromatized catalyst under the existence of hydrogen-containing gas and carry out aromatization modification reaction, described upgrading temperature of reaction is 250 ~ 600 DEG C, the volume ratio of hydrogen and petroleum naphtha is 20 ~ 400.
CN101538184 discloses a kind of method for aromatizing light hydrocarbons, comprises C
3~ C
12hydro carbons 250 ~ 650 DEG C, produce aromatic hydrocarbons and liquefied gas with aromatized catalyst contact reacts under the condition of 0.1 ~ 4.0MPa, described aromatized catalyst comprises complex carrier and content is following in the catalyst component: ZnO0.5 ~ 5.0 quality %; Rare earth oxide 0.1 ~ 5.0 quality %; VA race element 1.0 ~ 7.0 quality %.Described complex carrier comprises the ZSM series zeolite of 20 ~ 50 quality % and the binding agent of 50 ~ 80 quality %.This method is applicable to carry out with the reaction-renovation process of moving-bed.
CN101429452 provides a kind of catalytically cracked gasoline and C
4mixing raw material carries out with catalyst exposure the method that aromatization produces stop bracket gasoline on aromatization reactor, catalytically cracked gasoline and C
4olefin, enters fixed bed or simulation moving-bed aromatization reactor that molecular sieve catalyst is housed, contacts with aromatized catalyst, carry out alkene aromatization, its reaction conditions: temperature of reaction 250 ~ 340 DEG C, pressure 0.5 ~ 3.0MPa, weight space velocity is 0.5 ~ 10h
-1, C
4the mass ratio of alkene and catalytically cracked gasoline is 90: 10 ~ 2: 98; The carrier molecule sieve active ingredient of catalyzer is one or more in rare earth element, VIB, group VIII element, and active ingredient weight is 0.01 ~ 10% of carrier; Can significantly reduce feed gasoline olefin(e) centent, effectively improve octane value, reach the object of producing clean gasoline with high octane.
As mentioned above, the modification technology of existing carbon four carbon five carbon six alkane, is combined with aromizing by isomerization, aromizing, etherificate, technology realizes with aromizing is combined etc. in hydrogenating desulfurization.Isomerization technique makes catalyzer owing to adopting hydrofluoric acid and the vitriol oil, produces a large amount of diluted acid, serious environment pollution.Because carbon four carbon five carbon six alkane direct technology of aromatization temperature of reaction 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, aromatization technology is just in the loss making up octane value in hydrogenation, etherification procedure.
Contriver through thinking above, C
4/ C
5/ C
6in alkane transformation of the way technology, mainly undertaken by isomerization of paraffins and aromizing, but receive lower and had a strong impact on economic benefit due to severe reaction conditions, liquid.In gasoline, comparatively alkane is high for alkene octane value, but poor stability, and environmental protection standard requires more and more stricter to it, but in polymerization, cyclisation, alkylation, aromizing etc. are reacted, compare alkane reaction temperature low for alkene.Aromatization realizes mainly through many reactions steps such as cracking, oligomerisation, dehydrogenation, cyclisation, alkylation, de-alkyl.In alkene aromatization, the low generation well suppressing the reactions such as cracking, dehydrogenation, de-alkyl while ensureing olefin conversion of temperature of reaction, significantly will lower C
1~ C
4etc. low-carbon hydrocarbon generation quantity, improve gasoline yield.After providing the dehydrogenation of relatively high olefin(e) centent, after intermediate product and aromizing, high-carbon more than five liquid is received and aromatics yield is technology emphasis of the present invention.
Summary of the invention
The object of the present invention is to provide a kind of by refinery's low octane rating, low value-added be rich in carbon four carbon five carbon six alkane, through catalytic dehydrogenation, mix the technique of aromizing production high octane gasoline component with the raw material being rich in alkene.
