CN1063121A - Catalytic modification of poor quality gasoline-aromatization - Google Patents
Catalytic modification of poor quality gasoline-aromatization Download PDFInfo
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Abstract
The present invention relates to a kind of catalyst for performing catalytic reforming and catalytic upgrading-aromatization process that is used for inferior patrol.Catalyst component of the present invention comprises: the catalyst activity improving agent of 0.3～15.0m% (by metallic state, it is heavy to account for catalyzer, down with) is to be selected from Zn, Al and three kinds of metallic elements of rare earth two kinds or/or three kinds; 5.0 the hydrogen type molecular sieve that is introduced into active improving agent, particularly HZSM-5 of～94.5m%; Surplus is for being selected from aluminum oxide, silicon oxide or their mixture, and a kind of in the clay.It can be used for the catalytic reforming and the C of inferior patrol
2～C
4The aromizing of hydrocarbon molecule.Method of the present invention is that stock oil is contacted with described catalyzer, carries out the echelon reaction, with the improved well behaved gasoline component of acquisition octane value, and aromatic hydrocarbon product and the gas that is rich in hydrogen.
Description
The present invention relates to a kind of catalyst for performing catalytic reforming and catalytic reforming-technology of aromatization method thereof that is used for inferior patrol.
As everyone knows, be the catalyst made from platonic of carrier with the crystal formation aluminum oxide, perhaps catalyzer such as platiniferous rhenium, platinum tin, carrying out with light straight-run naphtha or straight-run spirit is the catalytic reforming of raw material, to obtain the stop bracket gasoline component, perhaps produces aromatic hydrocarbons.But this technology is subjected to the restriction of raw material sources.People carry out hydrofining to secondary processing of gasoline (as pressure gasoline, coker gasoline etc.) usually in order to enlarge raw material sources, as the additional source of its raw material.
In recent years, people are to silico-aluminate, and particularly the high silica alumina ratio molecular sieve is that the aromatization process of catalyzer has carried out a large amount of research, are that the process of catalyzer has been carried out a large amount of research with ZSM-5, ZSM-11 molecular sieve especially.U.S.P4,288,645[1] disclose with carrying the Zn aluminosilicate catalyst, produce the process of aromatic hydrocarbons mixture and hydrogen with the lighter hydrocarbons that contain 50% propane at least.It requires propane more preferably greater than 60%, and methane, ethane are less than 20%.E.P.0,147,111[2] a year gallium catalyzer is disclosed, with C
1/ C
4Process for raw material production aromatic hydrocarbons.It requires C
3/ C
4Greater than 50%.And think that the existence of ethane can improve C
1/ C
4Selectivity to the aromatic hydrocarbons conversion.E.P.0,283,212[3] disclose with C
2, C
3, C
4Paraffinic hydrocarbons is a raw material, contacts with the molecular sieve catalyst that soaks gallium and at least a rare earth element, carries out the process of aromizing, and pressure is 0.2～1.0MPa.E.P.0,327,189[4] disclose with coal funds-Tuo and synthesized the catalytic modification of poor quality gasoline process of producing.[4] be to contact with raw material down at 400～600 ℃ with the crystal aluminosilicate catalyzer that contains gallium, carry out aromatization, obtain high-octane gasoline component, its liquid receives 47%, and aromaticity content 97.7%(is heavy), E.P.0,230,356A[5] to have introduced with Hydrogen silicoaluminate gallium molecular sieve be catalyzer, contacts with petroleum naphtha (boiling point＜100 ℃), is converted into stop bracket gasoline.[5] mention in though the narration and can add the component of some other metallic elements as necessity, not seeing has concrete record to add the situation of other element.U.S.P.4,157,293[6] patent narrated in more detail a kind of introduce a certain amount of other element carry zinc Hydrogen ZSM-5 molecular sieve catalyst, solved in the reaction process because the problem that zinc runs off and causes the catalyzer aromatization activity to descend.[6] pointed out that the metal that is introduced into is IB, VIII family metal, germanium, rhenium, rare earth metal also can add.But do not see and address the situation that adds rare earth metal in the content of [6].
In prior art, though it is higher to contain gallium molecular sieve catalyst activity stability, the costing an arm and a leg of gallium.So people have invented a year zinc HZSM-5 molecular sieve catalyst.This activity of such catalysts is also fine, but zinc easily runs off in the aromizing operating process, causes the rapid deactivation of catalyzer.For addressing this problem, most employing is loaded with the method for two kinds of metals simultaneously in the prior art, and another kind of metal mostly is precious metal greatly, for example, VIII family precious metal, the Ag of IB family, Au, and rhenium etc.
The present invention will seek to solve the activity stability problem of aromatized catalyst from others, and can satisfy again with the inferior patrol simultaneously is the technical requirements of the catalytic reforming of raw material.
