CN103785370A - Metal chelating agent, preparation method and application thereof, and catalytic cracking method - Google Patents
Metal chelating agent, preparation method and application thereof, and catalytic cracking method Download PDFInfo
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- CN103785370A CN103785370A CN201210420936.0A CN201210420936A CN103785370A CN 103785370 A CN103785370 A CN 103785370A CN 201210420936 A CN201210420936 A CN 201210420936A CN 103785370 A CN103785370 A CN 103785370A
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Abstract
The invention provides a metal chelating agent, and a preparation method and an application thereof. The metal chelating agent contains magnesium oxide and stepped pores-distributed alumina, and at least parts of alumina and at least parts of magnesium oxide form a magnesium aluminate spinel structure; the stepped pores-distributed alumina contains macro-porous alumina and micro-porous alumina; in the macro-porous alumina, the volume of pores with the pore volume of 2-5nm is 20-35% of the volume of pores with the pore volume of 2-100nm, the volume of pores with the pore volume of 5-10nm is 25-45% of the volume of pores with the pore volume of 2-100nm, and the volume of pores with the pore volume of 10-60nm is 20-50% of the volume of pores with the pore volume of 2-100nm; and in the micro-porous alumina, the volume of pores with the pore volume of 2-5nm is 50-70% of the volume of pores with the pore volume of 2-100nm, the volume of pores with the pore volume of 5-10nm is 15-30% of the volume of pores with the pore volume of 2-100nm, and the volume of pores with the pore volume of 10-60nm is 10-20% of the volume of pores with the pore volume of 2-100nm. The invention also provides a catalytic cracking method. The metal chelating agent has a very good metal chelating effect, and can alleviate the destroys of vanadium to a cracking catalyst, improve the yields of liquid products and reduce the yields of dry gas and coke when the metal chelating agent is used in the catalytic cracking of high-vanadium heavy oil.
Description
Technical field
The present invention relates to the preparation method of a kind of metal traps and a kind of metal traps, and application and a kind of catalyst cracking method of metal traps in catalytic cracking.
Background technology
The constantly soaring processing cost that has increased considerably refinery of crude oil price, at present, catalytic cracking is the important means of refinery's processing of heavy oil, in order to reduce costs so that maximizing the benefits can process to realize by deep processing mink cell focus with poor oil.
But, higher heavy metal (as the vanadium) content of crude oil with poor quality.Vanadium-containing compound in oil is the metal complex that a class is very complicated, generally exists with the form of porphyrin vanadium and non-porphyrin vanadium.Metalloporphyrin boiling point generally, between 565-650 ℃, mainly concentrates in residual oil, but because its volatility is stronger, also can enter in catalytic cracking cut.Non-porphyrin metal compound may be the compound that the relative molecular weight together with the large molecular association of asphalitine is less than 400, and its part may be 4N, NO
2s or 4S; After the macromolecular three-dimensional structure of asphalitine is destroyed, these little molecules will be released.Vanadium is mainly that vanadium has caused irreversible destruction to catalyst to the pollution of catalytic cracking catalyst.Experiment shows, the vanadium that deposits 1000 μ g/g on poising agent is enough to zeolite to cause damage, and worsens product and distributes.
Conventionally use at present metal traps to carry out the trapping of heavy metal, to reduce the destruction of heavy metal (as vanadium) to Cracking catalyst.Spinelle is conventional metal traps material, and as US5603823A discloses a kind of vanadium trapping agent, it consists of the MgO of (a) 15-60w%, (b) Al of 30-60w%
2o
3and (c) rare earth of 10-30w%, rare earth is selected from lanthanum-oxides and/or neodymium oxides, wherein, and MgO and Al at least partly
2o
3form Mg-Al spinelle.
CN1148256C discloses a kind of composition and method of making the same containing magnesium aluminate spinel, the magnesia that said composition contains the heavy % of 25-30, the rare-earth oxide except cerium of the aluminium oxide of the heavy % of 60-70 and the heavy % of 5-15, wherein, magnesium and aluminium form spinel structure, the content of free magnesium is lower than 5 heavy % of total composition, and the most probable bore dia of described composition is not less than 10nm.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of metal traps with good metal trapping performance and its preparation method and application.
