CN108786782A - A kind of assistant for calalytic cracking and preparation method thereof reducing coke yield - Google Patents

A kind of assistant for calalytic cracking and preparation method thereof reducing coke yield Download PDF

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CN108786782A
CN108786782A CN201810569934.5A CN201810569934A CN108786782A CN 108786782 A CN108786782 A CN 108786782A CN 201810569934 A CN201810569934 A CN 201810569934A CN 108786782 A CN108786782 A CN 108786782A
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rare earth
preparation
assistant
acid
alumina material
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CN108786782B (en
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熊晓云
高雄厚
赵红娟
胡清勋
张忠东
王久江
王宝杰
刘宏海
赵晓争
张莉
田爱珍
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China Petroleum and Natural Gas Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

The present invention provides a kind of assistant for calalytic cracking and preparation method thereof reducing coke yield, the assistant for calalytic cracking is become by catalyst quality group in terms of 100 parts, 5~25 parts of the middle macropore silica-alumina material containing rare earth, preferably 8~20 parts；15~42 parts of alumina material, preferably 20~38 parts；1~10 part of heavy metal chelating agent；30~60 parts of clay.Assistant for calalytic cracking prepared by the present invention improves catalyst coke selectivity aspect and shows good reactivity worth, while it uses cheap modified feedstock in conversion heavy oil macromolecular, easy to operate, has prospects for commercial application.

Description

A kind of assistant for calalytic cracking and preparation method thereof reducing coke yield
Technical field
The present invention relates to a kind of assistant for calalytic cracking and preparation method thereof, belong to catalytic cracking field.
Background technology
Currently, reducing, greenhouse gas emission, prevention global warming has become global common recognition and countries in the world must be common The task of completion, low-carbon economy become the direction of future world development.The essence of low-carbon economy is that high efficiency of energy utilizes, cleans energy Source is developed, and core includes energy technology and emission-reduction technology innovation.International Energy Agency (IEA) publication《World energy outlook 2010》, the world energy sources development trend most as far as 2035 is predicted, says that growing fossil fuel demand will be after in report It is continuous to raise energy-related CO2 emission, although global emissions growth rate gradually declines during entire prediction, Discharge capacity still will continue to rise, and be up to 34,000,000,000 tons to the year two thousand twenty discharge capacity, 2035 can be more than 35,000,000,000 tons, than 2008 290 Hundred million tons of horizontal increase by 21%.
China is as developing country, while rapid economic development, it is necessary to pay attention to high energy consumption development pattern to China The utilization of resources, the significant impact of economic benefit and environmental protection.According to the data that BP is announced, Chinese carbon dioxide in 2010 is always arranged It is high-volume 83.3 hundred million tons, accounts for the 25% of global total release, become the most country of CO2 emission in the world, in Ge Benha On the climate Conference of the root world, Chinese Government makes the formal commitment, and arrives the year two thousand twenty, China production of units total value CO2Discharge is than under 2005 40%-45% drops, this is the arduous and urgent task of an exception, and low-carbon economy has become China and realizes sustainable development Major Strategic Demand.
Catalytic cracking unit is the main CO of oil plant2One of emission source.From reduction catalytic cracking unit CO2Discharge improves The angle of device benefit is set out, and reduction catalytic cracking carbon emission is most economical, most convenient, most efficient method is exploitation reduces coke Yield is the novel catalytic cracking catalyst or catalyst aid of target.
The exploitation of high-performance assistant for calalytic cracking, auxiliary agent is the deep conversion that refinery promotes heavy crude, improves production capacity, is increased It is effective means the most economic, flexible to increase value-added product.The catalyst and auxiliary agent technology for reducing coke yield become weight Point research direction mainly passes through the catalysis of super-stable Y molecular sieves technology and preparation with good pore structure and acid distribution at present Agent carrier material is realized.In terms of carrier material, preparation, the synthesis of the middle macroreticular acidic material based on sial base are main Research hotspot.
The sieve technology for reducing coke yield focuses primarily upon the preparation research of super-stable Y molecular sieves, such as CN200810102243.0, CN101537366A etc..And in terms of carrier, the diffuser efficiency for improving reactant, producing object is needed, Reduced cracking, with time modulation acid class type, improve acid centre reaction selectivity-synthesis have high pore volume, large aperture, The material of higher B/L acid ratio is main direction of studying.
Zheng Jinyu etc. (《Petroleum refining and chemical industry》, 2015,46 (9)：47-51) successfully made by techniques such as plastic, ageings It is standby go out a kind of unordered mesoporous silica-alumina materials (JSA) with structure of similar to thin diaspore, the material have higher specific surface area with Pore volume, specific surface area reach 300m2/ g or more, pore volume are more than 0.7cm3/ g, can several apertures in 6~7nm, simultaneously contain L acid in The heart and the acid sites B, but L acid quantity is apparently higher than the acid sites B.
Hensen, Emiel J.M etc. (《Journal of Physical Chemistry C》, 2012,116 (40)： Several amorphous silicon aluminum materials 21416-21429) are prepared for by modulation silica alumina ratio, pH and calcination temperature and use pyridine infrared Its acidity is characterized, the B acid and the calculation of L acid acidimeters provided by it obtains its B/L acid ratio between 0.27~0.31 Variation.
