CN1023687C - Catalytic modification of poor quality gasoline-aromatization - Google Patents
Catalytic modification of poor quality gasoline-aromatization Download PDFInfo
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- CN1023687C CN1023687C CN 92101228 CN92101228A CN1023687C CN 1023687 C CN1023687 C CN 1023687C CN 92101228 CN92101228 CN 92101228 CN 92101228 A CN92101228 A CN 92101228A CN 1023687 C CN1023687 C CN 1023687C
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Abstract
The present invention relates to a catalytic modification catalyst and a catalytic modification-aromatization method for poor-quality gasoline. The catalyst component comprises a catalyst activity improving agent which accounts for 0.3 to 15.0 m% of the weight of catalysts measured by metal states and is selected from two or three of the metallic elements comprising Zn, Al and rare earth; 5.0 to 94.5% of a hydrogenous molecular sieve led in the activity improving agent, particularly an HZSM-5 hydrogenous molecular sieve; one of aluminum oxide, silicon oxide or the mixture of aluminum oxide and silicon oxide; and the balance of clay. The catalyst can be used for catalytically modifying poor-quality gasoline and aromatizing C2 to C4 hydrocarbon molecules. The method is characterized in that raw oil is in contact with the catalyst to carry out echelon reaction to obtain a high-performance gasoline component with improved octane value, arene products and gas 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 aluminium oxide, perhaps catalyst such as platiniferous rhenium, platinum tin, carrying out with light straight-run naphtha or direct steaming gasoline is the catalytic reforming of raw material, to obtain the high-knock rating gasoline component, perhaps produces aromatic hydrocarbons.But this technology is subjected to the restriction of raw material sources.People carry out hydrofinishing 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 alumino-silicate, and particularly the high silica alumina ratio molecular sieve is that the aromatization process of catalyst has carried out a large amount of research, are that the process of catalyst 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 catalyst is disclosed, with C
5/ C
4Produce the process of aromatic hydrocarbons for raw material.It requires C
3/ C
4Greater than 50%.And think that the existence of ethane can improve C
3/ C
4Selectivity to the aromatic hydrocarbons conversion.E.P.0,283,212[3] disclose with C
2, C
5, C
4The alkane lighter hydrocarbons are raw material, contact with the molecular sieve catalyst that soaks gallium and at least a rare earth element, carry out the process of aromatisation, and pressure is 0.2-1.0MPa.E.P.0,327,189[4] disclose with the synthetic catalytic modification of poor quality gasoline process of producing of coal funds one holder.[4] be to contact with raw material down at 400-600 ℃ with the crystal aluminosilicate catalyst that contains gallium, carry out aromatization, obtain high-octane gasoline component, its liquid receives 47%, and arene content 97.7%(is heavy), E.P.0,230,356A[5] to have introduced with Hydrogen aluminosilicate gallium molecular sieve be catalyst, contacts with naphtha (boiling point＜100 ℃), is converted into high-knock rating 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 course of reaction because the problem that zinc runs off and causes the catalyst 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 is also fine with activity of such catalysts, but zinc easily runs off in the aromatisation operating process, causes the rapid deactivation of catalyst.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 noble metal greatly, for example, VIII family noble 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 specification requirement 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 method of operating, it be with raw material once by beds, carry out aromatization.After isolating the gasoline component by reaction product, the C in the gas stream
5, 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 disposal ability of this device that accounts for influences treating capacity.On the other hand, adopt the method for single hop bed, its reaction temperature 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 catalyst 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 catalyst, 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 number again, make it to become the higher well behaved gasoline component of octane number through catalytic reforming; Can make it have higher aromatization activity stability again, so that satisfy the some low-carbon (LC)s molecule hydrocarbon that contains that is produced in the catalytic reforming process is 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 the inferior patrol that is used for catalytic reforming to be contacted with catalyst carry out the echelon reaction.Specifically, what is called is carried out the echelon reaction and is meant: feedstock oil at first enters the first order (or crying first section) reactor, comprises catalyst contact of the present invention with being equipped with, and reacts the separating reaction product under certain condition.Through separating, obtain fluid product and comprise being mainly≤C of hydrogen
4The gas of low molecular hydrocarbons, this gas enters second level reactor as the unstripped gas of the second level (or crying second section) reaction, and comprises that catalyst of the present invention is housed to be contacted, and reacts under certain condition.Separating reaction product, the fluid 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 courses of reaction is referred to as the echelon reaction.
