CN103962175B - A kind of heavy oil cracking and gasifying bifunctional catalyst and preparation method thereof - Google Patents
A kind of heavy oil cracking and gasifying bifunctional catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of heavy oil pyrolysis and coke gasification bifunctional catalyst, it contains micro porous molecular sieve and gasification active component, wherein, described micro porous molecular sieve is a kind in Y type molecular sieve, super-stable Y molecular sieves, X-type molecular sieve or A type molecular sieve or the combination of at least 2 kinds, and described gasification reactivity component is alkali metal and/or alkali earth metal.Described catalyst may be used for heavy oil cracking and gasifying technology, as the catalyst for cracking heavy oil wide adaptability to raw oil, it is possible to processes high carbon residue, high-sulfur nitrogen and the heavy oil of high heavy metal, obtains the light ends oil of high value；Synthesis gas can be produced by the coke on gasification finish carbon deposition catalyst surface and in regenerative process, has relatively high hydrothermal stability as coke gasification agent.
Description
Technical field
The invention belongs to the technical field that Industrial Catalysis intersects with derived energy chemical, in particular it relates to a kind of for residual oil cracking and coke gasification bifunctional catalyst and preparation method thereof.
Background technology
Along with the decline of conventional crude resource, the heaviness of crude oil is constantly deepened with in poor quality degree.On the other hand, the demand of fuel petroleum and gas resources is sharply increased by socioeconomic fast development.Therefore, the working depth of crude oil particularly heavy crude is improved, it is achieved the higher value application of the heavy raw oil present situation to alleviating current petroleum resources nervous is significant.Heavy oil pyrolysis catalyst, particularly can process the bottleneck of the catalyst always restriction mink cell focus processing and utilization of high-sulfur, high heavy metal poor quality residue oil.
The catalyst that processing of heavy oil utilizes at present is concentrated mainly on the exploitation of residual oil cracking and heavy oil hydrogenation conversion catalyst.Low-carbon alkene catalyst for cracking (CN1043520A, CN1093101A) is produced about mink cell focus, its catalyst carrier is clay and inorganic oxide, and the mixture that active component is ZSM-5 and Y type molecular sieve, the raw oil that may be used for the various boiling range scopes including mink cell focus produces low-carbon alkene, has higher hydrothermal activity stability, conversion ratio and C compared with the catalyst that HZSM-5 zeolite is active component2-C4The productivity of alkene.Patent CN1179462A active component takes from cheap loess ore deposit to replace molecular sieve to make fixed bed or fluid catalyst, and this catalyst, in the cracking cracking reaction of heavy oil, has mithridatism strong, reaction temperature is low, and productivity is high, and product quality is excellent, save the energy, free of contamination feature.Patent CN1057408A relates to a kind of silica-rich zeolite catalyst for cracking, the carrier being made up of modified silica-rich zeolite and inorganic oxide or inorganic oxide and kaolin mixture is constituted, this catalyst is used for hydrocarbon catalytic cracking process, has higher catalytic cracking activity.Patent CN85109360A that Union Carbide Corp proposes gives a kind of catalyst for cracking can prepared by new non-zeolite molecular sieve, and centre also can be properly added the silicate zeolite cracking catalyst composition that other is conventional simultaneously.Research Institute of Petro-Chemical Engineering proposes the catalytic thermal cracking catalyst CN1660967A of a kind of increasing output of ethylene and propylene, catalyst is mainly made up of clay, mesoporous silicon aluminum, inorganic oxide and MFI structure zeolite, there is the ability of good cracking macromole hydrocarbon, improve the production capacity of hydrocarbon cracking preparing ethylene and propylene.Research Institute of Petro-Chemical Engineering proposes a kind of catalytic thermal cracking catalyst and preparation method thereof (CN102211038A in the recent period, CN102211039A), by introducing Zirconium oxide powder, gradually the pH value of serosity is regulated, anti-wear performance can be obtained good, the catalyst that the metallic pollution abilities such as degree of crystallinity is high, iron-resistant are strong, high for catalytic pyrolysis technique, yield of ethene and propene yield.In sum, the catalyst development that patent report obtains at present is for heavy oil deep thermal transition olefin process mostly, and carbon residue, heavy metal and the sulfur content of feedstock is had more strict requirements, it is impossible to adapt to the requirement of inferior raw material thermal cracking fecund intermediate oil.
