CN101869834A - Selective hydrogen burning catalyst for internal heating of petroleum hydrocarbon cracking raw materials and application thereof - Google Patents
Selective hydrogen burning catalyst for internal heating of petroleum hydrocarbon cracking raw materials and application thereof Download PDFInfo
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Abstract
The invention discloses a selective hydrogen burning catalyst for internal heating of petroleum hydrocarbon-kind cracking raw materials. The selective hydrogen burning catalyst comprises the following components: noble metal platinum, alkali metal, alkaline-earth metal or rare earth metal, various molecular sieves which have the diameter of more than 6 and have a regular pore structure, and a bonding agent. Under the action of the selective hydrogen burning catalyst, the mixed materials can realize the process of internal heating of hydrogen burning by a catalyst bed layer, so the temperature of the petroleum hydrocarbon cracking raw materials and a thinner can be increased to the temperature required by subsequent cracking reactions.
Description
Technical field
The present invention relates to a kind of hydrogen burning catalysts and application thereof, especially relate to a kind of be used for petroleum hydrocarbon cracking raw materials heating process selective hydrogen burning catalyst for reaction and application thereof.
Background technology
Because petroleum hydrocarbon cracking is produced the strong endothermic character of high temperature of low carbon olefin hydrocarbon, the petroleum hydrocarbon cracking needs a large amount of heat supplies, to reach the harsh conditions that cracking reaction needs.The reaction temperature of the steam heat cracking technology of present industrial employing up to 600-900 ℃ is by guaranteeing with indirect external heating mode at a large amount of hydrocarbon of tubular reactor external firing; Moreover, have only 40% heat to be used as the reaction heat supply in the pyrolysis furnace radiant section burning heat release; Therefore traditional steam heat cracking technology is faced with huge energy demand and the low problem of heat transfer efficiency that superhigh temperature is provided by outside indirect mode, needs to improve energy utilization efficiency.
Because the importance of energy problem, people seek new energy source always beyond the petrochemical industry resource, and wherein more noticeable is Hydrogen Energy.Utilize Hydrogen Energy to replace the application of traditional fossil energy to provide heat to heat reaction raw materials, obtained some achievements in research as utilizing hydroxide reaction.From the angle of supplying energy, the SMART styrene technology that provides with U.S. Pat 4914249 and US4812597 provides useful reference.This technology is the new technology that increases H 2 selective oxidation on the basis of ethylbenzene dehydrogenation, comprises dehydrogenation-hydroxide-continuation dehydrogenation three-step reaction.Concrete, adopt selective hydrogen burning catalyst to make the hydrogen in the logistics of ethylbenzene part dehydrogenation afterreaction under the situation that hydrocarbon species such as ethyl benzene/styrene exist, carry out selective combustion, utilize energy that hydrogen burning produces with direct-fired mode the temperature of logistics bring up to dehydrogenation reaction can take place temperature (approximately 500-600 ℃) with dehydrogenation once more, thereby replaced traditional intersegmental indirect external heating mode.This technology burning hydrogen optionally under the situation that hydrocarbon species exist, thus provide energy to improve the heat-transfer effect of logistics high-temperature heat supply process in direct-fired mode, improved heat transfer efficiency, saved energy; Because one of product of ethylbenzene dehydrogenation hydrogen is consumed by hydroxide reaction, also help ethylbenzene dehydrogenation reaction and move, thereby improved the conversion ratio of reaction simultaneously to generating the styrene direction.Inevitably can lose aromatic hydrocarbons and cause that cost of material rises owing to carry out hydroxide reaction, therefore, the key of SMART styrene technology successful implementation is to have developed high performance selective hydrogen burning catalyst.
Mostly the catalyst that is used for the hydrogen burning process of ethylbenzene part dehydrogenation logistics (being made up of ethylbenzene, styrene and other aromatic hydrocarbon and hydrogen) is with the aluminium oxide to be carrier, and platinum and tin are on active component or the metal oxide carrier that platinum is carried on tin etc.PtSnLi/Al is disclosed among U.S. Pat 4914249 and the US4812597
2O
3Catalyst is used for ethylbenzene dehydrogenation-hydrogen burning process, and the location of precious metals pt in catalyst wherein retrained.U.S. Pat 5872075 discloses and has adopted Pt to be carried on to have the specific specific surface and the Al of acid strength
2O
3Catalyst be used for ethylbenzene dehydrogenation-hydrogen burning process.U.S. Pat 5994606 discloses and has adopted Pt or the Pd catalyst of support type to be used for ethylbenzene dehydrogenation-hydrogen burning process, wherein with the oxide of Sn, Ti, Ta, Nb or their mixture as carrier.U.S. Pat 5001291 adopts Pd, Pt, Rh or Ru catalyst on the oxide that loads on tin, is used for ethylbenzene dehydrogenation-hydrogen burning process.