The present invention relates to a kind of with being rich in the paraffinic feedstock of carbon four carbon five carbon six, being rich in the method for the raw material production gasoline of alkene, the present invention is characterised in that first will be rich in the raw material of carbon four carbon five carbon six alkane, is fed through dehydrogenation reactor and contacts with dehydrogenation catalyst as reforming topped oil, oil field light hydrocarbon, pentane wet goods and hydrogen mix and carry out catalytic dehydrogenating reaction.Catalytic dehydrogenation product is through noncondensable gas tripping device, after isolating noncondensable gas be rich in the raw material of alkene, after hydrogen mixes, enter aromatization reactor to contact with aromatized catalyst and carry out aromatization, reacted product, by being separated, can be divided into dry gas, liquefied gas, gasoline component and diesel component.
The raw material being rich in carbon four carbon five carbon six alkane in the present invention refers to the hydro carbons being main ingredient with carbon four carbon five carbon six alkane of refinery's institute's by-product in process of production, as carbon four carbon five carbon six hydro carbons etc. that tops, coking light naphthar, oil field light hydrocarbon, pentane oil and other device reclaim, the content of general paraffinic hydrocarbons, more than 90%, is preferably 95%.The boiling range of raw material 95%, below 70 DEG C, preferably below 60 DEG C, can be same raw material, also can be different material mixing.Below be all weight percentage.
In the present invention, the raw material being rich in alkene of indication refers to that alkene content is more than 35%, preferably more than 45%, the boiling range of raw material 95% is within 75 DEG C, and preferably hydro carbons within 65 DEG C, as carbon after ether four, catalytically cracked C four, cracking c_4, catalytic light gasoline etc.
The raw material being rich in alkene in the present invention and the mass ratio being rich in carbon four carbon five carbon six alkane are 0.01: 1 ~ 100: 1.
Enter hydrogen in dehydrogenation reactor in the present invention and be 0.01: 1 ~ 1: 1 with the mass ratio of raw material and the mass ratio that enters hydrogen and hydro carbons in aromatization reactor being rich in carbon four carbon five carbon six alkane, be preferably 0.1: 1 ~ 0.5: 1.
Be not particularly limited dehydrogenation catalyst in the present invention, be rich in after carbon four carbon five carbon six paraffinic feedstock enters catalytic dehydrogenating reaction device after preheating, in catalytic dehydrogenation product, olefin(e) centent is preferably not less than 35%.Dehydrogenation catalyst is preferably made up of carrier and active ingredient, and catalyzer is preferably carrier with high-temperature inorganic oxide, as being TiO
2, Al
2o
3, SiO
2, one or several mixing among ZnO, also can be molecular sieve or molecular sieve and the mixing of above several high-temperature inorganic oxide.Preferably containing at least one metal in VIB, VIII, IA, IIA race is active ingredient, 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 composite 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, 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 not specified per-cent of the present invention is % by weight.
In the present invention, the reaction conditions of catalytic dehydrogenating reaction is preferably: 480 ~ 700 DEG C, pressure 0.01 ~ 3MPa, and liquid volume air speed is 0.1 ~ 10h
-1.The not specified air speed of the present invention is liquid volume air speed.
Be not particularly limited aromatized catalyst in the present invention, catalyzer is preferably containing molecular sieve and one or more active ingredients.Molecular sieve can be specifically 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 molecular sieve, two or more molecular sieve can be composite molecular screen or eutectic molecular sieve.Large pore molecular sieve is also not suitable for aromatization of the present invention, and this is that the feature of raw material causes, dehydrogenation intermediate product liquid after this catalytic unit receive 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 mixing among ZnO.The active ingredient supported can be one or several in rare earth element, IIIB, VIB, VIIB, VIII, IIB race element, as being La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, Pt etc., and preferably La, Pr, Ni, Co, Cr; The active ingredient weight supported is 0.01 ~ 8%.Catalyst shape can be bead, also can be strip.
In the present invention, the reaction conditions of aromatization is preferably: 260 ~ 600 DEG C, pressure 0.5 ~ 5.0MPa, and volume space velocity is 0.1 ~ 10h
-1.
Naphthene content and should be less than 10% in raw material, is preferably less than 5%.It is that the conversion of such raw material aromizing unit after dehydrogenation is limited that the raw material of such substances content more than 10% is not suitable for reason of the present invention, affects the quality of gasoline component in the present invention.