Catalysis gasification technique can process the inferior heavy oil of high-sulfur and produce light-end products and synthesis gas or hydrogen, and therefore, exploitation cracking and the bifunctional catalyst that gasifies have great importance.
CN101757903A reports the cracking gasification bifunctional catalyst using diaspore and Kaolin to prepare, containing on the basis of catalyst weight, 35～the boehmite of 60%, 2～the Alumina gel of 10%, 20～the Kaolin of 49.5%, the atomic ratio of 5～30% alkali and alkaline earth metal ions in terms of oxide, described alkali metal and alkaline-earth metal is in (0.05～0.9): 1.But this catalyst is only with alkali and alkaline earth metal ions as active component, and heavy oil conversion ratio relatively low (less than 70%), effective gas yield is less than 80%, it is impossible to meet needs.
CN101898143A discloses a kind of inferior heavy oil cracking and gasifying catalyst, including carrier, binding agent, gasification reactivity component and cracking active component, wherein described gasification reactivity component is alkali and alkaline earth metal ions, on the basis of catalyst total amount, to count content be 2～30% to oxide, alkali metal is (0.05～1.1) with the atomic ratio of alkaline-earth metal: 1, and cracking active component is silica alumina ratio shape-selective molecular sieve between 20～200.Described shape-selective molecular sieve is preferably ZSM-5 or ZRP.Owing to shape-selective molecular sieve duct is the most regular, relatively low to the catalysis activity of macromolecule hydrocarbon cracking, therefore, the heavy oil conversion ratio of this catalyst is relatively low (about 80%), and effective gas yield is less than 80%, it is impossible to meet needs.
Therefore, a kind of heavy oil conversion ratio of exploitation is high, and heavy oil pyrolysis that effectively gas yield is high and coke gasification bifunctional catalyst are the technical barriers of art.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of heavy oil pyrolysis and coke gasification bifunctional catalyst.Catalyst uses micro porous molecular sieve and macroporous aluminium oxide to prepare catalyst, and owing to the sour density of micro porous molecular sieve is big, acid distribution width, heavy oil conversion ratio is high, and light oil yield is high, by adding alkali metal or alkaline earth metal component, improves the gasification performance of catalyst；Catalyst hydrothermal stability is high, can be recycled for multiple times.
Described catalyst contains micro porous molecular sieve and gasification active component, wherein, described gasification reactivity component is alkali metal and/or alkali earth metal, described micro porous molecular sieve is Y type molecular sieve, super-stable Y molecular sieves, any a kind or the combination of at least 2 kinds in X-type molecular sieve or A type molecular sieve, the typical but non-limiting example of described combination includes the combination of Y type molecular sieve and super-stable Y molecular sieves, X-type molecular sieve and the combination of A type molecular sieve, Y type molecular sieve and the combination of X-type molecular sieve, Y type molecular sieve, X-type molecular sieve and the combination of A type molecular sieve, super-stable Y molecular sieves, X-type molecular sieve and the combination of A type molecular sieve, Y type molecular sieve, super-stable Y molecular sieves, X-type molecular sieve and the combination etc. of A type molecular sieve.Described Y type molecular sieve, super-stable Y molecular sieves, X-type molecular sieve and A type molecular sieve are all the known products of art, and one of ordinary skill in the art can be by commercially available acquisition, it is possible to prepare according to new technique/prior art；Described micro porous molecular sieve refers to that pore size is less than the molecular sieve of 2 nanometers.
Described catalyst is possibly together with carrier；Preferably, described carrier is macroporous aluminium oxide；Macroporous aluminium oxide of the present invention refers to the aluminium oxide of aperture 5～50 nanometer.
Preferably, described catalyst is made up of micro porous molecular sieve, macroporous aluminium oxide, gasification reactivity component and binding agent, wherein, described gasification reactivity component is alkali metal and/or alkali earth metal, and described micro porous molecular sieve is any a kind or the combination of at least 2 kinds in Y type molecular sieve, super-stable Y molecular sieves, X-type molecular sieve or A type molecular sieve.
Preferably, described binding agent is any a kind or the mixture of at least 2 kinds, particularly preferably Ludox in boehmite, Alumina gel or Ludox.