Disclose among Chinese patent CN1751792A and the CN1704158A with containing the compound modified Pt/Al of F
2O
3Catalysts and its preparation method.In Chinese patent CN1704160A, propose to add zirconium, metal pair Pt/Al such as titanium
2O
3Catalyst carries out modification, proposes to adopt honeycomb support to improve Pt/Al in Chinese CN1704159A
2O
3Catalyst performance.These patents all clearly propose catalyst and are applied in ethylbenzene dehydrogenation-hydrogen burning process, can solve the oxygen conversion or the not high enough problem of oxygen selectivity of catalyst for hydroxide reaction in the ethylbenzene dehydrogenation process.
As previously mentioned, existing petroleum hydrocarbon steam heat cracking technology mainly adopts indirect external heating mode to guarantee the reaction temperature of high-temperature steam thermal cracking, mode of heating in this mode of outer heating is indirectly compared directly will inevitably cause the loss in the energy transfer process.Transform the development of producing the low-carbon alkene technology in order to continue to promote petroleum hydrocarbon, in today and the future that the energy is becoming tight day by day, providing a kind of is that raw material is produced low-carbon alkene with the petroleum hydrocarbon, and the method that the while energy consumption reduces significantly is extremely necessary.If hydrogen can be mixed with petroleum hydrocarbon; mode by selective combustion hydrogen under the selective hydrogen burning catalyst effect discharges its chemical energy; the temperature that improves petroleum hydrocarbon raw material in direct-fired mode makes it to carry out follow-up hydrocarbon conversion chemical reaction; to be to improve heat-transfer effect; improve heat transfer efficiency; conserve energy is also protected environment, improves the petroleum hydrocarbon cracking and prepares one of effective way of low-carbon alkene technology.
Also do not find at present at the directly interior hydrogen burning technical process that heats of petroleum hydrocarbon cracking raw materials and the report of corresponding catalyst.In above-mentioned patented technology about ethylbenzene dehydrogenation-hydroxide technology and catalyst, from the compositing characteristic of catalyst, the basic Al that adopts with certain characteristic
2O
3As catalyst carrier; Improve from the temperature of ethylbenzene part dehydrogenation product, the temperature range that finally reaches is between 500-600 ℃ substantially.Because the complexity of petroleum hydrocarbon raw material and hydrocarbon vapours cracking process, simply the hydrogen selective oxidation catalyst that uses in the SMART styrene technology is applied to the petroleum hydrocarbon cracking process, also exist some and reforming reaction may take place, problem such as hydrocarbon raw material consumption is bigger as petroleum hydrocarbon raw material.Therefore, developing the hydrogen burning catalyst with novel high selectivity that is used for petroleum hydrocarbon cracking technology is vital for Hydrogen Energy being applied to the petroleum hydrocarbon cracking technology.
Summary of the invention
Purpose of the present invention just is to provide a kind of directly selective hydrogen burning catalyst of interior heating of petroleum hydrocarbon cracking raw materials that is used for.Under the effect of catalyst of the present invention, hydrogen and an amount of oxygen generation selective combustion reaction with the petroleum hydrocarbon cracking raw materials coexistence absorb the purpose that reaches the temperature that improves petroleum hydrocarbon cracking raw materials thereby the heat that discharges need not the petroleum hydrocarbon cracking raw materials that transmission is directly coexisted through medium.
The selective hydrogen burning catalyst that is used for heating in the petroleum hydrocarbon cracking raw materials of the present invention comprises following component:
A) in the platinum of metal 0.01-5%;
B) in the alkali metal of metal 0.05-5%;
C) at least a in the alkali earth metal of metal 1-20% and/or the thulium;
D) diameter of 40-75% greater than
Various molecular sieves with regular pore passage structure;
E) surplus is a binding agent;
Wherein said percentage composition is weight percentage, and with the total restatement of catalyst.
In catalyst of the present invention, be 0.01-5% in the content of metal platinum, be preferably 0.02-2%.
