CN104588051A - Catalytic cracking assistant, preparation method and application thereof - Google Patents
Catalytic cracking assistant, preparation method and application thereof Download PDFInfo
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- CN104588051A CN104588051A CN201310524716.7A CN201310524716A CN104588051A CN 104588051 A CN104588051 A CN 104588051A CN 201310524716 A CN201310524716 A CN 201310524716A CN 104588051 A CN104588051 A CN 104588051A
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Abstract
The invention discloses a catalytic cracking assistant, a preparation method and application thereof. The preparation method of the catalytic cracking assistant includes using an active mesoporous material, a phosphorous-aluminum adjuvant and/or a phosphorous-aluminum adjuvant precursor, and clay and/or a heat resistant inorganic oxide source to obtain the catalytic cracking assistant. Specifically, the active mesoporous material is prepared by the method comprising the steps of: subjecting an aluminum source and an alkali solution to neutralizing, gelatinizing and aging; carrying out contact treatment on a solid precipitate obtained by filtering and an ammonium salt or acid solution for certain time, and performing filtering to obtain a low sodium solid precipitate; and subjecting the obtained low sodium precipitate and a phosphorus source to contact treatment, carrying out drying and roasting to obtain the active mesoporous material with a pseudo-boehmite phase structure. In terms of a oxide weight ratio, the anhydrous compound of the active mesoporous material is (0-0.2)Na2O.(50-86)Al2O3.(12-50)SiO2.(0.5-10)P2O5. The catalytic cracking assistant provided by the invention has strong heavy oil cracking capacity, higher light oil yield and better coke selectivity when it is used for heavy oil catalytic cracking.
Description
Technical field
The present invention relates to a kind of assistant for calalytic cracking and preparation method thereof and application.Particularly, relate to a kind of preparation method of the assistant for calalytic cracking containing active mesopore material, and auxiliary agent is split in the catalysis that method is obtained thus, and the application of this assistant for calalytic cracking in RFCC.
Background technology
The constantly soaring of crude oil price has increased considerably the processing cost of refinery, and refinery reduces costs by buying poor oil at a low price on the one hand; Economic well-being of workers and staff is increased on the other hand by deep processing mink cell focus.The important means that catalytic cracking is processed as refinery heavy oil, has very important status in refinery, and it is not only oil plant heavy oil balance, produces the Main Means of clean fuel, the focus of the energy efficiency of oil plant especially.Therefore increasing refinery has turned to focus the deep conversion of mink cell focus, pursues and improves working ability, have more high value added product, to maximizing the benefits.This just means and will be transformed by heavy crude as much as possible, reduces oil yield at the bottom of tower.Secondly while being transformed by mink cell focus, more will pay close attention to the output of dry gas and coke, these products are not only worth low as far as possible, and its output is often by the restriction of device situation.Realize above-mentioned target and all require that catalyst has higher heavy oil conversion performance, at present the general heavy oil conversion performance strengthening major catalyst by adding heavy FCC co-catalyst.
EP0550271A1, US5051385A, catalyst disclosed in US5997729A adds siliceous material in the preparation process of aluminium-based catalyst, as waterglass, generate the host material of unformed large mesoporous aluminosilicate as auxiliary agent, promote the macromolecular conversion of heavy oil with the acting in conjunction of zeolites active component.
In addition, also have a class not containing the heavy oil transformation auxiliary agent of y-type zeolite, such as WO9712011A1 discloses oil cracking additive at the bottom of a kind of tower, is specifically related to two kinds of formulas.Formula one: the alumino-silicate compound containing the following component 1. heavy % of 5-30; 2. the heavy % of 15-30 can peptized alumina; 3. the non-peptized alumina of the heavy % of 5-25; 4. the clay of the heavy % of 30-60; 5. can also containing the metal traps being less than 2 heavy %.Formula two: with formula one unlike the compound 3. replaced with containing P, improve the wear resistance of auxiliary agent.The preparation method of the alumino-silicate compound the best wherein 1. mentioned is shown in US5045519A, and this patent adopts alcohol radical aluminium salt to be raw material, expensive, substantially increases the cost of auxiliary agent.
As can be seen here, prior art is attempting the various method can improving the co catalysis performance of auxiliary agent, although achieved certain achievement, facilitate the cracking of mink cell focus to a certain extent, but the existing method preparing assistant for calalytic cracking still exists cost high and heavy oil conversion performance the problem such as to have much room for improvement.
Summary of the invention
The object of the invention is to there is to overcome prior art the defect that the high and heavy oil conversion performance of cost has much room for improvement, providing assistant for calalytic cracking that a kind of heavy oil conversion performance is strong, light oil yield is high and preparation method thereof.
The invention provides a kind of preparation method of assistant for calalytic cracking, the method comprises the following steps: (1) is by aluminium source and aqueous slkali and after plastic, adding the ageing of silicon source, obtain solid sediment, having at least a kind of for containing sodium raw materials in wherein said aluminium source, aqueous slkali and silicon source; Gained solid sediment is mixed with ammonium salt or inorganic acid, filters and obtain the low sodium solid sediment that sodium oxide content is less than 0.3 % by weight; Low for gained sodium solid sediment is contacted with phosphorus source and obtains active mesopore material after drying and roasting; (2) described active mesopore material, phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source are mixed with water pull an oar, then carry out spraying dry, roasting, washing and drying; Wherein, with P
2o
5meter described phosphorus source with in the weight ratio of the described low sodium solid sediment of butt for 0.01-0.1:1.