Preferably, the silica alumina ratio of described micro porous molecular sieve is 3～55, more preferably 4～52, and particularly preferably 5～50.
Preferably, described micro porous molecular sieve weight/mass percentage composition in the catalyst is 2%～50%, more preferably 3%～45%, and particularly preferably 5%～40%.
Described gasification reactivity component is any a kind or the combination of at least 2 kinds in alkali metal simple substance, alkali metal oxide, alkali metal inorganic salt, alkaline-earth metal simple substance, alkaline earth oxide or earth alkali inorganic salt.
Any a kind or the combination of at least 2 kinds in lithium, sodium or potassium of the described alkali metal.The combination of described combination such as potassium and sodium, lithium and the combination of potassium, the combination etc. of sodium, lithium and potassium.
Any a kind or the combination of at least 2 kinds in beryllium, magnesium, calcium, strontium or barium of the described alkali earth metal.The combination of described combination such as magnesium and calcium, magnesium and the combination of the combination of barium, calcium and barium, the combination of beryllium, magnesium and calcium, the combination of magnesium, calcium and barium, the combination etc. of beryllium, magnesium, calcium, strontium and barium.
Described gasification reactivity component can be the mixture of Different Alkali metal simple-substance, the mixture of Different Alkali metal-oxide, the mixture of Different Alkali metal inorganic salt, identical alkali-metal oxide and the mixture of inorganic salt, the mixture of identical alkali-metal different types of inorganic salt, the mixture of Different Alkali earth metal simple substance, the mixture of Different Alkali soil metal oxide, the mixture of Different Alkali earth metal inorganic salt, the oxide of identical alkaline-earth metal and the mixture of inorganic salt, the mixture of different types of inorganic salt of identical alkaline-earth metal, etc.；Described inorganic salt can be any a kind or the mixture of at least 2 kinds in carbonate, hydroxide, sulfate, nitrate or sulfate.
Exemplary alkali metal oxide and the inorganic salt any a kind or the mixture of at least 2 kinds in sodium carbonate, potassium carbonate, lithium carbonate, sodium nitrate, potassium nitrate, lithium nitrate, lithium oxide, sodium oxide, potassium oxide, sodium chloride, potassium chloride or lithium chloride.The mixture of described mixture such as sodium carbonate and potassium carbonate, sodium carbonate and the mixture of the mixture of the mixture of potassium carbonate, lithium oxide and sodium oxide, sodium chloride and potassium chloride, etc..
Exemplary alkaline earth oxide and the inorganic salt any a kind or the mixture of at least 2 kinds in beryllium oxide, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, Strontium hydrate., beryllium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate, barium nitrate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate or brium carbonate.The mixture of described mixture such as calcium carbonate and magnesium carbonate, beryllium carbonate and the mixture of Strontium hydrate., barium hydroxide and the mixture of calcium hydroxide, magnesium hydroxide and the mixture of beryllium hydroxide, Barium monoxide and the mixture of strontium oxide, magnesium oxide and the mixture etc. of the mixture of the mixture of beryllium oxide, Strontium hydrate. and calcium hydroxide, Barium monoxide and magnesium oxide.
Preferably, any a kind or the mixture of at least 2 kinds during described gasification reactivity component is alkali metal and/or the carbonate of alkali earth metal, hydroxide, sulfate or nitrate；Described alkali metal and/or alkali earth metal are preferably sodium, potassium, any a kind or the combination of at least 2 kinds in magnesium or calcium, i.e., described gasification reactivity component is sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, sodium nitrate, potassium nitrate, in magnesium nitrate or calcium nitrate a kind or the mixture of at least 2 kinds, the typical but non-limiting example of described mixture includes: sodium carbonate and the mixture of calcium hydroxide, magnesium carbonate and the mixture of potassium hydroxide, potassium carbonate, magnesium carbonate and the mixture of calcium sulfate, calcium carbonate, sodium hydroxide and the mixture of magnesium nitrate, sodium sulfate, potassium sulfate, magnesium sulfate and the mixture of calcium sulfate, calcium carbonate, magnesium hydroxide, potassium sulfate, magnesium nitrate and the mixture etc. of calcium nitrate.