In catalyst of the present invention, be 0.05-5% in the alkali-metal content of metal, be preferably 0.5-4%.
In catalyst of the present invention, the content of alkali earth metal and/or thulium is 1-20%, is preferably 2-15%.When the concrete enforcement of catalyst of the present invention, can select alkaline-earth metal or rare earth metal separately, also can select more than one the element in alkaline-earth metal and the rare earth metal simultaneously for use.
In catalyst of the present invention, preferred described rare earth metal is selected from least a among La, Ce, the Pr; Described alkali metal is at least a among Li, Na and the K, and described alkaline-earth metal is at least a among Mg, Ca, Sr and the Ba.
In above-mentioned catalyst of the present invention, described component (d) diameter greater than
One or several the mixture of molecular screening with regular pore passage structure in Y zeolite, modenite, MCM-22 molecular sieve, MCM-41 molecular sieve and MCM-56 molecular sieve.
In above-mentioned catalyst of the present invention, described component (e) binding agent is selected from silica, aluminium oxide or their mixture, preferred silica.
The directly interior selective hydrogen burning catalyst that heats of cracking stock that is used for of the present invention can be selected conventional Preparation of catalysts method such as preparations such as infusion process, kneading method for use.Preparation of catalysts method of the present invention can be preferably as follows any of two kinds of methods:
Method one:, and then metal component be impregnated on the molecular sieve after the moulding at first with molecular sieve and bonding agent moulding.Concrete comprises: after molecular sieve of selecting and the roasting of binding agent extruded moulding, adopt alkali-metal solubility salt to flood this carrier earlier, and then through 30-150 ℃ of oven dry, 250-700 ℃ of roasting; Flood aforementioned macerate with solubility platinum salt again, then through 30-150 ℃ of oven dry, 250-700 ℃ of roasting; Adopt the solubility salt of alkaline-earth metal or rare earth metal to flood this macerate again, then through 30-150 ℃ of oven dry, 250-700 ℃ of roasting obtains the directly selective hydrogen burning catalyst of interior heating of cracking stock of the present invention.
Method two: at first adopt metal component to flood described molecular sieve, and then with bonding agent with the dipping after molecular sieve molded.Concrete, at first adopt the described molecular sieve of alkali-metal soluble-salt solution impregnation, through 30-150 ℃ of oven dry, after the 250-700 ℃ of roasting; Flood aforementioned macerate with solubility platinum salt again, through 30-150 ℃ of oven dry, after the 250-700 ℃ of roasting; Adopt the solubility salt of alkaline-earth metal or rare earth metal to flood aforementioned macerate again, through 30-150 ℃ of oven dry; With the molecular sieve extruded moulding of binding agent and this impregnating metal component, through 30-150 ℃ of oven dry, 250-700 ℃ of roasting obtains the directly selective hydrogen burning catalyst of interior heating of cracking stock of the present invention at last.
In Preparation of catalysts process of the present invention, preferred oven dry, roasting time are more than 1 hour.The preferred step impregnation of the dipping of metal component also can a step dipping.
Another object of the present invention provides the method that a kind of selective hydrogen burning catalyst of the present invention is used for the hydrogen burning of heating in the petroleum hydrocarbon cracking raw materials.
Concrete, the method for the hydrogen burning of heating comprises in the petroleum hydrocarbon cracking raw materials of the present invention:
With petroleum hydrocarbon cracking raw materials, hydrogen, oxygen and mixing diluents material is reaction raw materials, is 100-500 ℃ in inlet temperature, and reaction pressure is 0-0.3MPa, and the petroleum hydrocarbon cracking raw materials weight space velocity is 1-100 hour
-1, diluent/petroleum hydrocarbon cracking raw materials weight ratio is under the condition of 0.1-10, and described reaction raw materials is carried out hydrogen burning by the beds that loads catalyst of the present invention, heating petroleum hydrocarbon cracking raw materials and diluent.
Preferably, in the method for the invention, in the described reaction raw materials, the consumption molar ratio scope of described oxygen and hydrogen is 0.01-0.5; Hydrogen and petroleum hydrocarbon cracking raw materials consumption part by weight scope are 0.01-0.2; After making described reaction raw materials carry out hydrogen burning, temperature is brought up to the required temperature of the follow-up cracking reaction of petroleum hydrocarbon cracking raw materials.