The invention provides the assistant for calalytic cracking obtained by preparation method provided by the invention.
The invention provides by the application of assistant for calalytic cracking provided by the invention in RFCC.
By the preparation method of assistant for calalytic cracking provided by the invention, auxiliary agent is split in the catalysis of preparation containing active mesopore material, wherein phosphorous, the low sodium of active mesopore material has structure of similar to thin diaspore, when this assistant for calalytic cracking is used for RFCC, there is stronger heavy oil cracking ability, higher light oil productive rate and better coke selectivity.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of active mesopore material AMM-1;
Fig. 2 is the XRD spectra of DB-2.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of assistant for calalytic cracking, the method comprises the following steps: (1) is by aluminium source and aqueous slkali and after plastic, adding the ageing of silicon source, obtain solid sediment, having at least a kind of for containing sodium raw materials in wherein said aluminium source, aqueous slkali and silicon source; Gained solid sediment is mixed with ammonium salt or inorganic acid, filters and obtain the low sodium solid sediment that sodium oxide content is less than 0.3 % by weight; Low for gained sodium solid sediment is contacted with phosphorus source and obtains active mesopore material after drying and roasting; (2) described active mesopore material, phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source are mixed with water pull an oar, then carry out spraying dry, roasting, washing and drying; Wherein, with P
2o
5meter described phosphorus source with in the weight ratio of the described low sodium solid sediment of butt for 0.01-0.1:1.
According to the present invention, in the preparation method of the assistant for calalytic cracking provided, first prepare active mesopore material, then preparation adds the assistant for calalytic cracking of described active mesopore material.
In the present invention, the weight of roasting after 1 hour under the condition of about 800 DEG C is referred in the weight of butt.
According to the present invention, step (1) prepares described active mesopore material.Wherein, by aluminium source and aqueous slkali and plastic, the temperature of preferred plastic is room temperature to 85 DEG C, and the pH value of plastic is 7-11.More preferably the temperature of plastic is 20-80 DEG C.
In step (1), in aluminium source and aqueous slkali and after plastic, add the ageing of silicon source.Add the amount in silicon source, preferred described silicon source and described aluminium source are respectively with SiO
2and Al
2o
3the weight ratio of meter is 1:1.5-7.5.More preferably described silicon source and described aluminium source are respectively with SiO
2and Al
2o
3the weight ratio of meter is 1:1.5-3.2.Carry out the condition of ageing, the temperature of preferred ageing is room temperature to 90 DEG C, and the time of ageing is 1-5 hour.More preferably the temperature of ageing is 20-85 DEG C.
In step (1), have at least a kind of for containing sodium raw materials in described aluminium source, aqueous slkali and silicon source, the solid sediment obtained is containing sodium.Solid sediment is mixed with ammonium salt or inorganic acid, filters to obtain low sodium solid sediment.Solid sediment can be mixed with ammonium salt, processing procedure well-known to those skilled in the art can be taked, such as, solid sediment be pressed sediment (butt): ammonium salt: H
2the weight ratio mixing of O=1:0.1-1:5-30 is to exchange, and the temperature of preferred described mixing is room temperature to 100 DEG C, exchanges 1-3 time, at every turn exchange 0.5-1 hour, until in solid sediment sodium content in sodium oxide molybdena lower than 0.3 % by weight.Preferable case, described ammonium salt is at least one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and carbonic hydroammonium.
In step (1), solid sediment can also be mixed with inorganic acid, processing procedure well-known to those skilled in the art can be taked, such as, solid sediment be pressed sediment (butt): acid: H
2the weight ratio mixing of O=1:0.03-0.30:5-30, to exchange, is preferably 1:0.05-0.2:6-20, is further preferably 1:0.07-0.16:8-15; The temperature of preferred described mixing is room temperature to 100 DEG C, exchange once, at least exchange 0.2 hour, until in solid sediment sodium content in sodium oxide molybdena lower than 0.3 % by weight.Preferably, the temperature of described mixing is 30-80 DEG C, is preferably 40-70 DEG C; The time exchanged is 0.2-2 hour, is preferably 0.3-1.5 hour, is more preferably 0.5-1 hour.Under preferable case, described inorganic acid is selected from least one in sulfuric acid, hydrochloric acid and nitric acid.
In step (1), contacted with phosphorus source by low sodium solid sediment and obtain active mesopore material after drying and roasting, wherein preferred described phosphorus source is at least one in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and phosphoric acid.
Contact described in step (1) can have various ways, and a kind of preferred embodiment is that described contact is for grind described phosphorus source and described low sodium solid sediment.Another kind of preferred embodiment is that described contact comprises: described low sodium solid sediment and water are mixed to form slurries, described low sodium solid sediment in the weight ratio of butt and water for 1:5-20, again described phosphorus source is added described slurries, the condition of described contact comprises: temperature is room temperature to 90 DEG C, and the time is 0.2-5 hour.Described drying and roasting can except anhydrating or volatile materials, and are conducive to P elements deposition that described phosphorus source provides or move in the outer surface or duct of the active mesopore material formed, and obtain described active mesopore material.