The flow process of petroleum naphtha etc. 95% more than 75 DEG C not within raw material range of the present invention, owing to crossing the C of aromizing product after heavy constituent dehydrogenation
5above and aromatics yield, also greatly shorten the work-ing life of aromatized catalyst simultaneously, cost of the present invention can be increased undoubtedly.
Olefin(e) centent in dehydrogenation product and the olefin(e) centent be rich in olefin feedstock are generally greater than 35%, more preferably greater than 45%.Olefin(e) centent is too low will cause the too low and C of aromaticity content in aromizing unit product
5liquid is received not high, will affect the economic performance of present invention process.
In addition, in order to adapt to the change of pressure between present invention process dehydrogenation unit and aromizing unit and realize mass transfer, between Ying Liangge district, add the tripping device of noncondensable gas, as flash tank, absorption/Analytic Tower, refrigerating unit and compression set etc.
The catalytic dehydrogenating reaction device related in the present invention, aromatization reactor are fixed-bed reactor, can be that a reactor is used alone, realized by reaction-catalyst regeneration two process intervals, also two or more reactor parallel connection use can carry out cyclical operation, the parallel connection of multiple reactor and series combination can also be divided to use.When the catalyzer in one or several reactor is due to carbon distribution serious inactivation, by switching material import and export, decaying catalyst regeneration Posterior circle uses, the continuous operation of realization response, regeneration system rapidly.
Method of the present invention can be more specifically: the raw material and the hydrogen that first make to be rich in carbon four carbon five carbon six alkane are blended in 480 ~ 600 DEG C, pressure 0.01 ~ 3.0MPa, and volume space velocity is 0.1 ~ 10h
-1under carry out catalytic dehydrogenating reaction, to make in dehydrogenation product olefin(e) centent more than 45%, then dehydrogenation product after noncondensable gas tripping device be rich in the raw material of alkene, hydrogen mixes, then at 260 ~ 560 DEG C, pressure 0.5 ~ 5.0MPa, volume space velocity is 0.1 ~ 8h
-1under carry out aromizing, make liquid product yield more than 43% in aromatization products, high octane gasoline component yield more than 40%.
Aromizing, dehydrogenation etherificate dual-function catalyst technology are different respectively for utilize technology such as aromizing, the weight component after first etherificate of the present invention and existing carbon four carbon five carbon six alkane, because this technology adopts first for raw material dehydrogenation, mixes rear aromizing with the raw material being rich in alkene, independently dehydrogenation unit can ensure higher olefins yield, receives with the aromatics yield and carbon more than five liquid that improve aromizing unit.Aromizing unit process temperature is lower, well inhibits the generation of dry gas and propane, diesel component, improves the yield of gasoline component.
Accompanying drawing explanation
Fig. 1 is application process flow diagram of the present invention.
In figure: 1-catalytic dehydrogenating reaction device, 2-aromatization reactor, 3-separation system, 4-noncondensable gas tripping device.
The hydro carbons that the raw material being rich in alkene using method of the present invention can be produced from refinery and tops, oil field light hydrocarbon, pentane wet goods are rich in carbon four carbon five carbon six alkane, itself can not use as gasoline, upgrading is low olefin-content, the gasoline component of high non-benzene aromaticity content and diesel component, well improves the added value of raw material.
Embodiment
Below by embodiment in detail the present invention is described in detail.Table 1 ~ table 6 adopts by embodiment the character of raw material, and table 7 is the character of reaction product.Wherein raw material A is circulating water plant of Dushanzi Refinery reforming topped oil, raw material B is circulating water plant of Dushanzi Refinery hydrocracking light naphthar, raw material C is circulating water plant of Dushanzi Refinery aromatic hydrocarbons pentane oil, raw material D is Lanzhou Petrochemical Company catalysis workshop mixed c 4, raw material E is that Daqing Refinery company one heavily urges mixed c 4, and raw material F is Lanzhou Petrochemical ethylene plant petroleum naphtha.
