CN1298425C - Aromatization catalyst, its preparation method and application - Google Patents
Aromatization catalyst, its preparation method and application Download PDFInfo
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- CN1298425C CN1298425C CNB200410060301XA CN200410060301A CN1298425C CN 1298425 C CN1298425 C CN 1298425C CN B200410060301X A CNB200410060301X A CN B200410060301XA CN 200410060301 A CN200410060301 A CN 200410060301A CN 1298425 C CN1298425 C CN 1298425C
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Abstract
The present invention discloses an aromatization catalyst, and a preparation method and application of the catalyst. The catalyst of the present invention is composed of 50 to 90 wt. % of molecular sieves, 0 to 32 wt. % of carriers and 4 to 20 wt. % of adhesive, wherein the molecular sieves are formed by modification HZSM-5 molecular sieves and Y-shaped molecular sieves. Modification elements used by the modification HZSM-5 molecular sieves are zinc, phosphorus and rare earth metal, and the weight percentage content of the modification elements is from 0.01 to 20.0%. of the ZSM-5. The catalyst prepared by using the method of the present invention has the advantages of high aromatization activity, high intensity, high stability and high flowability. The catalyst of the present invention can be used for modifying poor-quality gasoline to produce gasoline components with high octane values or arene. The product produced by using the method of the present invention has the advantages of high yield, stable product performance and stable product distribution.
Description
Technical field
The invention belongs to the petroleum refining field, relate to a kind of aromatized catalyst and its production and application.
Background technology
China's gasoline more than 70% from catalytic cracking unit, and the raw material of China catalytic cracking unit processing has and (comprises Daqing crude oil for the paraffin base class more than 50%, Jilin crude oil, the former wet goods in north, Shen, be referred to as the grand celebration quasi-oil), because it is low that it has density, content of beary metal is low, sulfur content is low, the hydrogen content height, characteristics such as saturated hydrocarbon content height, be that distillate or atmospheric residue all are good catalytically cracked materials, yet its octane number is low to be the weak point of this class raw material, and the catalytic cracking unit Study of Gasoline method octane number aggregate level of processing this class feedstock oil is between 87.5 to 89.5.Along with the raising of environmental requirement, forbid leading.Therefore, the octane number of raising gasoline has been the task of top priority.
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 is the catalytic reforming of raw material with direct steaming gasoline or naphtha, can obtain high octane gasoline component, perhaps aromatic hydrocarbon product.But this technology is subjected to the restriction of raw material sources.People are in order to enlarge raw material sources, proposition is carried out hydrofinishing to secondary processing of gasoline (as pressure gasoline, coker gasoline etc.), as the additional source of its raw material, but cause the work flow complexity and the processing cost of reforming process bigger, the business economic benefit is subjected to very big influence.Technology of aromatization then need not carry out preliminary treatment to raw material, reaction system need not faced hydrogen, do not require the band press operation yet, the fluid product that can obtain and reform similar is formed, and the aromatization carburetion contains the hydro carbons of high branched-chain component and more aromatic components, as high components of octane number such as benzene, aromatic hydrocarbon and isohydrocarbons,, can be used as gasoline high-octane rating blend component fully by concocting the octane number that can improve gasoline effectively.
In recent years, people are to alumino-silicate, are that the aromatization process of catalyst has carried out a large amount of research with the high silica alumina ratio molecular sieve particularly, are that the process of catalyst has been carried out a large amount of research with ZSM-5, ZSM-11 molecular sieve especially.Disclose with carrying a zinc aluminosilicate catalyst as USP4288645, produced 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%.The disclosed catalyst of CN1063121A is with two kinds or three kinds in Zn, Al and three kinds of metallic elements of rare earth Hydrogen ZSM-5 molecular sieve to be carried out modification to make catalyst, is used for the catalytic reforming and the C of inferior patrol
2～C
4The aromatisation of hydrocarbon molecule.The catalyst that is adopted consists of 5.0～94.5% hydrogen type molecular sieve, choose two kinds or three kinds in zinc with 0.3～15%, aluminium and the rare earth element and carry out composite modifiedly, surplus is a kind of as binding agent of the mixture that is selected from aluminium oxide, silica or aluminium oxide and silica, clay.
