CN101367048A - Preparation method and uses of condensate oil aromatization catalyst - Google Patents
Preparation method and uses of condensate oil aromatization catalyst Download PDFInfo
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- CN101367048A CN101367048A CNA2008102236687A CN200810223668A CN101367048A CN 101367048 A CN101367048 A CN 101367048A CN A2008102236687 A CNA2008102236687 A CN A2008102236687A CN 200810223668 A CN200810223668 A CN 200810223668A CN 101367048 A CN101367048 A CN 101367048A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method and application of aromatization catalyst for gas condensate. The method is to load metal active components onto a nano molecular sieve, which comprises 0.1 to 10.0 weight percent of noble metal platinum, 1.0 to 10.0 weight percent of a second metal M, 89.0 to 98.9 weight percent of a carrier, wherein the carrier is composed of 60 to 90 weight percent of a nano HZSM-5 molecular sieve and titanium dioxide, the balance being aluminum oxide, the noble metal platinum is a fist active component. The catalyst is applicable to production of aromatic hydrocarbon through aromatization of gas condensate. With gas condensate as the raw material, benzene, toluene, xylene (BTX) together with a byproduct of 18 to 28 weight percent of high quality liquid gas are produced in a reactor of moving bed under the conditions of a total reaction pressure of between 0.5 and 2.0 Mpa, a temperature of between 400 and 580 DEG C, a weight space velocity of the raw material of between 0.5 and 4.0 h <-1>. The catalyst has high actively and selectivity anti-carbon capacity, reusability and high yield rate of aromatic hydrocarbon products.
Description
Technical field
The present invention relates to a kind of preparation method and application of condensate oil aromatization catalyst, more particularly, is a kind of molecular sieve carried reactive metal aromatized catalyst of condensate and preparation method thereof that is used for, and with the aromatization method of described catalyst to condensate.
Background technology
Along with oil step up exploitation and condensate gas field large scale mining, will a large amount of condensate product (C of generation
3-C
12), condensate is the liquid hydrocarbon without fractionation that reclaims with natural gas and casing-head gas, and it is the mixture of short hydrocarbon and long chain hydrocarbon, and at 60 ~ 80 weight %, diesel yield is usually at 20 ~ 40m% usually for the yield of naphtha." West-east Gas is the great engineering project that China carried out at the beginning of 21 century; a large amount of natural gas condensate resource that obtains in gas exploitation course; and the condensate component differs greatly because of oil gas field structure difference; highly volatile; the storage process loss is big; also dangerous, so the heavy industrialization of condensate is processed with certain degree of difficulty.For the bigger oil gas field of condensate yield.Generally can be with its raw material as ethylene industry, but the centering small field then should select suitable way to be used as the case may be.Current, condensate is except that producing ethene, the propylene as tube cracking furnace, also has a large amount of condensates to act as a fuel oil and burnt, and causes its use very uneconomical.
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 or aromatic hydrocarbon product.But this technology is subjected to the restriction of raw material sources.People propose secondary processing of gasoline (as pressure gasoline, coker gasoline etc.) is carried out hydrofinishing in order to enlarge raw material sources, as the additional source of its raw material, but cause the work flow complexity and the processing cost of reforming process to strengthen.Condensate is directly produced aromatic hydrocarbons (benzene,toluene,xylene) through aromatisation, and it not only provides new raw material sources for industrial chemicals aromatic hydrocarbons, has also opened up new approach for the comprehensive utilization of petroleum resources.Technology of aromatization then need not carry out degree of depth preliminary treatment to raw material, reaction system need not faced hydrogen, do not require operation with high pressure yet, the fluid product that can obtain and reform similar is formed, the aromatization carburetion contains high branched-chain component and more aromatic components, as high-octane rating components such as benzene, aromatic hydrocarbons and isoparaffins, can be used for doing the high-knock rating gasoline blend component or produce aromatic hydrocarbon product.
