CN102974337B - Catalytic cracking auxiliary agent and preparation method thereof - Google Patents
Catalytic cracking auxiliary agent and preparation method thereof Download PDFInfo
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- CN102974337B CN102974337B CN201110261093.XA CN201110261093A CN102974337B CN 102974337 B CN102974337 B CN 102974337B CN 201110261093 A CN201110261093 A CN 201110261093A CN 102974337 B CN102974337 B CN 102974337B
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Abstract
The invention provides a catalytic cracking auxiliary agent and a preparation method thereof. The catalytic cracking auxiliary agent contains a mesoporous silica alumina material, a metal trapping agent and clay and/or heat-resistant inorganic oxide, wherein the mesoporous silica alumina material is obtained by the following steps of mix-pulping the mesoporous silica alumina material without ion exchange with water to obtain a slurry liquid; and contacting the slurry liquid with an inorganic acid for at least 0.2 hour at a temperature ranging from room temperature to 100 DEG C, so as to make the sodium oxide content in the mesoporous silica alumina material no higher than 0.2 wt%, wherein the weight ratio of the mesoporous silica alumina material without ion exchange, water and the inorganic acid is 1 : 5-30 : 0.03-0.3. The catalytic cracking auxiliary agent has relatively strong heavy oil cracking ability, high light oil yield and good coke selectivity when being used for the catalytic cracking of the heavy oil.
Description
Technical field
The present invention relates to a kind of assistant for calalytic cracking and preparation method thereof.
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 once again, 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, as WO9712011A1, disclose oil cracking additive at the bottom of a kind of tower, be 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 problem such as the existing method preparing assistant for calalytic cracking still exists that cost is high, anti-metallic contamination performance and heavy oil conversion performance have much room for improvement.
Summary of the invention
The technical problem to be solved in the present invention is to provide assistant for calalytic cracking that a kind of heavy oil conversion performance is strong, light oil yield is high and anti-metallic contamination performance is good and preparation method thereof.
The invention provides a kind of assistant for calalytic cracking, this assistant for calalytic cracking contains mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide, wherein, described mesoporous silica-alumina materials is obtained by the method comprised the following steps: mixed with water by the mesoporous silica-alumina materials without ion-exchange and pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3.
The invention provides a kind of preparation method of assistant for calalytic cracking, the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange is mixed with water pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than 0.2 % by weight mesoporous silica-alumina materials, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) by the described mesoporous silica-alumina materials, metal traps and the clay that obtain in step (1) and/or heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor mixing making beating, then spraying dry, washing, filtration and drying is carried out successively.
Assistant for calalytic cracking of the present invention is pulled an oar by adopting the mesoporous silica-alumina materials without ion-exchange to mix with water, is obtained slurries, mix with inorganic acid again, the mesoporous silica-alumina materials that mesoporous silica-alumina materials that at least 0.2 hour this ad hoc approach obtains replaces the method for removing Na that conventional ammonium exchanges or ammonium exchanges and inorganic acid combines to obtain is exchanged in room temperature to 100 DEG C, when making assistant for calalytic cracking of the present invention for RFCC, there is stronger heavy oil cracking ability, higher light oil productive rate and better coke selectivity.
And, in the preparation method of described assistant for calalytic cracking of the present invention, without the need to carrying out ammonium exchange in the preparation process of described mesoporous silica-alumina materials, can not ammonia nitrogen waste water be produced, the preparation process making this assistant for calalytic cracking relatively environmental protection and cost is lower.
In addition, inorganic acid only need be used in the preparation process of described mesoporous silica-alumina materials to carry out ion-exchange and can obtain sodium oxide content lower than the mesoporous silica-alumina materials of 0.2 % by weight, thus reduce production cost and improve production efficiency.
Accompanying drawing explanation
Fig. 1 is the X-ray diffracting spectrum of the mesoporous silica-alumina materials that mesoporous silica-alumina materials of the present invention and traditional ammonium switching method obtain, wherein, curve 1 is the spectral line processing the mesoporous catalysis material obtained through twice ammonium exchange described in CN1565733A, and curve 2 is the spectral lines of the mesoporous silica-alumina materials that preparation embodiment 1 obtains.