Xu, Bin etc. (《Journal of Physical Chemistry C》, 2007,111 (32)：12075-12079) The Blang acid site concentration and intensity in amorphous silicon aluminium are inquired into, and is compared itself and ZSM-5 by various characterizing methods. It is prepared for the amorphous silicon aluminum material of ASA (15), ASA (7), the different silica alumina ratios of (3) three kinds of ASA, with the reduction of silica alumina ratio, hole Volume is gradually reduced, the pore volume that three kinds of materials pass through nitrogen adsorption assay is respectively 0.60,0.49,0.29cm3/ g, B/L Sour ratio is 0.15 or so.
Zheng Jinyu etc. (《Petroleum journal (PETROLEUM PROCESSING)》, 2010,26 (6)：846-851) select 3 kinds of industrial oxidation aluminiums Material makes tetraethoxy-silicane (TEOS) that hydrolysis occur while achieving the purpose that activated alumina, realizes to oxygen by acid catalyzed reaction Change the Si modification of aluminium.The result shows that Si modification makes the relative crystallinity of alumina material decrease, Si-O- can be effectively formed Al keys, but there are surface Silicon-rich phenomenons；Modified material can form the acid sites B, but B acid amount and L acid molar ratio values are 0.1 or so； Modification is conducive to the raising of material hydrothermal stability, is remarkably improved and is lived by its cracking as the catalyst of addO-on therapy Property, especially heavy oil conversion performance improves product distribution.
Maryam KhosraviMardkhe etc. (《Applied Catalysis,A:General》, 2014,482：16- 23) a kind of alumina material of silicon doping is described, XRD shows that it still has aluminium oxide characteristic diffraction peak.Pass through modulation silicon Content, can get macropore volume, large aperture silicon doped aluminium, pore volume is in 0.33~1.83cm3In/g range, aperture is most High reachable 51.6nm.But its three kinds of different silicone content aluminium oxide (5%, 15%, 27%) material prepared, B/L acid ratios difference It is 0.28,0.33,0.29.
CN03147975.8 describes a kind of phase structure of the mesoporous silica-alumina material with boehmite, with oxide weight The anhydrous chemical expression of gauge is：(0-0.3)Na2O·(40-90)Al2O3·(10-60)SiO2, specific surface area is 200~400m2/ g, pore volume are 0.5~2.0ml/g, and average pore size is 8~20nm, and most probable pore size is 5~15nm.
The invention provides a kind of acidic silicon-aluminium catalytic materials by CN201110251792.6, have boehmite crystalline phase knot Structure；In terms of oxide weight, anhydrous chemical expression is：(0~0.2) Na2O (44~46) SiO2(54~56) Al2O3, pore volume is 0.5~1.0ml/g, and average pore size is 8~15nm, the infrared B acid of 200 DEG C of pyridines measured of the catalysis material Ratio with L acid is 0.130~0.150.
CN201110251761.0 inventions provide a kind of mesoporous acidic silicon-aluminium catalytic material, have boehmite crystalline phase Structure, pore volume are 1.0~2.0ml/g, and average pore size is 8~20nm, the pyridine which measures under the conditions of 200 DEG C The ratio of infrared B acid and L acid is 0.060~0.085.
CN201210409663.X provides a kind of preparation method of silicon-containing alumina dry glue, and the silicon-containing alumina of preparation is dry Glue roasts 2~6 hours through 500 DEG C~950 DEG C, and the property of gained silicon-containing alumina is as follows：Pore volume is 0.55~1.10ml/g, Pore size distribution is as follows：Pore volume of the bore dia in the hole of 10nm~50nm accounts for 30%~80%, B acid/L acid 0.110 of total pore volume ~0.251.
Assistant for calalytic cracking without zeolite component usually requires preferable heavy oil conversion performance and coke selectivity, and shows With the presence of catalytic cracking carrier material boehmite and report amorphous silicon aluminum material pore volume it is small, aperture is low, B/L acid The problems such as ratio is small, and hydrothermal stability is poor, coke selectivity and heavy oil conversion performance are still difficult to reach perfect condition.
Invention content
The present invention provides a kind of assistant for calalytic cracking and preparation method thereof reducing coke yield, and prepared by this method urges Changing cracking additive has good pore structure and acid distribution, and being applied to catalytic cracking has better heavy oil conversion performance and coke Charcoal selectivity.
A kind of assistant for calalytic cracking reducing coke yield of the present invention：Become with assistant for calalytic cracking quality group 100 parts of meters, 5~25 parts of the middle macropore silica-alumina material containing rare earth, preferably 8~20 parts；15~42 parts of alumina material, preferably 20~ 38 parts；1~10 part of heavy metal chelating agent；30~60 parts of clay.
Middle macropore silica-alumina material provided by the present invention containing rare earth is in terms of oxide weight, anhydrous chemical expression For：(0-0.3)Na2O:(2-16)Al2O3:(75-92)SiO2:(2-10)RE2O3；Its pore volume is 0.8-2mlg-1, specific surface area For 150-350m2g-1, for most probable pore size in 30-100nm, B/L acid ratios are 0.6-1.9.