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.The disclosed catalyst of CN106312A 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 the hydrogen type molecular sieve of 5.0 ~ 94.5 weight %, with two kinds in zinc, aluminium and the thulium of 0.3 ~ 15 weight % or three kinds Hydrogen ZSM-5 molecular sieve is carried out composite modifiedly, and surplus is for being selected from aluminium oxide.The mixture of silica or aluminium oxide and silica, clay a kind of as binding agent.
CN1080313A discloses a kind of catalytic modification of poor quality gasoline-aromatization method, and its catalyst is the rare earth modified HZSM-5 zeolite of Zn-Al or Zn-Al-, and is binding agent with aluminium oxide or silica.This technology adopts the two-part reaction unit, first order reactor makes raw material and catalyst haptoreaction under non-hydrogen, 300 ~ 500 ℃, the condition of 0.05 ~ 1.2MPa, weight (hourly) space velocity (WHSV) 0.2 ~ 10, reaction is produced thing through gas-liquid separation, the liquid discharge device aftercut that C5 is above, again the gasoline fraction that obtains is sent into second level reactor, carry out aromatization under 0.05 ~ 1.5MPa, volume space velocity 20 ~ 2000,480 ~ 650 ℃ of conditions of bed temperature, reaction is produced thing and is obtained aromatic hydrocarbons mixture and the gas that is rich in hydrogen through gas-liquid separation.Its weak point is that feedstock oil obtains the liquid of 45-65% (it is heavy to account for feedstock oil) after first order reaction, and liquid yield is not high, and crackate is too much.
In existing technology, adopt fixed bed reactors processing to handle, contain gallium or contain Zn molecular sieve catalyst activity stability higher, but zinc is easy to run off in aromatization process, the catalyst green coke is fast, cause catalysqt deactivation rapid, address these problems the method that is loaded with two kinds of metals simultaneously that normally adopts, in course of reaction, adopt the method for ladder-elevating temperature simultaneously and reactor is frequently switched regeneration according to the inactivation situation of catalyst.CN1185997A discloses a kind of catalyst with metal component that is used for producing arenes from natural gasoline, it is made up of three kinds of metals, its mainly be by zeolite with mainly be to make catalyst carrier after the alundum (Al gel mixed-forming extrusion, the method by ion-exchange, absorption, dipping then.Metal component zinc, gallium, platinum are introduced the zeolite catalysis agent carrier, and catalyst is made in drying, roasting, adopts fixed bed reactors to be used for condensate and produces aromatic hydrocarbons.But use 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 of device or the regeneration of stopping work simultaneously, complex operation, and have respectively quality instability of product, particularly the dry gas yied increase is bigger in the later stage product.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of preparation method of condensate oil aromatization catalyst, this catalyst has higher aromatization activity and selectivity, and carbon accumulation resisting ability is strong, intensity height, good stability, aromatic hydrocarbon product yield height.
Another object of the present invention provides the method for condensate aromatisation in moving-burden bed reactor.
A kind of preparation method of condensate oil aromatization catalyst is characterized in that:
Condensate oil modifying catalyst is a carried metal active component on nano molecular sieve, comprises the noble metal platinum of 0.1 ~ 1.0 weight %, second metal M of 1.0 ~ 10.0 weight %, the carrier of 89.0 ~ 98.9 weight %.Wherein said carrier is made up of the aluminium oxide of 60～80 weight % modified nano molecular sieves, 10～20 weight % titanium dioxide and surplus.The supported active metal component comprises the noble metal platinum and second metal M, at first use platinum that nanometer HZSM-5 molecular sieve is carried out modification, noble metal platinum is first active component, its weight percentage is 0.1 ~ 1.0 weight %, be preferably 0.15～0.35 weight %, treat after the carrier moulding that in load second metal M, its weight percentage is 1.0 ~ 10.0 weight %, second metal M refers to a kind of among Zn, Co, Ni, W, Fe, Cu, Mn, Zr, the Mo.