In step (1), described aluminium source can be the conventional various aluminium sources used in the preparation technology of active mesopore material, such as can for being selected from least one in aluminum nitrate, aluminum sulfate and aluminium chloride.
In the present invention, described aqueous slkali can be the aqueous slkali of various routine, such as, can be at least one in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
In the present invention, described silicon source can be the conventional various sial used in the preparation technology of active mesopore material, such as, can be at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and Silica hydrogel.
According to the present invention, although described aluminium source, silicon source and aqueous slkali suitably can be selected separately from the above-mentioned material enumerated, but, having at least in usual described aluminium source, aqueous slkali and silicon source is a kind of for containing the raw material of sodium, thus ensures that the described active mesopore material of so preparation has the central hole structure of appropriate size.According to one of the present invention preferred embodiment, described aluminium source is selected from least one in aluminum nitrate, aluminum sulfate and aluminium chloride, described alkali is selected from least one in ammoniacal liquor, potassium hydroxide, NaOH and sodium metaaluminate, and described silicon source is selected from least one in waterglass, sodium metasilicate, silicon tetraethyl and silica.
In the present invention, the described material containing sodium referred to containing sodium raw materials in aluminium source, alkali and silicon source.
According to the present invention, by the above-mentioned preparation condition in preparation method's step (1) of assistant for calalytic cracking provided by the invention, active mesopore material can be obtained.Under preferable case, described active mesopore material in the anhydrous chemical expression of oxide weight is: (0-0.2) Na
2o (50-86) Al
2o
3(12-50) SiO
2(0.5-10) P
2o
5.
According to the present invention, by the preparation condition of described preparation method's step (1) provided by the invention, under preferable case, described active mesopore material has boehmite phase structure, and its XRD spectra as shown in Figure 1.
According to the present invention, by the preparation condition of described preparation method's step (1) provided by the invention, under preferable case, the surface area of described active mesopore material is 200-600m
2/ g, pore volume is 0.3-1.8cm
3/ g, average pore size is 8-18nm; Preferably, the surface area of described active mesopore material is 250-550m
2/ g, pore volume is 0.6-1.6cm
3/ g, average pore size is 8-15nm.
In described assistant for calalytic cracking of the present invention, in the described active mesopore material adopting described active mesopore material to prepare, be more preferably less than 0.2 % by weight in the sodium content of sodium oxide molybdena.
A kind of embodiment of active mesopore material of the present invention comprises: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, controlling plastic pH value is 7-11; According to SiO
2: Al
2o
3the weight ratio of=1:1.5-7.5 adds silicon source, and ageing 1-5 hour at room temperature to 90 DEG C, obtains solid sediment; By gained solid sediment and ammonium salt or acid solution contact pairs certain hour, filter obtain sodium oxide content lower than 0.3 % by weight low sodium solid sediment; By low for gained sodium solid sediment and phosphorus source according to phosphorus source (with P
2o
5meter): the weight ratio contact pairs of low sodium solid sediment butt=0.01-0.1:1, and at 100 DEG C-150 DEG C dry 10-20 hour, or roasting 1-4 hour at 500 DEG C-700 DEG C again, obtain described active mesopore material.
According to the present invention, the active mesopore material preparation formation assistant for calalytic cracking of step (2) for step (1) is prepared.Step (2) can be carried out with reference to prior art.
According to the present invention, in step (2), the addition of each component can be carried out with reference to prior art, the present invention to this without particular/special requirement, under preferable case, the addition in active mesopore material described in step (2), phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source makes in the assistant for calalytic cracking obtained, by butt, the weight ratio of described active mesopore material, phosphorus aluminium auxiliary agent and clay and/or heat-resistant inorganic oxide is 1:0.001-5:0.1-100, be preferably 1:0.01-3.5:0.1-40, be more preferably 1:0.1-2.5:0.1-20.
In the present invention, preferably phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor are carried out mixing with described active mesopore material and clay and pull an oar.Described phosphorus aluminium auxiliary agent can be the phosphorus aluminium auxiliary agent that this area routine uses, and does not repeat them here.The phosphorus aluminium auxiliary agent precursor that described phosphorus aluminium auxiliary agent precursor can be commonly used for this area can be the material changing described phosphorus aluminium auxiliary agent under the condition of the described roasting of step (3) into.A preferred embodiment of the invention, described phosphorus aluminium auxiliary agent precursor can be the phosphorus aluminium glue of polyhydrone conjunction phosphorus aluminium compound, and more preferably the pH of described phosphorus aluminium glue is 1.0-3.5, supposition is because the phosphorus aluminium glue molecule of described poly hydration phosphorus aluminium compound is difficult to more greatly enter in active mesopore material duct, thus good cementation can be played, make the wear resistance finally significantly improving auxiliary agent.