For realizing aforementioned object, on the one hand, the invention provides a kind of metal traps, this metal traps contains magnesia and has the aluminium oxide of stepped pore distribution, and aluminium oxide and at least partly magnesia formation magnesia-alumina spinel structure at least partly;
The aluminium oxide wherein, with stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; Take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
On the other hand, the invention provides a kind of preparation method of metal traps, wherein, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained to the first slurries;
(2) described the first slurries are contacted and obtain the second slurries with magnesium hydroxide and/or magnesia;
(3) described the second slurries are contacted with macroporous aluminium oxide and obtain the 3rd slurries;
(4) described the 3rd slurries are sprayed after dry and carry out roasting;
Wherein, take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
On the one hand, the invention provides a kind of metal traps that adopts the preparation method of metal traps of the present invention to prepare again.
On the one hand, the invention provides the application of a kind of metal traps of the present invention in catalytic cracking again.
Again on the one hand, the invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, heavy oil feedstock is contacted with the catalyst mixture that contains metal traps and catalytic cracking catalyst, wherein, described metal traps is metal traps of the present invention.
Metal traps of the present invention has good metal trapping effect, and metal traps provided by the invention, for high vanadium RFCC, can be slowed down to the destruction of vanadium to Cracking catalyst, improves liquid product yield, reduces dry gas and coking yield.For example, when vanadium trapping agent provided by the invention and industrial cracking catalyst are by weight for 6:94 mixes, when on catalyst mixture, Ni content is about 2000ppm, content of vanadium and is about 4500ppm, compared with independent use industrial cracking catalyst, heavy oil yield is reduced to 10.27 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.22 % by weight by 71.60 % by weight, dry gas is selectively down to 0.0340 by 0.0358, and coke selectivity is down to 0.1787 by 0.1910.As can be seen here, metal traps provided by the invention can more effectively become high-value product by heavy oil transformation.
Other features and advantages of the present invention are described in detail the specific embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with the specific embodiment one below.In the accompanying drawings:
Fig. 1 is the pore size distribution figure of macroporous aluminium oxide A used in the present invention, aperture aluminium oxide A;
Fig. 2 is the fresh state (being called fresh dose in figure) of the metal traps A1 for preparing according to the method for embodiment 1 and hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 800 ℃, 100% water vapour atmosphere pore size distribution figure;
Fig. 3 is the fresh state (being called fresh dose in figure) of the metal traps B1 for preparing according to the method for comparative example 1 and hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 800 ℃, 100% water vapour atmosphere pore size distribution figure;
Fig. 4 is the XRD spectra of the metal traps A1 preparing according to the method for embodiment 1 and the metal traps B1 preparing according to the method for comparative example 1.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of metal traps, this metal traps contains magnesia and has the aluminium oxide of stepped pore distribution, and aluminium oxide and at least partly magnesia formation magnesia-alumina spinel structure at least partly;
The aluminium oxide wherein, with stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; Take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
According to metal traps of the present invention, under preferable case, take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-30%, and the pore volume in 5-10nm hole accounts for 25-40%, and the pore volume in 10-60nm hole accounts for 25-45%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%, and remaining is the pore volume content in 60-100nm hole; More preferably in situation, take the pore volume in 2-100nm hole as benchmark, in described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 52-68%, the pore volume in 5-10nm hole accounts for 15-30%, the pore volume in 10-60nm hole accounts for 11-18%, take the volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 60-100nm hole is preferably no more than 10%, and in described little porous aluminum oxide, the pore volume in 60-100nm hole is no more than 5%.In the present invention, the hole of described 2-5nm refers to that aperture is more than or equal to 2nm, be less than the hole of 5nm, the hole of 5-10nm, refer to that aperture is more than or equal to the hole that 5nm is less than 10nm, the hole of 10-60nm refers to that aperture is more than or equal to 10nm, is less than the hole of 60nm, and 2-100nm refers to that aperture is more than or equal to the hole that 2nm is less than or equal to 100nm.