In aromatization process, particularly in the catalytic modification of poor quality gasoline process, be to adopt single hop (fixed bed) formula working method, it be with raw material once by beds, carry out aromatization.After isolating the gasoline component by resultant of reaction, the C in the gas stream
3, C
4It is heavy that content reaches 30%() more than.As not reclaimed, and directly discharging, this part hydrocarbon resource will be lost; Enter reactor if be circulated back to reactor inlet with raw material, although can partly recycle C like this
3, C
4Hydrocarbon, the processing power of this device that will account for influences treatment capacity.On the other hand, adopt the method for single hop bed, its temperature of reaction is generally all between 500～600 ℃, thereby liquid is received not high, heavy at 50%(usually) about, and the hydrogen concentration of off-gas is relatively low, is unfavorable for the recycling of hydrogen.
The object of the present invention is to provide a kind of catalytic modification of poor quality gasoline catalyzer that is used for, and be the catalytic reforming-aromatization method of raw material with inferior patrol.Needs at catalytic modification of poor quality gasoline-aromatization method, task of the present invention is to provide a kind of catalyzer, make it have imperfect components such as the sulphur that can remove in the inferior patrol, nitrogen compound, improve stability, can improve gasoline (being reformulated gasoline) octane value again, make it to become the higher well behaved gasoline component of octane value through catalytic reforming; Can make it have higher aromatization activity stability again, so that satisfy the some amount low-carbon (LC) molecule hydrocarbon that contains that is produced in the catalytic reforming process be converted into aromatic hydrocarbons, so as to realizing making full use of to the raw material hydrocarbon resource, receive thereby improve liquid, can improve the hydrogeneous tolerance of gas of discharger simultaneously again effectively.Its technical solution is that the inferior patrol that is used for catalytic reforming is contacted with catalyzer, carries out the echelon reaction.Specifically, what is called is carried out the echelon reaction and is meant: stock oil at first enters the first step (or crying first section) reactor, comprises catalyzer contact of the present invention with being equipped with, and reacts the separating reaction resultant under certain condition.Through separating, obtain liquid product and comprise being mainly≤C of hydrogen
4The gas of low molecular hydrocarbon, this gas enters second stage reactor as the unstripped gas of the second stage (or crying second section) reaction, and comprises that catalyzer of the present invention is housed to be contacted, and reacts under certain condition.Separating reaction resultant, the liquid product that obtains are aromatic hydrocarbons mixture, and gas is for being rich in hydrogen gas, hydrogeneous 50-70%(body).The combination of these two reaction process is referred to as the echelon reaction.
The present invention is used for the catalyzer of catalytic modification of poor quality gasoline-aromatization method, and its composition comprises:
(I) 0.3～15m%(is by metallic state, and it is heavy to account for catalyzer, and) the catalyst activity improving agent that is stated from the hydrogen type molecular sieve is by choosing two kinds or three kinds in zinc, aluminium and three kinds of metallic elements of rare earth, compound use down together.
The silica alumina ratio that is introduced into active improving agent (I) of (II) 5.0～94.5m% is the hydrogen type molecular sieve of 10-500, comprises HZSM-5, HZSM-7, HZSM-8, HZSM-11, HZSM-12, HZSM-35 molecular sieve etc., particularly HZSM-5 molecular sieve.
(III) surplus is that a kind of in the mixture that is selected from aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, the clay is binding agent.
Content 0.5～the 10.0m% of active improving agent is better, and 0.8～8.0m% is best.When active improving agent is when choosing two kinds of compound uses of metallic element, the relative weight between them is such as down:
1. be 0.10～0.90 better Zn/(Zn+Al), 0.2～0.8 is best;
2. be 0.10～0.95 better Zn/(Zn+ rare earth), 0.3～0.90 is best;
3. be 0.1～0.99 better Al/(Al+ rare earth), 0.3～0.90 is better.
When choosing three kinds of metallic elements, during compound use, the relative weight between them is such as down:
The Zn/(Al+ rare earth) be 0.05～15 better, 0.1～10 is best, and wherein the Al/ rare earth is 0.1～40 better, and 0.2～20 is best.
In the superincumbent narration, and in the listed relational expression of choosing metallic element, all rare earth is treated as a kind of element, but be not defined as a kind of in the rare earth element, rare earth element comprises each element in the group of the lanthanides.That is to say, when selecting rare earth element for use, can be in the lanthanon such as La, Ce, Pr, Nd any, also can be their two or more the mixture of arbitrary proportion, and mishmetal.
Contained molecular sieve is a hydrogen type molecular sieve in the catalyzer composition of the present invention, particularly the HZSM-5 molecular sieve.The sial atomic ratio of this molecular sieve analog should be and is not less than 10 high-silica zeolite, is generally 10～500,20～400 better, and 30～300 is best.This molecular sieve analog, for example HZSM-5 both can also can buy satisfactory commodity from manufacturer according to prior art oneself preparation.