Detailed description of the invention
The invention provides a kind of assistant for calalytic cracking, this assistant for calalytic cracking contains mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide, wherein, described mesoporous silica-alumina materials is obtained by the method comprised the following steps: mixed with water by the mesoporous silica-alumina materials without ion-exchange and pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1: 5-30: 0.03-0.3.
In the present invention, in the weight ratio without the mesoporous silica-alumina materials of ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.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.
The present invention is to the kind of described inorganic acid without particular/special requirement, and conventional inorganic acid all can realize object of the present invention, under preferable case, the inorganic acid used be selected from sulfuric acid, hydrochloric acid and nitric acid one or more.
In order to better realize object of the present invention, under preferable case, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange and water and inorganic acid is 1: 6-20: 0.05-0.2, is further preferably 1: 8-15: 0.07-0.16.
The present invention to the described mode that gained slurries are contacted with inorganic acid without particular/special requirement, they can be mixed with random order, such as inorganic acid can be joined in slurries and mix, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode mixes for being joined in slurries by inorganic acid.
In the present invention, the condition that described slurries contact with inorganic acid can for conventional ion exchange conditions.For the present invention, under preferable case, the temperature of described contact is 30-80 DEG C, is preferably 40-70 DEG C; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hour, is more preferably 0.5-1 hour.
In the present invention, described mesoporous silica-alumina materials preferably has boehmite crystal phase structure, and its X-ray diffracting spectrum is as shown in the curve 2 of Fig. 1.And, in described mesoporous silica-alumina materials, in the anhydrous chemical expression of oxide weight be: (0-0.2) Na
2o (40-90) Al
2o
3(10-60) SiO
2.
In the present invention, the various mesoporous silica-alumina materials without any ion-exchange that the described mesoporous silica-alumina materials without ion-exchange can be commonly used for this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to the method for routine, and its preparation method such as can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3the weight ratio of=1: 0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, then filters.In the present invention, the sial sediment obtained after described filtration directly can be used as the described mesoporous silica-alumina materials without ion-exchange, is used as the described mesoporous silica-alumina materials without ion-exchange after also can being carried out drying and/or roasting.
In the present invention, described aluminium source can be the conventional various aluminium sources used in the preparation technology of mesoporous silica-alumina materials, such as can one or more for being selected from aluminum nitrate, aluminum sulfate and aluminium chloride.
In the present invention, described silicon source can be the conventional various sial used in the preparation technology of mesoporous silica-alumina materials, such as, can be at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and Silica hydrogel.
In the present invention, described aqueous slkali can be the aqueous slkali of various routine, such as, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
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 mesoporous silica-alumina materials without ion-exchange of so preparation has the meso-hole structure of appropriate size.According to one of the present invention preferred embodiment, described aluminium source be selected from aluminum nitrate, aluminum sulfate and aluminium chloride one or more, described alkali be selected from ammoniacal liquor, potassium hydroxide, NaOH and sodium metaaluminate one or more, described silicon source be selected from waterglass, sodium metasilicate, silicon tetraethyl and silica one or more, and have at least a kind of for containing sodium raw materials in aluminium source wherein, alkali and silicon source.
In the present invention, the described material containing sodium referred to containing sodium raw materials in aluminium source, alkali and silicon source.
In the present invention, described without in the mesoporous silica-alumina materials of ion-exchange in the sodium content of sodium oxide molybdena for 0.5-15 % by weight.And in described assistant for calalytic cracking of the present invention, adopt in the described described mesoporous silica-alumina materials prepared without the mesoporous silica-alumina materials of ion-exchange and be generally less than 0.2 % by weight in the sodium content of sodium oxide molybdena.
In assistant for calalytic cracking of the present invention, the amount of various composition all can refer to prior art and carries out, the present invention to this without particular/special requirement, under preferable case, in described assistant for calalytic cracking, by butt, the weight ratio of described mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide is 1: 0.001-5: 0.1-100, is preferably 1: 0.01-2: 0.1-40, is more preferably 1: 0.02-1.5: 0.1-10.