The HZSM-5 molecular sieve that the present invention uses is commercially available nanometer HZSM-5 molecular sieve, and its silica alumina ratio is 20～500, is preferably 25～200, and restricted index is 1～2.
The preparation method of condensate oil aromatization catalyst comprises: (1) at first carries out modification to nanometer HZSM-5 molecular sieve, uses the solution contain noble metal platinum that nanometer HZSM-5 molecular sieve is flooded, and after dry, the roasting, and then molecular sieve is carried out hydrothermal treatment consists; (2) modified Nano HZSM-5 molecular sieve after this handles and titanium dioxide, boehmite are pulverized fully mixing of back, ball milling to 400～1000 orders, add rolling moulding still, the dilution proportion that binding agent and water are pressed 1:5～1:10, spray into off and on by atomization plant in the mixture of molecular sieve and carrier, the continuous rolling moulding is 1.4 ~ 2.0 millimeters a bead until being shaped to diameter, then 80～120 ℃ dry 4～16 hours down, 400～600 ℃ of roasting temperatures 2～6 hours; (3) adopt the soluble-salt solution of second metal M to carry out the second reactive metal M on the dip loading, then 80～120 ℃ dry 4～16 hours down, 400～600 ℃ of roasting temperatures 2～6 hours, make catalyst of the present invention.
The purpose of in the described method molecular sieve being carried out hydrothermal treatment consists is to regulate its acidity, and its treatment temperature is preferably 500 ~ 550 ℃, and the processing time is preferably 3 ~ 8 hours, and the weight ratio of total water amount and catalyst is 1 ~ 4 during processing.The hydrothermal treatment consists condition should suitably be regulated according to the silica alumina ratio of molecular sieve, the height of acid cracked activity, is in the state of coordinating most with acid function and the dehydrogenation functionality that guarantees catalyst.The consumption of maceration extract is 0.5 ~ 1.5 milliliter in every gram carrier during activity component impregnation, preferred 0.8 ~ 1.2 milliliter, the precursor of platinum can be selected from chloroplatinic acid, ammonium chloroplatinate, platinum nitrate etc. in the solution of described platiniferous, and the soluble-salt of described second metal M can be nitrate or carbonate.
In the above-mentioned catalyst preparation process, described baking temperature is 80 ~ 120 ℃, and the time is 4 ~ 16 hours, is preferably 6～8 hours, and sintering temperature is 400 ~ 600 ℃, is preferably 450 ~ 550 ℃, and the time is 2 ~ 6 hours, is preferably 2 ~ 4 hours.
Aromatized catalyst provided by the invention can be used for the aromatization modification of condensate to generate aromatic component, also can make the high-knock rating gasoline blend component.
The application process of aromatized catalyst of the present invention in the condensate oil aromatization process, the condition of carrying out moving bed reaction under conditions of non-hydrogen is: 400 ~ 580 ℃ of reaction temperatures, reaction stagnation pressure 0.5 ~ 2.0MPa, raw material weight air speed 0.5 ~ 4.Oh
-1, be preferably 0.8 ~ 2.5h
-1Regeneration condition during catalyst regeneration is: 400～550 ℃ of regeneration temperatures, the time of staying in regenerator is 1～200 minute, adopts air regenesis.This catalyst has higher activity and selectivity, and carbon accumulation resisting ability is strong, and iterative regenerable uses, and aromatic hydrocarbon product yield height uses moving-burden bed reactor can produce BTX three benzaldehyde products, simultaneously the high-quality liquefied gas of by-product 18 ~ 28 weight %.
Compared with prior art, nanometer HZSM-5 in the catalyst of the present invention all shows superior performance owing to having bigger external surface area and higher intracrystalline diffusion rate at aspects such as the utilization rate that improves catalyst, the big molecule conversion capability of enhancing, minimizing deep reaction, raising selectivity and reduction coking and deactivations.With aluminium colloidal sol is binding agent, adopt modified molecular screen and rolling forming technique, make catalyst of the present invention according to preparation method of the present invention make easily have diameter be 1.4 ~ 2.0 millimeters bead shape and have good aromatization performance and regenerability, so catalyst of the present invention has higher aromatization activity, intensity, stability and mobile.