In existing technology, adopt the fixed bed reaction form, contain gallium or contain Zn molecular sieve catalyst activity stability higher, but exist cost an arm and a leg or in aromatization process zinc easily run off, the catalyst green coke is fast, cause the rapid deactivation of catalyst, address these problems the method that is loaded with two kinds of metals simultaneously that normally adopts, and another kind of metal mostly is noble metal greatly; In course of reaction, adopt the mode of ladder-elevating temperature simultaneously and reactor is frequently switched regeneration according to the inactivation situation of catalyst.The disclosed catalyst of CN1063121A has stronger acidity, therefore in fixed bed reactors aromatized catalyst be easy to because of the green coke inactivation fast, need to adopt a plurality of reactor series connection and alternating temperature operation, cause the frequent switching regeneration or the shut-down regeneration of device simultaneously, the investment of complex operation, catalyst is big, have product distributed mass instability, particularly the dry gas yied increase is bigger in the later stage product, the hydrogen yield instability that aromatisation is produced, and the operation of follow-up combined unit is exerted an influence.
Summary of the invention
The present invention be directed to the easy green coke of aromatized catalyst in the prior art and the shortcoming of inactivation and propose a kind of new aromatized catalyst, this catalyst has higher aromatization activity, intensity, stability and mobile.
In addition, the present invention also is described in detail to the preparation method of this aromatized catalyst with in the technologic application of moving bed catalytic modification of poor quality gasoline.
The aromatized catalyst that the present invention proposes is by 50～90 weight % molecular sieves, and 0～32 weight % carrier and 4～20 weight % binding agents are formed.Wherein molecular sieve is modified HZSM-5 molecular sieve and Y zeolite, and the used modifying element of modified HZSM-5 molecular sieve is zinc, phosphorus and rare earth metal, and wherein the weight percentage of modifying element in ZSM-5 is 0.01～20.0%, is preferably 0.1～10.0%; Y zeolite can be that the content of rare earth that obtains after the rare earth ion exchange is 0.01～25.0%, be preferably 0.1～20.0% REY molecular sieve, also can be through various chemistry and/or physical method,, stabilisation higher as the silica alumina ratio that obtains after the processing such as hydro-thermal method, acidic treatment, aluminium-eliminating and silicon-replenishing method or silicon tetrachloride method high-Si Y-type molecular sieve (abbreviating the REUSY molecular sieve as), it accounts for 0.1～20% of total catalyst weight, and preferably 0.5～15%.Carrier is for being selected from Al
2O
3, ZrO
2, in kaolin, ZnO and the aluminum-spinel two or more, its weight percentage in catalyst is preferably 5～20%, binding agent is polymeric aluminum chloride colloidal sol, Ludox, aluminum phosphate colloidal sol or their mixture, its weight percentage in catalyst preferably 5～15%.
Rare earth metal of the present invention is meant lanthanum or cerium or contains lanthanum and/or the norium of cerium that specifically must contain lanthanum or cerium in this rare earth metal, other thulium is selected arbitrarily.
HZSM～5 molecular sieves that the present invention uses are commercially available HZSM-5 molecular sieve, its SiO
2/ Al
2O
3Than being 20～500, be preferably 25～200, restricted index is 1～2.
The preparation method of aromatized catalyst of the present invention is, molecular sieve and carrier are pulverized fully mixing of back, ball milling to 400～1000 orders, add rolling moulding still, with binding agent and water dilution proportion by 1: 5～1: 10, spray into off and on by atomization plant in the mixture of molecular sieve and carrier, the continuous rolling moulding, until being shaped to diameter is 1.4～2.0 millimeters bead, following dry 2～10 hours at 80～120 ℃ then, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst of the present invention.
Aromatized catalyst provided by the invention can be used for the aromatization modification of inferior patrol and produces technologies such as aromatic hydrocarbons, liquefied gas production aromatic hydrocarbons, also can partly substitute reforming process and produce aromatic hydrocarbons.