Preferably, described gasification reactivity component weight/mass percentage composition in the catalyst is 2%～40%, more preferably 3%～35%, and particularly preferably 5%～30%, wherein, described gasification reactivity component is in terms of metal-oxide.
Described catalyst uses micro porous molecular sieve and macroporous aluminium oxide to prepare catalyst, owing to the sour density of micro porous molecular sieve is big, and acid distribution width, heavy oil conversion ratio is high, light oil yield is high, by adding alkali metal or alkaline earth metal component, improves the gasification performance of catalyst；Catalyst hydrothermal stability is high, can be recycled for multiple times；On the other hand, by adjusting micro porous molecular sieve and the content of gasification active component in catalyst, the acid active sites on the basic activated position of catalytic gasification effect and the micro porous molecular sieve of catalytic cracking effect is made to reach an equilibrium point, thus realize cracking and gasification dual catalytic, and heavy oil conversion ratio and the light oil yield of excellence can be obtained.
Heavy oil pyrolysis of the present invention and coke gasification bifunctional catalyst can be used for mink cell focus thermal cracking coupling coke gasification technique, particularly preferred for patent CN102115675A(heavy oil lightening method and device) one developed couples coke gasification technique for mink cell focus thermal cracking.
An object of the present invention also resides in a kind of described heavy oil pyrolysis of offer and the preparation method of coke gasification bifunctional catalyst.
The preparation method of described heavy oil pyrolysis and coke gasification bifunctional catalyst comprises the following steps:
(1) in binding agent serosity, press formula ratio add micro porous molecular sieve and carrier, mixing；
(2) in the mixed system that step (1) obtains, add mineral acid, mixing, be subsequently adding gasification reactivity component source；
(3) mixing, molding, it is dried, roasting obtains described catalyst.
Described binding agent serosity be prepared as art known technology, do not repeat them here.When described binding agent uses Alumina gel, it is any a kind or the combination of at least 2 kinds in aluminate, aluminium hydroxide, aluminium oxide, aluminium salt for preparing the aluminum source of Alumina gel, particularly preferably any a kind or the combination of at least 2 kinds in aluminum sulfate, sodium metaaluminate or aluminium oxide.
Preferably, described mineral acid is 2:100～30:100, more preferably 3:100～28:100, particularly preferably 5:100～25:100 with the mass ratio of the total aluminum of catalyst, and wherein, described total aluminum is in terms of aluminium oxide.
Preferably, described mineral acid is any a kind or the combination of at least 2 kinds in hydrochloric acid, carbonic acid, acetic acid, sulphuric acid or nitric acid, particularly preferably any a kind or the combination of at least 2 kinds in hydrochloric acid, sulphuric acid or nitric acid.
Preferably, stirring it is mixed into described in.
The catalyst using the method for the invention to prepare can realize inferior heavy oil conversion ratio and arrive 75%～100%, light oil productivity 50%～90%.
Compared with prior art, present invention have an advantage that
(1) described catalyst has heavy oil pyrolysis and coke gasification is difunctional, and heavy oil conversion ratio is more than 90%, reaches as high as more than 99%, and gasification aspect, charcoal conversion ratio is up to 90%；
(2) the described catalyst wide adaptability to raw oil, it is possible to process high carbon residue, high-sulfur nitrogen and the inferior heavy oil of high heavy metal, obtains the light ends oil of high value；The oil kind that processes raw material comprises crude oil with poor quality, viscous crude, Atmospheric vacuum residual oil, pyrolysis of coal tar, recycle oil, clarified oil, Colophonium, oil-sand and shale oil etc..
(3) use macropore carrier as catalyst substrates, heavy raw oil can be improved and be positioned at the contact of heavy oil molecules in catalyst pore structure intrinsic permeability, increase surface activity, improve the conversion ratio of heavy oil medium pitch macromole；The most relatively low molecular sieve content (non-traditional petroleum industry molecular sieve type) ensures that catalyst has preferable sulfur resistive nitrogen, preventing from heavy metal performance；
(4) synthesis gas can be produced by the coke on gasification finish carbon deposition catalyst surface as coke gasification agent；Due to the alkali metal component in catalyst, surface char gasification regenerative response speed can be improved, improve the hydrogen content in gasification synthesis gas simultaneously；Described catalyst produces hydrogen or synthesis gas through gasification, and wherein hydrogen content is up to 40%, and carbon monoxide content is up to 50%, and methane content is up to 10%；
(5) catalyst uses the alumina host of high hydrothermal stability, and relatively low molecular sieve component (such as the ultra-steady Y molecular sieve of high hydrothermal stability) content ensure that relatively high hydrothermal stability in catalyst regeneration process.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of one of the heavy oil lighting technological principle needed for the catalyst evaluating present invention offer；This figure comes from CN102115675A(Li Qiang, Wang Yin, Zhang Yuming, Dong Li, Gao Shiqiu, Xu Guangwen, a kind of heavy oil lightening method and device).