According to the preferred embodiment of the present invention, described phosphorus aluminium glue such as can prepare as follows: aluminium source, clay are obtained slurries with water mixing making beating, then phosphorus source is joined in described slurries, at 50-100 DEG C, contact 0.1-10h obtain the phosphorus aluminium glue that described pH value is 1.0-3.5.More preferably, in situation, the consumption in described aluminium source, clay and phosphorus source makes in the phosphorus aluminium glue prepared, in butt, and the Al containing 14-25 % by weight
2o
3, the P of 55-80 % by weight
2o
5, and the clay of 0.1-20 % by weight.
According to the preferred embodiment of the present invention, the selection of the kind of described aluminium source, phosphorus source and clay can be carried out with reference to prior art, and for the present invention, under preferable case, described aluminium source is preferably boehmite, γ-Al
2o
3; Equally, under preferable case, described phosphorus source is phosphoric acid and/or P
2o
5; Described clay is preferably tired de-soil and/or kaolin.
In the present invention, in the assistant for calalytic cracking that preparation method provided by the invention obtains, clay and/or heat-resistant inorganic oxide refer to the mixture of clay, heat-resistant inorganic oxide or clay and heat-resistant inorganic oxide, namely in the present invention, the weight of clay and/or heat-resistant inorganic oxide refers to the gross weight of clay and heat-resistant inorganic oxide, such as, if time in assistant for calalytic cracking only containing clay, then the weight of clay and/or heat-resistant inorganic oxide refers to the weight of clay, if time in assistant for calalytic cracking only containing heat-resistant inorganic oxide, then the weight of clay and/or heat-resistant inorganic oxide refers to the weight of heat-resistant inorganic oxide, if time in assistant for calalytic cracking simultaneously containing heat-resistant inorganic oxide and clay, then the weight of clay and/or heat-resistant inorganic oxide refers to the gross weight of both heat-resistant inorganic oxide and clay.
According to the present invention, the present invention to the kind of described clay without particular/special requirement, the clay can commonly used for this area, under preferable case, can be selected from kaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil and hydrotalcite one or more; Be more preferably be selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
According to the present invention, described heat-resistant inorganic oxide source is heat-resistant inorganic oxide and/or the heat-resistant inorganic oxide precursor that can change heat-resistant inorganic oxide under the condition of the described roasting of step (2) into.
In the present invention, the heat-resistant inorganic oxide precursor that described heat-resistant inorganic oxide precursor can be commonly used for this area, can be such as Ludox, Alumina gel etc., this is no longer going to repeat them.
According to the present invention, the present invention to the kind of described heat-resistant inorganic oxide without particular/special requirement, can be the conventional heat-resistant inorganic oxide in this area, be preferably one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide.
Preparation method provided by the invention can also comprise and add metal traps, preferably, this metal traps is free on outside described active mesopore material, more preferably in situation, by butt, the consumption of described metal traps makes in the assistant for calalytic cracking prepared, and by butt, the content of described metal traps is no more than 20 % by weight.
The present invention is to the kind of described metal traps without particular/special requirement, and can be the conventional metal traps of the component of the pollution metals such as trapping V, Ni, Fe, Ca, under preferable case, described metal traps be its precursor of rare earth oxide and/or rare earth oxide.More preferably, in situation, the precursor metal traps of described rare earth oxide is one or more in rare earth chloride, carbonated rare earth and rare earth hydrate.Wherein, rare earth element can be one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.
The introducing method of described metal traps can carry out with reference to prior art, such as can in pulping process in the form of an ion, metal traps is incorporated in described clay and/or described heat-resistant inorganic oxide or directly adds metal traps particle in argillaceous and/or described heat-resistant inorganic oxide slurries by complex form, or metal traps is deposited in described clay and/or described heat-resistant inorganic oxide in advance by coprecipitation, or introduces metal traps in the rear washing process of described assistant for calalytic cracking.Introduce metal traps by aforementioned various mode, final metal traps is all free on outside described active mesopore material, and those skilled in the art all can know this, do not repeat them here.
According to described method provided by the invention, in step (2), active mesopore material, phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source are mixed with water and pulls an oar, and follow-up spraying dry, roasting, washing and drying, the implementation method of these operations all can adopt conventional method to implement, their specific implementation method such as has detailed description in patent application CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, quotes as a reference in the lump here.
In the present invention, described spraying dry, roasting, washing and drying are prior art, do not repeat them here.There is no particular limitation, as long as can obtain assistant for calalytic cracking of the present invention for the order of described spraying dry, roasting, washing and drying.Preferably can carry out described spraying dry, roasting, washing and drying successively.
The invention provides the assistant for calalytic cracking obtained by preparation method provided by the invention.
The invention provides by the application of assistant for calalytic cracking provided by the invention in RFCC.
The using method of assistant for calalytic cracking provided by the invention can be carried out with reference to prior art, can be such as: add catalytic cracking unit by after described assistant for calalytic cracking and major catalyst physical mixed, also can add catalytic cracking unit separately, then mix with major catalyst in device.The weight ratio of assistant for calalytic cracking and major catalyst can be carried out with reference to prior art, is preferably 1:2-25, is more preferably 1:4-20.