The application process of aromatized catalyst of the present invention in modifying inferior patrol production high octane gasoline component or aromatic hydrocarbons, the condition of carrying out the moving bed aromatization under the non-hydrogen state is: reaction temperature is 350～550 ℃, reaction pressure is 0.1～0.5Mpa, and air speed is 0.5～5h
-1, be preferably 1.0～3.0h
-1, when producing the high-knock rating gasoline blend component, reaction temperature is preferably 350～450 ℃, be preferably 460～550 ℃ when producing aromatic hydrocarbons, regeneration condition during catalyst regeneration is: regeneration temperature is 400～550 ℃, and the time of staying in regenerator is 1～600 minute, adopts air regenesis.
Compared with prior art, HZSM-5 molecular sieve in the catalyst of the present invention is a kind of high silicon, novel molecular sieve with three dimensional intersection straight channel, has oleophylic, hydrophobic, characteristics such as heat endurance height, adopt aluminium colloidal sol or Ludox as binding agent, adopt modified molecular screen and rolling forming technique, make catalyst of the present invention can make easily according to preparation method of the present invention that to have diameter be 1.4～2.0 millimeters bead shape and have good aromatization reaction regeneration performance, so catalyst of the present invention has higher aromatization activity, intensity, stable and mobile.
Aromatized catalyst provided by the invention is applied on the moving bed, thereby avoided that catalyst is easy to green coke and inactivation in the fixed bed technology of aromatization, and need to adopt shortcoming and defect such as a plurality of reactor series connection and alternating temperature operation, this application process can be maintained fixed on the basis of technology of aromatization advantage, further improve the reaction and the reproduced state of catalyst, realization response regeneration serialization, aromatization is operated under the optimum condition near fresh catalyst all the time, reaction temperature can be kept constant, product distributes and more optimizes (productive rate of aromatization carburetion and hydrogen is higher), yield is more stable, device has higher running rate, promptly realize long-term operation, and raw material is had bigger adaptability.When device adopts single reactor and single regenerator to constitute, invest also little.In addition, the required catalyst of device also saves 1/2nd than fixed bed.
In addition, in moving-burden bed reactor, can realize the cyclic regeneration of aromatized catalyst, rely on the deadweight of catalyst on the one hand, in regenerator (and reactor), move from top to bottom, on the other hand, the catalyst (or reaction bottom reclaimable catalyst) that moves to the bottom after the regeneration relies on Pneumatic Conveying Technology, rises to reactor (or regenerator) top, react (regeneration), constitute the process that pulsed is bordering on serialization.
The moving bed reaction regenerative process has ripe commercial Application at petrochemical industry, as the naphtha continuous reformer.Moving-burden bed reactor requires the physical property of catalyst: bulk density is less than 0.8g/cm
3, size distribution should be greater than 99% φ 1.4～2.0mm's; Crushing strength is greater than the 40N. grain
-1And wear resistance is better.The existing aromatized catalyst that is used for fixing bed, molecular sieve content is higher, use nitric acid as binding agent simultaneously, and bonding molecular sieve limited in one's ability can not be made the spheric granules catalyst that satisfies above-mentioned requirements.And the composition and the preparation method of employing catalyst of the present invention then can make easily and satisfy the spheric granules catalyst that the moving bed regeneration technology requires, thereby realize the moving bed aromatization.
The raw material of moving bed aromatization of the present invention is low octane value gasoline or naphtha, to its arene underwater content no requirement (NR), also need not carry out preliminary treatment to raw material; Reaction-regeneration can be carried out continuously, thereby can keep constant reaction temperature, makes product yield height, properties of product and product distributional stability.Aromatized catalyst performance with the inventive method preparation is good, active and stability is high, can obtain good product simultaneously again and distribute.
In this specification related percentage composition not specifically mark be weight percentage.
The specific embodiment
With embodiment catalyst of the present invention and preparation thereof and application are further described below, but embodiment does not limit the scope of the invention.