A kind of preparation method of assistant for calalytic cracking reducing coke yield of the present invention, prepares first containing rare earth Middle macropore silica-alumina material：NaY zeolite directed agents and siliceous solution are pressed into SiO2Mass ratio 1:3~1:5 mixing, stir evenly after with Acid solution is in 60-90 DEG C and plastic aging, plastic pH value 7-10, ageing time 0.5 hour or more；PH value 4-6 is then adjusted, is pressed Total Al in solution after additional silicon source is introduced into2O3(containing Al in directed agents and additional silicon source2O3)：Total SiO2(containing directed agents and siliceous molten SiO in liquid2Additional silicon source is added in)=0.04-0.2 weight ratios, stirs 30min or more；Using aqueous slkali tune gel pH 7-10, More than 70-100 DEG C of aging 1h；Obtained solid sediment is filtered, washed, carry out ammonium salt exchange removal heteroion, then with Earth solution mixes, and ammonia spirit is added thereto, adjusts pH value 6-9, is stirred 30 minutes or more at 60-100 DEG C, through filtering, Dry at 100-150 DEG C again after washing, 400-650 DEG C of roasting obtains the middle macropore silica-alumina material containing rare earth.It then will oxidation Aluminium, clay, the middle macropore silica-alumina material containing rare earth, heavy metal chelating agent, deionized water are uniformly mixed, and mashing obtains mixing slurry Liquid, mixed serum is spray-dried to obtain atomized microball, atomized microball is fired again, ion exchange, drying, the obtained present invention urges Change cracking additive.
Y-type zeolite directed agents do not do special limit in the preparation of middle macropore silica-alumina material provided by the present invention containing rare earth It is fixed, it is (14~16) SiO using common directed agents, such as constitutive molar ratio of directed agents2:(0.7~1.3) Al2O3:(14 ~16) Na2O:(300~330) H2O, method of the preparation method with reference to described in CN1081425A.
Siliceous solution is selected from water in the preparation method of the middle macropore silica-alumina material containing rare earth provided by the present invention Glass, sodium metasilicate are one or more in silicon tetraethyl aqueous solution；Used additional silicon source is selected from aluminum sulfate, aluminum nitrate, chlorine Change one or more in aluminium, sodium metaaluminate；Used acid solution can be inorganic acid either organic acid, such as nitric acid, sulphur It is one or more in acid, hydrochloric acid, acetic acid, formic acid, carbonic acid；Used aqueous slkali is selected from sodium hydroxide, potassium hydroxide, ammonia It is one or more in water, sodium metaaluminate.
Ammonium salt employed in the preparation method of middle macropore silica-alumina material provided by the present invention containing rare earth exchanges, be by The solid sediment of filtering gained presses sediment (butt)：Ammonium salt：H20=1：(0.1-1)：The weight ratio of (5-10) room temperature extremely It exchanges 1-3 times at 100 DEG C, exchanges 0.3-1 hours every time, until sodium content mass percent is less than in solid sediment 0.3wt%.It is one or more in ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate, ammonium hydrogen carbonate to exchange ammonium salt used.
Rare earth in the preparation method middle rare earth solution of middle macropore silica-alumina material of the present invention containing rare earth is selected from chlorine Change one or more in lanthanum, cerium chloride, lanthanum nitrate, cerous nitrate, nitric acid rare earth, rare earth chloride.
In preparation method of the present invention, mixed serum passes through burin-in process：Aging temperature is 40~90 DEG C, when aging Between be 0.5~3 hour.Spray drying of the present invention, spray tower fire box temperature are controlled at 450~550 DEG C, tail gas temperature of spraying Degree control is at 150~300 DEG C.Ion exchange of the present invention is exchanged using acid or ammonium salt exchanges, pH value control 2.5~ 3.5, swap time is 0.5~3 hour.Aluminium oxide of the present invention can be Alpha-alumina, beta-alumina, gama-alumina, δ-aluminium oxide, η-aluminium oxide, θ-aluminium oxide, the predecessor boehmite of aluminium oxide, Aluminum sol, one kind in aluminium hydroxide or It is a variety of.Aluminium oxide is preferably to be obtained using the predecessor of two kinds of aluminium oxide, such as can be molten respectively from boehmite and aluminium The mixture of glue.
Clay in the present invention is kaolin, halloysite, montmorillonite, bentonite, diatomite, sepiolite, concave convex rod It is one or more in stone, rectorite, galapectite, hydrotalcite, saponite.More preferably kaolin, halloysite, diatomite, It is one or more in sepiolite, attapulgite, rectorite, galapectite.
The present invention, without particular/special requirement, can be heavy metal chelating agent commonly used in the art to the heavy metal chelating agent. Such as petrochemical industry 2000,29, (368-373) and Journal of Molecular Catalysis, 2005,19 (6) 504-510, in disclose different metals Trapping agent, there is magnesia, strontium oxide strontia, barium monoxide, rare earth oxide, aluminium oxide, silica, the forerunner of zirconium oxide or these substances Object.Present invention preferably employs the predecessors of rare earth oxide and/or rare earth oxide as metal traps.Before the rare earth oxide It is preferably the one or more of rare earth chloride, nitric acid rare earth, carbonated rare earth and hydrogen-oxygen rare earth to drive object.Wherein, rare earth element can be with It is one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium.
A kind of preparation method of assistant for calalytic cracking reducing coke yield disclosed in this invention, the catalytic cracking Auxiliary agent mesostroma also may include that other common matrix, the common matrix of others are not done specifically in addition to the aluminium oxide, clay It limits, is the common knowledge of this field；Other common matrix are generally selected from silica and its silica predecessor, magnesia and Its, the mixtures of one or more substances in precursor compound for MgO.The silica is selected from Ludox, silica gel, mesoporous two One or more in silica, white carbon, aerosil, the silica predecessor is selected from sodium metasilicate, inclined silicon Sour sodium, it is one or more in waterglass, positive esters of silicon acis；The precursor compound for MgO is selected from magnesia, magnesium chloride, hydroxide It is one or more in magnesium, magnesium nitrate, magnesium carbonate
Reaction mainly follows carbonium ion mechanism and radical reaction mechanism in catalytic cracking, compared with free radical mechanism, Carbonium ion reaction has better reaction selectivity, and carbonium ion is mainly induced by the acid sites B and generated.In auxiliary agent of the present invention The middle macropore silica-alumina material containing rare earth is introduced, which has large aperture, high pore volume, high B/L acid ratio, high stability Feature is converting heavy oil macromolecular by the auxiliary agent of the introducing exploitation of the material, is reducing secondary cracking, improve catalyst coke choosing It selects sex expression and goes out reactivity worth more more superior than conventional method, while it uses cheap modified feedstock, it is easy to operate, there is work Industry application prospect.