When assistant for calalytic cracking of the present invention is used for RFCC, there is stronger heavy oil cracking ability, higher liquid product yield and lower coking yield.Such as when auxiliary agent provided by the invention and major catalyst are by weight when mixing for 15:85, compared with major catalyst, heavy oil is reduced to 8.14 % by weight by 10.52 % by weight, total liquid product yield (liquefied gas+gasoline+diesel oil) is increased to 85.21% by 82.18%, and coke selectivity (coke yield × (100-conversion ratio)/conversion ratio) is down to 1.8459% by 2.2542%.Visible, heavy oil transformation more effectively can be become high-value product by assistant for calalytic cracking provided by the invention.Meanwhile, auxiliary agent provided by the invention has excellent wear resistance, such as when mesopore material content active in auxiliary agent up to 50 % by weight time, with contrast auxiliary agent compared with abrasion index can reduce by 2.3 units.
Compared with prior art, assistant for calalytic cracking good hydrothermal stability provided by the invention, is conducive to the large molecule Efficient Conversion of heavy oil and becomes value product.
The following examples will be further described the present invention, but not thereby limiting the invention.
In an embodiment with in comparative example:
Alumina gel provides (Al by catalyst asphalt in Shenli Refinery of China Petrochemical Industry
2o
3content is 21.5 % by weight), kaolin is provided (solid content is 76.9 % by weight) by Chinese Suzhou, and boehmite is provided (solid content is 60.8 % by weight) by Shandong Aluminum Plant.Industrial catalyst C1(trade mark MLC-500) and C2(trade mark GOR-II) provided by Sinopec asphalt in Shenli Refinery, in comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In embodiments, Na in active mesopore material product
2o, Al
2o
3, SiO
2content with x-ray fluorescence method measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publish).
The specific area of active mesopore material, pore volume, average pore size are measured by nitrogen absorption under low temperature-desorption method.
Conversion ratio=(C5+ gasoline) yield+yield of liquefied gas+(H
2-C2) yield+coking yield
Preparation example 1-7 is for illustration of the preparation method of active mesopore material.
Preparation example 1
(1) solid sediment processed.Be 90g Al by concentration
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3the NaAlO of/L, Crater corrosion 2.5
2solution is reaction raw materials, and flows plastic and regulate plastic pH=9.5, and the temperature of plastic is 50 DEG C, obtains plastic slurries; Adding concentration is with vigorous stirring 60gSiO
2the waterglass of/L, at the temperature of ageing is 70 DEG C, ageing 2 hours, obtains solid sediment.
(2) low sodium solid sediment is made.Use NH
4cl solution presses solid sediment (butt): ammonium salt: H
2weight ratio=the 1:0.8:15 of O, at 60 DEG C to solid sediment carry out ion-exchange removing sodium ion, exchange repeat twice, carry out 0.5 hour at every turn, obtain sodium oxide content lower than 0.2 % by weight low sodium solid sediment.
(3) P Modification.Low sodium solid sediment is mixed with water and pulls an oar, and add diammonium hydrogen phosphate, the mixed serum that obtains is reacted 1 hour at 70 DEG C again, to filter after washing at 120 DEG C dry 10 hours, obtain active mesopore material AMM-1.Wherein, low sodium solid sediment (butt): H
2weight ratio=the 1:8 of O; Diammonium hydrogen phosphate is (with P
2o
5meter): the weight ratio=0.022:1 of low sodium solid sediment (butt).
The XRD spectra of AMM-1 as shown in Figure 1, has boehmite phase structure.
The chemical composition of AMM-1 and pore structure analysis result are in table 1.
Preparation example 2
According to the method for preparation example 1, unlike, with " diammonium hydrogen phosphate is (with P in step (3)
2o
5meter): the weight ratio=0.06:1 of low sodium solid sediment (butt) " and " reacting 2 hours at 60 DEG C ", it is alternative that " diammonium hydrogen phosphate is (with P
2o
5meter): the weight ratio=0.022:1 of low sodium solid sediment (butt) " and " reacting 1 hour at 70 DEG C ", obtain active mesopore material AMM-2.
AMM-2 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-2 and pore structure analysis result are in table 1.
Preparation example 3
According to the method for preparation example 1, unlike, with " diammonium hydrogen phosphate is (with P in step (3)
2o
5meter): the weight ratio=0.095:1 of low sodium solid sediment (butt) " and " reacting 2 hours at 70 DEG C " substitutes, and " diammonium hydrogen phosphate is (with P
2o
5meter): the weight ratio=0.022:1 of low sodium solid sediment (butt) " and " reacting 1 hour at 70 DEG C ", obtain active mesopore material AMM-3.
AMM-3 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-3 and pore structure analysis result are in table 1.
Preparation example 4
(1) solid sediment processed.Be 90g Al by concentration
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3the NaAlO of/L, Crater corrosion 1.7
2solution is reaction raw materials, and flows plastic and regulate plastic pH=10.5, and the temperature of plastic is 50 DEG C, obtains plastic slurries; Adding concentration is with vigorous stirring 60g SiO
2the waterglass of/L, at the temperature of ageing is 60 DEG C, ageing 3 hours, obtains solid sediment.