Embodiment all adopts technique as shown in Figure 1, and reactor all adopts 200ml fixed bed reactor.The tripping device of noncondensable gas is flash tank, and embodiment 1 ~ 3 is single reactor periodical operation for catalytic dehydrogenating reaction device and aromatization reactor, and in 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 Haitai company HTPB-DH dehydrogenation catalyst, wherein with Al
2o
3for carrier with Pt and Cl for active ingredient, wherein the mass content of Pt is 1%, and chlorine mass content is 2%, and specific surface area is 200m
2/ g, pore volume 0.5ml/g, diameter is 1.59mm, bulk density 0.6g/cm
3.
Aromatized catalyst adopts the method for CN1586721A Catalyst Preparation Example 3 and adds active ingredient Ni, its concrete preparation process is as follows: employing Hydrothermal Synthesis goes out the former powder of supersiliceous zeolite that grain fineness number is less than 500nm, at 110 DEG C dry 3 hours, 550 DEG C of dryings 24 hours.Then according to the Ni (NO of the drying of 80g zeolite 20g aluminum oxide butt and 3.66g
3)
2powder hand mix is even, then uses the dust technology kneading of 10%, then to use after twin screw extruder extruded moulding at 110 DEG C dry 3 hours, after 550 DEG C of constant temperature 3 hours.Then with 0.6mol/L, exchange that liquid-solid volume ratio is 10, each 1 hour swap time, exchange 5 times, liquid is changed in centre.With deionized water wash after exchange completes, and at 110 DEG C dry 3 hours, at 550 DEG C, constant temperature is after 5 hours, and cooling uses.
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material A, and entering hydrogen in dehydrogenation reactor is 0.25: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane, temperature of reaction 480 DEG C, and volume space velocity 0.1h
-1, catalytic dehydrogenation under the condition of reaction pressure 0.01MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 37.1%.The mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.25: 1, and the raw material being rich in alkene adopts raw material D, and raw material D is 0.01: 1 with the ratio being rich in carbon four carbon five carbon six paraffinic feedstock.The reaction conditions of aromizing is: temperature of reaction 340 DEG C, volume space velocity 0.8h
-1, reaction pressure 1.8MPa, acquired results lists in table 7.
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 takes a certain amount of (NH
4)
6mo
7o
244H
2o is dissolved in after in hot water and floods γ-Al
2o
3, stirring is evaporated to dry, dry 10h at 120 DEG C, finally roasting 4h at 550 DEG C, obtained catalyzer.
What aromatized catalyst adopted Dalian University of Technology to provide 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%, and profile is the cylindrical bars of the long 3mm of diameter 1.5mm, bulk density 0.65g/ml, specific surface area 340m
2/ g, pore volume is 0.25ml/g.
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material B, and it is 0.1: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane that change enters hydrogen in dehydrogenation reactor, and the processing condition of catalytic dehydrogenation are temperature of reaction 700 DEG C, volume space velocity 1.0h
-1, reaction pressure 0.15MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 51.6%.Changing the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.1: 1, and the raw material being rich in alkene adopts raw material D, and raw material D and the ratio being rich in carbon four carbon five carbon six paraffinic feedstock are 0.3: 1.The processing condition changing aromizing are temperature of reaction 380 DEG C, volume space velocity 0.1h
-1, reaction pressure 2.2MPa.Experimental results lists in table 7.
Embodiment 3
Dehydrogenation catalyst adopts the method preparation of embodiment 1 in patent CN101618319.2.24 grams of calcium oxide and 3.1 grams of polyoxyethylene glycol are dissolved in 120ml deionized water, 240 DEG C of hydrothermal treatment consists 24 hours, 600 DEG C of calcinations are after 5 hours, it is mixed with 7.2 grams of chromium nitrates, 6 grams of aluminium sesquioxides with appropriate dehydrated alcohol, after dry 12 hours, evenly, at 550 DEG C, calcination is for subsequent use after 3 hours in grinding.
Aromatized catalyst adopts Zibo Xin Hong Chemical Co., Ltd. OCTC-02 aromatization of gas catalyzer.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.