Embodiment 1
Get commercially available silica alumina ratio and be 60 HZSM-5 molecular sieve 1500 grams, restrain Zn (NO with containing 206
3)
2Solution 1000ml and with contain 25 the gram mixed chlorinated rare earths (wherein containing lanthana 21%, cerium oxide 11%) solution 200ml exchange.Promptly under 40 ℃, stir exchange 2 hours fast, filter slurries then, 110 ℃ of following dry cakes 2 hours, filter cake restrains (NH with containing 63.9 again after roasting, pulverizing
4)
2HPO
4Solution 1000ML exchange 2 hours again.After drying, roasting, the pulverizing, get modified HZSM-5 molecular sieve a, wherein Zn content is 2.7%, and the rare earth oxide total amount is 0.5% (wherein lanthana 0.3%, cerium oxide 0.2%), and P content is 1%.
(the pH value is 3.0, contains Al with 714 gram aluminium sol solutions
2O
321%), adds 100 ml deionized water.500 gram modified zsm-5 zeolite a, 150 gram REY type molecular sieves and 200 gram boehmites mix, ball milling to 400～1000 orders, taking a morsel adds in the spin still, starts bowling machine, sprays into the aluminium sol solution off and on, until being shaped to diameter is 1.8～2.0 millimeters pellet catalyst, then 80～120 ℃ dry 2～10 hours down, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst A.Press butt and calculate, contain 50% modified zsm-5 zeolite, contain 15%REY, salic 35%.
Embodiment 2
Get commercially available silica alumina ratio and be 35 HZSM-5 molecular sieve 1500 grams, restrain Zn (NO with containing 420
3)
2Solution 1000ml and with contain 50 the gram lanthanum nitrates (wherein lanthanum content is 13.1%) solution 200ml exchange.Promptly under 40 ℃, stir exchange 2 hours fast, filter slurries then, 110 ℃ dry 2 hours down, after roasting, pulverizing, restrain (NH with containing 63.9 again
4)
2HPO
4Solution 1000ML exchange 2 hours again.Get modified HZSM-5 molecular sieve b after drying, roasting, the pulverizing, wherein Zn content is 5.6%, and rare-earth elements of lanthanum content is 0.398%, and P content is 1%.
(the pH value is 3.0, contains Al to get 476 gram aluminium sol solutions
2O
321%), adds 100 ml deionized water.600 gram modified zsm-5 zeolite b, 80 gram REUSY type molecular sieves and 220 gram boehmites mix, ball milling to 400～1000 orders, taking a morsel adds in the spin still, starts bowling machine, sprays into the aluminium sol solution off and on, until being shaped to diameter is 1.8～2.0 millimeters pellet catalyst, then 80～120 ℃ dry 2～10 hours down, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst B.Press butt and calculate, contain 60% modified zsm-5 zeolite, contain 8%REUSY, salic 32%.
Embodiment 3
Get commercially available silica alumina ratio and be 100 HZSM-5 molecular sieve 1500 grams, restrain Zn (NO with containing 420
3)
2Solution 1000ml and with contain 100 the gram lanthanum nitrates (wherein lanthanum content is 13.1%) (solution 200ml exchange.Promptly under 40 ℃, stir exchange 2 hours fast, filter slurries then, 110 ℃ dry 2 hours down, after roasting, pulverizing, restrain (NH with containing 63.9 again
4)
2HPO
4Solution 1000ML exchange 2 hours again.Get modified HZSM-5 molecular sieve c after drying, roasting, the pulverizing, wherein Zn content is 5.6%, and rare-earth elements of lanthanum content is 0.8%,, P content is 1%.
(the pH value is 3.0, contains Al to get 476 gram aluminium sol solutions
2O
321%), adds 100 ml deionized water.600 gram modified zsm-5 zeolite c, 80 gram REY type molecular sieves and 220 gram boehmites mix, ball milling to 400～1000 orders, and taking a morsel adds in the spin still, starts bowling machine, sprays into the aluminium sol solution off and on.Until being shaped to diameter is 1.8～2.0 millimeters pellet catalyst, then 80～120 ℃ dry 2～10 hours down, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst C.Press butt and calculate, contain 60% modified zsm-5 zeolite, contain 8%REY, salic 32%.