In the method for the invention, the oxygen that adds in the petroleum hydrocarbon cracking raw materials can be the mist of air, oxygen and nitrogen.
In the method for the invention, the temperature of the inlet of generation hydrogen burning reaction logistics is usually more than 200 ℃, and preferably more than 300 ℃, the final temperature of hydrogen burning reaction depends on factors such as reaction logistics composition, reaction condition.
The oxygen conversion of indication of the present invention and oxygen selectivity obtain by following account form.
The amount of oxygen X100% that adds before oxygen conversion=(amount of oxygen--the reacted amount of oxygen of-oxidation of hydrogen that adds before the oxidation of hydrogen reaction)/oxidation of hydrogen
The oxygen combustion hydrogen selective=with the amount of oxygen X100% of the amount of oxygen of hydrogen reaction/participation oxidation of hydrogen reaction
Selective hydrogen burning catalyst of the present invention and in the hydrocarbon cracking raw material, add the method for pining for using and have following beneficial effect:
1, selective hydrogen burning catalyst of the present invention is in the presence of petroleum hydrocarbon cracking raw materials, has the performance of the high conversion of the high selectivity of oxidation of hydrogen and oxygen; Under this catalyst action, the hydrogen that coexists with the alkanes cracking stock can burn, and discharges the heating that heat is directly used in cracking stock.
2, the premium properties of selective hydrogen burning catalyst of the present invention makes that heating process is an energy source with the combustion of hydrogen release heat promptly in the hydrocarbon raw material cracking, in adopting mode of heating improve the temperature of petroleum hydrocarbon cracking raw materials can successful implementation;
3, the directly selective hydrogen burning technology of interior heating of petroleum hydrocarbon cracking raw materials that is used for of the present invention; compare with the indirect outer heating process in the existing cracking technology; to help improving the heat-transfer effect of logistics heat supplying process, and improve heat transfer efficiency, conserve energy is also protected environment.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
Comparative Examples 1
Get the alumina particle carrier, 1200 ℃ of roastings were immersed in the solution of the hydrochloric acid that contains chloroplatinic acid after 4 hours in muffle furnace, took out back 120 ℃ of oven dry, and 450 ℃ of air-treatments 2 hours obtain catalyst A.
Comparative Examples 2
Get the alumina particle carrier, 1200 ℃ of roastings after 4 hours in muffle furnace are immersed in and contain Ca (NO
3)
2The aqueous solution in, take out back 120 ℃ of oven dry 2 hours and in 500 ℃ of roastings 2 hours; Be immersed in the solution that contains chloroplatinate acid again, take out back 120 ℃ of oven dry, 450 ℃ of air-treatments 2 hours obtain catalyst B.
Comparative Examples 3
Get the alumina particle carrier, 1200 ℃ of roastings after 4 hours in muffle furnace are immersed in and contain Li NO
3The aqueous solution in, take out back 120 ℃ of oven dry 2 hours and in 500 ℃ of roastings 2 hours; Be immersed in again and contain SnCl
2Hydrochloric acid solution in, take out back 120 ℃ of oven dry 2 hours and in 500 ℃ of roastings 2 hours; Be immersed in the solution that contains chloroplatinate acid again, take out back 120 ℃ of oven dry, 450 ℃ of air-treatments 2 hours obtain catalyst C.
Embodiment 1
The preparation method of H type molecular sieve:
After the template agent is removed in 550 ℃ of following roastings, is 1: 10 ratio in molecular sieve (g) with exchange liquid (ml) with molecular screen primary powder, uses NH
4NO
3Solution (0.8mol/L) exchanges 5h in 90 ℃ of water-baths, filter; Filter cake is used with the exchange liquid of equivalent last time and is exchanged twice repeatedly again, filters, and is washed with distilled water to and does not have NO in the filtrate
3 -Exist, 110 ℃ of dryings, 550 ℃ of roastings promptly obtain H type molecular sieve.
Embodiment 2
The MCM-41 molecular screen primary powder is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.With this molecular sieve and silica (specific area＞200M
2The high-purity silicon oxide of/g), the sesbania powder mixes in proportion, adds an amount of rare nitric acid behind the mixing, is squeezed into diameter 3mm column type after stirring evenly, 120 ℃ of dryings and in 550 ℃ of roastings obtain containing the bar of MCM-41 molecular sieve and silica.Get a certain amount of column type particle, under the room temperature with containing LiNO
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.This impregnated with particles in the solution of the hydrochloric acid that contains chloroplatinic acid, is taken out back 120 ℃ of oven dry, and 450 ℃ of air-treatments obtained containing platinum grain in 2 hours.Under the room temperature with containing Ca (NO
3)
2The solution impregnation aforementioned particles, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst D.