Fig. 2 is the schematic diagram of an embodiment of the catalyst preparation flow that the present invention provides；
Fig. 3 be embodiment 1 preparation catalyst before gasification SEM figure；
Fig. 4 be embodiment 1 preparation catalyst after gasification SEM figure.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art, it will be clearly understood that the only help of described embodiment understands the present invention, are not construed as the concrete restriction to the present invention.
Embodiment 1
The preparation method of catalyst: take 10g aluminum sulfate and be dissolved in 30mL water, adds sodium hydroxide solution regulation pH value and prepares Alumina gel；Adding Y type molecular sieve and the mixture of macroporous aluminium oxide, mass ratio 1:1, stir 1 hour, wherein molecular sieve content in the catalyst is 40%, and macroporous aluminium oxide content in the catalyst is 40%；Adding a certain amount of concentrated hydrochloric acid (36%), the mass ratio of hydrochloric acid and the total aluminum of catalyst (in terms of aluminium oxide), as 15:100, stirs 30 minutes, add the magnesium chloride solution of 20mL5mol/L, continue stirring 30 minutes, spray shaping, 120 DEG C of dry 6h, 550 DEG C of roasting 4h, obtain required catalyst.
Test:
Being evaluated the mink cell focus needed for experiment, evaluating data is as shown in table 1.
Table 1 residual oil physical property characterizes tables of data
With 10% heavy resid as raw material, with the catalyst of preparation in embodiment 1, the heavy oil lighting technique shown in Fig. 1 is investigated the cracking performance under different temperatures.Table 2 is catalyst conversion ratio at various temperatures and products distribution.
Table 2 reaction temperature conversion ratio and the impact on products distribution
After cracking experiments terminates, switching to nitrogen atmosphere, after being warming up to 900 DEG C, keep ten minutes, switch to steam, start gasification, the gas of generation drainage is collected, gas component gas chromatographic detection.After gasification 40min, switch to nitrogen atmosphere, cooling.Gasification experiment result: reaction temperature 900 DEG C, response time 40min, gasifying agent steam, conversion ratio 97.09%, gas composition is as follows.
From table 3 it can be seen that hydrogen content is up to 65% in gasification gas, effective gas H2+ CO reaches 86.4%.
Table 3 gasify gas composition and percentage composition
Fig. 3 and Fig. 4 is the stereoscan photograph of clay catalyst before and after gasification respectively, SEM scheme it can also be seen that after gasification, the only surface of small part catalyst is destroyed, and partial hole structure occurs.
Embodiment 2
Take 10g sodium metaaluminate to be dissolved in 30mL water, add sodium hydroxide solution regulation pH value and prepare Alumina gel；Add X-type molecular sieve and the mixture of macroporous aluminium oxide, mass ratio 1:3, stir 2 hours；Add a certain amount of concentrated nitric acid (36%), the mass ratio of nitric acid and the total aluminum of catalyst (in terms of aluminium oxide) is as 2:100, stir 50 minutes, add the calcium nitrate solution of 3mol/L, continue stirring 30 minutes, spray shaping, 120 DEG C of dry 6h, 580 DEG C of roasting 4h, obtain required catalyst, in described catalyst, X-type molecular sieve content is 2wt%, and the content of calcium constituent (in terms of calcium oxide) is as 2wt%.
The catalyst using the method described in embodiment 1 to obtain embodiment 2 is tested.Cracking experiments the results are shown in Table shown in 4.Gasification experiment result: reaction temperature 900 DEG C, response time 40min, gasifying agent steam, conversion ratio 95.97%, effective gas H2+ CO reaches 86.8%.