Preparation of catalysts of the present invention, be to adopt well-known ion exchange method or/and pickling process, with selected Metal Zn-Al or Zn-rare earth or Al-rare earth or Zn-Al rare earth introducing hydrogen type molecular sieve, make its amount that is stated from the molecular sieve reach the desired content range of preparation catalyzer.As active improving agent, no matter be to select two kinds of metals (such as Zn-Al, Zn-rare earth etc.) or three kinds of compound uses of metallic element for use, when carrying out ion-exchange or dipping, the metal-salt that each can be introduced into is mixed with certain density single solution respectively; Carry out ion-exchange or dipping respectively; Also can be mixed with the mixing solutions of two kinds of metal-salts or three kinds of metal-salts by certain mol proportion, carry out ion-exchange or dipping.Process ion-exchange is or/and the molecular sieve that is loaded with above-mentioned active improving agent of dip treating, even with binding agent by specified weight ratio thorough mixing, add again then that an amount of nitric acid is mediated, moulding, oven dry, under air atmosphere,, promptly obtain the catalyzer finished product in 500-600 ℃ of roasting 2-10 hour.Metal-salt comprises nitrate, hydrochloride, vitriol, phosphoric acid salt etc.
Carry out catalytic modification of poor quality gasoline and aromizing with catalyzer of the present invention, its effect is satisfactory.
Catalytic modification of poor quality gasoline-aromatization method of the present invention has following advantage:
1, can under conditions of non-hydrogen, carry out as the first step reaction of catalytic modification of poor quality gasoline; From first step reactor resultant, separate the reformulated gasoline octane value that obtains and reach 80-92, the gas that obtains can be directly as the unstripped gas of second stage reactor, carry out aromizing, needn't return first step reactor, thereby help enlarging the treatment capacity of first step reaction unit.
2, can effectively utilize the hydrocarbon resource of stock oil.That is, will be from containing≤C that first step reactor is produced
4The gas of hydrocarbon (comprising alkane and alkene) enters second stage reactor, carries out aromatization again, has recycled the low molecular hydrocarbon (C in the first step reactor discharging gas
2-C
4) resource, and it is heavy to obtain containing 90-100%() aromatic hydrocarbons mixture, thereby improved the liquid receipts, it is heavy total liquid to be received reach 55-75%(to account for raw material).
3, owing to reclaimed most low molecular hydrocarbon from first step reactor discharging gas, the hydrogen content in the off-gas of present method is greatly improved (being approximately 50～70%), helps recycling the hydrogen resource.
4, the reformulated gasoline that obtains by present method, its sulphur, nitrogen content about 60-80% that can descend, stability be improved significantly.
The said inferior patrol of the present invention comprises: coker gasoline, pressure gasoline, visbreaking gasoline, shale spirit, artificially synthetic gasoline, oil-gas field winterization gasoline, petroleum naphtha, straight-run spirit and two kinds or two or more blend gasolines among them.Hydrocracking gasoline, catalytic gasoline also can be used as the stock oil of the inventive method.Inferior patrol is as the catalytic reforming raw material, can contain (for example to account for 1.0～40%(V) the C that contains from other process unit of inferior patrol in right amount
2-C
4Alkane is or/and the gas of alkene allows to contain a spot of methane and hydrogen partial in these gases.But preferably will combine with the logistics of first step reactor resulting gas from the gas of other technology, as the unstripped gas of second stage reactor, its blending ratio is unrestricted.Said inferior patrol is meant that mainly octane value (motor method) is lower than 55 gasoline fraction, and perhaps sulphur, nitrogen, gum level are high, perhaps the gasoline fraction that does not meet the product specification standard of stability difference.
A kind of catalytic modification of poor quality gasoline-aromatization method that is used for provided by the invention, obtaining 45～65m%(after can making described stock oil through first step reactor, to account for stock oil heavy) liquid, the octane value 80-92 of its gasoline fraction can obtain 4-15%(after through second stage reactor again to account for stock oil heavy by separating the gas obtain in the first step reactor product) aromatic hydrocarbons mixture.