Condensate oil aromatization 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 deficiencies 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, and as the naphtha continuous reformer, moving-burden bed reactor requires the physical property of catalyst: bulk density is less than 0.8 gram per centimeter
3, size distribution should be greater than 99% 1.4 ~ 2.0 millimeters of ф's; Ew Year gift money intensity is greater than the 40N. grain
-1And abrasion 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 of catalyst of the present invention and preparation method 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 aromatization of the present invention is a condensate, and aromatization carries out under conditions of non-hydrogen, 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.Condensate oil aromatization catalyst performance with the inventive method preparation is good, active and stability is high, can obtain good product simultaneously again and distribute.
The specific embodiment
Describe the present invention in detail with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1
Prepare catalyst of the present invention.
(1) getting commercially available silica alumina ratio is 38 nanometer HZSM-5 molecular sieve, 1500 grams, flood for 1000 milliliters with the solution that contain 11.2 gram chloroplatinic acids, then 120 ℃ dry 12 hours down, 450 ℃ of roastings 3 hours;
(2) hydrothermal treatment consists: the molecular sieve behind (1) step load platinum is packed in the tubular reactor, in air stream, be warming up to 520 ℃ under the normal pressure, change water flowing steam treated 8 hours then under this temperature, feed dry air again and purge cooling, total inflow is 3000 grams in the steam treatment process;
(3) (the pH value is 3.0 to get 700 gram aluminium colloidal sols, salic 21%), adds 100 ml deionized water, make binding agent, then (2) being obtained the nanometer HZSM-5 molecular sieve after the modification, commercially available titanium dioxide 250 grams pulverizes with 200 gram boehmites and then fully mixes, ball milling to 400～1000 orders adds in the rolling still, starts the rolling still, spray into the aluminium sol solution batch (-type), until the bead that is shaped to 1.8 ~ 2.0 millimeters of diameters, then 120 ℃ of dryings 12 hours, 550 ℃ of roastings 3 hours;
(4) get (3) step bead that obtains 100 grams, floods for 100 milliliters with the solution that contain 23.4 gram zinc nitrates, again 120 ℃ of dryings 12 hours, 550 ℃ of roastings 3 hours make catalyst A.
Press butt and calculate, contain 66.8 weight % modified Nano HZSM-5 molecular sieves in the catalyst A, 12.0 weight % titanium dioxide, salic 16.0 weight %, wherein the reactive metal platinum content is 0.2 weight %, another metallic zinc content is 5.0 weight %.
Embodiment 2
Method by embodiment 1 prepares other several catalyst B, C, different is to change second metal types and content, be respectively B (nickel 5.0 weight %, (4) step in contain 26.5 the gram nickel nitrates 100 milliliters of dippings of solution), C (cobalt 5.0 weight %, (4) step in contain 26.0 the gram cobalt nitrates 100 milliliters of dippings of solution).
Embodiment 3
Method by embodiment 1 prepares catalyst, and different is that the boehmite amount of mixing with nanometer HZSM-5 molecular sieve is 250 grams, and all the other carriers and tenor are constant, make catalyst D.
Embodiment 4
Method by embodiment 1 prepares catalyst, and different is when mixing with modified Nano HZSM-5 powder, and the addition of titanium dioxide changes 300 grams into, and all the other carriers and tenor are constant, make catalyst E.
Embodiment 5
In moving-burden bed reactor, be raw material with the condensate, its boiling range is 30 ~ 255 ℃, d
25°
CDensity is 0.7943 grams per milliliter, and group composition is: alkane 79.8%, and cycloalkane 17.45%, aromatic hydrocarbons 2.75%, adopting the catalyst A that makes is test catalyst, under the conditions of non-hydrogen, at reaction pressure 0.5MPa, air speed 1.0h
-1, investigated the aromatisation performance of catalyst under the differential responses temperature, the results are shown in Table 1 and table 2.