Table 4
Embodiment 3
Use the Alumina gel of embodiment 1；Add A type molecular sieve and the mixture of macroporous aluminium oxide, mass ratio 1:5, stir 1.5 hours；Add a certain amount of dense carbonic acid (40%), the mass ratio of carbonic acid and the total aluminum of catalyst (in terms of aluminium oxide), as 25:100, stirs 60 minutes, adds the solution of potassium carbonate of 3mol/L, continue stirring 30 minutes, spray shaping, 120 DEG C of dry 6h, 540 DEG C of roasting 4h, obtain required catalyst, in described catalyst, A type molecular sieve content is 45wt%, gasification reactivity constituent content (calculating with potassium oxide and calcium oxide) as 40wt%, wherein potassium element and calcium constituent mol ratio 1:1 in gasification reactivity component.
The catalyst using the method described in embodiment 1 to obtain embodiment 3 is tested.Cracking experiments the results are shown in Table shown in 5.Gasification experiment result: reaction temperature 900 DEG C, response time 40min, gasifying agent steam, conversion ratio 96.07%, effective gas H2+ CO reaches 86.9%.
Table 5
Embodiment 4
Use the Alumina gel of embodiment 1；Add super-stable Y molecular sieves and the mixture of macroporous aluminium oxide, mass ratio 2:1, stir 1.5 hours；Add a certain amount of concentrated sulphuric acid (40%), the mass ratio of sulphuric acid and the total aluminum of catalyst (in terms of aluminium oxide) is as 30:100, stir 60 minutes, add the metabisulfite solution of 3mol/L, continue stirring 30 minutes, spray shaping, 120 DEG C of dry 6h, 540 DEG C of roasting 4h, obtain required catalyst, in described catalyst, super-stable Y molecular sieves content is 50wt%, and the content of sodium element (in terms of sodium oxide) is as 35wt%.
The catalyst using the method described in embodiment 1 to obtain embodiment 4 is tested.Cracking experiments the results are shown in Table shown in 6.Gasification experiment result: reaction temperature 900 DEG C, response time 40min, gasifying agent steam, conversion ratio 96.21%, effective gas H2+ CO reaches 86.4%.
Table 6
Having above example to understand, catalyst heavy oil conversion ratio of the present invention and effective gas yield are the highest, and have relatively high hydrothermal stability.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment, but the invention is not limited in above-mentioned detailed process equipment and technological process, i.e. do not mean that the present invention has to rely on above-mentioned detailed process equipment and technological process could be implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (22)
1. a heavy oil pyrolysis and coke gasification bifunctional catalyst, it contains micro porous molecular sieve and gasification active component, it is characterized in that, described micro porous molecular sieve is Y type molecular sieve, super-stable Y molecular sieves, in X-type molecular sieve or A type molecular sieve a kind or the combination of at least 2 kinds, described gasification reactivity component is alkali metal and/or alkali earth metal, described catalyst is possibly together with carrier, described carrier is macroporous aluminium oxide, described micro porous molecular sieve weight/mass percentage composition in the catalyst is 2%～50%, described gasification reactivity component weight/mass percentage composition in the catalyst is 2%～40%, wherein, described gasification reactivity component is in terms of metal-oxide.
2. catalyst as claimed in claim 1, it is characterised in that described catalyst is made up of micro porous molecular sieve, macroporous aluminium oxide, gasification reactivity component and binding agent.
3. catalyst as claimed in claim 2, it is characterised in that described binding agent is any a kind or the mixture of at least 2 kinds in boehmite, Alumina gel or Ludox.
4. catalyst as claimed in claim 3, it is characterised in that described binding agent is Ludox.
5. the catalyst as described in any one of claim 1-4, it is characterised in that the silica alumina ratio of described micro porous molecular sieve is 3～55.
6. catalyst as claimed in claim 5, it is characterised in that the silica alumina ratio of described micro porous molecular sieve is 4～52.
7. catalyst as claimed in claim 6, it is characterised in that the silica alumina ratio of described micro porous molecular sieve is 5～50.
8. the catalyst as described in any one of claim 1-4, it is characterised in that described micro porous molecular sieve weight/mass percentage composition in the catalyst is 3%～45%.
9. catalyst as claimed in claim 8, it is characterised in that described micro porous molecular sieve weight/mass percentage composition in the catalyst is 5%～40%.