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material C, and it is temperature of reaction 570 DEG C that change enters the reaction conditions that in dehydrogenation reactor, hydrogen and the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane are 0.5: 1 catalytic dehydrogenation, volume space velocity 3.0h
-1, reaction pressure 1.7MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 54.9%.Changing the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.5: 1, and the raw material being rich in alkene adopts raw material D, and raw material D and the ratio being rich in carbon four carbon five carbon six paraffinic feedstock are 25: 1.The reaction conditions changing aromizing is: temperature of reaction 600 DEG C, volume space velocity 5h
-1, reaction pressure 2.8MPa.Acquired results lists in table 7.
Embodiment 4
Dehydrogenation catalyst adopts the method preparation of embodiment 4 in CN101940922A.Its concrete steps are: the chromic oxide first taking 117.5 grams, is dissolved in deionized water and fully stirs, and being mixed with weight concentration is 47% chromic oxide solution.Configuration weight concentration be the Alkitrate of 3.86%.Then by 55.0 grams of pseudo-boehmites, 2.2 grams of wilkinites, the chromic oxide solution prepared with 7.59 grams fully mixes, and mediates, is extruded into bead.And then at 120 DEG C dry 3 hours, and then 500 DEG C of constant temperature 3 hours, 620 DEG C of constant temperature 2 hours, finally 760 DEG C of roastings 4 hours under 20% water and 80% air.Getting the chromic oxide solution 11.39 grams prepared again, flooding 20 minutes by joining burned sample, 120 DEG C of dryings 3 hours, 550 DEG C of constant temperature calcinings 5 hours.Get the Alkitrate dipping prepared again, 120 DEG C of dryings 3 hours, for subsequent use 620 DEG C of constant temperature calcinings 6 hours.
Aromatized catalyst adopts the method for CN1586721A Catalyst Preparation Example 3 and adds active ingredient Pr, and its concrete preparation process is as follows: adopt Hydrothermal Synthesis to go out ZSM-11 zeolite powder, at 110 DEG C dry 3 hours, 550 DEG C of dryings 24 hours.Then according to the Pr (NO of the drying of 70g zeolite 30g aluminum oxide butt and 7g
3)
2powder hand mix is even, then uses the dust technology kneading of 10%, then to use after twin screw extruder extruded moulding at 110 DEG C dry 3 hours, after 550 DEG C of constant temperature 3 hours.Then with 1mol/L, exchange that liquid-solid volume ratio is 5, each 2 hours swap times, exchange 3 times, liquid is changed in centre.With deionized water wash after exchange completes, and at 110 DEG C dry 3 hours, at 550 DEG C, constant temperature is after 5 hours, and cooling uses.
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material A, and it is temperature of reaction 600 DEG C that change enters the reaction conditions that in dehydrogenation reactor, hydrogen and the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane are 0.3: 1 catalytic dehydrogenation, volume space velocity 5.0h
-1, reaction pressure 1.1MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 64.0%.Changing the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.3: 1, and the raw material being rich in alkene adopts raw material E, and raw material E and the ratio being rich in carbon four carbon five carbon six paraffinic feedstock are 60: 1.The reaction conditions changing aromizing is: temperature of reaction 260 DEG C, volume space velocity 8h
-1, reaction pressure 4.1MPa.Acquired results lists in table 7.
Embodiment 5
Dehydrogenation catalyst adopts the method preparation of embodiment 9 in patent CN96121452.X.Take 17 grams of Cr (NO
3)
3.9H
2o, 1.1 grams of Cu (NO
3)
23H
2o, 80.8 grams of Al (NO
3)
3.9H
2o, uses coprecipitation method Kaolinite Preparation of Catalyst, and KOH (or NaOH) solution of 10% selected by precipitation agent, nitrate is dissolved in distilled water, add precipitation agent while stirring, make it be fully formed gel, and pH value is 8.5 ~ 9, aging 3 hours, filter, at 110 DEG C, dry 20 hours, 650 DEG C of roastings 7 hours, for subsequent use after crushing and screening.
Aromatized catalyst adopts the preparation method of catalyzer C1 in embodiment 1 in patent CN101898150A.Concrete steps are as follows: get 100 grams of SiO
2/ Al
2o
3molecule mol ratio is the HZSM-5 molecular sieve of 65, is first that 6.32 mg/ml phosphoric acid solutions flood 8 hours with 100 ml concns, and 110 DEG C of dryings are after 4 hours, then is the LaCl of 3.04 mg/ml with 100 ml concns
3.