(2) low sodium solid sediment is made.By solid sediment (butt): HCl:H
2weight ratio=the 1:0.1:10 of O, carries out exchange 30 minutes to solid sediment at 60 DEG C, filter wash sodium oxide content lower than 0.2 % by weight low sodium solid sediment.
(3) P Modification.Low sodium solid sediment is mixed with water and pulls an oar, and add phosphoric acid, the mixed serum that obtains is reacted 1 hour at 60 DEG C again, to filter after washing at 120 DEG C dry 10 hours, obtain active mesopore material AMM-4.Wherein, low sodium solid sediment (butt): H
2weight ratio=the 1:10 of O; Phosphoric acid is (with P
2o
5meter): the weight ratio=0.015:1 of low sodium solid sediment (butt).
AMM-4 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-4 and pore structure analysis result are in table 1.
Preparation example 5
According to the method for preparation example 4, unlike, with " phosphoric acid is (with P in step (3)
2o
5meter): the weight ratio=0.052:1 of low sodium solid sediment (butt) " and " reacting 2 hours at 70 DEG C " substitutes, and " phosphoric acid is (with P
2o
5meter): the weight ratio=0.015:1 of low sodium solid sediment (butt) " and " reacting 1 hour at 60 DEG C "; And by the drying sample obtained again at 450 DEG C roasting after 2 hours, obtain active mesopore material AMM-5.
AMM-5 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-5 and pore structure analysis result are in table 1.
Preparation example 6
(1) solid sediment processed.Be 90g Al by concentration
2o
3the Al of/L
2(SO
4)
3solution and ammoniacal liquor also flow plastic, hierarchy of control plastic pH=10.5, and the temperature of plastic is 40 DEG C; Adding concentration is with vigorous stirring 60g SiO
2the waterglass of/L, at the temperature of ageing is 50 DEG C, ageing 3 hours, obtains solid sediment.
(2) low sodium solid sediment is made.By solid sediment (butt): NH
4cl:H
2weight ratio=the 1:0.1:10 of O, carries out exchange 30 minutes to solid sediment at 60 DEG C, filter wash sodium oxide content lower than 0.2 % by weight low sodium solid sediment.
(3) P Modification.Directly mixed with phosphoric acid by low sodium solid sediment, the mixture after grinding evenly, in 120 DEG C of dryings 10 hours, obtains active mesopore material AMM-6.Wherein, phosphoric acid is (with P
2o
5meter): the weight ratio=0.016:1 of low sodium solid sediment (butt).
AMM-6 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-6 and pore structure analysis result are in table 1.
Preparation example 7
According to the method for preparation example 6, unlike, with " phosphoric acid is (with P in step (3)
2o
5meter): the weight ratio=0.03:1 of low sodium solid sediment (butt) " substitute that " phosphoric acid is (with P
2o
5meter): the weight ratio=0.016:1 of low sodium solid sediment (butt) "; And by the drying sample obtained again at 550 DEG C roasting after 4 hours, obtain active mesopore material AMM-7.
AMM-7 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of AMM-7 and pore structure analysis result are in table 1.
Preparation comparative example 1
This comparative example illustrates the preparation for the mesopore material contrasted.
(1) solid sediment processed.Take concentration as 90g Al
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3the NaAlO of/L, Crater corrosion 2.5
2solution is reaction raw materials, and flows plastic and regulate plastic pH=9.0, and the temperature of plastic is 50 DEG C, obtains plastic slurries; Adding concentration is with vigorous stirring 60gSiO
2the waterglass of/L, at the temperature of ageing is 70 DEG C, ageing 2 hours, obtains sial sediment.
(2) low sodium sial sediment is made.Use NH
4cl solution presses sial sediment (butt): ammonium salt: H
2weight ratio=the 1:0.8:15 of O, at 60 DEG C, ion-exchange removing sodium ion is carried out to sial sediment, exchange repeats twice, carry out 0.5 hour at every turn, sodium oxide content lower than 0.2 % by weight low sodium sial sediment, at 120 DEG C dry 10 hours again, obtain mesoporous silicon aluminum DB-1.
DB-1 has the feature of XRD spectra in Fig. 1, has boehmite phase structure.
The chemical composition of DB-1 and pore structure analysis result are in table 1.
Preparation comparative example 2
This comparative example illustrates the preparation for the mesopore material contrasted.
According to boehmite: the weight ratio of water is 1:15, industrial boehmite is mixed with water and pulls an oar, stir the watery hydrochloric acid adding metering after 30 minutes, continue stirring 10 minutes, add tetraethoxy-silicane, be warming up to 80 DEG C of reactions 4 hours, add phosphoric acid again, continue stirring 1 hour, then at 120 DEG C dry 10 hours, then roasting obtains comparative sample DB-2 in 4 hours at 550 DEG C.
The XRD spectra of DB-2 as shown in Figure 2, have boehmite phase structure, but degree of crystallinity is higher.
The chemical composition of DB-2 and pore structure analysis result are in table 1.
Table 1
Preparation embodiment 8-11 is preparation method and composition that the present invention's phosphorus aluminium used auxiliary agent precursor is described.