Embodiment 4
Get commercially available silica alumina ratio and be 200 HZSM-5 molecular sieve 1500 grams, restrain Zn (NO with containing 420
3)
2Solution 1000ml and with contain 150 the gram mixed chlorinated rare earths (wherein containing lanthana 21%, cerium oxide 11%) solution 200ml exchange.Promptly under 40 ℃, stir exchange 2 hours fast, filter slurries then, 110 ℃ dry 2 hours down, after roasting, pulverizing, restrain (NH with containing 63.9 again
4)
2HPO
4Solution 1000ML exchange 2 hours again.Get modified HZSM-5 molecular sieve d after drying, roasting, the pulverizing, wherein Zn content is 5.6%, and ree content is 1.5% (wherein lanthanum 1%, cerium 0.5%), and P content is 1%.
(the pH value is 3.0, contains Al with 476 gram aluminium sol solutions
2O
321%), adds 100 ml deionized water.600 gram modified zsm-5 zeolite d, 80 gram REY type molecular sieves and 220 gram boehmites mix, ball milling to 400～1000 orders, and taking a morsel adds in the spin still, starts bowling machine, sprays into the aluminium sol solution off and on.Until being shaped to diameter is 1.8～2.0 millimeters pellet catalyst, then 80～120 ℃ dry 2～10 hours down, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst D.Press butt and calculate, contain 60% modified zsm-5 zeolite, contain 8%REY, salic 32%.
Embodiment 5
Get commercially available silica alumina ratio and be 500 HZSM-5 molecular sieve 1500 grams, restrain Zn (NO with containing 420
3O
2Solution 1000ml and with contain 100 the gram cerous nitrates (wherein cerium 13.38%) solution 200ml exchange.Promptly under 40 ℃, stir exchange 2 hours fast, filter slurries then, 110 ℃ dry 2 hours down, after roasting, pulverizing, restrain (NH with containing 63.9 again
4)
2HPO
4Solution 1000ML exchange 2 hours again.Get modified HZSM-5 molecular sieve e after drying, roasting, the pulverizing, wherein Zn content is 5.6%, and the rare earth element cerium content is 0.78%, and P content is 1%.
(the pH value is 3.0, contains Al with 476 gram aluminium sol solutions
2O
321%), adds 100 ml deionized water.600 gram modified zsm-5 zeolite e, 80 gram REY type molecular sieves and 220 gram boehmites mix, ball milling to 400～1000 orders, and taking a morsel adds in the spin still, starts bowling machine, sprays into the aluminium sol solution off and on.Until being shaped to diameter is 1.8～2.0 millimeters pellet catalyst, then 80～120 ℃ dry 2～10 hours down, 500～600 ℃ of roasting temperatures 1～6 hour, catalyst E.Press butt and calculate, contain 60% modified zsm-5 zeolite, contain 8%REY, salic 32%.
Embodiment 6
Method according to embodiment two prepares catalyst, and (the pH value is 3.0, contains Al just the aluminium sol solution to be adjusted into 381 grams
2O
321%), adds deionized water and be adjusted into 150 milliliters.REY type molecular sieve is adjusted into 10 grams and boehmite is 320 grams, makes catalyst F.Press butt and calculate, contain 60% modified zsm-5 zeolite b, contain 1%REY, salic 39%.
Embodiment 7
Method according to embodiment two prepares catalyst, and just the content with modified zsm-5 zeolite b is adjusted into 650 grams, and the aluminium sol solution is adjusted into 571 grams, and (the pH value is 3.0, contains Al
2O
321%), adds deionized water and be adjusted into 150 milliliters.REY type molecular sieve is adjusted into 50 grams and boehmite is 257 grams, makes catalyst G.Press butt and calculate, contain 65% modified zsm-5 zeolite b, contain 5%REY, salic 30%.
Embodiment 8
Method according to embodiment two prepares catalyst, and just the content with modified zsm-5 zeolite b is adjusted into 690 grams, and the aluminium sol solution is adjusted into 571 grams, and (the pH value is 3.0, contains Al
2O
321%), adds deionized water and be adjusted into 150 milliliters.REY type molecular sieve is adjusted into 10 grams and boehmite is 257 grams, makes catalyst H.Press butt and calculate, contain 69% modified zsm-5 zeolite b, contain 1%REY, salic 30%.