Embodiment 6
In moving-burden bed reactor, be raw material with condensate among the embodiment 5, under conditions of non-hydrogen, at reaction pressure 0.5MPa, air speed 1.0h
-1, 500 ℃ of reaction temperatures are carried out the evaluation of aromatisation performance for stability to the catalyst A that makes among the embodiment 1, and experimental result sees Table 3.
Embodiment 7
In moving-burden bed reactor, be raw material with condensate among the embodiment 5, under conditions of non-hydrogen, at reaction pressure 0.5MPa, air speed 1.Oh
-1, 500 ℃ of reaction temperatures are carried out aromatisation performance evaluation to the catalyst A-E that makes among the embodiment 1～3, and experimental result sees Table 4.
As shown in Table 4, catalyst A of the present invention is in 1200 hours stability running, and arene content maintains comparatively stable level in liquid yield and the liquid, and no significant change illustrates that catalyst of the present invention has good activity stability.
The aromatisation performance of table 1 catalyst A when the differential responses temperature
Table 2 temperature optionally influences condensate oil aromatization tail gas hydrocarbon component
Table 3 different catalysts aromatization performance
Table 4 catalyst A stability experiment result
| Reaction time, hour | 100 | 300 | 500 | 800 | 1200 |
| Dry gas, weight % | 4.6 | 4.4 | 4.5 | 4.6 | 4.5 |
| Liquefied gas, weight % | 25.4 | 24.1 | 23.6 | 24.1 | 24.2 |
| Liquid yield, weight % | 68.6 | 69.7 | 70.1 | 68.9 | 69.7 |
| Arene content in the liquid, weight % | 69.98 | 70.34 | 70.10 | 69.89 | 69.99 |
Claims (4)
1. the preparation method of a condensate oil aromatization catalyst is characterized in that:
Condensate oil aromatization catalyst is a carried metal active component on nano molecular sieve, the noble metal platinum that comprises 0.1～1.0 weight %, 1.0 second metal M of～10.0 weight %, 89.0 the carrier of～98.9 weight %, wherein said carrier is made up of the aluminium oxide of 60～80 weight % modified nano molecular sieves, 10～20 weight % titanium dioxide and surplus;
The preparation method of condensate oil aromatization catalyst, load bimetallic active component at first, the supported active metal component comprises the noble metal platinum and second metal M, at first use platinum that nanometer HZSM-5 molecular sieve is carried out modification, noble metal platinum is first active component, treat after the carrier moulding load second metal M again, the second metallized metal M refers to a kind of among Zn, Co, Ni, W, Fe, Cu, Mn, Zr, the Mo;
Preparation process comprises:
(1) at first nanometer HZSM-5 molecular sieve is carried out modification, use the solution contain noble metal platinum that nanometer HZSM-5 molecular sieve is flooded, after dry, the roasting, and then molecular sieve carried out hydrothermal treatment consists;
(2) modified Nano HZSM-5 molecular sieve after this handles and titanium dioxide, boehmite are pulverized fully mixing of back, ball milling to 400～1000 orders, add rolling moulding still, the dilution proportion that binding agent and water are pressed 1:5～1:10, spray into off and on by atomization plant in the mixture of molecular sieve and carrier, the continuous rolling moulding is 1.4～2.0 millimeters a bead until being shaped to diameter, then 80～120 ℃ dry 4～16 hours down, 400～600 ℃ of roasting temperatures 2～6 hours;
(3) adopt the soluble-salt solution of second metal M to carry out the second reactive metal M on the dip loading, then 80～120 ℃ dry 4～16 hours down, 400～600 ℃ of roasting temperatures 2～6 hours, make catalyst of the present invention.