Preparation embodiment 8
By 0.74 kilogram of boehmite (containing Al
2o
30.45 kilogram), 0.39 kilogram of kaolin (butt 0.30 kilogram) pulls an oar 30 minutes with 16 kilograms of decationizing water, in slurries, 2.03 kilograms of SPA aqueous solution (mass concentration is 85%) are added under stirring, be warming up to 70 DEG C, then react 45 minutes at this temperature, i.e. the phosphorus aluminium auxiliary agent precursor PAL-1 of obtained phosphorous aluminium compound.Material proportion is in table 2.In table, data are all in butt.
Preparation embodiment 9-11
Prepare phosphorus aluminium auxiliary agent precursor PAL-2, PAL-3 and PAL-4 according to preparation embodiment 8, unlike the concrete material that adopts and composition in Table 2(with butt or with oxide basis).
Table 2
Embodiment 1-7 is for illustration of the preparation method of assistant for calalytic cracking provided by the invention.
Embodiment 1-7
After active mesopore material AMM-1 to AMM-7, heat-resistant inorganic oxide source, phosphorus aluminium auxiliary agent precursor PAL-1 to PAL-4 and clay fully being mixed according to a certain percentage, making beating obtains slurries (solid content is 35 % by weight), spray shaping, 400 DEG C of roastings obtained auxiliary agent precursor after 2 hours.Get 100 grams of auxiliary agent precursors to drop in 1 liter of aqueous ammonium chloride solution and wash (ammonium chloride amount is 2 % by weight of auxiliary agent precursor butt), drying and make finished product assistant for calalytic cracking A1-A7.Assistant for calalytic cracking A1-A7 prepared by embodiment 1-7 feeds intake in table 3.
Comparative example 1
Assistant for calalytic cracking is prepared according to the preparation method of embodiment 6, unlike, replace AMM-6 with DB-1, obtain assistant for calalytic cracking B1.Feed intake in table 3.
Comparative example 2
Assistant for calalytic cracking is prepared according to the preparation method of embodiment 4, unlike, replace AMM-4 with DB-2, obtain assistant for calalytic cracking B2.Feed intake in table 3.
Comparative example 3
By the method preparation contrast auxiliary agent B 3 of embodiment 3, just do not add phosphorus aluminium auxiliary agent.Specifically feed intake in table 3.
Test case 1
For illustration of the application of catalytic cracking catalyst provided by the invention in RFCC.
The auxiliary agent that Example 1-7 provides carries out intensity index (i.e. abrasion index) and measures, wherein assay method (measures with straight tube intensity meter according to RIPP strength test standard method, see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the Yang Cui volume such as surely, Science Press, nineteen ninety publishes) carry out, record its intensity index A.I. respectively, the results are shown in table 4.
Test comparison example 1
The auxiliary agent B 1-B3 getting comparative example 1-3 carries out intensity index mensuration, and assay method is identical with test case 1, and test result is in table 4.
Table 3
Table 4
| Embodiment is numbered | Auxiliary agent | A.I. | Comparative example is numbered | Auxiliary agent | A.I. |
| Embodiment 1 | A1 | 0.7 | Comparative example 1 | B1 | 2.5 |
| Embodiment 2 | A2 | 1.9 | Comparative example 2 | B2 | 1.8 |
| Embodiment 3 | A3 | 2.6 | Comparative example 3 | B3 | 4.9 |
| Embodiment 4 | A4 | 1.8 | |||
| Embodiment 5 | A5 | 1.6 | |||
| Embodiment 6 | A6 | 2.4 | |||
| Embodiment 7 | A7 | 2.3 |
As can be seen from Table 4, in containing the auxiliary agent of mesoporous silica-alumina materials, add the wear resistance that phosphorus al binder effectively can improve auxiliary agent, substantially suitable with conventional FCC catalyst intensity, achieve the controllability of auxiliary agent intensity.
Test case 2
Auxiliary agent B 3 and industrial catalyst C1(trade mark MLC-500 that the auxiliary agent A 3 that Example 3 provides, comparative example 3 provide, Sinopec asphalt in Shenli Refinery) by weight 20:80 physical mixed, 800 DEG C, aging 17 hours of 100% steam, at the upper catalytic performance investigating aging rear catalyst of ACE device (a kind of small fixed flowing bed).Feedstock oil character in table 5, appreciation condition and the results are shown in Table 6.
Table 5
Table 6
As can be seen from Table 6, auxiliary agent provided by the invention, while obviously improving auxiliary agent wear resistance, have good heavy oil conversion performance, and coke selectivity makes moderate progress, and total liquid yield (total recovery of liquefied gas, gasoline and diesel oil) improves.
Test case 3
Identical with the method for test case 1, unlike auxiliary agent A 4, A6 that the catalyst adopted provides for embodiment, the auxiliary agent B 2 that comparative example provides, B1 and industrial catalyst C2(trade mark GOR-II, Sinopec asphalt in Shenli Refinery) catalyst respectively after physical mixed.Appreciation condition and the results are shown in Table 7.
Table 7
As can be seen from Table 7, heavy oil transformation, while obviously improving wear resistance, can be become high-value product by auxiliary agent provided by the invention effectively, and the addition simultaneously adjusting auxiliary agent can obtain different product slates, makes the application of auxiliary agent more flexible.