Description of the drawings
Fig. 1 is silica-alumina material Pyridine adsorption IR spectra figure prepared by embodiment 3；
Fig. 2 is silica-alumina material pore distribution curve prepared by embodiment 3.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation Test method without specific conditions in example, usually according to normal condition.
NaY zeolite directed agents in the present invention, aluminum sulfate solution, La, Ce mixed rare earth solution, waterglass, boehmite, Kaolin, Aluminum sol pick up from Catalyst Factory of Lanzhou Petrochemical Company, remaining reagent is given birth to using Sinopharm Chemical Reagent Co., Ltd. The analytical reagents of production.
Embodiment further instruction technical solutions according to the invention will be passed through below.
1, primary analysis method
1 primary analysis method of the present invention of table
Project Method Standard code
RE2O3, m% XRF methods /
Na2O XRF methods /
Pore volume, cm3.g-1 Water droplet method Q/SYLS0521-2002
2. abrasion index test method
The tear strength of atomized microball is thought of a way measurement using gas, and before measurement, atomized microball is without any roasting：It will Atomized microball is placed in the device MS-C type wear index analyzers for measuring abrasion index, with gas shock 5 hours, first 1 hour The fine powder amount of collection is that itself (is less than 15 containing band, the latter 4 hours fine powder amounts collected as the fine powder amount generated in prepared by microballoon μm), it is abrasion index that the latter 4 hours fine powder quality collected, which account for the percentage of sample gross mass,.
3. water droplet method pore volume measures
80g or so catalyst samples are taken to be placed in evaporating dish, 480 DEG C of calcinations 1 hour are taken out cooling in drier, are taken 20g samples are added in triangular flask, are accurate to 0.1g.Add distilled water into triangular flask from buret, with the addition of dampening, catalysis Agent mobility is deteriorated, and is stirred continuously and is shaken up with glass bar, until sample loses flowability, and all condenses together, writes down consumption Water calculates sample pore volume using Vp=V/m.Vp- sample pore volumes, ml/g；V- consumption titration water volumes, ml；M- samples Quality, g.
3. catalyst aid is evaluated：
Poising agent micro-activity is measured with reference to ASTM D-3907, catalyst inventory 5g, oil ratio 3.2, reaction temperature 460℃。
The auxiliary agent of the present invention carries out reactivity worth evaluation using ACE.Through 800 DEG C, 100% vapor aging before auxiliary agent evaluation 17h, auxiliary agent after aging and poising agent (the poising agent micro-activity for urging device China Petroleum 3,000,000/year of Lanzhou Petrochemical again 65%, RE2O33.9%, V 6000ppm, Ni 3800ppm, Fe 3900ppm) by weight 1:4 are uniformly mixed, original used Material oil is that wide fraction wax oil and Xinjiang decompression residuum, intermingled dregs ratio 30% are depressurized in Xinjiang.Raw material oil nature is shown in Table 2.Evaluation condition： 510 degrees Celsius of reaction temperature, oil ratio 5.0.
2 catalyst choice of table evaluates raw materials used oil nature
Embodiment 1
Middle macropore silica-alumina material containing rare earth
It takes 26.8ml NaY zeolites directed agents to be uniformly mixed with 51.2ml 250g/l waterglass, is diluted with water Si02It is dense Degree is 40g/L (with Si02Meter, similarly hereinafter), stir evenly after and 6mol/L sulfuric acid solutions at 60 DEG C in and plastic aging, plastic PH value=8 continue constant temperature aging 1.5h after acid adding under stirring condition；After aging be added dropwise 6mol/L sulfuric acid to pH value= 4,9.9ml 90g/L liquor alumini chloridis (A1 is slowly added under the conditions of being subsequently agitated for203Meter, similarly hereinafter), continue to stir after addition 2h；10wt% sodium hydroxide solution tune pH value=7 are added, constant temperature aging 1.5h under being stirred at 90 DEG C.Products obtained therefrom is through filtering, washing After washing, obtained solid sediment is pressed into ammonium nitrate：Solid sediment (butt)：Water=1:0.5:8 progress ion exchanges remove it Middle sodium ion, exchange are repeated twice, each 0.5h, washing filtering are carried out after having exchanged every time, then by obtained solid sediment By RE2O3：Solid sediment (butt)：Water=0.06:1:8 are added water and lanthanum chloride solution, be added with stirring ammonium hydroxide tune pH value= 6,60 DEG C are stirred 45 minutes, and products obtained therefrom dry 18h at 120 DEG C after being filtered, washed, 550 degree of roasting 3h are up to the present invention The middle macropore silica-alumina material GL-1 containing rare earth provided, elementary analytical chemistry group become 0.12Na2O:5.5RE2O3：6.9Al2O3: 87.5SiO2:.Its pore volume is 1.85mlg-1, specific surface area 194m2g-1, most probable pore size 87nm, B/L acid ratio is 1.88。
Catalyst aid
Weighing 1.967 kilograms of boehmites, (solid content 61.0%, Shanxi Aluminium Plant product pick up from Lanzhou Petrochemical Company and urge Agent factory, similarly hereinafter), (solid content 81%, butt, Chinese kaolinite scholar company industrial products pick up from Lanzhou to 2.272 kilograms of kaolin Petro-chemical corporation's catalyst plant, similarly hereinafter), 8.5 kilograms of deionized waters are added, 1.165 kilograms of Aluminum sol (contains Al2O320.6wt%, it is blue The catalyst plant production of state petro-chemical corporation, similarly hereinafter), it stirs 1 hour, the hydrochloric acid of 274 milliliter of 37 weight % is added, after stirring 1 hour, Earth solution 1230.8ml (content 325gL are added in aging thereto at 50 DEG C after 2 hours-1, La, Ce mischmetal picks up from orchid State Effect of Catalysis In Petrochemistry agent factory, similarly hereinafter), the middle macropore silica-alumina material GL-1320g (butt, similarly hereinafter) containing rare earth, deionized water 1.2kg, Stirring is spray-dried after 45 minutes.