Embodiment 9
Method according to embodiment two prepares catalyst, and just the content with modified zsm-5 zeolite b is adjusted into 700 grams, and the aluminium sol solution is adjusted into 619 grams, and (the pH value is 3.0, contains Al
2O
321%), adds deionized water and be adjusted into 150 milliliters.REY type molecular sieve is adjusted into 100 grams and boehmite is 100 grams, makes catalyst I.Press butt and calculate, contain 70% modified zsm-5 zeolite b, contain 10%REY, salic 20%.
Embodiment 10
Method according to embodiment two prepares catalyst, and just the content with modified zsm-5 zeolite b is adjusted into 750 grams, and the aluminium sol solution is adjusted into 476 grams, and (the pH value is 3.0, contains Al
2O
321%), adds deionized water and be adjusted into 150 milliliters.REY type molecular sieve is adjusted into 30 grams and boehmite is 171 grams, makes catalyst J.Press butt and calculate, contain 75% modified zsm-5 zeolite b, contain 3%REY, salic 22%.
Embodiment 11
Method according to embodiment two prepares catalyst, and just the content with modified zsm-5 zeolite b is adjusted into 800 grams, and the aluminium sol solution is adjusted into 714 grams, and (the pH value is 3.0, contains Al
2O
321%), adds deionized water and be adjusted into 170 milliliters.REY type molecular sieve is adjusted into 50 grams, makes catalyst K.Press butt and calculate, contain 80% modified zsm-5 zeolite b, contain 5%REY, salic 15%.
Embodiment 12
On moving-burden bed reactor, be raw material with the naphtha of Shengli crude, be catalyst with the catalyst B that makes, under the non-hydrogen state, in reaction pressure 0.1Mpa (gauge pressure), air speed is 1.0h
-1, investigate the aromatisation performance of catalyst under the differential responses temperature, the results are shown in Table 1 and table 2.
The aromatization performance of table 1 catalyst when the differential responses temperature
| Reaction temperature ℃ | 375 | 410 | 430 | 460 | 500 | 540 | |
| Air speed, h -1 | 1 | ||||||
| Catalyst | B | ||||||
| Dry gas, % | 1.07 | 2.34 | 4.81 | 8.6 | 14.5 | 18.46 | |
| Liquefied gas, % | 20.95 | 27.68 | 29.8 | 32.8 | 30.6 | 18.13 | |
| Liquid is received, % | 76.41 | 68.64 | 63.9 | 57.3 | 53.46 | 62.03 | |
| Content in the liquid, % | Benzene | 2.73 | 3.15 | 5.6 | 8.4 | 11.13 | 19.92 |
| Toluene | 9.15 | 12.91 | 14.7 | 29.4 | 30.43 | 36.98 | |
| Dimethylbenzene | 10.03 | 13.014 | 14.5 | 15.3 | 16.87 | 16.32 | |
| Ethylbenzene | 1.37 | 1.42 | 1.37 | 1.46 | 1.332 | 1.02 | |
| C 9 | 3.58 | 3.93 | 3.85 | 3.45 | 3.07 | 2.14 | |
| C 10 | 0.2 | 0.19 | 0.23 | 0.29 | 0.38 | 0.2 | |
| Total virtue | 27.06 | 34.61 | 40.25 | 58.3 | 63.2 | 76.58 | |
| Loss+coke, % | 1.57 | 1.34 | 1.49 | 1.3 | 1.44 | 1.38 | |
| Add up to | 100 | 100 | 100 | 100 | |||
| RON | 90.5 | 91.8 | 93.3 | 95.1 | 96.4 | 104.5 | |
Table 2 cracked gas is formed, %
| Reaction temperature/℃ | 375 | 410 | 430 | 460 | 500 | 540 |
| Air speed/h -1 | 1 | |||||
| Hydrogen | 0.14 | 0.35 | 0.72 | 1.34 | 2.11 | 2.25 |
| Methane | 0.24 | 0.68 | 1.33 | 2.62 | 4.31 | 5.28 |
| Ethane | 0.35 | 0.83 | 1.81 | 3.13 | 4.8 | 7.24 |
| Ethene | 0.33 | 0.47 | 0.95 | 1.51 | 3.29 | 3.69 |
| Propane | 12.58 | 17 | 17.92 | 20.62 | 19.55 | 12.38 |
| Propylene | 0.84 | 1.04 | 1.84 | 2.63 | 3.36 | 2.88 |
| Butane | 7.24 | 9.13 | 9.4 | 8.7 | 6.54 | 2.04 |
| Butylene | 0.4 | 0.5 | 0.64 | 0.85 | 1.15 | 0.82 |
Embodiment 13
On moving-burden bed reactor, be raw material with the naphtha of Shengli crude, under the non-hydrogen state, in reaction pressure 0.1Mpa (gauge pressure), volume space velocity is 1.0h
-1, reaction temperature is 410 ℃, to embodiment 1,2, the aromatisation performance of the catalyst of 6～11 preparations is estimated, and the results are shown in Table 3.