Claims (20)
1. a preparation method for assistant for calalytic cracking, the method comprises the following steps:
(1) by aluminium source and aqueous slkali and after plastic, adding the ageing of silicon source, obtain solid sediment, having at least a kind of for containing sodium raw materials in wherein said aluminium source, aqueous slkali and silicon source; Gained solid sediment is mixed with ammonium salt or inorganic acid, filters and obtain the low sodium solid sediment that sodium oxide content is less than 0.3 % by weight; Low for gained sodium solid sediment is contacted with phosphorus source and obtains active mesopore material after drying and roasting;
(2) described active mesopore material, phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source are mixed with water pull an oar, then carry out spraying dry, roasting, washing and drying;
Wherein, with P
2o
5meter described phosphorus source with in the weight ratio of the described low sodium solid sediment of butt for 0.01-0.1:1.
2. preparation method according to claim 1, wherein, described in step (1), active mesopore material in the anhydrous chemical expression of oxide weight is: (0-0.2) Na
2o (50-86) Al
2o
3(12-50) SiO
2(0.5-10) P
2o
5.
3. preparation method according to claim 1, wherein, described active mesopore material has boehmite phase structure.
4. preparation method according to claim 1, wherein, the surface area of described active mesopore material is 200-600m
2/ g, pore volume is 0.3-1.8cm
3/ g, average pore size is 8-18nm.
5. preparation method according to claim 4, wherein, the surface area of described active mesopore material is 250-550m
2/ g, pore volume is 0.6-1.6cm
3/ g, average pore size is 8-15nm.
6. preparation method according to claim 1, wherein, in step (1), described phosphorus source is at least one in ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP) and phosphoric acid.
7. preparation method according to claim 1, wherein, in step (1), described contact is ground in described phosphorus source and described low sodium solid sediment.
8. preparation method according to claim 1, wherein, in step (1), described contact comprises: described low sodium solid sediment and water are mixed to form slurries, described low sodium solid sediment in the weight ratio of butt and water for 1:5-20, again described phosphorus source is added described slurries, the condition of described contact comprises: temperature is room temperature to 90 DEG C, and the time is 0.2-5 hour.
9. preparation method according to claim 1, wherein, in step (1), the condition of described drying comprises: temperature is 100-150 DEG C, and the time is 10-20 hour, and the condition of described roasting comprises: temperature is 500-700 DEG C, and the time is 1-4 hour.
10. according to the preparation method in claim 1-9 described in any one, wherein, the temperature of plastic is room temperature to 85 DEG C in step (1), and the pH value of plastic is 7-11; Described silicon source and described aluminium source are respectively with SiO
2and Al
2o
3the weight ratio of meter is 1:1.5-7.5, and the temperature of ageing is room temperature to 90 DEG C, and the time of ageing is 1-5 hour; The temperature of described mixing is room temperature to 100 DEG C.
11. preparation methods according to claim 1, wherein, described aluminium source is selected from least one in aluminum nitrate, aluminum sulfate and aluminium chloride, described alkali is selected from least one in ammoniacal liquor, potassium hydroxide, NaOH and sodium metaaluminate, and described silicon source is selected from least one in waterglass, sodium metasilicate, silicon tetraethyl and silica.
12. preparation methods according to claim 1, wherein, described ammonium salt is at least one in ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and carbonic hydroammonium.
13. preparation methods according to claim 1, wherein, described inorganic acid is selected from least one in sulfuric acid, hydrochloric acid and nitric acid.
14. preparation methods according to claim 1, wherein, the addition in active mesopore material described in step (2), phosphorus aluminium auxiliary agent and/or phosphorus aluminium auxiliary agent precursor, clay and/or heat-resistant inorganic oxide source makes in the assistant for calalytic cracking obtained, by butt, the weight ratio of described active mesopore material, phosphorus aluminium auxiliary agent and clay and/or heat-resistant inorganic oxide is 1:0.001-5:0.1-100.
15. preparation methods according to claim 1 or 14, wherein, described phosphorus aluminium auxiliary agent precursor is the phosphorus aluminium glue of pH value 1.0-3.5.
16. preparation methods according to claim 1, wherein, described heat-resistant inorganic oxide source is heat-resistant inorganic oxide and/or the heat-resistant inorganic oxide precursor that can change heat-resistant inorganic oxide under the condition of the described roasting of step (2) into.
17. preparation methods according to claim 16, wherein, described heat-resistant inorganic oxide is at least one in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide.
18. preparation methods according to claim 1, wherein, described clay is selected from least one in kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
19. assistant for calalytic cracking obtained by the preparation method in claim 1-18 described in any one.
20. application of assistant for calalytic cracking according to claim 19 in RFCC.
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|---|---|---|---|---|
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN102247882A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst |
| CN102974376A (en) * | 2011-09-06 | 2013-03-20 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method thereof |
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| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN102247882A (en) * | 2010-05-20 | 2011-11-23 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing phosphorus-containing alumina and application of catalyst |
| CN102974376A (en) * | 2011-09-06 | 2013-03-20 | 中国石油化工股份有限公司 | Catalytic cracking auxiliary agent and preparation method thereof |
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