The present invention is used for the catalyst 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 catalyst, and) the catalyst activity improver 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 improver (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 aluminium oxide, silica or aluminium oxide and silica, the clay is binding agent.
Content 0.5～the 10.0m% of active improver is better, and 0.8～8.0m% is best.When active improver 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), 0.3～0.9 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 lanthanide series 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 catalyst 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 or/and infusion 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 catalyst.As active improver, 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 slaine that each can be introduced into is mixed with certain density single solution respectively; Carry out respectively from exchange or dipping; Also can be mixed with the mixed solution of two kinds of slaines or three kinds of slaines 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 improver of impregnation process, fully mix with the weight ratio of binding agent by appointment, add again then that an amount of nitric acid is mediated, moulding, oven dry, under air atmosphere in 500-600 ℃ of roasting 2-10 hour, promptly obtain the catalyst finished product.Slaine comprises nitrate, hydrochloride, sulfate, phosphate etc.
Carry out catalytic modification of poor quality gasoline and aromatisation with catalyst 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 order reaction of catalytic modification of poor quality gasoline; From first order reactor product, separate the reformulated gasoline octane number that obtains and reach 80-92, the gas that obtains can be directly as the unstripped gas of second level reactor, carry out aromatisation, needn't return first order reactor, thereby help enlarging the treating capacity of first order reaction unit.
2. can effectively utilize the hydrocarbon resource of feedstock oil.That is, will be from containing≤C that first order reactor is produced
4The gas of hydrocarbon (comprising alkane and alkene) enters second level reactor, carries out aromatization again, has recycled the low molecular hydrocarbons (C in the first order 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 hydrocarbons from first order reactor discharging gas, the hydrogen content in the off-gas of this method is greatly improved (being approximately 50～70%), helps recycling the hydrogen resource.
4. the reformulated gasoline that obtains by this 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 gasoline, artificially synthetic gasoline, oil gas field winterization gasoline, naphtha, direct steaming gasoline and two kinds or two or more blend gasolines among them.Hydrocracking gasoline, catalytic gasoline also can be used as the feedstock oil of the inventive method.Inferior patrol is as the catalytic reforming raw material, can contain the C that contains from other process unit of an amount of (for example account for inferior patrol 1.0～40%(V))
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 order reactor resulting gas from the gas of other technology, as the unstripped gas of second level reactor, its mixed proportion is unrestricted.Said inferior patrol is meant that mainly octane number (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 feedstock oil through first order reactor, to account for feedstock oil heavy) liquid, the octane number 80-92 of its gasoline fraction can obtain 4-15%(after through second level reactor again to account for feedstock oil heavy by separating the gas obtain in the first order 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 order reactor of catalytic reforming with in the second level reactor that carries out aromatisation, the catalyst that supplies catalytic reforming and aromatization is housed respectively, feedstock oil, gas are contacted with catalyst, and its processing step is as follows:
Entering the first order reactor that is laid with heating system after the preheating of raw material petroleum hydrocarbon, is that 0.05-1.2MPa, weight (hourly) space velocity (WHSV) are to carry out the reaction of catalyst upgrading under 0.2-10, bed temperature 300-550 ℃ and the conditions of non-hydrogen at pressure; Reaction product comes out from this reactor, through further being cooled to enter gas-liquid separator then about 35 ℃ after the heat exchanger 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 level 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, reaction product is after the heat exchanger 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 piece-rate system for being separated into monomer aromatic hydrocarbons, and the gas that is rich in hydrogen goes out device.