In the present invention, 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.
The present invention is to the kind of described metal traps without particular/special requirement, and the metal traps can commonly used for this area, wherein, is preferably the precursor of rare earth oxide and/or described rare earth oxide.The precursor of described rare earth oxide be preferably in rare earth chloride, carbonated rare earth and rare earth hydrate one or more.Wherein, rare earth element can be one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium.Preferably, described metal traps is free on outside mesoporous silica-alumina materials.
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.
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.
The preparation method of assistant for calalytic cracking described in the present invention can carry out with reference to prior art, its preparation method can comprise mesoporous silica-alumina materials, heat-resistant inorganic oxide or heat-resistant inorganic oxide precursor and clay mixing making beating, granulation and washing, filter and dry step, and in plastic process in the form of an ion, complex form introduces metal traps to containing heat-resistant inorganic oxide, in the slurries of heat-resistant inorganic oxide precursor or clay, or directly add metal traps particle, or in advance metal traps is deposited in described clay or described inorganic oxide by coprecipitation, or in the rear washing process of described assistant for calalytic cracking, introduce metal traps.Introduce metal traps by aforementioned various mode, make final metal traps all be free on outside described mesoporous silica-alumina materials, those skilled in the art all can know this.
According to one of the present invention preferred embodiment, the invention provides a kind of preparation method of assistant for calalytic cracking, the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange is mixed with water pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than 0.2 % by weight mesoporous silica-alumina materials, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1: 5-30: 0.03-0.3;
(2) by the described mesoporous silica-alumina materials, metal traps and the clay that obtain in step (1) and/or heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor mixing making beating, then spraying dry, washing, filtration and drying is carried out successively.
In method of the present invention, only the preparation method of assistant for calalytic cracking is described, no longer carries out repeated description with the identical technical characteristic in product.In the present invention, in the weight ratio without the mesoporous silica-alumina materials of ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.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 method of the present invention, the present invention is to the kind of described inorganic acid without particular/special requirement, and conventional inorganic acid all can realize object of the present invention, under preferable case, the inorganic acid used be selected from sulfuric acid, hydrochloric acid and nitric acid one or more.
In order to better realize object of the present invention, under preferable case, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange and water and inorganic acid is 1: 6-20: 0.05-0.2, is further preferably 1: 8-15: 0.07-0.16.
According to method provided by the invention, the present invention to the described mode that gained slurries are contacted with inorganic acid without particular/special requirement, they can be mixed with random order, such as inorganic acid can be joined in slurries and mix, also slurries can be joined in inorganic acid and mix, wherein, preferred hybrid mode mixes for being joined in slurries by inorganic acid.
According to method provided by the invention, the condition contacted with inorganic acid by described slurries can for conventional ion exchange conditions.Under preferable case, the temperature of described contact is 30-80 DEG C, is preferably 40-70 DEG C; The time of contact is 0.2-2 hour, is preferably 0.3-1.5 hour, is more preferably 0.5-1 hour.
According to method provided by the invention, in step (1), the various mesoporous silica-alumina materials without any ion-exchange that the described mesoporous silica-alumina materials without ion-exchange can be commonly used for this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to the method for routine, and its preparation method such as can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3the weight ratio of=1: 0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, then filters.In the present invention, the sial sediment obtained after described filtration directly can be used as the described mesoporous silica-alumina materials without ion-exchange, is used as the described mesoporous silica-alumina materials without ion-exchange after also can being carried out drying and/or roasting.Described aluminium source, silicon source and aqueous slkali all with describe above identical.
Preparation in accordance with the present invention, under preferable case, the consumption of described mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor makes in the assistant for calalytic cracking prepared, by butt, the weight ratio of the weight ratio of mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide is 1: 0.001-5: 0.1-100, be preferably 1: 0.01-2: 0.1-40, be more preferably 1: 0.02-1.5: 0.1-10.