In the present invention, the BET specific area of preferred described macroporous aluminium oxide is not less than 350m
2g
-1, pore volume is preferably not less than 0.70mLg
-1.
In the present invention, pore size distribution (claiming again pore volume distribution), aperture, pore volume adopt low-temperature nitrogen adsorption method to measure (referring to " Petrochemical Engineering Analysis method (RIPP test method) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).
The aluminium oxide (comprising described macroporous aluminium oxide and described little porous aluminum oxide) described in of the present invention with stepped pore distribution also has detailed introduction in Chinese patent CN101745417B.The present invention quotes for the present invention is described in the lump at this.
According to metal traps of the present invention, meeting the described macroporous aluminium oxide of requirement of the present invention and little porous aluminum oxide can obtain by synthetic, also can be commercially available, the present invention to this without specific (special) requirements.
According to metal traps of the present invention, there is macroporous aluminium oxide that the aluminium oxide of stepped pore distribution contains 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight described in preferably; More preferably described in, there is macroporous aluminium oxide that the aluminium oxide of stepped pore distribution contains 15-85 % by weight and the little porous aluminum oxide of 15-85 % by weight.
According to metal traps of the present invention, can well realize object of the present invention as long as there is the aluminium oxide of stepped pore distribution described in containing in assurance metal traps of the present invention, in described metal traps, there is optional wider range of the content of the aluminium oxide of stepped pore distribution, for the present invention, in preferred described metal traps, contain the aluminium oxide with stepped pore distribution of 5-95 % by weight and the magnesia of 5-95 % by weight.
According to metal traps of the present invention, according to needing, in described metal traps, also contain the 3rd component, described the 3rd component be except described magnesia, described in there is heat-resistant inorganic oxide and/or the clay the aluminium oxide of stepped pore distribution.Optional wider range of the content of described the 3rd component, specifically can select according to actual needs, the present invention to this without specific (special) requirements, the general gross weight take metal traps is as benchmark, the content of described the 3rd component is 0.001-30 % by weight, preferred, in described metal traps, contain described the 3rd component of the aluminium oxide with stepped pore distribution of 10-95 % by weight and the magnesia of 5-60 % by weight and aequum.
According to metal traps of the present invention, optional wider range of the kind of described heat-resistant inorganic oxide, meet the conventional heat-resistant inorganic oxide of the prior art of aforementioned requirement (in this area conventionally also referred to as binding agent oxide) and all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide is selected from silica, one or more in the aluminium oxide except the described aluminium oxide with stepped pore distribution and the metal oxide outside magnesia (as calcium oxide, titanium oxide, zirconia).
According to metal traps of the present invention, optional wider range of the kind of described clay, the conventional clay in this area all can be used for the present invention, for the present invention, preferred described clay is selected from one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite, and more preferably described clay is selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
The preparation method of metal traps described in the present invention can carry out with reference to prior art, it can adopt the method for this area routine to prepare, according to one embodiment of the present invention, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) little porous aluminum oxide, macroporous aluminium oxide, deionized water and sour mixed pulp are obtained to the first slurries;
(2) described the first slurries are contacted and obtain the second slurries with magnesium hydroxide and/or magnesia;
(3) described the second slurries are sprayed after dry and carry out roasting;
Wherein, take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
According to one of the present invention preferred embodiment, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained to the first slurries;
(2) described the first slurries are contacted and obtain the second slurries with magnesium hydroxide and/or magnesia;
(3) described the second slurries are contacted with macroporous aluminium oxide and obtain the 3rd slurries;
(4) described the 3rd slurries are sprayed after dry and carry out roasting;
Wherein, take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