The microballoon of spray drying gained is then stirred 30 points through 580 DEG C of roasting 1h in pH=3.7 aqueous hydrochloric acid solutions Clock filters, 8 hours dry at 160 DEG C, obtains assistant for calalytic cracking CAT-1 provided by the invention.
The group of assistant for calalytic cracking CAT-1 becomes：46 heavy % of kaolin, the aluminium oxide from boehmite are 30 Weight %, the aluminium oxide from Aluminum sol are 6 heavy %, and rare earth oxide is 10 heavy % (being free of GL-1 middle rare earth), containing big in rare earth Hole silica-alumina material GL-1 is 8 heavy %.
Embodiment 2
Middle macropore silica-alumina material containing rare earth
It takes 22.23ml NaY zeolites directed agents to be uniformly mixed with 40.89ml ethyl orthosilicates, is diluted with water Si02Concentration For 50g/L, after stirring evenly and during 5mol/L salpeter solutions are at 80 DEG C and plastic aging, plastic pH value=9, after acid adding Continue constant temperature aging 1h under stirring condition；5mol/L nitric acid is added dropwise after aging to pH value=6, under the conditions of being subsequently agitated for slowly 4.76ml 90g/L aluminum nitrate solutions are added, continue to stir 1.5h after addition；10wt% potassium hydroxide solution tune pH is added Value=9, constant temperature aging 2h under being stirred at 95 DEG C.Products obtained therefrom presses ammonium nitrate after being filtered, washed, by obtained solid sediment： Solid sediment (butt)：Water=1:0.7:9 progress ion exchange removal wherein sodium ion, exchanges are repeated twice, each 0.5h, Washing filtering is carried out after having exchanged every time, and obtained solid sediment is then pressed into RE2O3：Solid sediment (butt)：Water= 0.08:1:9 are added water and solution of cerium chloride by oxidation, are added with stirring ammonium hydroxide tune pH value=7,70 DEG C and stir 60 minutes, products obtained therefrom warp 15h is dried after being filtered, washed at 110 DEG C, 600 degree of roasting 2h are up to the middle macropore silica-alumina material provided by the invention containing rare earth GL-2, elementary analytical chemistry group become 0.06Na2O::6.9RE2O3:4.6Al2O3:88.4SiO2.Its pore volume is 1.67mlg-1, Specific surface area is 291m2g-1, for most probable pore size in 43nm, B/L acid ratios are 1.54.
Catalyst aid
1.23 kilograms of boehmites are weighed, 6.4 kilograms of deionized waters, Aluminum sol 1.019 is added in 2.0 kilograms of kaolin Kilogram, stir 2 hours, be added the hydrochloric acid of 165 milliliter of 37 weight %, after stirring 1.8 hours, at 60 DEG C after aging 1.5 hours to Earth solution 184.6ml, the middle macropore silica-alumina material GL-2 360g (butt, similarly hereinafter) containing rare earth, deionized water is wherein added 1.5kg, stirring are spray-dried after sixty minutes.
The microballoon of spray drying gained is then stirred 60 through 550 DEG C of roasting 1.5h in pH=3.5 aqueous hydrochloric acid solutions Minute, it filters, it is 4 hours dry at 150 DEG C, obtain assistant for calalytic cracking CAT-2 provided by the invention.
The group of assistant for calalytic cracking CAT-2 becomes：54 heavy % of kaolin, the aluminium oxide from boehmite are 25 Weight %, the aluminium oxide from Aluminum sol are 7 heavy %, and rare earth oxide is 2 heavy % (being free of GL-2 middle rare earth), the middle macropore containing rare earth Silica-alumina material GL-2 is 12 heavy %.
Embodiment 3
Middle macropore silica-alumina material containing rare earth
It takes 13.4ml NaY zeolites directed agents and the sodium silicate aqueous solution of 46ml 200g/L to be uniformly mixed, is diluted with water Si02A concentration of 45g/L, stir evenly after and 5.5mol/L hydrochloric acid solutions at 90 DEG C in and plastic aging, plastic pH value= 10, continue constant temperature aging 2.5h after acid adding under stirring condition；After aging be added dropwise 5.5mol/L sulfuric acid to pH value= 5.5, it is slowly added to 12.41ml 90g/L aluminum sulfate solutions under the conditions of being subsequently agitated for, continues to stir 1.0h after addition；It is added Ammonium hydroxide tune pH value=10, constant temperature aging 2.5h under being stirred at 70 DEG C.Products obtained therefrom precipitates obtained solid after being filtered, washed Object presses ammonium sulfate：Solid sediment (butt)：Water=1:0.8:10 carry out ion exchange removal wherein sodium ion, exchange and repeat two Secondary, each 0.5h carries out washing filtering after having exchanged every time, obtained solid sediment is then pressed RE2O3：Solid sediment is (dry Base)：Water=0.04:1:7 are added water and lanthanum nitrate hexahydrate, are added with stirring ammonium hydroxide tune pH value=8,90 DEG C and stir 120 minutes, institute Product dry 10h at 130 DEG C after being filtered, washed is obtained, 580 degree of roasting 2.5h are up to provided by the invention containing big in rare earth Hole silica-alumina material GL-3, elementary analytical chemistry group become 0.08Na2O:4.1RE2O3:9.9Al2O3:85.9SiO2.Its pore volume is 1.54mlg-1, specific surface area 153m2g-1, for most probable pore size in 64nm, B/L acid ratios are 1.61.