In first order reactor and second level reactor, both can load the catalyst 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 improver, this molecular sieve comprises the binding agent (Al of HZSM-5, HZSM-7, HZSM-8, HZSM-11, HZSM-12, HZSM-35 etc. and some
2O
3, SiO
2, Al
2O and SiO
2Mixture, clay etc.) catalyst that constitutes, also can load and other suitable catalyst of catalyst activity stability of the present invention, for example: crystalline aluminosilicate gallium salt, carry the HZSM-5 catalyst of gallium, year Ga-Zn or Pd-Zn or Ga-rare earth isoreactivity improver, and other has the catalyst of similar functions, and other has the catalyst of similar functions.
The process equipment that method of the present invention is related mainly comprises reactor, oil pump, compressor, heat exchanger, cooler and gas-liquid separator.Reactor can adopt fixed bed, fixed fluidized bed, moving bed, fluid 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 heating furnace), also can adopt the heating system that is laid with other form, to satisfy the reaction temperature of device inner catalyst bed.When adopting fixed bed, no matter be first order reactor or second level reactor, preferably be together in parallel by two or more fixed beds respectively, formation can a continued operation and a bank of reactor of switching regeneration in turn.Version in the reactor can be varied, as long as but the requirement that can satisfy the technical process of this method all can adopt.For example, the reaction bed in the reactor can be single hose (or being the monotubular formula), also can be that multitube is knockdown, or the like.
Feeding manner.Feedstock oil or unstripped gas both can be entered by reactor top, also can be entered by reactor lower part.
The regeneration of catalyst.With the fixed bed is example, after operation after a while, when activity of such catalysts drops to a certain degree, need regenerate to catalyst.Renovation process is identical with known technology basically.Specifically, bed to be generated is carried out inert gas (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. feedstock oil;
2. raw oil pump;
3,11. heat exchangers;
4. first order reactor (stove formula reactor);
5. come the product of autoreactor 4;
6,14. coolers;
7,15. gas-liquid separators;
8. be mainly C
5, C
4The hydrogen-containing gas of hydrocarbon;
9.C
5Above liquid hydrocarbon;
10. compressor;
12. second level reactor (stove formula reactor)
13. product from 12;
16. be rich in the gas of hydrogen;
17. aromatic hydrocarbons mixture;
18. from being mainly≤C of other process unit
4Hydrocarbon;
A, b, c, d are respectively the signal pipeline that connects regenerative system, dot.(address fractionation in the literary composition, separating technology equipment is known technology, omit in the accompanying drawing.）
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) enters from the 4-1 bottom by b, purges, and switches then sweep gas, makes oxygen-containing gas through b(or a) enters 4-1, burns at 550-700 ℃. After burning end, carry out again inert gas purge. Regeneration finishes.
Enumerating embodiment below is further described, but does not limit the scope of the invention catalyst of the present invention and catalyst upgrading-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, quick stirring to pulp, 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
550ml stirs, mediates, and extruded moulding 110 ℃ times dry 2 to 3 hours, 500 ℃ of following roastings 4 to 6 hours, makes catalyst 1 then.By analysis, it is heavy to contain Zn2.5%(), La1.2%(is heavy).
Example 2 is got example 1 described molecular sieve 40 grams, uses the Zn(NO of 0.1M respectively
3)
2The Al of solution 40ml and 0.6M
2(SO
4)
5Solution 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)
5Powder mixes, and adds 8% HNO
3Solution 50ml stirs, kneading, moulding, 500 ℃ roasting 8-10 hour, make catalyst 2.Analysis result: Zn2.44%(is heavy), Al, 2.3%(is heavy).
Example 3. is got the above-mentioned molecular sieve of 40 grams, with the La(NO of 0.1M
5)
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 catalyst 3 that makes contains Al2.3m%, La1.2m%.