Preparation in accordance with the present invention, described macroporous aluminium oxide and little porous aluminum oxide are described in detail in the aforementioned process of introducing metal traps of the present invention of the present invention, do not repeat them here.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to aforementioned techniques scheme of the present invention, optional wider range of various material consumptions in preparation process, for the present invention, in aluminium oxide in the metal traps that the consumption of preferred described macroporous aluminium oxide and little porous aluminum oxide makes to prepare, contain 10-90 % by weight, preferably macroporous aluminium oxide and the 10-90 % by weight of 15-85 % by weight, the preferably little porous aluminum oxide of 15-85 % by weight, and in the metal traps that total consumption of described macroporous aluminium oxide and little porous aluminum oxide makes to prepare, the total content of macroporous aluminium oxide and little porous aluminum oxide is 5-95 % by weight.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to aforementioned techniques scheme of the present invention, optional wider range of various material consumptions in preparation process as previously mentioned, for the present invention, the magnesia that contains 5-95 % by weight in the metal traps that preferred described magnesium hydroxide and/or magnesian consumption make to prepare.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to aforementioned techniques scheme of the present invention, optional wider range of the condition of mixed pulp described in step (1), specifically can carry out with reference to prior art, the pH value that makes the first slurries for the consumption of acid in preferred steps of the present invention (1) is 1-3.0; It is 8-20 % by weight that the consumption of the medium and small porous aluminum oxide of step (1) and deionized water makes the solid content of the first slurries.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to aforementioned techniques scheme of the present invention, optional wider range of the condition of contact described in step (2), for the present invention, described in preferred steps (2), the condition of contact comprises: temperature is 0-70 ℃, is preferably 15-60 ℃; Time is more than 15min, to be preferably 15-90min.Preparation in accordance with the present invention, carry out realizing object of the present invention according to aforementioned techniques scheme of the present invention, optional wider range of the condition of contact described in step (3), for the present invention, described in preferred steps (3), the condition of contact comprises: temperature is 10-60 ℃, and the time is 20-60min.
Preparation in accordance with the present invention, according to needing to introduce the 3rd material in the process of the described metal traps of preparation, particularly for example can the mixed pulp of step (1) and/or step (2) by described the first slurries and magnesium hydroxide and/or magnesian contact and/or step (3) will in the contact process of described the second slurries and macroporous aluminium oxide, introduce the 3rd material, the solid that also described the 3rd material can be obtained with step (4) roasting contacts by load to be introduced, for the present invention, the mixed pulp of preferred steps (1) and/or step (2) by described the first slurries and magnesium hydroxide and/or magnesian contact and/or step (3) described the second slurries are carried out with contacting under the 3rd material exists of macroporous aluminium oxide, wherein, described the 3rd material can be clay, except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, one or more in heat-resistant inorganic oxide beyond described magnesium hydroxide and/or the presoma of heat-resistant inorganic oxide, preferred, total consumption of described macroporous aluminium oxide and little porous aluminum oxide, described magnesium hydroxide and/or magnesian consumption, in the metal traps that the consumption of described the 3rd material makes to prepare, contain macroporous aluminium oxide and the little porous aluminum oxide of 10-95 % by weight, the oxide of described the 3rd material of the magnesia of 5-60 % by weight and aequum.
Preparation in accordance with the present invention, the kind of described clay and heat-resistant inorganic oxide is described in detail in the aforementioned part of introducing metal traps of the present invention, and at this, it is no longer repeated.
Preparation in accordance with the present invention, optional wider range of the kind of described heat-resistant inorganic oxide presoma, the conventional heat-resistant inorganic oxide presoma (this area is also referred to as binding agent) in this area that meets aforementioned requirement all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide presoma is selected from one or more in Ludox, waterglass, boehmite, aluminium colloidal sol and silicon-aluminum sol.
Preparation in accordance with the present invention, described spraying method dry, dry, roasting all can be carried out with reference to prior art, the present invention to this without specific (special) requirements.
The invention provides a kind of metal traps preparing according to preparation method of the present invention.
The invention provides the application of metal traps of the present invention in catalytic cracking.
Metal traps of the present invention has good metal trapping effect, and metal traps provided by the invention, for high vanadium RFCC, can be slowed down to the destruction of vanadium to Cracking catalyst, improves liquid product yield, reduces dry gas and coking yield.For example, when vanadium trapping agent provided by the invention and industrial cracking catalyst are by weight for 6:94 mixes, when on catalyst mixture, Ni content is about 2000ppm, content of vanadium and is about 4500ppm, compared with independent use industrial cracking catalyst, heavy oil yield is reduced to 10.27 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.22 % by weight by 71.60 % by weight, dry gas is selectively down to 0.0340 by 0.0358, and coke selectivity is down to 0.1787 by 0.1910.As can be seen here, metal traps provided by the invention can more effectively become high-value product by heavy oil transformation.
The invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, heavy oil feedstock is contacted with the catalyst mixture that contains metal traps and catalytic cracking catalyst, and wherein, described metal traps is metal traps of the present invention.
According to catalyst cracking method of the present invention, in preferred described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99, is preferably 1:5.7-99, more preferably 1:6-32.
According to catalyst cracking method of the present invention, described catalytic cracking condition can be the conventional catalytic cracking condition in this area, and the present invention, is not described in detail at this without specific (special) requirements this.
Below by embodiment, the present invention is further described, but not thereby limiting the invention.
In the present invention, refer to the weight of roasting after 1 hour under the condition of approximately 800 ℃ in the weight of butt.
In the present invention, the solid content of material refers to the weight ratio before weight and the roasting of material after high-temperature roasting, i.e. the water content % of solid content=100%-material of material.
In the present invention, oil ratio refers to the mass ratio of catalyst and feedstock oil.
In the present invention, if not otherwise specified, ppm is ppm by weight.
In an embodiment with comparative example in:
Aluminium colloidal sol provides (Al by catalyst asphalt in Shenli Refinery of China Petrochemical Industry
2o
3content is 21.5 % by weight), kaolin originates from Chinese Suzhou (solid content is 76.9 % by weight), and boehmite provides (solid content is 60.8 % by weight) by Shandong Aluminum Plant, and magnesia effluent Bei Meishen Chemical Co., Ltd. provides.Industrial catalyst C(trade mark HGY) provided by Sinopec Shandong catalyst branch company, in comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In each embodiment, abrasion index and bulk density adopt RIPP standard method to measure (referring to " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).In catalyst mixture, Ni, V content are measured with x-ray fluorescence method; The thing of metal traps adopts XRD method to measure mutually.
The present embodiment is for illustrating the preparation process of metal traps provided by the invention.
(1) aperture aluminium oxide A is added in deionized water, after being uniformly dispersed, add hydrochloric acid, contact and obtain the first slurries after 30 minutes, the pH value of the first slurries is 1.1, and slurry solid content is 15 % by weight;
(2) then add MgO slurries (containing MgO 750g) that deionized water disperses to described the first slurries, temperature obtains the second slurries after being controlled at and contacting 60 minutes at 55 ℃, and the pH value of the second slurries is 9.6, and solid content is 28 % by weight;
(3) then add in macroporous aluminium oxide to the second slurries and obtain the 3rd slurries, at 10-40 ℃, contact 15min;
(4) by after described the 3rd slurries spray drying forming, roasting direct, roasting condition is 550 ℃/2h, obtains metal traps A1;
Wherein, (the pore size distribution figure of macroporous aluminium oxide A, aperture aluminium oxide A is shown in Fig. 1) in table 1 listed in the pore size distribution of aluminium oxide, and formula, preparation parameter and the abrasion index of A1 are listed in table 2.The XRD spectra of A1 is shown in Fig. 4, as seen from Figure 4, contains magnesia-alumina spinel structure in metal traps A1, and in metal traps, at least part of magnesia and aluminium oxide have formed magnesia-alumina spinel structure;
Wherein, the fresh state of metal traps A1 and under 800 ℃, 100% water vapour atmosphere the pore size distribution figure of hydrothermal aging after 17 hours see Fig. 2; Metal traps A1 mesopore after hydrothermal aging remains intact as seen from Figure 2, and larger pore volume is provided.
Embodiment 2-8
Example 2-8 is for illustrating the preparation process of metal traps provided by the invention.
Prepare metal traps A2-A8 according to the method for embodiment 1, different is that formula, preparation parameter and abrasion index are listed in table 2.
Embodiment 9
Prepare metal traps A9 according to the method for embodiment 1, different, there is no step (3), and directly macroporous aluminium oxide is added together with little porous aluminum oxide in step (1), all the other Step By Conditions are all identical, obtain metal traps A9.