10. the catalyst as described in any one of claim 1-4, it is characterised in that described gasification reactivity component is any a kind or the mixture of at least 2 kinds in alkali metal and/or the carbonate of alkali earth metal, hydroxide, sulfate or nitrate.
11. catalyst as claimed in claim 10, it is characterised in that described alkali metal and/or alkali earth metal are any a kind or the combination of at least 2 kinds in sodium, potassium, magnesium or calcium.
12. catalyst as described in any one of claim 1-4, it is characterised in that described gasification reactivity component weight/mass percentage composition in the catalyst is 3%～35%, wherein, described gasification reactivity component is in terms of metal-oxide.
13. catalyst as claimed in claim 12, it is characterised in that described gasification reactivity component weight/mass percentage composition in the catalyst is 5%～30%, wherein, described gasification reactivity component is in terms of metal-oxide.
14. 1 kinds of preparation methoies of catalyst as described in any one of claim 1-13, comprise the following steps:
(1) in binding agent serosity, press formula ratio add micro porous molecular sieve and carrier, mixing；
(2) in the mixed system that step (1) obtains, add mineral acid, mixing, be subsequently adding gasification reactivity component source；
(3) mixing, molding, it is dried, roasting obtains described catalyst.
15. methods as claimed in claim 14, it is characterised in that described binding agent is Alumina gel.
16. methods as claimed in claim 15, it is characterised in that the aluminum source being used for preparing Alumina gel is any a kind or the combination of at least 2 kinds in aluminate, aluminium hydroxide, aluminium oxide, aluminium salt.
17. methods as claimed in claim 16, it is characterised in that the aluminum source being used for preparing Alumina gel is any a kind or the combination of at least 2 kinds in aluminum sulfate, sodium metaaluminate or aluminium oxide.
18. methods as claimed in claim 14, it is characterised in that described mineral acid is 2:100～30:100 with the mass ratio of the total aluminum of catalyst, and wherein, described total aluminum is in terms of aluminium oxide.
19. methods as claimed in claim 18, it is characterised in that described mineral acid is 3:100～28:100 with the mass ratio of the total aluminum of catalyst, and wherein, described total aluminum is in terms of aluminium oxide.
20. methods as claimed in claim 19, it is characterised in that described mineral acid is 5:100～25:100 with the mass ratio of the total aluminum of catalyst, and wherein, described total aluminum is in terms of aluminium oxide.
21. methods as claimed in claim 14, it is characterised in that described mineral acid is any a kind or the combination of at least 2 kinds in hydrochloric acid, carbonic acid, sulphuric acid or nitric acid.
22. methods as claimed in claim 21, it is characterised in that described mineral acid is any a kind or the combination of at least 2 kinds in hydrochloric acid, sulphuric acid or nitric acid.
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| CN114100670B (en) * | 2020-08-31 | 2023-08-11 | 中国石油化工股份有限公司 | Sulfur-tolerant shift catalyst and preparation method thereof |
| CN113134348B (en) * | 2021-04-23 | 2023-05-05 | 中国石油化工股份有限公司 | Application of contact agent, modified contact agent, and preparation method and application of modified contact agent |
| CN115582141B (en) * | 2021-07-06 | 2023-08-22 | 中国石油天然气股份有限公司 | Catalyst for slurry cracking and coke gasification thereof and preparation method thereof |
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| CN101250428A (en) * | 2008-04-07 | 2008-08-27 | 华东理工大学 | In-situ crystallization cracking catalyst and preparation method thereof |
| CN101898143A (en) * | 2009-05-27 | 2010-12-01 | 中国石油化工股份有限公司 | Inferior heavy oil cracking and gasifying catalyst |
| CN102133542A (en) * | 2010-01-27 | 2011-07-27 | 华东理工大学 | Compound type cracking catalyst and preparation method thereof |
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| CN101250428A (en) * | 2008-04-07 | 2008-08-27 | 华东理工大学 | In-situ crystallization cracking catalyst and preparation method thereof |
| CN101898143A (en) * | 2009-05-27 | 2010-12-01 | 中国石油化工股份有限公司 | Inferior heavy oil cracking and gasifying catalyst |
| CN102133542A (en) * | 2010-01-27 | 2011-07-27 | 华东理工大学 | Compound type cracking catalyst and preparation method thereof |
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