6h
2o solution impregnation 8 hours, makes La content in the catalyst be 8wt%, then 110 DEG C of dryings 4 hours, and 550 DEG C of roastings 4 hours are for subsequent use.
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material B, and it is 0.15: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane that change enters hydrogen in dehydrogenation reactor, and the reaction conditions of catalytic dehydrogenation is temperature of reaction 650 DEG C, volume space velocity 8.0h
-1, reaction pressure 2.4MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 35.6%.Changing the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.15: 1, and the raw material being rich in alkene adopts raw material E, and raw material E and the ratio being rich in carbon four carbon five carbon six paraffinic feedstock are 100: 1.The reaction conditions changing aromizing is: temperature of reaction 400 DEG C, volume space velocity 1.5h
-1, reaction pressure 5.0MPa.Acquired results lists in table 7.
Embodiment 6
Dehydrogenation catalyst adopts the step Kaolinite Preparation of Catalyst of catalyst preparing in embodiment 1 in patent CN101623633A.First the former powder of ZSM-5 molecular sieve is at the SnCl of carrier at 0.16M
22H
2in 80 DEG C of dipping 10hr in O solution, the charge capacity of the Sn in catalyzer is made to reach 4wt%, and then dry 6hr at 120 DEG C.Dried sample is roasting 4hr under 550 DEG C of air atmosphere.Powder after roasting is at the H of 0.03M
2ptCl
66H
2at 80 DEG C, flood 4hr in O solution, make finally to obtain the catalyzer that Pt content is 20wt%, then dry 6hr at 120 DEG C, roasting 4hr at 550 DEG C.After for subsequent use at 550 DEG C of hydrogen reducing 12hr.
Aromatized catalyst adopts the method preparation that in patent CN98101358.9, in embodiment 1 prepared by aromatized catalyst.Concrete preparation process is: by 10gHZSM-5 and Al
2o
3than be 65: 35 carrier in pour the Zn (NH that concentration is 54 mg/ml into
3)
4(NO
3)
2the aqueous solution 12 milliliters, floods 2 hours.Then deionized water rinsing twice is used, 120 DEG C of dryings 6 hours.Then 8 milliliters of chloride containing mishmetal (industrial goods are used, 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 flood two hours, 110 DEG C of dryings 16 hours, 540 DEG C of roastings are after 6 hours, 540 DEG C of steam treatment 2 hours.Make rare earth oxide content 0.34wt%, Zn content 2.1wt% in catalyzer
The raw material being rich in carbon four carbon five carbon six alkane adopts raw material C, and it is temperature of reaction 550 DEG C that change enters the reaction conditions that in dehydrogenation reactor, hydrogen and the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane are 0.5: 1 catalytic dehydrogenation, volume space velocity 10.0h
-1, reaction pressure 3.0MPa, being obtained by reacting olefin(e) centent in dehydrogenation product is 44.7%.Changing the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.5: 1, and the raw material being rich in alkene adopts raw material E, and the ratio of raw material E and carbon four carbon five carbon six raw material is 1: 1.The reaction conditions of aromizing is temperature of reaction 560 DEG C, volume space velocity 3.5h
-1, reaction pressure 0.5MPa.Acquired results lists in table 7.
Comparative example 1:
Repeat embodiment 1, change dehydrogenation unit in its technological process and do not use, raw material A and D are directly carried out aromizing, product separation.Products therefrom character lists in table 7.
Comparative example 2:
Repeat embodiment 1, feed change A is raw material F, and products therefrom character lists in table 7.