Example 4. is got 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 Al(NO of solution 40ml, 0.6M
5)
5Solution 80ml exchanges respectively, and other makes catalyst 4 with example 1, wherein: Zn2.5m%, La0.2m%, Al2.3m%.
Get remaining 1/2nd, the Zn(NO with 8%
3)
2The Al(NO of solution 40ml, 0.6M
5)
5Solution 120ml exchanges respectively, and other makes catalyst 5 with example 1, wherein: Zn1.3%, Al3.4%, La0.2%.
Example 5, the Zn(NO with 15%
3)
3The Ce(NO of solution 40ml, 0.02M
5)
5Solution 80ml, other makes catalyst 6 with example 1, wherein contains: Zn2.5%, Ce0.21%.
Example 6. is used 15%Zn(NO
5)
5Solution 40ml, the Al(NO of 0.6M
3)
5Solution 80ml, the Ce(NO of 0.02M
5)
5La(NO with 0.02M
5)
5Each 80ml of solution exchanges molecular sieve respectively, and other makes catalyst 7 with example 1, wherein contains: Zn2.5%, Al2.2%, Ce0.19%, La0.2%.
Below, we carry out activity rating and engineer testing with catalyst of the present invention.
Feedstock oil character such as following table: (table 1 is seen the literary composition back)
Example 7. is used small fixed, in adorn 15 the gram catalyst.With coker gasoline and winterization gasoline (seeing Table 1) is raw material, and 550 ℃ of bed temperatures, weight (hourly) space velocity (WHSV) 1.5 is carried out aromatisation experiment, result such as table 2 under the normal pressure conditions of non-hydrogen.(table 2 is seen the literary composition back)
Arene 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. is of a size of 38 * 4 * 800 fixed bed reactors with two and is cascaded by process pipelines, as catalytic reforming-technology of aromatization experimental rig.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.Feedstock oil enters from first order reactor top, and reaction product is come out by the bottom, through the cooler cooling, at room temperature carries out gas-liquid separation.Liquid goes out device, and gas enters from the second reactor top through compressor compression back, carries out aromatization, and reaction product is come out by the bottom, through the 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.Operating condition and result of the test are listed in table 3.
The C that from the first reactor product, obtains
5Above liquid hydrocarbon cuts into the fraction of gasoline fraction and＞205 ℃ through the true boiling point distillation device.The gasoline fraction physicochemical property is listed in table 4.(table 3, table 4 are seen the literary composition back)
Table 1
The raw material boiling range, ℃ density refractive power sulfur content, nitrogen content, it is heavy that hydrocarbon system forms %()
G/cm is done in title fore-running 10% 50% 90%
3Index ppm ppm alkane cycloalkanes aromatic hydrocarbons
Winterization gasoline 38 49 71 138 183 0.6888 1.389 129.4＜2 63.3 33.2 3.5
Coker gasoline 39 83 132 170 185 0.7340-1,370 182--5.0
Table 2
Raw material winterization gasoline coker gasoline
The catalyst numbering, No 12345
Liquid yield, %(weigh 54.90 56.03 51.48 56.00 56.49
Arene content, % 97.3 90.2 92.5 94.0 96.0
Gas composition, the %(body
H 62.63 63.25 57.80 53.20 55.60
CH 8.00 8.60 4.52 13.82 10.12
C 18.20 16.10 17.20 15.82 16.21
C 10.44 10.85 12.50 13.18 11.98
C 0.73 1.20 7.98 3.98 6.09
Table 4
Test number 1234
Boiling range, ℃
Initial boiling point 25 24 35 28
10% 30 31 72 65
50% 49 50 115 110
90% 125 132 175 179
Do 180 184 194 194
Residual+loss, % 4.0 3.5 3.0 3.0
Saturated vapor pressure, KPa--69.1 69.4
Existent gum, mg/100ml does not have 55
Sulfur content, m% 0.0014 0.0012 0.0011 0.05
Corrosion 1a 1a 1a 1a
Water-soluble soda acid does not have
Acidity, mgKOH/100ml 0.31 0.31 0.29 0.35
Mechanical admixture and moisture do not have