In the present invention, clay and/or heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor refer in clay, heat-resistant inorganic oxide and heat-resistant inorganic oxide precursor one or more.
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, the kind of described heat-resistant inorganic oxide, in aforementioned detailed description, does not repeat them here.
According to described method provided by the invention, in step (2), by described mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor mixing making beating, and follow-up spraying dry, washing, filtration 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.
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 light oil productive rate, preferably anti-metallic contamination ability and lower coking yield and dry gas yield.
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 80 % by weight) by Chinese Suzhou, and boehmite is provided (solid content is 65.8 % by weight) by Shandong Aluminum Plant.Industrial catalyst C1 (trade mark MLC-500) and C2 (trade mark GOR-II) is provided by Sinopec catalyst asphalt in Shenli Refinery, and in comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In embodiments, Na in 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).
Preparation embodiment 1-7 is for illustration of the preparation method of the present invention's mesoporous silica-alumina materials used.
Preparation embodiment 1
The preparation process of mesoporous silica-alumina materials SSA-1 is basic identical with the mesoporous silica-alumina materials SA-1 of embodiment in CN1565733A 1, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-1, namely the sial sediment after aging filtration, with water by 1: 10 weight ratio mix and pull an oar, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1: 0.07 joins in above-mentioned slurries, 30 minutes are contacted at 55 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-1.The X-ray diffraction spectral line of this sample is shown in the curve 2 in Fig. 1.The elementary analysis weight chemistry of this sample consists of 0.14Na
2o73.6Al
2o
326.1SiO
2.
Preparation embodiment 2
The preparation process of mesoporous silica-alumina materials SSA-2 is basic identical with the mesoporous silica-alumina materials SA-2 of embodiment in CN1565733A 2, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-2, namely the sial sediment after aging filtration, with water by 1: 10 weight ratio mix and pull an oar, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1: 0.12 joins in above-mentioned slurries, 40 minutes are contacted at 55 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-2.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.1Na
2o58.9Al
2o
340.9SiO
2.
Preparation embodiment 3
The preparation process of mesoporous silica-alumina materials SSA-3 is basic identical with the mesoporous silica-alumina materials SA-3 of embodiment in CN1565733A 3, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-3, namely the sial sediment after aging filtration, with water by 1: 12 weight ratio mix and pull an oar, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1: 0.09 joins in above-mentioned slurries, 40 minutes are contacted at 50 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-3.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.09Na
2o73.9Al
2o
325.9SiO
2.
Preparation embodiment 4
The preparation process of mesoporous silica-alumina materials SSA-4 is basic identical with the mesoporous silica-alumina materials SA-4 of embodiment in CN1565733A 4, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-4, namely the sial sediment after aging filtration, with water by 1: 12 weight ratio mix and pull an oar, again by HCl solution (concentration is 10 % by weight) by sediment (butt): the weight ratio of HCl=1: 0.14 joins in above-mentioned slurries, 30 minutes are contacted at 60 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-4.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.06Na
2o73.8Al
2o
326.0SiO
2.
Preparation embodiment 5
The preparation process of mesoporous silica-alumina materials SSA-5 is basic identical with the mesoporous silica-alumina materials SA-5 of embodiment in CN1565733A 5, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-5, namely the sial sediment after aging filtration, with water by 1: 5 weight ratio mix and pull an oar, again by these slurries by sediment (butt): the weight ratio of HCl=1: 0.08 joins in rare HCl solution (concentration is 10 % by weight), 60 minutes are contacted at 50 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-5.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.17Na
2o74.0Al
2o
325.6SiO
2.
Preparation embodiment 6
The preparation process of mesoporous silica-alumina materials SSA-6 is basic identical with the mesoporous silica-alumina materials SA-5 of embodiment in CN1565733A 5, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-5, namely the sial sediment after aging filtration, with water by 1: 6 weight ratio mix and pull an oar, again by these slurries by sediment (butt): the weight ratio of HCl=1: 0.11 joins in rare HCl solution (concentration is 10 % by weight), 40 minutes are contacted at 50 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-6.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.11Na
2o74.2Al
2o
325.6SiO
2.