Of the present invention is the catalytic reforming-aromatization method of raw material with the inferior patrol, it is characterized in that, in carrying out the first step reactor of catalytic reforming with in the second stage reactor that carries out aromizing, the catalyzer that supplies catalytic reforming and aromatization is housed respectively, stock oil, gas are contacted with catalyzer, and its processing step is as follows:
Stock oil enters the first step reactor that is laid with heating system after preheating, be that 0.05-1.2MPa, weight hourly space velocity are to carry out the catalytic reforming reaction under 0.2-10, bed temperature 300-550 ℃ and the conditions of non-hydrogen at pressure; Resultant of reaction comes out from this reactor, through further being cooled to enter gas-liquid separator then about 35 ℃ after the interchanger heat exchange again, carries out gas-liquid separation.After the separation, the C that obtains
5Above liquid hydrocarbon product is sent into fractionating system, carries out the fractionation cutting, just obtains gasoline fraction; What obtain contains≤C
4Gas stream send into the second stage reactor that is laid with heating system through preheating, under pressure 0.05～1.5MPa, long-pending body air speed 20-2000, bed temperature 480-650 ℃ condition, carry out aromatization, resultant of reaction is after the interchanger heat exchange, further be cooled to about 35 ℃ again, enter gas-liquid separator then, carry out gas-liquid separation.After the separation, the aromatic hydrocarbons mixture that obtains can be sent into separation system for being separated into monomer aromatic hydrocarbons, and the gas that is rich in hydrogen goes out device.
In first step reactor and second stage reactor, both can load the catalyzer of the present invention's preparation, promptly be loaded with the hydrogen type molecular sieve of the high silica alumina ratio (〉=10) of Zn-Al, Zn-rare earth, Al-rare earth and Zn-Al-active rare-earth improving agent, this molecular sieve comprises the binding agent (Al of HZSM-5, HZSM-7, HZSM-8, HZSM-11, HZSM-12, HZSM-35 etc. and some amount
2O
3, SiO
2, Al
2O and SiO
2Mixture, clay etc.) catalyzer that constitutes, also can load and other suitable catalyzer of catalyst activity stability of the present invention, for example: crystalline aluminosilicate gallium salt, carry the HZSM-5 catalyzer of gallium, year Ga-Zn or Pd-Zn or Ga-rare earth isoreactivity improving agent, and other has the catalyzer of similar functions.
The processing unit that method of the present invention is related mainly comprises reactor, oil pump, pneumatic plant, interchanger, water cooler and gas-liquid separator.Reactor can adopt fixed bed, fixed fluidized bed, moving-bed, fluidized-bed.Reactor should be equipped with or be laid with heating system.Such as fixed bed, both can be stove formula reactor (being that reactor is in the process furnace), also can adopt the heating system that is laid with other form, to satisfy the temperature of reaction of device inner catalyst bed.When adopting fixed bed, no matter be first step reactor or second stage reactor, preferably be together in parallel by two or more fixed beds respectively, formation can operate continuously and is switched regenerated one bank of reactor in turn.Structure formation in the reactor can be varied, as long as but the requirement that can satisfy the technological process of present method all can adopt.For example, the reaction bed in the reactor can be single hose (or being single skeleton symbol), also can be that multitube is knockdown, or the like.
Feeding manner.Stock oil or unstripped gas both can be entered by reactor top, also can be entered by reactor lower part.
The regeneration of catalyzer.With the fixed bed is example, after operation after a while, when activity of such catalysts drops to a certain degree, need regenerate to catalyzer.Renovation process is identical with known technology basically.Specifically, bed to be generated is carried out rare gas element (N for example after switching
2Gas) purge, feed oxygen-containing gas then, burn under 550～700 ℃, keep after 10～24 hours and feed inert gas replacement again, regeneration finishes.
Below in conjunction with accompanying drawing catalytic reforming-aromatization method of the present invention is described in detail, accompanying drawing does not limit method of the present invention.
Description of drawings:
1 stock oil; 2 raw oil pumps;
3,11 interchanger; 4 first step reactors (stove formula reactor);
5 come the resultant of autoreactor 4; 6,14 water coolers;
7,15 gas-liquid separators; 8 are mainly C
3, C
4The hydrogen-containing gas of hydrocarbon;
9 C
3Above liquid hydrocarbon; 10 pneumatic plants;
12 second stage reactors (stove formula reactor) 13 are from 12 reaction product;
16 are rich in the gas of hydrogen; 17 aromatic hydrocarbons mixtures;
18 being mainly≤C from other process unit
4Hydrocarbon;
A, b, c, d are respectively the signal pipeline that connects regeneration system rapidly, dot.(address fractionation in the literary composition, separating technology equipment is known technology, omit in the accompanying drawing.）
Feedstock oil 1 is sent to heat exchanger 3 by pump 2, comes out by 3 after heat exchange, enters from first order reactor 4 tops, at bed temperature 300-550 ℃, during weight (hourly) space velocity (WHSV) 0.2-10-1, carry out the catalytic reforming reaction under pressure 0.05-1.2MPa and the conditions of non-hydrogen, coming out in reaction product 5 autoreactors 4 bottoms, carries out heat exchange by heat exchanger 3, enters then cooler 6 and further be cooled to enter gas-liquid separator 7 about 35 ℃ again. After the separation, the fluid product 9 that obtains comes out from 7 bottoms, delivers to fractionating system for the fractionation cutting; The gas 8 that obtains is mainly C3、C
4The hydrogen-containing gas of hydrocarbon (methane, ethane, ethene and fraction propylene, the butylene etc. that wherein also contain fraction), after compressor 10 pressurizations, enter heat exchanger 11 heat exchange, enter from second level reactor 12 tops then, when 0.05-1.5MPa, volume space velocity 20-2000-1, carry out aromatization under 480～650 ℃ of conditions of bed temperature. Coming out in reaction product 13 autoreactors 12 bottoms, enters cooler 14 and further be cooled to about 35 ℃ after heat exchanger 11 heat exchange, sends into gas-liquid separator 15 again and carry out gas, liquid separation. After the separation, the mixture 17 of aromatic hydrocarbons comes out from 15 bottoms, sends into piece-rate system for further being separated into monomer aromatic hydrocarbons, is rich in the gas 16 of hydrogen by 15 top dischargers.