The catalyst aromatization performance of table 3 different molecular sieve content
| Reaction temperature ℃ | 410 | ||||||||
| Air speed h -1 | 1.0 | ||||||||
| Catalyst | A | B | F | G | H | I | J | K | |
| Dry gas, % | 2.11 | 2.34 | 2.44 | 2.53 | 2.68 | 2.87 | 2.91 | 2.98 | |
| Liquefied gas, % | 26.95 | 27.68 | 28.7 | 29.27 | 30.6 | 31.24 | 32 | 32.2 | |
| Liquid is received, % | 69.55 | 68.64 | 67.5 | 66.83 | 65.46 | 64.54 | 63.86 | 63.49 | |
| Content % in the liquid | Benzene | 2.88 | 3.15 | 3.36 | 3.54 | 3.75 | 3.99 | 4.15 | 4.34 |
| Toluene | 9.78 | 12.91 | 12.9 | 13.24 | 13.83 | 14.66 | 14.78 | 15.11 | |
| Dimethylbenzene | 11.03 | 13.01 | 14.5 | 15.3 | 15.97 | 16.32 | 16.86 | 17.64 | |
| Ethylbenzene | 1.4 | 1.42 | 1.46 | 1.57 | 1.65 | 1.73 | 1.82 | 1.98 | |
| C 9 | 3.64 | 3.93 | 4.21 | 4.48 | 4.88 | 5.11 | 5.33 | 6.1 | |
| C 10 | 0.22 | 0.19 | 0.23 | 0.32 | 0.38 | 0.45 | 0.49 | 0.55 | |
| Total virtue | 28.95 | 34.61 | 36.66 | 38.45 | 40.46 | 42.26 | 43.43 | 45.72 | |
| Loss+coke, % | 1.39 | 1.34 | 1.36 | 1.37 | 1.26 | 1.35 | 1.23 | 1.33 | |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
| RON | 88.2 | 91.8 | 92 | 92.1 | 92.4 | 92.8 | 93.1 | 93.5 | |
Embodiment 14
Naphtha with Shengli crude is a raw material, under the non-hydrogen state, utilize catalyst B to carry out the aromatisation test at fixed bed and moving-burden bed reactor respectively, investigate of the influence of two kinds of technologies properties of product and distribution, reaction pressure is 0.1Mpa (gauge pressure) under two kinds of situations, and volume space velocity is 1.0h
-1, the results are shown in Table 4.
Two kinds of technology contrasts of table 4
| Technology type | The fixed bed aromatisation | The moving bed aromatisation | |
| Reaction temperature/℃ | 320～460 | 410 | |
| Product distribution % | Dry gas+loss+coke | 5.7 | 3.68 |
| Liquefied gas | 28.1 | 27.68 | |
| Reformulated gasoline | 66.2 | 68.64 | |
| Total light receipts | 94.3 | 96.32 | |
| The gasoline main character | Aromatic hydrocarbons, v% | 30 | 34.61 |
| Alkene, v% | 0 | 0 | |
| Benzene, v% | 1.8 | 3.15 | |
| Octane number RON | 90.3 | 91.8 | |
Claims (7)
1. aromatized catalyst, it is characterized in that: this catalyst is by 50～90 weight % molecular sieves, 0～32 weight % carrier and 4～20 weight % binding agents are formed, wherein molecular sieve is modified HZSM-5 molecular sieve and Y zeolite, the used modifying element of modified HZSM-5 molecular sieve is a zinc, phosphorus and rare earth metal, the weight percentage of modifying element in ZSM-5 is 0.01～20.0%, Y zeolite is that the content of rare earth that obtains after rare earth ion exchange is 0.01～25.0% REY molecular sieve, or the high-Si Y-type molecular sieve that after various chemistry and/or physical method processing, obtains, account for 0.1～20% of total catalyst weight.