Embodiment 3
The former powder of Y molecular sieve is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.Press embodiment 2 described methods, with containing LiNO
3Solution and the solution that contains the hydrochloric acid of chloroplatinic acid successively Li, platinum be impregnated on the described column type bar that contains Y molecular sieve and silica.Then under the room temperature with containing Mg (NO
3)
2This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst E.
Embodiment 4
The MCM-56 molecular screen primary powder is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.Press embodiment 2 described methods, with containing NaNO
3Solution and the solution that contains chloroplatinate acid successively Na, platinum be impregnated on the column type bar particle of the described MCM-56 of containing molecular sieve and silica.Then under the room temperature with containing Ba (NO
3)
2This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst F.
Embodiment 5
The former powder of mordenite molecular sieve is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.Press embodiment 2 described methods, with containing NaNO
3Solution and the solution that contains chloroplatinate acid successively Na, platinum be impregnated on the described column type bar particle that contains mordenite molecular sieve and silica.Then under the room temperature with containing Sr (NO
3)
2This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst G.
Embodiment 6
The former powder of mordenite molecular sieve is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.Press embodiment 2 described methods, with containing NaNO
3Solution and the solution that contains chloroplatinate acid successively Na, platinum be impregnated on the described column type bar particle that contains mordenite molecular sieve and silica.Then under the room temperature with containing La (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst H.
Embodiment 7
The former powder of mordenite molecular sieve is obtained H type molecular sieve according to embodiment 1 described preparation method's processing.Press embodiment 2 described methods, with containing NaNO
3Solution and the solution that contains chloroplatinate acid successively Na, platinum be impregnated on the described column type bar particle that contains mordenite molecular sieve and silica.Then under the room temperature with containing Ce (NO
3)
3This particle of solution impregnation, after the isolated by filtration, 120 ℃ of dryings and in 550 ℃ of roastings.Obtain catalyst I.
Embodiment 8
It is to carry out in 25 millimeters the stainless steel reaction pipe that the direct-fired hydrogen burning of cracking stock naphtha is reflected at internal diameter, in adorn 30 milliliters of catalyst.Reaction pressure is a normal pressure, and naphtha liquid air speed is 3 hours
-1, water/weight of oil ratio is 1, and hydrogen/weight of oil ratio is 0.1, and oxygen/hydrogen volume ratio is 0.5.400 ℃ of reaction inlet temperatures.In the temperature of reactor outlet with thermocouple measurement reaction afterproduct.Utilize the composition of gas chromatographic measurement reactant and product, calculate catalyst and directly heat oxygen conversion and oxygen selectivity in the hydrogen burning reaction at cracking stock.
The composition and the content of different catalysts are listed in table 1; With the method for embodiment 8 different catalysts is carried out reactivity worth and investigate, reactivity worth the results are shown in Table 2.
Table 1 catalyst is formed and content
Remarks: all content are wt% among the Ben Biaoge.
Table 2 different hydro combustion catalyst heating pyrolyze material performance
| Catalyst | Warm eventually ℃ of logistics | Oxygen conversion % | Oxygen annealing in hydrogen atmosphere selectivity % |
| ??A | ??845 | ??95 | ??94 |
| ??B | ??856 | ??94 | ??96 |
| ??C | ??843 | ??94 | ??97 |
| ??D | ??855 | ??95 | ??98 |
| ??E | ??846 | ??94 | ??98 |
| ??F | ??859 | ??94 | ??99 |
| ??G | ??853 | ??95 | ??99 |
| ??H | ??856 | ??94 | ??99 |
| ??I | ??849 | ??95 | ??99 |
Claims (9)
1. one kind is used for the interior selective hydrogen burning catalyst that heats of petroleum hydrocarbon cracking raw materials, and it comprises following component:
A) platinum of 0.01-5%;
B) alkali metal of 0.05-5%;
C) at least a in the alkaline-earth metal of 1-20% and/or the rare earth metal;
D) 40-75% be selected from diameter greater than
Have at least a in the molecular sieve of regular pore passage structure;
E) surplus is a binding agent;
Wherein, the content of described metallic element is all in metal simple-substance, and described percentage composition is weight percentage, and with the total restatement of catalyst.