Comparative example 1
This comparative example is for illustrating the preparation process of contrast metal traps B1.
(1) boehmite 250g(is pressed to Al
2o
3meter) add in deionized water, after being uniformly dispersed, add hydrochloric acid, contact and obtain the first slurries after 30 minutes, the pH value of the first slurries is 1.5, solid content is 15 % by weight;
(2) then add MgO slurries (containing MgO 750g) that deionized water disperses to described the first slurries, obtain second slurries after contacting 60 minutes at 76 ℃, the pH value of the second slurries is 9.9, and solid content is 28 % by weight;
By the second slurries spray drying forming, roasting direct, roasting condition is 550 ℃/2h, obtains metal traps B1.Formula, preparation parameter and the abrasion index of B1 are listed in table 3.The XRD spectra of B1 is shown in Fig. 4, as seen from Figure 4, contains magnesia-alumina spinel structure in metal traps A1, and in metal traps, at least part of magnesia and aluminium oxide have formed magnesia-alumina spinel structure;
Wherein, the fresh state of metal traps B1 and under 800 ℃, 100% water vapour atmosphere the pore size distribution figure of hydrothermal aging after 17 hours see Fig. 3; After metal traps B 1 hydrothermal aging, substantially do not form mesopore as seen from Figure 3.
Comparative example 2-3
According to the method preparation contrast metal traps B2-B3 of comparative example 1, different, formula, preparation parameter and the abrasion index of B2, B3 are listed in table 3.From abrasion index, only use contrast auxiliary agent B 3 intensity differences of macroporous aluminium oxide, be not suitable for catalytic cracking process.
Table 1
Table 2
Table 3
Embodiment 10-18
Embodiment 10-18 is for illustrating the heavy metal-polluted dyeing method of metal traps and industrial cracking catalyst mixture and the metal traps of the present invention Catalytic Cracking Performance for catalytic cracking.
First the solid content of analytical industry Cracking catalyst C and metal traps A1-A9 provided by the invention, then obtain catalyst mixture with butt metering physical mixed, catalyst mixture first carries out cyclic polluting (to deposit Ni and V) on circulation aging equipment, on catalyst mixture after cyclic polluting, Ni, V content are in table 5 and table 6, wherein
Cycle is polluted step and is comprised: catalyst mixture is introduced after heavy metal (Ni and V) by meter Xie Er infusion process, then the catalyst mixture of introducing after heavy metal is packed in D-100 device (small fixed flowing bed), on D-100 device, processes as follows:
(a), under nitrogen atmosphere, with the heating rate of 20 ℃/min, be heated to 600 ℃;
(b) with the heating rate of 1.5 ℃/min, be heated to after 780 ℃, constant temperature, at 780 ℃, is changed as follows and is processed atmosphere in thermostatic process:
(i) the nitrogen (wherein, containing the propylene of 5 volume % in nitrogen) to contain 40 volume %, the atmosphere of the steam of 60 volume % is processed 10 minutes,
(ii) the nitrogen (pure nitrogen gas, without propylene) to contain 40 volume %, the atmosphere of the steam of 60 volume % is processed 10 minutes,
(iii) (contain 4000 μ mol/mol SO with the air that contains 40 volume %
2), the atmosphere of the steam of 60 volume % is processed 10 minutes,
(iv) to contain the nitrogen of 40 volume %, the atmosphere of the steam of 60 volume % is processed 10 minutes; Then by aforementioned order again repetitive cycling step (i)-(iv) respectively once, then repeating step (i), end loop pollute step;
Then carry out aging step: the catalyst mixture after cyclic polluting at 788 ℃, in the atmosphere of the air of the steam that contains 80 volume % and 20 volume % aging 8 hours;
Then the catalytic performance of investigating the catalyst mixture after cyclic polluting-aging on ACE device, wherein, feedstock oil enters with catalyst mixture and contacts in reactor bottom, and wherein, raw materials used oil nature is in table 4, appreciation condition and the results are shown in Table 5 and table 6.