Preparation embodiment 7
The preparation process of mesoporous silica-alumina materials SSA-7 is basic identical with the mesoporous silica-alumina materials SA-5 of embodiment in CN1565733A 5, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-5, namely the sial sediment after aging filtration, with water by 1: 8 weight ratio mix and pull an oar, again by these slurries by sediment (butt): the weight ratio of HCl=1: 0.15 joins in rare HCl solution (concentration is 10 % by weight), 20 minutes are contacted at 50 DEG C, after filtration, obtain mesoporous silica-alumina materials after dry and roasting, be designated as SSA-7.This sample has the feature of the X-ray diffraction spectral line of curve 2 in Fig. 1; Its elementary analysis weight chemistry consists of 0.05Na
2o74.2Al
2o
325.7SiO
2.
Preparation comparative example 1
Mesoporous silica-alumina materials SH-SA-1 is obtained according to the method implementing 1 in CN100497531C.
Embodiment 1-7 illustrates the preparation method of assistant for calalytic cracking provided by the invention.
Embodiment 1
Boehmite and kaolin are mixed making beating according to a certain percentage, add mixed chlorinated rare earth (in mixing RECl3 rare earth, with oximeter, RE
2o
3> 98 % by weight, CeO
2with La
2o
3mass ratio is 1.66) (concentration of the mixed chlorinated rare earth aqueous solution is 300g/L to the aqueous solution, following examples are identical), and add hydrochloric acid and make slurries pH=3.0, then mesoporous silica-alumina materials SSA-1 is added, be uniformly dispersed and obtain slurries (solid content is 35 % by weight), roasting 2 hours at 400 DEG C after spray drying forming.The product got after 100 grams of roastings drops into 1 liter of aqueous ammonium chloride solution washing (amount of ammonium chloride is 2 % by weight of catalyst butt), dry obtained finished product auxiliary agent A 1.Specifically feed intake in table 1, wherein the inventory of rare earth chloride is in rare earth oxide.
Embodiment 2
SSA-2, Alumina gel and kaolin are mixed making beating according to a certain percentage, add mixed rare earth carbonate (with oxide basis, RE
2o
3> 98 quality %, CeO
2with La
2o
3mass ratio is 1.52) solid, then add a certain amount of hydrochloric acid and make slurries pH=3.0, be uniformly dispersed and obtain slurries (solid content is 35 % by weight), spray shaping, 400 DEG C, roasting in 2 hours.Get 100 grams of catalyst and drop into 1 liter of aqueous ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), dry obtained finished product auxiliary agent A 2.Specifically feed intake in table 1.
Embodiment 3
First in the mixed chlorinated rare earth aqueous solution, slowly instill ammoniacal liquor, filter and obtain RE (OH)
3(with oxide basis, RE
2o
3> 98 quality %, CeO
2with La
2o
3mass ratio is 1.66), for subsequent use.SSA-3, boehmite, Alumina gel and kaolin are mixed making beating according to a certain percentage, adds a certain amount of hydrochloric acid and make slurries pH=3.0, finally add the RE (OH) prepared above
3, be uniformly dispersed and obtain slurries (solid content is 35 % by weight), spray shaping.Roasting in 400 DEG C, 2 hours, gets 100 grams of catalyst and drops into 1 liter of aqueous ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), dry obtained finished product auxiliary agent A 3.Specifically feed intake in table 1.
Embodiment 4
Boehmite, Alumina gel and kaolin are mixed making beating according to a certain percentage, adds LaCl
3the aqueous solution (concentration is 300g/L), adds a certain amount of hydrochloric acid and makes slurries pH=3.0, then add SSA-4, being uniformly dispersed obtains slurries (solid content is 35 % by weight), spray shaping.Roasting in 400 DEG C, 2 hours, gets 100 grams of catalyst and drops into 1 liter of aqueous ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), dry obtained finished product auxiliary agent A 4.Specifically feed intake in table 1.