2. catalyst according to claim 1 is characterized in that: the percentage composition of described component (a) platinum is 0.01-2%.
3. catalyst according to claim 1 is characterized in that: the alkali-metal percentage composition of described component (b) is 0.5-4%.
4. catalyst according to claim 1 is characterized in that: the percentage composition of described component (c) alkaline-earth metal and/or rare earth metal is 2-15%.
5. catalyst according to claim 1 is characterized in that: described alkali metal is selected from least a among Li, Na and the K, and described rare earth metal is selected from least a among La, Ce and the Pr; Described alkaline-earth metal is at least a among Mg, Ca, Sr and the Ba.
6. according to the described catalyst of one of claim 1-5, it is characterized in that: described component (d) diameter greater than
One or several the mixture of molecular screening with regular pore passage structure in Y zeolite, modenite, MCM-22 molecular sieve, MCM-41 molecular sieve and MCM-56 molecular sieve.
7. catalyst according to claim 6 is characterized in that: described component (e) binding agent is silica, aluminium oxide or their mixture.
8. method that is used for the selective hydrogen burning of heating in the petroleum hydrocarbon cracking raw materials, it comprises:
With petroleum hydrocarbon cracking raw materials, hydrogen, oxygen and mixing diluents material is reaction raw materials, is 100-500 ℃ in inlet temperature, and reaction pressure is 0-0.3MPa, and the petroleum hydrocarbon cracking raw materials weight space velocity is 1-100 hour
-1Diluent/petroleum hydrocarbon cracking raw materials weight ratio is under the condition of 0.1-10, described reaction raw materials is carried out hydrogen burning by beds, heating petroleum hydrocarbon cracking raw materials and diluent wherein, wherein used catalyst is the described catalyst of one of claim 1-7.
9. the method for the selective hydrogen burning of heating in the petroleum hydrocarbon cracking raw materials according to claim 8, it is characterized in that: in described reaction raw materials, the consumption molar ratio scope of described oxygen and hydrogen is 0.01-0.5; Hydrogen and petroleum hydrocarbon cracking raw materials consumption part by weight scope are 0.01-0.2; After described reaction raw materials carries out hydrogen burning, make wherein petroleum hydrocarbon cracking raw materials and the temperature of diluent bring up to the required temperature of follow-up cracking reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924220A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Method for yield increase of ethylbenzene |
| WO2020151901A1 (en) * | 2019-01-25 | 2020-07-30 | Pierre Dumons | Method and device for producing energy products by catalytic cracking of a solid hydrocarbon material without coke formation |
| CN113563918A (en) * | 2021-08-13 | 2021-10-29 | 捷创(东营)能源技术有限责任公司 | Brownian gas participated catalytic cracking method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4812597A (en) * | 1987-09-02 | 1989-03-14 | Uop Inc. | Dehydrogenation of dehydrogenatable hydrocarbons |
| CN1223602A (en) * | 1996-05-29 | 1999-07-21 | 埃克森化学专利公司 | Metal-containing zeolite catalyst, preparation thereof and use for hydrocarbon conversion |
| CN1128011C (en) * | 2001-07-06 | 2003-11-19 | 厦门大学 | Carried noble metal complete-combustion catalyst and its prepn |
-
2009
- 2009-04-27 CN CN 200910082943 patent/CN101869834B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924220A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Method for yield increase of ethylbenzene |
| CN102924220B (en) * | 2011-08-08 | 2015-02-11 | 中国石油化工股份有限公司 | Method for yield increase of ethylbenzene |
| WO2020151901A1 (en) * | 2019-01-25 | 2020-07-30 | Pierre Dumons | Method and device for producing energy products by catalytic cracking of a solid hydrocarbon material without coke formation |
| FR3092117A1 (en) * | 2019-01-25 | 2020-07-31 | Pierre Dumons | PROCESS AND DEVICE FOR THE PRODUCTION OF ENERGY PRODUCTS BY CATALYTIC CRACKING OF A SOLID HYDROCARBONATED MATERIAL WITHOUT COKE FORMATION |
| CN113563918A (en) * | 2021-08-13 | 2021-10-29 | 捷创(东营)能源技术有限责任公司 | Brownian gas participated catalytic cracking method |
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