Catalyst aid
0.574 kilogram of boehmite is weighed, 8.0 kilograms of deionized waters, Aluminum sol is added in 2.549 kilograms of kaolin It 1.699 kilograms, stirs 1.5 hours, the hydrochloric acid of 100 milliliter of 37 weight %, after stirring 2 hours, aging 1.8 hours at 55 DEG C is added Earth solution 538.5ml, the middle macropore silica-alumina material GL-3 560g (butt, similarly hereinafter) containing rare earth, deionization is added thereto afterwards Water 2.3kg, stirring are spray-dried after 80 minutes.
The microballoon of spray drying gained is then stirred 45 through 600 DEG C of roasting 0.8h in pH=3.2 aqueous hydrochloric acid solutions Minute, it filters, it is 6 hours dry at 140 DEG C, obtain assistant for calalytic cracking CAT-3 provided by the invention.
The group of assistant for calalytic cracking CAT-3 becomes：59 heavy % of kaolin, the aluminium oxide from boehmite are 10 Weight %, the aluminium oxide from Aluminum sol are 10 heavy %, and rare earth oxide is 5 heavy % (being free of GL-3 middle rare earth), containing big in rare earth Hole silica-alumina material GL-3 is 16 heavy %.
Embodiment 4
Middle macropore silica-alumina material containing rare earth
It takes 40.2ml NaY zeolites directed agents to be uniformly mixed with 98.4ml 250g/l waterglass, is diluted with water Si02It is dense Degree be 55g/L, stir evenly after and 4.5mol/L hydrochloric acid solutions at 85 DEG C in and plastic aging, plastic pH value=9.5, acid adding After continue constant temperature aging 1.8h under stirring condition；4.5mol/L acetums are added dropwise after aging to pH value=4.5, with 57.0ml 90g/L liquor alumini chloridis are slowly added under stirring condition afterwards, continue to stir 2.2h after addition；Ammonium hydroxide tune is added PH value=9.5, constant temperature aging 1.8h under being stirred at 80 DEG C.Products obtained therefrom presses chlorine after being filtered, washed, by obtained solid sediment Change ammonium：Solid sediment (butt)：Water=1:0.4:7 progress ion exchange removal wherein sodium ion, exchanges are repeated twice, every time 0.5h carries out washing filtering after having exchanged every time, obtained solid sediment is then pressed RE2O3：Solid sediment (butt)：Water =0.1:1:10 are added water and cerous nitrate solution, are added with stirring ammonium hydroxide tune pH value=9,80 DEG C and stir 80 minutes, products obtained therefrom 8h is dried at 140 DEG C after being filtered, washed, 620 degree of roasting 1.5h are up to the middle macropore sial provided by the invention containing rare earth Material GL-4, elementary analytical chemistry group become 0.15Na2O:9.3RE2O3:14.3Al2O3:76.3SiO2.Its pore volume is 1.02mlg-1, specific surface area 319m2g-1, for most probable pore size in 31nm, B/L acid ratios are 0.96.
Catalyst aid
1.107 kilograms of boehmites are weighed, 9.5 kilograms of deionized waters, Aluminum sol is added in 2.722 kilograms of kaolin It 1.966 kilograms, stirs 2.2 hours, the hydrochloric acid of 149 milliliter of 37 weight % is added, after stirring 2.5 hours, aging 2.2 is small at 65 DEG C When after earth solution 1246.2ml is added thereto, the middle macropore silica-alumina material GL-4 810g (butt, similarly hereinafter) containing rare earth are gone Ionized water 3.5kg, stirring are spray-dried after 90 minutes.
The microballoon of spray drying gained is then stirred 80 through 500 DEG C of roasting 1.3h in pH=2.8 aqueous hydrochloric acid solutions Minute, it filters, it is 20 hours dry at 100 DEG C, obtain assistant for calalytic cracking CAT-4 provided by the invention.
The group of assistant for calalytic cracking CAT-4 becomes：49 heavy % of kaolin, the aluminium oxide from boehmite are 15 Weight %, the aluminium oxide from Aluminum sol are 9 heavy %, and rare earth oxide is 9 heavy % (being free of GL-4 middle rare earth), the middle macropore containing rare earth Silica-alumina material GL-4 is 18 heavy %.