Comparative example 4-6
Comparative example 4-6 is for illustrating the heavy metal-polluted dyeing method of comparative catalyst's mixture and contrasting the Catalytic Cracking Performance of metal traps for catalytic cracking.
According to the method for embodiment 10-18 carry out metallic pollution and and catalytic cracking, the auxiliary agent B 1 that the catalyst mixture that different is adopts provides for independent industrial catalyst C, comparative example 1, the auxiliary agent B that comparative example 2 provides 2 and industrial catalyst C are by weight the catalyst mixture after physical mixed, pollute on rear catalyst mixture Ni, V content in table 5 and table 6, appreciation condition and the results are shown in Table 5 and table 6.
Table 4
| Density/(g/cm 3(20℃)) | 0.9048 |
| Viscosity (80 ℃)/(mm 2/s) | 18.54 |
| Viscosity (100 ℃)/(mm 2/s) | 10.89 |
| Condensation point/℃ | 38 |
| Aniline point/℃ | 92.5 |
| Carbon residue/% | 2.8 |
| Refractive power (70 ℃) | 1.4912 |
| Constituent content/quality % | |
| C | 86.09 |
| H | 12.51 |
| S | 0.65 |
| N | 0.28 |
| Boiling range (D1160)/℃ | |
| Initial boiling point | 233 |
| 5% | 295 |
| 10% | 333 |
| 30% | 395 |
| 50% | 429 |
| 70% | 470 |
| 90% | 539 |
Can find out from the data of table 5, in catalytic cracking catalyst, add metal traps provided by the invention can slow down the destruction of vanadium to catalytic cracking catalyst, improve the selective of coke and dry gas, increase total liquid product yield, simultaneously, from dry gas yield, metal traps of the present invention also has the effect of certain anti-nickel contamination.
Table 5
In the present invention, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield, total liquid are received (claiming again total liquid product yield)=yield of gasoline+diesel yield+yield of liquefied gas, coke selectivity=coking yield/conversion ratio, dry gas selective=dry gas yield/conversion ratio.
Table 6
Can find out from the data of table 6, metal traps provided by the invention has better vanadium trapping ability, can more effectively improve the selective of coke and dry gas for catalytic cracking process, increases total liquid product yield.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in the above-mentioned specific embodiment, in reconcilable situation, can combine by any suitable mode.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. a metal traps, this metal traps contains magnesia and has the aluminium oxide of stepped pore distribution, and aluminium oxide and at least partly magnesia formation magnesia-alumina spinel structure at least partly;
The aluminium oxide wherein, with stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; Take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
2. metal traps according to claim 1, wherein, described in there is macroporous aluminium oxide that the aluminium oxide of stepped pore distribution contains 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight.
3. metal traps according to claim 1 and 2, wherein, contains the aluminium oxide with stepped pore distribution of 5-95 % by weight and the magnesia of 5-95 % by weight in described metal traps.
4. according to the metal traps described in any one in claim 1-3, wherein, in described metal traps, also contain the 3rd component, described the 3rd component be except described magnesia, described in there is heat-resistant inorganic oxide and/or the clay the aluminium oxide of stepped pore distribution.
5. metal traps according to claim 4, wherein, contains described the 3rd component of the aluminium oxide with stepped pore distribution of 10-95 % by weight and the magnesia of 5-60 % by weight and aequum in described metal traps.
6. metal traps according to claim 4, wherein, described heat-resistant inorganic oxide is selected from silica, one or more in the aluminium oxide except the described aluminium oxide with stepped pore distribution and the metal oxide outside magnesia.
7. metal traps according to claim 4, wherein, described clay is selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
8. a preparation method for metal traps, wherein, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained to the first slurries;
(2) described the first slurries are contacted and obtain the second slurries with magnesium hydroxide and/or magnesia;
(3) described the second slurries are contacted with macroporous aluminium oxide and obtain the 3rd slurries;
(4) described the 3rd slurries are sprayed after dry and carry out roasting;
Wherein, take the pore volume in 2-100nm hole as benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
9. want the preparation method described in 8 according to right, wherein, in aluminium oxide in the metal traps that the consumption of described macroporous aluminium oxide and little porous aluminum oxide makes to prepare, contain the macroporous aluminium oxide of 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight, and in total consumption of described macroporous aluminium oxide and little porous aluminum oxide metal traps of making to prepare, the total content of macroporous aluminium oxide and little porous aluminum oxide is 5-95 % by weight.