In catalytic reforming-technology of aromatization process, the operating condition of first order reactor is at bed temperature 320-520 ℃, weight (hourly) space velocity (WHSV) 0.3～8, better, best under 360-500 ℃, weight (hourly) space velocity (WHSV) 0.5～5, pressure 0.05～0.6MPa condition under pressure 0.05～1.0MPa condition; The operating condition of second level reactor is 500～600 ℃ of bed temperatures, and is best under volume space velocity 100～1000, the pressure 0.1～1.2MPa condition.
After operation after a while, the activity of catalyst in reactor drops to a certain degree, and it is switched regeneration. For example, first order reactor 4-1 is after switching, from the inert gas of regenerative system (N for example2Gas), (or by a from 4-1 top) advances from the 4-1 bottom by b Enter, purge, switch then sweep gas, make oxygen-containing gas through b(or a) enter 4-1, burn at 550-700 ℃. After burning end, carry out again inert gas purge. Regeneration ending.
Enumerating embodiment below is further described, but does not limit the scope of the invention catalyzer of the present invention and catalytic reforming-technology of aromatization method.
Embodiment
Example 1, the HZSM-5 molecular sieves (by the finished product that factory buys, its silica alumina ratio is 60, down with) of getting 40 grams add 15% Zn(NO
3)
2Solution 40ml, quick stirring to pulp in 40 ℃ of exchanges 2.5 hours, filters, washing 1 to 2 time, in 110 ℃ dry 2 hours down, 500 ℃ of following roastings are 3 hours again, grind, and add the La(NO of 0.1M then
3)
3Solution 80ml stirs fast, and 40 ℃ of exchanges 2.5 hours are down filtered, washing, in 110 ℃ dry 2 hours down, grind again, the aluminium hydrate powder commercially available with 40 grams mixes, and adds 8% HNO
350ml stirs, mediates, then, extruded moulding, 110 ℃ were descended dry 2 to 3 hours, and 500 ℃ of following roastings 4 to 6 hours, made catalyzer 1.By analysis, it is heavy to contain Zn 2.5%(), La 1.2%(is heavy).
Example 2, get described molecular sieve 40 grams of example 1, use the Zn(NO of 0.1M respectively
3)
2The Al of solution 40ml and 0.6M
2(SO
4)
3Solution 80ml floods.Promptly, filter slurries then successively at 40 ℃ of following quick stirring to pulps 2 hours, 110 ℃ dry 2 hours down, dipping again after the grinding.Drying, grinding back and 40 Al that restrain
2(OH)
3Powder mixes, and adds 8% HNO
3Solution 50ml stirs, kneading, moulding, 500 ℃ roasting 8-10 hour, make catalyzer 2.Analytical results: Zn2.44%(is heavy), Al, 2.3%(is heavy).
Example 3, get the above-mentioned molecular sieve of 40 grams, with the La(NO of 0.1M
3)
3The Al(NO of solution 80ml and 0.6M
3)
3Solution 80ml mixes the back impregnated zeolite, 40 ℃ of quick down stirrings, making beating 2 hours, filters slurries.In 110 ℃ of dryings 2 hours, grind back and 40 gram Al(OH then)
3Powder mixes, and adds 8% HNO
350ml stirs, mediates, moulding then, 500 ℃ of following roastings 3 hours, and the catalyzer 3 that makes contains Al 2.3m%, La 1.2m%.
Example 4, get the above-mentioned molecular sieve of 80 grams, with the La(NO of 0.02M
3)
3Solution 160ml by example 1 described preparation method, makes earlier and carries the lanthanum molecular sieve.Get then its 1/2nd, the Zn(NO with 15%
3)
2The AI(NO of solution 40ml, 0.6M
3)
3Solution 80ml exchanges respectively, and other makes catalyzer 4 with example 1, wherein: Zn 2.5m%, La 0.2m%, Al 2.3m%.