Embodiment 5
Middle macropore silica-alumina material containing rare earth
It takes 20.1ml NaY zeolites directed agents to be uniformly mixed with 47.7ml ethyl orthosilicates, is diluted with water Si02It is a concentration of 60g/L, after stirring evenly and during 4mol/L hydrochloric acid solutions are at 70 DEG C and plastic aging, plastic pH value=7 are stirred after acid adding Continue constant temperature aging 2h under the conditions of mixing；4mol/L hydrochloric acid is added dropwise after aging to pH value=5, slowly adds under the conditions of being subsequently agitated for Enter 27.7ml 90g/L aluminum sulfate solutions, continues to stir 1.8h after addition；Ammonium hydroxide tune pH value=8 are added, are stirred at 85 DEG C Lower constant temperature aging 1.2h.Products obtained therefrom presses ammonium chloride after being filtered, washed, by obtained solid sediment：Solid sediment is (dry Base)：Water=1:0.3:6 progress ion exchange removal wherein sodium ion, exchanges are repeated twice, each 0.5h, after having exchanged every time Washing filtering is carried out, obtained solid sediment is then pressed into RE2O3：Solid sediment (butt)：Water=0.02:1:12 are added water With lanthanum, cerium mixed chlorinated rare earth solution, it is added with stirring ammonium hydroxide tune pH value=8.5,95 DEG C and stirs 100 minutes, products obtained therefrom warp 20h is dried after being filtered, washed at 100 DEG C, 500 degree of roasting 3.5h are up to the middle macropore silicon aluminium provided by the invention containing rare earth Expect that GL-5, elementary analytical chemistry group become 0.10Na2O:2.1RE2O3:12.9Al2O3:84.9SiO2.Its pore volume is 1.25mlg-1, specific surface area 255m2g-1, for most probable pore size in 52nm, B/L acid ratios are 1.38.
Catalyst aid
1.639 kilograms of boehmites are weighed, 9.0 kilograms of deionized waters, Aluminum sol is added in 2.778 kilograms of kaolin It 1.942 kilograms, stirs 1.8 hours, the hydrochloric acid of 192 milliliter of 37 weight %, after stirring 1.5 hours, aging 1 hour at 70 DEG C is added Earth solution 1076.9ml, middle macropore silica-alumina material GL-5 1000g, deionized water 4.0kg containing rare earth is added thereto afterwards, Stirring is spray-dried after 70 minutes.
The microballoon of spray drying gained is then stirred 100 points through 450 DEG C of roasting 2h in pH=3.0 aqueous hydrochloric acid solutions Clock filters, 10 hours dry at 120 DEG C, obtains assistant for calalytic cracking CAT-5 provided by the invention.
The group of assistant for calalytic cracking CAT-5 becomes：45 heavy % of kaolin, the aluminium oxide from boehmite are 20 Weight %, the aluminium oxide from Aluminum sol are 8 heavy %, and rare earth oxide is 7 heavy % (being free of GL-5 middle rare earth), the middle macropore containing rare earth Silica-alumina material GL-5 is 20 heavy %.
Comparative example 1
It is prepared for comparison assistant for calalytic cracking with reference to embodiment 4, boehmite content is to intend thin water aluminium in embodiment 4 Stone and the sum of middle macropore silica-alumina material containing rare earth.
Catalyst aid
2.434 kilograms of boehmites are weighed, 9.5 kilograms of deionized waters, Aluminum sol is added in 2.722 kilograms of kaolin It 1.966 kilograms, stirs 2.2 hours, the hydrochloric acid of 149 milliliter of 37 weight % is added, after stirring 2.5 hours, aging 2.2 is small at 65 DEG C When after be added earth solution 1246.2ml, deionized water 3.5kg thereto, stirring is spray-dried after 90 minutes.
The microballoon of spray drying gained is then stirred 80 through 500 DEG C of roasting 1.3h in pH=2.8 aqueous hydrochloric acid solutions Minute, it filters, it is 20 hours dry at 100 DEG C, obtain assistant for calalytic cracking DB-1 provided by the invention.
The group of assistant for calalytic cracking DB-1 becomes：49 heavy % of kaolin, the aluminium oxide from boehmite are 33 heavy %, Aluminium oxide from Aluminum sol is 9 heavy %, and rare earth oxide is 9 heavy %.
3 assistant for calalytic cracking physicochemical property of table
* pore volume is measured using water droplet method.
4 assistant for calalytic cracking of the present invention of table urged again with China Petroleum 3,000,000/year of Lanzhou Petrochemical respectively the poising agent of device by Weight ratio 4:After 1 compounding, ACE evaluates data
Assistant for calalytic cracking physicochemical property and ACE evaluation results show that CAT-4 is made compared with comparative example using the present invention Standby assistant for calalytic cracking pore volume increases, and after being compounded with industrial poising agent, shows that heavy oil conversion performance is strong, total liquid yield increases Add, the good feature of coke selectivity
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art The protection domain of the claims in the present invention should all be belonged to.

Claims (21)

1. a kind of assistant for calalytic cracking reducing coke yield, which is characterized in that the auxiliary agent quality group becomes 100 parts of meters, contains 5~25 parts of the middle macropore silica-alumina material of rare earth, preferably 8~20 parts；15~42 parts of alumina material, preferably 20~38 parts；With much money Belong to 1~10 part of trapping agent；30~60 parts of clay, the middle macropore silica-alumina material containing rare earth are anhydrous in terms of oxide weight Chemical expression is：Na2O:Al2O3:SiO2:RE2O3=0-0.3:2-16:75-92:2-10；Its pore volume is 0.8-2mlg-1, Specific surface area is 150-350m2g-1, for most probable pore size in 30-100nm, B/L acid ratios are 0.6-1.9.
2. assistant for calalytic cracking according to claim 1, which is characterized in that the aluminium oxide is Alpha-alumina, beta oxidation Predecessor boehmite, Aluminum sol, the hydrogen-oxygen of aluminium, gama-alumina, δ-aluminium oxide, η-aluminium oxide, θ-aluminium oxide, aluminium oxide Change one or more in aluminium.