2. according to the described Preparation of catalysts method of claim 1, it is characterized in that the application of described catalyst in condensate oil aromatization, the condition of carrying out the moving bed aromatization under conditions of non-hydrogen is 400～580 ℃ of reaction temperatures, reaction stagnation pressure 0.5～2.0MPa, raw material weight air speed 0.5～4.0h
-1, the regeneration temperature during catalyst regeneration is 350～550 ℃, the time of staying in regenerator is 1～200 minute, adopts air regenesis.
3. according to the described Preparation of catalysts method of claim 1, it is characterized in that:
(1) the hydrothermal treatment consists process is that the platiniferous nanometer HZSM-5 molecular sieve after the roasting is warming up to 400～600 ℃ behind the load platinum in air stream in the step, handles 1～12 hour with pure water vapor again, and the weight ratio of total water amount and catalyst is 1～4 during processing.
4. according to the described Preparation of catalysts method of claim 1, it is characterized in that:
Dipping temperature during the dipping active metal component is 20～60 ℃, the consumption of maceration extract is 0.5～1.5 milliliter in every gram carrier during dipping, the soluble-salt of described platinum is selected from chloroplatinic acid, ammonium chloroplatinate, platinum nitrate, and the soluble-salt of second metal M is nitrate or carbonate.
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| CN103183580A (en) * | 2013-02-07 | 2013-07-03 | 大连理工大学 | Method of using Au-loaded zeolite catalyst to transform C6 or more aliphatic hydrocarbon into aromatic hydrocarbon |
| CN104511292A (en) * | 2013-09-27 | 2015-04-15 | 中国石油天然气股份有限公司 | A continuous-reforming catalyst and a preparing method thereof |
| CN108404972A (en) * | 2018-02-08 | 2018-08-17 | 中国石油大学(北京) | A kind of aromatized catalyst and preparation method thereof and regeneration method and aromatization method |
| CN109622022A (en) * | 2018-12-05 | 2019-04-16 | 大连理工大学 | A kind of preparation method and application of high dispersive Pt modified Nano HZSM-5 catalyst |
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| CN108404972A (en) * | 2018-02-08 | 2018-08-17 | 中国石油大学(北京) | A kind of aromatized catalyst and preparation method thereof and regeneration method and aromatization method |
| CN111013642A (en) * | 2018-10-10 | 2020-04-17 | 中国石油化工股份有限公司 | Anti-carbon deposition catalyst for preparing propylene by propane dehydrogenation and preparation method thereof |
| CN111013642B (en) * | 2018-10-10 | 2022-10-14 | 中国石油化工股份有限公司 | Anti-carbon deposition catalyst for preparing propylene by propane dehydrogenation and preparation method thereof |
| CN109622022A (en) * | 2018-12-05 | 2019-04-16 | 大连理工大学 | A kind of preparation method and application of high dispersive Pt modified Nano HZSM-5 catalyst |
| WO2021236149A1 (en) * | 2020-05-21 | 2021-11-25 | Saudi Arabian Oil Company | Conversion of light naphtha to enhanced value products in an integrated two-zone reactor process |
| US11365358B2 (en) | 2020-05-21 | 2022-06-21 | Saudi Arabian Oil Company | Conversion of light naphtha to enhanced value products in an integrated two-zone reactor process |
| CN114073977A (en) * | 2020-08-21 | 2022-02-22 | 国家能源投资集团有限责任公司 | Noble metal supported catalyst, preparation method and application thereof, and method for improving aromatic hydrocarbon yield in process of preparing aromatic hydrocarbon from light hydrocarbon |
| CN117358291A (en) * | 2023-12-08 | 2024-01-09 | 山东新和成药业有限公司 | Catalyst for preparing oxabicyclo hexadecene, and preparation method and application thereof |
| CN117358291B (en) * | 2023-12-08 | 2024-02-27 | 山东新和成药业有限公司 | Catalyst for preparing oxabicyclo hexadecene, and preparation method and application thereof |
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