Get remaining 1/2nd, the Zn(NO with 8%
3)
2The Al(NO of solution 40ml, 0.6M
3)
3Solution 120ml exchanges respectively, and other makes catalyzer 5 with example 1, wherein: Zn 1.3%, AL 3.4%, La 0.2%.
Example 5, Zn(NO with 15%
3)
3The Ce(NO of solution 40ml, 0.02M
3)
3Solution 80ml, other makes catalyzer 6 with example 1, wherein contains: Zn 2.5%, and Ce 0.21%.
Example 6, use 15%Zn(NO
3)
3Solution 40ml, the Al(NO of 0.6M
3)
3Solution 80ml, the Ce(NO of 0.02M
3)
3La(NO with 0.02M
3)
3Each 80ml of solution exchanges molecular sieve respectively, and other makes catalyzer 7 with example 1, wherein contains: Zn 2.5%, AL 2.2%, and Ce 0.19%, and La 0.2%.
Below, we carry out activity rating and technological test with catalyzer of the present invention.
Stock oil character such as following table:
Table 1
Example 7, use small fixed, in adorn 15 gram catalyzer.With coker gasoline and winterization gasoline (seeing Table 1) is raw material, and 550 ℃ of bed temperatures, weight hourly space velocity 1.5 is carried out aromatisation experiment, result such as table 2 under the normal pressure conditions of non-hydrogen.
Table 2
| Raw material | Winterization gasoline | Coker gasoline | |||
| The catalyzer numbering, NO | 1 | 2 | 3 | 4 | 5 |
| Liquid yield, %(heavy aromatics content, the % gas composition, %(body H CH C C C | 54.90 97.3 62.63 8.00 18.20 10.44 0.73 | 56.03 90.2 63.25 8.60 16.10 10.85 1.20 | 51.48 92.5 57.80 4.52 17.20 12.50 7.98 | 56.00 94.8 53.20 13.82 15.82 13.18 3.98 | 56.49 96.0 55.60 10.12 16.21 11.98 6.09 |
Aromaticity content is 92.5～98.2% in the liquid that is obtained by example 7, and activity of such catalysts that hence one can see that is very high.
Example 8, be of a size of 38 * 4 * 800 fixed-bed reactor with two and be cascaded, as catalytic reforming-technology of aromatization testing apparatus by process pipeline.Last reactor i.e. first reactor is done the catalytic reforming reactor, apparatus with catalyst inside 1, and back one reactor (i.e. second reactor) is done aromatization reactor, apparatus with catalyst inside 4.Stock oil enters from first step reactor top, and resultant of reaction is come out by the bottom, through the water cooler cooling, at room temperature carries out gas-liquid separation.Liquid goes out device, and gas enters from the second reactor top through pneumatic plant compression back, carries out aromatization, and resultant of reaction is come out by the bottom, through the water cooler laggard promoting the circulation of qi liquid separation that cools.Be rich in the dry gas discharger of hydrogen, liquid is aromatic hydrocarbons mixture.Operational condition and test-results are listed in table 3.
The C that from the first reactor resultant, obtains
5Above liquid hydrocarbon cuts into the fraction of gasoline fraction and＞205 ℃ through the true boiling point distillation device.The gasoline fraction physico-chemical property is listed in table 4.