Table 1 raw material A composition (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 | Alkene | 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 | Aromatic hydrocarbons |
| C 4 | 0.24 | 11.73 | 0.07 | ||
| C 5 | 0.32 | 53.16 | 32.36 | 0.86 |
Table 4 raw material D forms (W%)
| Component | ω％ | Component | ω％ |
| Propane | 0.04 | Iso-butylene | 17.11 |
| Propylene | 0.01 | Cis-butene-2 | 12.51 |
| Trimethylmethane | 29.50 | Iso-pentane | 0.66 |
| Normal butane | 9.16 | 1,3-butadiene | 0.09 |
| Trans-butene-2 | 17.51 | 2-methyl-2-butene | 0.01 |
| 1-butylene | 13.39 | 1-amylene | 0.01 |
Table 5 raw material E forms
| Component | ω％ | Component | ω％ |
| Propane | 0.00 | Iso-butylene | 12.45 |
| Propylene | 0.00 | Cis-butene-2 | 12.79 |
| Trimethylmethane | 34.29 | Iso-pentane | 0.06 |
| Normal butane | 10.38 | 1,3-butadiene | 0.07 |
| Trans-butene-2 | 17.33 | 2-methyl-2-butene | 0.02 |
| 1-butylene | 12.63 | 1-amylene | 0.04 |
The composition of table 6 raw material F
| 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 catalytic dehydrogenation of table 7 carbon four carbon five carbon six alkane, aromizing
Claims (29)
1., by the technique of raw material production gasoline being rich in carbon four carbon five carbon six alkane, it is characterized in that first the raw material being rich in carbon four carbon five carbon six alkane and hydrogen being mixed and be fed through dehydrogenation reactor and contact with dehydrogenation catalyst and carry out catalytic dehydrogenating reaction; Catalytic dehydrogenation product through noncondensable gas tripping device, after isolating noncondensable gas be rich in the raw material of alkene, after hydrogen mixes, enter aromatization reactor and contact with aromatized catalyst and carry out aromatization; Reacted product, by being separated, is divided into dry gas, liquefied gas, gasoline component and diesel component.
2. technique according to claim 1, is characterized in that the boiling range of the raw material 95 % by weight being rich in carbon four carbon five carbon six alkane is below 70 DEG C.
3. technique according to claim 2, is characterized in that the boiling range of the raw material 95 % by weight being rich in carbon four carbon five carbon six alkane is below 60 DEG C.
4. technique according to claim 1, is characterized in that the feed paraffins content being rich in carbon four carbon five carbon six alkane is more than 90 % by weight.
5. technique according to claim 4, is characterized in that the feed paraffins content being rich in carbon four carbon five carbon six alkane is more than 95 % by weight.
6. technique according to claim 1, it is characterized in that catalytic dehydrogenating reaction condition is: 480 ~ 700 DEG C, pressure 0.01 ~ 3MPa, volume space velocity is 0.1 ~ 10h
-1, entering hydrogen in dehydrogenation reactor is 0.01: 1 ~ 1: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane.
7. technique according to claim 1, the raw material that it is characterized in that being rich in alkene refers to carbon four, catalytically cracked C four and/or cracking c_4 after the light FCC gasoline of olefin(e) centent more than 35%, ether.
8. technique according to claim 7, the raw material that it is characterized in that being rich in alkene refers to carbon four, catalytically cracked C four and/or cracking c_4 after the light FCC gasoline of olefin(e) centent more than 45%, ether.
9. technique according to claim 1, is characterized in that the raw material being rich in alkene is 0.01: 1 ~ 100: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane.
10. technique according to claim 6, it is characterized in that entering hydrogen in dehydrogenation reactor is 0.1: 1 ~ 0.5: 1 with the mass ratio of the raw material being rich in carbon four carbon five carbon six alkane.
11. techniques according to claim 1, it is characterized in that aromatization condition is: 260 ~ 600 DEG C, pressure 0.5 ~ 5.0MPa, volume space velocity is 0.1 ~ 10h
-1, the mass ratio entering hydrogen and hydro carbons in aromatization reactor is 0.01: 1 ~ 1: 1.
12. techniques according to claim 11, the mass ratio that it is characterized in that entering hydrogen and hydro carbons in aromatization reactor is 0.1: 1 ~ 0.5: 1.
13. techniques according to claim 1, is characterized in that catalytic dehydrogenating reaction device and aromatization reactor are fixed-bed reactor, are respectively a reactor or the parallel connection of multiple reactor or connect.
14. techniques according to claim 1, is characterized in that catalytic dehydrogenating reaction device is connected with the tripping device with noncondensable gas between aromatization reactor.