Embodiment 5
SSA-5, Ludox and kaolin are mixed making beating according to a certain percentage, then adds a certain amount of hydrochloric acid and make slurries pH=3.0, be uniformly dispersed and obtain slurries (solid content is 35 % by weight), spray shaping.Roasting in 400 DEG C, 2 hours, gets 100 grams of catalyst and drops into 1 liter of aqueous ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), then use rare earth chloride solution washing assisant, dry obtained finished product auxiliary agent A 5.Specifically feed intake in table 1.
Embodiment 6
Boehmite and Alumina gel are mixed making beating according to a certain percentage, adds mixing RECl
3rare earth (mixing RECl
3in rare earth, with oximeter, RE
2o
3> 98 % by weight, CeO
2with La
2o
3mass ratio is 1.66) aqueous solution (concentration is 300g/L), add a certain amount of hydrochloric acid and make slurries pH=3.0, add SSA-6 again, being uniformly dispersed obtains slurries (solid content is 35 % by weight), spray shaping, 400 DEG C of roastings roasting in 2 hours, gets that 100 grams of catalyst drop into 1 liter of ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), finished product auxiliary agent A 6 is made in drying.Specifically feed intake in table 1.
Embodiment 7
SSA-7 and kaolin are mixed making beating according to a certain percentage, is uniformly dispersed and obtains slurries (solid content is 35 % by weight), spray shaping.Roasting in 400 DEG C, 2 hours, gets 100 grams of catalyst and drops into 1 liter of aqueous ammonium chloride solution washing (ammonium chloride amount is 2 % by weight of catalyst butt), then use lanthanum chloride solution drip washing auxiliary agent, dry obtained finished product auxiliary agent A 7.Specifically feed intake in table 1.
Table 1
Comparative example 1
By the method preparation contrast auxiliary agent B 1 of embodiment 1, just replace SSA-1 with SA-1.
Comparative example 2
By the method preparation contrast auxiliary agent B 2 of embodiment 2, just replace SSA-2 with SA-2.
Comparative example 3
By the method preparation contrast auxiliary agent B 3 of embodiment 3, just replace SSA-3 with SA-3.Specifically feed intake in table 4.
Comparative example 4
By the method preparation contrast auxiliary agent B 4 of embodiment 4, just replace SSA-4 with SA-4.Specifically feed intake in table 4.
Comparative example 5
By the method preparation contrast auxiliary agent B 5 of embodiment 5, just replace SSA-5 with SA-5.
Comparative example 6
By the method preparation contrast auxiliary agent B 6 of embodiment 1, just replace SSA-1 with SH-SA-1.
Comparative example 7
According to the method preparation contrast auxiliary agent B 7 of embodiment 6, do not add mixed chlorinated rare earth unlike in preparation process.
Test case 1
The auxiliary agent A 1 that Example 1, embodiment 2, embodiment 5-7 provide, A2, A5-A7 and industrial catalyst C1 are by constant weight physical mixed (be shown in table 2), catalyst C1, C1 and auxiliary agent A 1, the mixed catalyst of A2, A5-A7 are polluted in the cocycle of circulation aging equipment, deposition Ni, V, then 800 DEG C, aging 8 hours of 100% steam, ACE device is investigated the catalytic performance of aging rear catalyst.On catalyst, Ni, V content is in table 2, raw materials used oil nature in table 3, appreciation condition and the results are shown in Table 4.