3. assistant for calalytic cracking according to claim 2, which is characterized in that the aluminium oxide is that boehmite and aluminium are molten The mixture of glue.
4. assistant for calalytic cracking according to claim 1, which is characterized in that the clay be kaolin, halloysite, It is one or more in montmorillonite, bentonite, diatomite, sepiolite, attapulgite, rectorite, galapectite, hydrotalcite, saponite.
5. assistant for calalytic cracking according to claim 4, which is characterized in that the clay be kaolin, halloysite, It is one or more in diatomite, sepiolite, attapulgite, rectorite, galapectite.
6. assistant for calalytic cracking according to claim 1, which is characterized in that the metal traps are magnesia, oxidation The predecessor of strontium, barium monoxide, rare earth oxide, aluminium oxide, silica, zirconium oxide or these substances.
7. assistant for calalytic cracking according to claim 1, which is characterized in that the metal traps be rare earth oxide and/ Or the predecessor of rare earth oxide.
8. assistant for calalytic cracking according to claim 7, which is characterized in that the predecessor of the rare earth oxide is that chlorination is dilute Soil, nitric acid rare earth, carbonated rare earth and hydrogen-oxygen rare earth it is one or more, wherein rare earth element can be lanthanum, cerium, praseodymium, neodymium, promethium, It is one or more in samarium, europium.
9. a kind of preparation method for the assistant for calalytic cracking reducing coke yield is claim 1-8 any one of them drop The preparation method of the assistant for calalytic cracking of low coke yield, which is characterized in that the preparation method comprises the following steps, makes first The standby middle macropore silica-alumina material containing rare earth：NaY zeolite directed agents and siliceous solution are pressed into SiO2Mass ratio 1:3~1:5 mixing, are stirred After mixing uniformly and acid solution is in 60-90 DEG C and plastic aging, plastic pH value 7-10, ageing time 0.5 hour or more；Then adjust PH value 4-6, total Al in solution after being introduced by additional silicon source2O3：Total SiO2Additional silicon source, stirring is added in=0.04-0.2 weight ratios 30min or more；Using aqueous slkali tune gel pH 7-10, more than 70-100 DEG C of aging 1h；Obtained solid sediment is filtered, Washing carries out ammonium salt and exchanges removal heteroion, then mixed with earth solution, ammonia spirit is added thereto, adjust pH value 6-9, It is stirred 30 minutes or more at 60-100 DEG C, dry at 100-150 DEG C again after being filtered, washed, 400-650 DEG C of roasting obtains Middle macropore silica-alumina material containing rare earth；Then by aluminium oxide, clay, the middle macropore silica-alumina material containing rare earth, heavy metal chelating agent, Deionized water is uniformly mixed, and mashing obtains mixed serum, and mixed serum is spray-dried to obtain atomized microball, and atomized microball passes through again Assistant for calalytic cracking is made in roasting, ion exchange, drying.
10. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Siliceous solution described in preparation is selected from waterglass, and sodium metasilicate is one or more in silicon tetraethyl aqueous solution.
11. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Additional silicon source described in preparation is one or more in aluminum sulfate, aluminum nitrate, aluminium chloride, sodium metaaluminate.
12. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Acid solution described in preparation is inorganic acid either organic acid.
13. the preparation method according to claim 9 or 12, which is characterized in that the middle macropore silicon aluminium containing rare earth Acid solution described in the preparation of material is one or more in nitric acid, sulfuric acid, hydrochloric acid, acetic acid, formic acid, carbonic acid.
14. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Aqueous slkali described in preparation is one or more in sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium metaaluminate.
15. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Ammonium salt described in preparation exchanges, and is that will filter the solid sediment of gained by weight sediment butt：Ammonium salt：H2O=1： 0.1-1：5-10, to exchanging 1-3 times at 100 DEG C, is exchanged 0.3-1 hour every time in room temperature, up to sodium content matter in solid sediment It measures percentage and is less than 0.3wt%.
16. the preparation method according to claim 9 or 15, which is characterized in that the middle macropore silicon aluminium containing rare earth The one kind of ammonium salt used in ammonium chloride, ammonium nitrate, ammonium carbonate, ammonium sulfate, ammonium hydrogen carbonate is exchanged described in the preparation of material Or it is a variety of.
17. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth Rare earth in earth solution described in preparation, selected from lanthanum chloride, cerium chloride, lanthanum nitrate, cerous nitrate, nitric acid rare earth, rare earth chloride In it is one or more.
18. preparation method according to claim 9, which is characterized in that the middle macropore silica-alumina material containing rare earth The constitutive molar ratio of directed agents described in preparation is SiO2:Al2O3:Na2O:H2O=14~16:0.7~1.3:14~16:300~ 330。
19. preparation method according to claim 9, which is characterized in that the mixed serum passes through burin-in process：Aging temperature Degree is 40~90 DEG C, and ageing time is 0.5~3 hour.
20. preparation method according to claim 9, which is characterized in that the spray drying, the control of spray tower fire box temperature At 450~550 DEG C, spraying exhaust temperature control is at 150~300 DEG C.
21. preparation method according to claim 9, which is characterized in that the ion exchange is exchanged using acid or ammonium salt is handed over It changes, 2.5~3.5, swap time is 0.5~3 hour for pH value control.
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CN1508225A (en) * 2002-12-19 2004-06-30 中国石油化工股份有限公司 One-time through hydrocracking process
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CN117046506B (en) * 2023-10-11 2023-12-08 山东久元新材料有限公司 Oil refining powder solid auxiliary agent and preparation method thereof

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