10. preparation method according to claim 8 or claim 9, wherein, the magnesia that contains 5-95 % by weight in the metal traps that described magnesium hydroxide and/or magnesian consumption make to prepare.
Preparation method in 11. according to Claim 8-10 described in any one, wherein,
It is 1-3.0 that the consumption of the middle acid of step (1) makes the pH value of the first slurries;
It is 8-20 % by weight that the consumption of the medium and small porous aluminum oxide of step (1) and deionized water makes the solid content of the first slurries.
Preparation method in 12. according to Claim 8-11 described in any one, wherein, described in step (2), the condition of contact comprises: temperature is 0-70 ℃, and the time is more than 15min.
Preparation method in 13. according to Claim 8-12 described in any one, wherein, described in step (3), the condition of contact comprises: temperature is 10-60 ℃, and the time is 2-20min.
Preparation method in 14. according to Claim 8-13 described in any one, wherein, the mixed pulp of step (1) and/or step (2) by described the first slurries and magnesium hydroxide and/or magnesian contact and/or step (3) described the second slurries are carried out with contacting under the 3rd material exists of macroporous aluminium oxide, described the 3rd material is clay, one or more in the heat-resistant inorganic oxide except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide and/or the presoma of heat-resistant inorganic oxide.
15. preparation methods according to claim 14, wherein, the macroporous aluminium oxide that contains 10-95 % by weight in the metal traps that the consumption of total consumption of described macroporous aluminium oxide and little porous aluminum oxide, described magnesium hydroxide and/or magnesian consumption, described the 3rd material makes to prepare and little porous aluminum oxide, the oxide of described the 3rd material of the magnesia of 5-60 % by weight and aequum.
16. preparation methods according to claim 14, wherein, described heat-resistant inorganic oxide presoma is selected from one or more in Ludox, waterglass, boehmite, aluminium colloidal sol and silicon-aluminum sol.
17. 1 kinds of metal traps that prepared by the preparation method described in any one in claim 8-16.
The application of metal traps in 18. claim 1-7 and claim 17 described in any one in catalytic cracking.
19. 1 kinds of catalyst cracking methods, the method comprises: under catalytic cracking condition, heavy oil feedstock is contacted with the catalyst mixture that contains metal traps and catalytic cracking catalyst, it is characterized in that, described metal traps is the metal traps described in any one in claim 1-7 and claim 17.
20. methods according to claim 19, wherein, in described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99.
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| CN106732696A (en) * | 2016-12-01 | 2017-05-31 | 中国石油大学(华东) | A kind of magnesium aluminate spinel compoud for being enclosed with silicon phosphorus aluminium lamination and its application |
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| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1879960A (en) * | 2005-06-15 | 2006-12-20 | 中国石油天然气股份有限公司 | Heavy metal resistant catalytic cracking adjuvant and process for preparing same |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| WO2011154973A1 (en) * | 2010-06-07 | 2011-12-15 | Indian Oil Corporation Limited | Metal passivator additive and process for preparing |
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| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1879960A (en) * | 2005-06-15 | 2006-12-20 | 中国石油天然气股份有限公司 | Heavy metal resistant catalytic cracking adjuvant and process for preparing same |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| WO2011154973A1 (en) * | 2010-06-07 | 2011-12-15 | Indian Oil Corporation Limited | Metal passivator additive and process for preparing |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106732696A (en) * | 2016-12-01 | 2017-05-31 | 中国石油大学(华东) | A kind of magnesium aluminate spinel compoud for being enclosed with silicon phosphorus aluminium lamination and its application |
| CN106732696B (en) * | 2016-12-01 | 2019-04-05 | 中国石油大学(华东) | A kind of magnesium aluminate spinel compoud and its application being enclosed with silicon phosphorus aluminium layer |
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