Table 2
| Tenor | 100C1 | 95C1+5A1 | 90C1+10A2 | 92C1+8A5 | 70C1+30A6 | 88C1+12A7 |
| Ni，ppm | 2890 | 3110 | 2960 | 3030 | 2870 | 3130 |
| V，ppm | 3020 | 3150 | 2990 | 3220 | 3080 | 3170 |
| Tenor | 95C1+5B1 | 90C1+10B2 | 92C1+8B5 | 95C1+5B6 | 95C1+5B7 | |
| Ni，ppm | 3090 | 2970 | 3010 | 3080 | 3130 | |
| V，ppm | 3120 | 2910 | 3180 | 3130 | 3150 |
Table 3
| Density (20 DEG C), gram per centimeter 3 | 0.9044 |
| Viscosity, millimeter 2/ second | 1.5217(20℃) |
| 100℃ | 9.96 |
| Freezing point, DEG C | 40 |
| Carbon residue, % by weight | 3.0 |
| Element forms, and % by weight | |
| C | 85.98 |
| H | 12.86 |
| S | 0.55 |
| N | 0.18 |
| Boiling range, DEG C | |
| Initial boiling point | 243 |
| 5％ | 294 |
| 10％ | 316 |
| 30％ | 395 |
| 50％ | 429 |
| 70％ | 473 |
| 90％ | - |
Table 4
Test comparison example 1
Test according to the method for test case 1, the auxiliary agent B 1, B2 and B5-B7 and the industrial catalyst C1 that there is provided for comparative example 1,2 and 5-7 unlike the catalyst catalyst (see table 8) after physical mixed, on catalyst, Ni, V content is in table 2, appreciation condition and the results are shown in Table 5.
Table 5
As can be seen from the data of table 4, table 5, auxiliary agent provided by the invention has better heavy oil conversion performance and anti-metallic contamination ability.
Test case 2
Test according to the method for test case 1, the auxiliary agent A 3 provided for embodiment 3 unlike catalyst and the catalyst of industrial catalyst C1 after 20: 80 physical mixed, Ni, V content, appreciation condition and the results are shown in Table 6 on catalyst.
Test comparison example 2
Test according to the method for test case 1, the auxiliary agent B 3 provided for comparative example 3 unlike catalyst and the catalyst of industrial catalyst C1 after 20: 80 physical mixed, Ni, V content, appreciation condition and the results are shown in Table 6 on catalyst.
Table 6
From the evaluation result of table 6, A3 has better heavy oil conversion performance compared with contrast medium B3.
Test case 3
Test according to the method for test case 1, the auxiliary agent A 4 provided for embodiment 4 unlike catalyst and the catalyst of industrial catalyst C2 after 15: 85 physical mixed, Ni, V content, appreciation condition and the results are shown in Table 7 on catalyst.
Test comparison example 3
Test according to the method for test case 1, the auxiliary agent B 4 provided for comparative example 4 unlike catalyst and the catalyst of industrial catalyst C2 after 15: 85 physical mixed, Ni, V content, appreciation condition and the results are shown in Table 7 on catalyst.
Table 7
From the evaluation result of table 7, auxiliary agent provided by the invention, compared with contrast auxiliary agent, can strengthen anti-metallic contamination ability after interpolation vanadium trapping agent, and while raising heavy oil conversion performance, do not increase coke output, effectively heavy oil transformation is become high-value product.
Claims (17)
1. an assistant for calalytic cracking, this assistant for calalytic cracking contains mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide, it is characterized in that, described mesoporous silica-alumina materials is obtained by the method comprised the following steps: mixed with water by the mesoporous silica-alumina materials without ion-exchange and pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the described mesoporous silica-alumina materials without ion-exchange, the weight ratio of water and inorganic acid is 1:5-30:0.03-0.3, described without in the mesoporous silica-alumina materials of ion-exchange, sodium content counts 0.5-15 % by weight with sodium oxide molybdena, the described mesoporous silica-alumina materials without ion-exchange is obtained by the preparation method comprised the following steps: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH value of plastic terminal is 7-11, then according to SiO
2: Al
2o
3the weight ratio of=1:0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, then filters.
2. assistant for calalytic cracking according to claim 1, wherein, described inorganic acid be selected from sulfuric acid, hydrochloric acid and nitric acid one or more.
3. assistant for calalytic cracking according to claim 1, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange and water and inorganic acid is 1:6-20:0.05-0.2.
4. assistant for calalytic cracking according to claim 3, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange and water and inorganic acid is 1:8-15:0.07-0.16.