15. techniques according to claim 1, is characterized in that tripping device comprises flash tank, absorption/Analytic Tower, refrigerating unit and/or compression set.
16. techniques according to claim 1, is characterized in that dehydrogenation catalyst is made up of carrier and active ingredient, and active ingredient is containing at least one in VIB, VIII, IA, IIA element, and the content of active ingredient is 0.1% ~ 20% of catalyst weight.
17. techniques according to claim 1, it is characterized in that dehydrogenation catalyst is the multi-metal-oxide catalyst that coprecipitation method obtains, active metal component is containing at least one in VIIB, VIII, IA, IIA race.
18. techniques according to claim 16, is characterized in that the carrier of dehydrogenation catalyst is TiO
2, Al
2o
3, SiO
2, one or several mixture among ZnO.
19. techniques according to claim 16, is characterized in that the carrier of dehydrogenation catalyst is the mixture of molecular sieve or molecular sieve and high-temperature inorganic oxide.
20. techniques according to claim 16, is characterized in that active ingredient is one or several in Na, Zn, Rb, Cs, Mg, Sr, Pt, Ba, Re, Mn, Cl, F, Br.
21. techniques according to claim 19, it is characterized in that molecular sieve is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, aluminium silicophosphate molecular sieve, two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
22. techniques according to claim 1, it is characterized in that aromatized catalyst contains molecular sieve and one or more active ingredients, active ingredient weight is 0.01 ~ 8%.
23. techniques according to claim 1, is characterized in that aromatized catalyst contains high-temperature inorganic oxide and one or more active ingredients molecular sieve supported.
24. techniques according to claim 23, is characterized in that in aromatized catalyst, high-temperature inorganic oxide is TiO
2, Al
2o
3, SiO
2, one or several mixture among ZnO.
25. techniques according to claim 22 or 23, the molecular sieve that it is characterized in that in aromatized catalyst is micropore, mesoporous or/and one or several mixing in mesoporous molecular sieve.
26. techniques according to claim 25, the molecular sieve that it is characterized in that in aromatized catalyst is one or more in ZSM-5, ZSM-11, ZSM-12, ZSM-35, MCM-22, Y type, aluminium silicophosphate molecular sieve, and two or more molecular sieve is composite molecular screen or eutectic molecular sieve.
27. techniques according to claim 22 or 23, the active ingredient that it is characterized in that in aromatized catalyst is one or several in rare earth element, IIIB, VIB, VIIB, VIII, IIB race element.
28. techniques according to claim 27, the active ingredient that it is characterized in that in aromatized catalyst is one or more in La, Pr, Nd, Zn, Cr, Mo, Mn, W, Co, Ni, Pt.
29. techniques according to claim 28, the active ingredient that it is characterized in that in aromatized catalyst is one or more in La, Pr, Ni, Co, Cr.
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| CN106365940B (en) * | 2015-07-22 | 2020-03-10 | 中国石油天然气股份有限公司 | Process for improving additional value of topped oil light hydrocarbon through conversion |
| CN106365948B (en) * | 2015-07-22 | 2020-04-10 | 中国石油天然气股份有限公司 | Method for preparing high-octane gasoline component and butadiene by mixing C4 |
| CN106867579B (en) * | 2015-12-14 | 2018-12-25 | 中国石油天然气股份有限公司 | A kind of method that lower carbon number hydrocarbons produces alkadienes and gasoline component |
| CN106064822B (en) * | 2016-05-30 | 2018-03-23 | 中国科学院大连化学物理研究所 | A kind of MWW/MEL cocrystallization molecular sieve and its synthetic method |
| CN110437873B (en) * | 2018-05-03 | 2021-09-28 | 中国石油天然气股份有限公司 | Utilization method of hydrocarbon oil rich in carbon four-carbon pentaalkane |
| CN113493699B (en) * | 2020-04-06 | 2023-09-15 | 国家能源投资集团有限责任公司 | Method for producing aromatic hydrocarbon and/or liquid fuel from light hydrocarbon |
| CN114426447A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Process for producing aromatic hydrocarbon by using alkane rich in carbon, four carbon and five carbon as raw material |
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