Table 3
| Raw material | The oil field winterization gasoline | Coker gasoline | ||
| Test number | 1 2 3 | 4 | ||
| First step reactor | Pressure, the MPa temperature of reaction, ℃ weight hourly space velocity, the time liquid receive, m% (to raw material) is wherein: gasoline, m%＞205 ℃ m% gas yield, m% (to raw material) gas composition, the %(body) H 2C 1C 2C 3+C 4Coke, m% (to raw material) loss, m% (to raw material) | 0.05 0.05 0.10 380 400 420 1.3 1.3 1.8 68.98 59.10 53.52 68.98 59.10 50.52 - - 3.00 26.32 36.28 41.39 11.52 11.76 13.07 1.57 5.20 2.88? 3.10 3.79 4.76 83.78 79.23 79.27 1.35 1.61 1.68 3.35 3.01 3.41 | 0.10 420 1.3 56.66 52.66 4.00 38.34 5.67 1.15 7.49 85.69 2.00 3.00 | |
| Second stage reactor | Pressure, the MPa temperature of reaction, ℃ volume space velocity, the time liquid receive, m% (to raw material) wherein contains aromatic hydrocarbons, the m% gas recovery ratio, m% (to raw material) gas composition, the %(body) H 2C 1C 2C 3+C 4Coke, m% (to raw material) loss, m% (to raw material) | 0.1 0.1 0.1 500 550 580 190 190 220 4.38 9.40 8.54 100 100 100 20.00 24.98 30.65 25.67 58.39 54.76 8.08 15.57 17.13 8.97 10.76 11.65 57.28 15.28 16.46 0.94 0.92 1.00 1.00 0.98 1.20 | 0.2 550 200 8.00 99.4 28.24 54.29 16.39 12.73 16.59 1.10 1.00 | |
Table 4
| Test number | 1 2 3 4 |
| Boiling range, ℃ initial boiling point 10% 50% 90% is done residual+loss, the % saturated vapor pressure, the KPa existent gum, the mg/100ml sulphur content, m% corrosive water dissolubility soda acid acidity, mgKOH/100ml mechanical impurity and moisture octane value, MON | 25 24 35 28 30 31 72 65 49 50 115 110 125 132 175 179 180 184 194 194 4.0 3.5 3.0 3.0--69.1 69.4 do not have 55 0.0014 0.0012 0.0011 0.05 1a 1a 1a 1a nothing 0.31 0.31 0.29 0.35 does not have 79.6 81.3 89.4 92 |
Claims (12)
1, a kind of catalytic modification of poor quality gasoline that is used for--the catalyzer of aromatization method is characterized in that the composition of this catalyzer comprises:
(by metallic state, it is heavy to account for catalyzer, and) catalyst activity improving agent is by choosing two or three compound use in Zn, AL and three kinds of metallic elements of rare earth (comprising mishmetal) down together for (I) 0.3～15m%;
The silica alumina ratio that is introduced into (I) of (II) 5.0～94.5m% is 10～500 hydrogen type molecular sieve, comprises HZSM-5, HZSM-7, HZSM-8, HZSM-11, HZSM-12, HZSM-35 etc., particularly HZSM-5;
(III) surplus is that a kind of in the mixture that is selected from aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, the clay is binding agent.
2, catalyzer according to claim 1 is characterized in that this activity of such catalysts improving agent content 0.5～10.0m% is better, and 0.8～8.0m% is best; When active improving agent is when choosing two kinds of compound uses of metallic element, the relative weight between them is such as down:
1. be 0.10～0.90 better Zn/(Zn+AL), 0.2～0.80 is best;
2. be 0.10～0.95 better Zn/(Zn+ rare earth), 0.3～0.90 is best;
3. be 0.1～0.99 better AL/(AL+ rare earth), 0.3～0.90 is best;
When choosing three kinds of elements compounding uses, the relative weight between them is such as following:
The Zn/(AL+ rare earth) be 0.05～15 better, 0.1～10 is best, and wherein the AL/ rare earth is 0.1～40 better, and 0.2～20 is best.
3, catalyzer according to claim 1 and 2 is characterized in that described active improving agent is the compound use of Zn-AL or Zn-rare earth or AL-rare earth or Zn-AL-rare earth.
4, according to claim 1 or 2 or 3 described catalyzer, it is characterized in that being used as the rare earth element of active improving agent, comprise the single-element in the lanthanon, and two or more mixture or the mishmetal in them.
5, catalyzer according to claim 1 is characterized in that said hydrogen type molecular sieve is HZSM-5, and its content is that 10～90m% is better, and 20～85m% is best; The silica alumina ratio of this molecular sieve is 20～400 better, and 30～300 is best.
6, a kind of catalytic modification of poor quality gasoline-aromatization method is characterized in that in first step reactor with in the reactor of the second stage catalyzer that supplies catalytic reforming and aromizing being housed respectively, and raw material is contacted with catalyzer, and its processing step is as follows:
Stock oil enters first step reactor after preheating, carry out the catalytic reforming reaction under pressure 0.05～1.2MPa, weight space velocity 0.2-10, bed temperature 300-550 ℃ and conditions of non-hydrogen; Resultant of reaction comes out from this reactor, through further being cooled to carry out gas-liquid separation then about 35 ℃ after the heat exchange again; C
5Above liquid goes out device, delivers to fractionating system and carries out the fractionation cutting, obtains gasoline fraction, contains≤C
4Gas send into second stage reactor through preheating, under pressure 0.05-1.5MPa, volume space velocity 20-2000,480～650 ℃ of conditions of bed temperature, carry out aromatization; Resultant of reaction is through further being cooled to carry out gas-liquid separation then about 35 ℃ again after the heat exchange, the aromatic hydrocarbons mixture that obtains goes out device respectively with the gas that is rich in hydrogen.