5. according to the assistant for calalytic cracking in claim 1-4 described in any one, wherein, the temperature of contact is 30-80 DEG C, and the time is 0.3-1.5 hour.
6. according to the assistant for calalytic cracking in claim 1-4 described in any one, wherein, the described mode contacted with inorganic acid by gained slurries is for join inorganic acid in slurries.
7. according to the assistant for calalytic cracking in claim 1-4 described in any one, wherein, described mesoporous silica-alumina materials has boehmite crystal phase structure, is: 0-0.2Na in the anhydrous chemical expression of oxide weight
2o40-90Al
2o
310-60SiO
2.
8. assistant for calalytic cracking according to claim 1, wherein, described aluminium source be selected from aluminum nitrate, aluminum sulfate and aluminium chloride one or more, described alkali be selected from ammoniacal liquor, potassium hydroxide, NaOH and sodium metaaluminate one or more, described silicon source be selected from waterglass, sodium metasilicate, silicon tetraethyl and silica one or more, and have at least a kind of for containing sodium raw materials in aluminium source wherein, alkali and silicon source.
9. according to the assistant for calalytic cracking in claim 1-4 described in any one, wherein, in described assistant for calalytic cracking, by butt, the weight ratio of described mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide is 1:0.001-5:0.1-100.
10. assistant for calalytic cracking according to claim 9, wherein, in described assistant for calalytic cracking, by butt, the weight ratio of described mesoporous silica-alumina materials, metal traps and clay and/or heat-resistant inorganic oxide is 1:0.01-2:0.1-40.
11. according to the assistant for calalytic cracking in claim 1-4 and 10 described in any one, and wherein, described metal traps is the precursor of rare earth oxide and/or described rare earth oxide.
12. assistant for calalytic cracking according to claim 11, wherein, the precursor of described rare earth oxide is one or more in rare earth chloride, carbonated rare earth and rare earth hydrate.
13. according to the assistant for calalytic cracking in claim 1-4 and 10 described in any one, and wherein, described heat-resistant inorganic oxide is one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide and beryllium oxide.
14. according to the assistant for calalytic cracking in claim 1-4 and 10 described in any one, wherein, described clay be selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
The preparation method of 15. 1 kinds of assistant for calalytic cracking, the method comprises the following steps:
(1) mesoporous silica-alumina materials without ion-exchange is mixed with water pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, obtain sodium oxide content not higher than 0.2 % by weight mesoporous silica-alumina materials, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3; Described without in the mesoporous silica-alumina materials of ion-exchange, sodium content counts 0.5-15 % by weight with sodium oxide molybdena; The preparation method of the described mesoporous silica-alumina materials without ion-exchange comprises: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH of plastic terminal is 7-11; Then according to SiO
2: Al
2o
3the weight ratio of=1:0.6-9 adds silicon source, and aging 1-10 hour at room temperature to 90 DEG C, then filters.
(2) the described mesoporous silica-alumina materials, metal traps, clay and/or the heat-resistant inorganic oxide that obtain in step (1) and/or the mixing of heat-resistant inorganic oxide precursor are pulled an oar, then carry out spraying dry, washing, filtration and drying successively.
16. preparation methods according to claim 15, wherein, in step (1), described inorganic acid be selected from sulfuric acid, hydrochloric acid and nitric acid one or more.
17. preparation methods according to claim 15 or 16, wherein, in step (1), the Contact Temperature of described slurries and inorganic acid is 30-80 DEG C, and time of contact is 0.2-2 hour.
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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 |
| CN100497531C (en) * | 2005-04-29 | 2009-06-10 | 中国石油化工股份有限公司 | Cracking catalyst |
| CN101027128B (en) * | 2004-09-08 | 2011-07-06 | 英特凯特公司 | Additives for metal contaminant removal |
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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 |
| CN101027128B (en) * | 2004-09-08 | 2011-07-06 | 英特凯特公司 | Additives for metal contaminant removal |
| CN100497531C (en) * | 2005-04-29 | 2009-06-10 | 中国石油化工股份有限公司 | Cracking catalyst |
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