2. catalyst according to claim 1 is characterized in that: described Y zeolite accounts for 0.5～15% of total catalyst weight, and carrier accounts for 5～20% of total catalyst weight, and binding agent accounts for 5～15% of total catalyst weight.
3. catalyst according to claim 1 is characterized in that: the weight percentage of modifying element in ZSM-5 is 0.1～10.0% in the modified HZSM-5 molecular sieve.
4. catalyst according to claim 1 is characterized in that: described rare earth metal is lanthanum or cerium or contains lanthanum and/or the norium of cerium.
5. the preparation method of the described aromatized catalyst of claim 1, it is characterized in that: this method is that molecular sieve and carrier are pulverized fully mixing of back, join behind ball milling to 400～1000 orders in the rolling moulding still, with binding agent and water dilution proportion by 1: 5～1: 10, spray into off and in the mixture of molecular sieve and carrier, the continuous rolling moulding, until being shaped to diameter is 1.4～2.0 millimeters bead, following dry 2～10 hours at 80～120 ℃ then, 500～600 ℃ of roasting temperatures 1～6 hour, aromatized catalyst.
6. the application of the described aromatized catalyst of claim 1 in modifying inferior patrol production high octane gasoline component or aromatic hydrocarbons, it is characterized in that: the condition of carrying out the moving bed aromatization under the non-hydrogen state is, reaction temperature is 350～550 ℃, reaction pressure is 0.1～0.5Mpa, and air speed is 0.5～5h
-1, the regeneration temperature during catalyst regeneration is 400～550 ℃, the time of staying in regenerator is 1～600 minute, adopts air regenesis.
7. according to the application of the described aromatized catalyst of claim 6, it is characterized in that: when aromatized catalyst was used for the production high octane gasoline component, reaction temperature was 350～450 ℃; When being used to produce aromatic hydrocarbons, reaction temperature is 460～550 ℃.
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| CN101314731B (en) * | 2007-05-31 | 2012-01-25 | 中国石油化工股份有限公司 | Aromatization method without hydrogen for light hydrocarbon |
| CN101733140B (en) * | 2008-11-18 | 2012-01-11 | 中国石油天然气股份有限公司 | Preparation method of shape-selective molecular sieve composition |
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| CN102218341B (en) * | 2010-04-13 | 2013-01-02 | 中国石油化工集团公司 | Aromatization catalyst and applications thereof |
| CN103357430B (en) * | 2012-03-30 | 2015-08-19 | 中国科学院大连化学物理研究所 | A kind of aromatisation cocrystallized molecular sieve catalyst, preparation method and application thereof |
| CN103657708A (en) * | 2012-09-07 | 2014-03-26 | 中国石油天然气集团公司 | Catalyst for aromatization and quality modification of catalytic gasoline |
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| CN107952476B (en) * | 2017-12-13 | 2021-02-09 | 中石化炼化工程（集团）股份有限公司 | Catalyst for preparing gasoline blending component by coupling alcohol naphtha, preparation method and application thereof |
| CN109749774B (en) * | 2019-01-31 | 2020-01-14 | 东方傲立石化有限公司 | Naphtha aromatization method |
| CN114425408B (en) * | 2020-10-14 | 2024-01-30 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method thereof |
| CN114762832B (en) * | 2021-01-12 | 2023-12-08 | 洛阳市科创石化科技开发有限公司 | Preparation method and application of catalyst for producing mixed propylbenzene by alkylation of benzene and carbon tetraolefin |
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