7, a kind of catalytic modification of poor quality gasoline-aromatization method according to claim 6, it is characterized in that the catalyzer in the said reactor of packing into is to be loaded with Zn-AL, Zn-rare earth, AL-rare earth or/and the hydrogen type molecular sieve of the high silica alumina ratio (〉=10) of Zn-AL-active rare-earth improving agent, this molecular sieve comprises HZSM-5, HZSM-7, HZSM-8, HZSM-11, HZSM-12, HZSM-35 etc., binding agent (the Al of HZSM-5 and some amount particularly
2O
3, SiO
2, Al
2O
3And SiO
2Mixture, clay etc.) catalyzer that constitutes, its composition comprises: it is heavy that active improving agent is that 0.3～15m%(accounts for catalyzer), 0.5～10m% is better, 0.8～8m% is best, hydrogen type molecular sieve is 5～94.5m%, and 10～90m% is better, 20～85m% is best, and surplus is a binding agent; Also can be silicon metal aluminic acid gallium salt, carry the HZSM-5 catalyzer of gallium, year Ga-Zn or Pd-Zn or Ga-rare earth isoreactivity improving agent, and other have the catalyzer of similar functions.
8, method according to claim 6, it is characterized in that first step reactor is better under pressure 0.05～1.0MPa, weight hourly space velocity 0.3～8,320～520 ℃ of conditions of bed temperature, best under 0.05～0.6MPa, weight space velocity 0.5-5,360～500 ℃ of conditions of bed temperature.
9, method according to claim 6 is characterized in that second stage reactor at pressure 0.1～1.2MPa, volume space velocity 100-1000, and is best under the bed temperature 500-600 ℃ condition.
10, method according to claim 6, it is characterized in that described first step reactor and second stage reactor, when adopting fixed-bed reactor, the reactor that constitutes by the fixed bed that can carry out blocked operation in turn of two parallel connections at least respectively preferably, this fixed bed both can be a single hose, also can be the multitube block form.
11, method according to claim 6, it is characterized in that the raw material that is used as catalytic reforming comprises: coker gasoline, pressure gasoline, catalytic gasoline, visbreaking gasoline, shale spirit, artificially synthetic gasoline, petroleum naphtha, straight-run spirit, winterization gasoline, hydrofined gasoline, and two or more the blend gasoline among them.
12, method according to claim 6 is characterized in that being used as the unstripped gas of aromatization, both can be containing≤C from first step reaction
4Gas stream, also can be the similar gas of will sneak into simultaneously in this gas stream from other process unit, for example: thermally splitting, coking, hydrocracking, catalytic cracking etc. the device gas.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101228 CN1023687C (en) | 1992-03-05 | 1992-03-05 | Catalytic modification of poor quality gasoline-aromatization |
| CN 93102129 CN1032697C (en) | 1992-03-05 | 1993-03-02 | Catalytic upgrading-aromatization process of poor gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92101228 CN1023687C (en) | 1992-03-05 | 1992-03-05 | Catalytic modification of poor quality gasoline-aromatization |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93102129 Division CN1032697C (en) | 1992-03-05 | 1993-03-02 | Catalytic upgrading-aromatization process of poor gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063121A true CN1063121A (en) | 1992-07-29 |
| CN1023687C CN1023687C (en) | 1994-02-09 |
Family
ID=4939015
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92101228 Expired - Lifetime CN1023687C (en) | 1992-03-05 | 1992-03-05 | Catalytic modification of poor quality gasoline-aromatization |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041216C (en) * | 1993-04-26 | 1998-12-16 | 美孚石油公司 | Synthetic layered material, MCM-56, its synthesis and use |
| CN1058284C (en) * | 1998-04-10 | 2000-11-08 | 中国石油化工总公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101314732B (en) * | 2007-05-31 | 2011-12-21 | 中国石油化工股份有限公司 | Continuous aromatization modification method for hydrocarbons |
| CN106675639A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for producing isobutene and high-octane petrol by taking n-butene as raw material |
| US11041127B2 (en) | 2017-08-15 | 2021-06-22 | Sabic Global Technologies B.V. | Shale gas and condensate to chemicals |
-
1992
- 1992-03-05 CN CN 92101228 patent/CN1023687C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041216C (en) * | 1993-04-26 | 1998-12-16 | 美孚石油公司 | Synthetic layered material, MCM-56, its synthesis and use |
| CN1058284C (en) * | 1998-04-10 | 2000-11-08 | 中国石油化工总公司 | Light hydrocarbon aromatization catalyst and its preparing process |
| CN101314732B (en) * | 2007-05-31 | 2011-12-21 | 中国石油化工股份有限公司 | Continuous aromatization modification method for hydrocarbons |
| CN106675639A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for producing isobutene and high-octane petrol by taking n-butene as raw material |
| CN106675639B (en) * | 2015-11-09 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method that isobutene and high-knock rating gasoline are produced using n-butene as raw material |
| US11041127B2 (en) | 2017-08-15 | 2021-06-22 | Sabic Global Technologies B.V. | Shale gas and condensate to chemicals |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1023687C (en) | 1994-02-09 |
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