Octane number, MON 79.6 81.3 89.4 92
Table 3
Raw material oil field winterization gasoline coker gasoline
Test number 1234
Pressure, MPa 0.05 0.05 0.10 0.10
Reaction temperature, ℃ 380 400 420 420
Weight (hourly) space velocity (WHSV), the time 1.3 1.3 1.8 1.3
Liquid is received, and m%(is to raw material) 68.98 59.10 53.52 56.66
Wherein: gasoline, m% 68.98 59.10 50.52 52.66
The＞205 ℃, m%--3.00 4.00
One
The level gas yield, m%(is to raw material) 26.32 36.28 41.39 38.34
Inverse gas is formed, the %(body)
Should
Device H
211.52 11.76 13.07 5.67
C
11.57 5.20 2.88 1.15
C
23.10 3.79 4.76 7.49
C
3+C
483.78 79.23 79.27 85.69
Coke, m%(is to raw material) 1.35 1.61 1.68 2.00
Loss, m%(is to raw material) 3.35 3.01 3.41 3.00
Pressure, MPa 0.1 0.1 0.1 0.2
Reaction temperature, ℃ 500 550 580 550
Volume space velocity, the time 190 190 220 200
Liquid is received, and m%(is to raw material) 4.38 9.40 8.54 8.00
Wherein contain aromatic hydrocarbons, m% 100 100 100 99.4
The
Two gas recovery ratios, m%(is to raw material) 20.00 24.98 30.65 28.24
Level
Inverse gas is formed, the %(body)
Answer H
225.67 58.39 54.76 54.29
Device C
18.08 15.57 17.13 16.39
C
28.97 10.76 11.65 12.73
C
3+C
457.28 15.28 16.46 16.59
Coke, m%(is to raw material) 0.94 0.92 1.00 1.10
Loss, m%(is to raw material) 1.00 0.98 1.20 1.00
Claims (6)
1, a kind of catalyst that is used for catalytic modification of poor quality gasoline-aromatization method is characterized in that the composition of this catalyst comprises:
(by metallic state, it is heavy to account for catalyst, and) catalyst activity improver is the compound use of Zn, two kinds of elements of Al down together, and Zn/ (Zn+Al) relative weight is than being 0.10-0.90 for (I) 0.3-15m%;
The HZSM-5 molecular sieve of the silica alumina ratio 10-500 that is introduced into (I) of (II) 5.0-94.5m%;
(III) surplus is that a kind of in the mixture that is selected from aluminium oxide, aluminium hydroxide, silica or aluminium oxide and silica, the clay is binding agent.
2, catalyst according to claim 1 is characterized in that this activity of such catalysts improver is 0.5-10.0m%.
3, catalyst according to claim 1 and 2 is characterized in that this activity of such catalysts improver is 0.8-8.0m%.
4, catalyst according to claim 1 is characterized in that activity of such catalysts improver Zn/(Zn+Al) relative weight than for 0.20-0.80.
5, catalyst according to claim 1, the silica alumina ratio that it is characterized in that the HZSM-5 molecular sieve is 20-400; Its content is 10-90m%.
6, catalyst according to claim 1, the silica alumina ratio that it is characterized in that the HZSM-5 molecular sieve is 30-300; Its content is 20-85m%.
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 CN1063121A (en) | 1992-07-29 |
| CN1023687C true CN1023687C (en) | 1994-02-09 |
Family
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Family Applications (1)
| 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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1023687C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered 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 |
| 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 |
| DE112018004207B4 (en) | 2017-08-15 | 2022-09-22 | Sabic Global Technologies B.V. | Shale gas and condensate in chemicals |
-
1992
- 1992-03-05 CN CN 92101228 patent/CN1023687C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1063121A (en) | 1992-07-29 |
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| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
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Expiration termination date: 20120305 Granted publication date: 19940209 |