CN103789013A - 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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- CN103789013A CN103789013A CN201210420784.4A CN201210420784A CN103789013A CN 103789013 A CN103789013 A CN 103789013A CN 201210420784 A CN201210420784 A CN 201210420784A CN 103789013 A CN103789013 A CN 103789013A
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Abstract
The invention provides a metal chelating agent, and a preparation method and an application thereof. The bulk density of the metal chelating agent is 0.85-1.2g/cm<3>. The invention provides a catalytic cracking method. The catalytic cracking method comprises a step that a heavy oil raw material contacts with a catalyst mixture containing the metal chelating agent and a catalytic cracking catalyst under catalytic cracking conditions. The metal chelating agent has a very good metal chelating effect, for example, the metal chelating agent 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 tooling cost that has increased considerably refinery of crude oil price, at present, catalytic cracking is the important means of refinery's heavy oil upgrading, in order to reduce costs so that maximizing the benefits can process to realize by deep processing mink cell focus with poor quality 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 association of bituminous matter macromole is less than 400, and its part may be 4N, NO
2s or 4S; After the macromolecular three-dimensional structure of bituminous matter is destroyed, these small molecules will be released.Vanadium is mainly that vanadium has caused irreversible destruction to catalyzer to the pollution of catalytic cracking catalyst.Experiment shows, the vanadium that deposits 1000 μ g/g on poiser 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.Spinel 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 spinel.
US5057205 discloses a kind of vanadium trapping agent for catalytic cracking process, consist of alkaline earth metal oxide and alkaline-earth metal spinel, its weight ratio is 90:10～10:90, its feature is that median size is less than cracking catalyst, specifically be less than 40 μ m, object is to utilize particle size differences that two kinds of practical physical are separated.Correspondingly, require catalytic cracking unit to have two revivifiers, so that vanadium trapping agent is regenerated separately, return separately from riser tube bottom.This patent text claims to do like this and can preferentially contact raw material by vanadium trapping agent, preferentially catches vanadium compound, reduces the probability of cracking agent contact vanadium compound; The destruction of vanadium to cracking catalyst in water-heat process has also been avoided in regeneration separately.Although there is above-mentioned advantage, complex process, conventional catalytic cracking unit cannot be implemented.
CN1148256C discloses a kind of composition and method of making the same containing magnesium-aluminium spinel, the magnesium oxide that said composition contains the heavy % of 25-30, the rare-earth oxide except cerium of the aluminum 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 the preparation method of the simple metal traps of a kind of technique, and the metal traps tap density being prepared by the method is high, usually above catalytic cracking catalyst.
For realizing aforementioned object, on the one hand, the invention provides a kind of metal traps, wherein, the tap density of described metal traps is 0.85-1.2g/cm
3.
On the other hand, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) aluminium hydroxide and/or 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 magnesium oxide, described the second slurries are sprayed to be dried obtains solid;
(3) described solid is contacted with water soluble magnesium source solution, by dry the mixture after contact or moist after carry out roasting.
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 provided by the invention has good metal trapping effect, for example, adopt metal traps provided by the invention for high vanadium heavy oil fluid catalytic cracking, can slow down the destruction of vanadium to cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Particularly, when metal traps provided by the invention and industrial cracking catalyst are by weight mixing for 12:88, when on catalyst mixture, Ni content is about 3000ppm, content of vanadium and is about 4000ppm, compared with independent use industrial cracking catalyst, heavy oil yield is reduced to 10.53 % by weight by 12.45 % by weight, total liquid product yield is increased to 73.92 % by weight by 70.78 % by weight, and dry gas selectivity is down to 0.0353 by 0.0439, and coke selectivity is down to 0.1785 by 0.1920.As can be seen here, metal traps provided by the invention can more effectively become high-value product by heavy oil conversion.Supposition is because the tap density of metal traps of the present invention is greater than catalytic cracking catalyst, for example, while therefore in use entering upstriker reactor (riser tube or fluidized-bed reactor) from the metal traps of revivifier and catalytic cracking catalyst, metal traps is compared with catalytic cracking catalyst, preferential contact stock oil (for example, containing vanadium raw materials oil), thereby be conducive to trapping metals compound, improved thus metal trapping ability.
And compared with prior art, the metal traps of high-bulk-density provided by the invention is with low cost, easy to use.
Other features and advantages of the present invention are described in detail the 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 specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the XRD spectra of metal traps A1 of the present invention and contrast metal traps B 1.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, 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, wherein, the tap density of described metal traps is 0.85-1.2g/cm
3, be preferably 0.87-1.13g/cm
3.
In the present invention, tap density adopts 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).
According to metal traps of the present invention, optional a wider range of the kind of the component of described metal traps and the content of component, it specifically can be selected with reference to the metal traps of prior art, for the present invention, preferred described metal traps contains magnesium oxide and aluminum oxide, and magnesium oxide and at least partly aluminum oxide formation magnesia-alumina spinel structure at least partly, more preferably, in described metal traps, contain the magnesium oxide of 5-95 % by weight, the aluminum oxide 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 is heat-resistant inorganic oxide and/or the clay except magnesium oxide and aluminum oxide, optional a wider range of the content of described the 3rd component, specifically can select according to actual needs, the present invention to this without particular requirement, the general gross weight take metal traps is as benchmark, the content of described the 3rd component is 0.001-30 % by weight, more preferably, in described metal traps, contain the magnesium oxide of 5-60 % by weight, described the 3rd component of the aluminum oxide of 10-95 % by weight and equal amount.
According to metal traps of the present invention, optional a 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 compound) and all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide is selected from silicon-dioxide, one or more in the metal oxide (as calcium oxide, titanium oxide and zirconium white) except magnesium oxide and aluminum oxide.
According to metal traps of the present invention, optional a 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, halloysite, 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 adopt the whole bag of tricks to prepare, and the metal traps in above-mentioned scope that the present inventor finds to adopt tap density that the present invention preparation method as described below prepares metal traps within the scope of the invention to prepare than other preparation method has better metal trapping effect.
According to one of the present invention preferred embodiment, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) aluminium hydroxide and/or 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 magnesium oxide, described the second slurries are sprayed to be dried obtains solid;
(3) described solid is contacted with water soluble magnesium source solution, by dry the mixture after contact or moist after carry out roasting.
Not only tap density is in above-mentioned scope for the metal traps preparing according to the aforesaid preparation method of the present invention, and the heavy oil fluid catalytic cracking of using it for high metal (as vanadium) content has high liquid product yield, the advantages such as low dry gas and coking yield.
Preparation in accordance with the present invention, can realize object of the present invention according to aforementioned techniques scheme, optional a wider range of the consumption in described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source, for the present invention, preferably, in magnesium oxide, the consumption weight ratio in described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source is 5-10:1.
Preparation in accordance with the present invention, can realize object of the present invention according to aforementioned techniques scheme, optional a wider range of the condition of mixed pulp in step (1), and for the present invention, it is 1-3.5 that the consumption of the middle acid of preferred steps (1) makes the pH value of the first slurries; It is 8-20 % by weight that the consumption of the middle aluminium hydroxide of step (1) and/or aluminum oxide and deionized water makes the solid content of the first slurries, and the aluminum oxide that contains 5-95 % by weight in the metal traps that makes to prepare.
Preparation in accordance with the present invention, can realize object of the present invention according to aforementioned techniques scheme, optional a 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 ℃, be preferably 15-60 ℃, the time is more than 15min, to be preferably 15-90min.
Preparation in accordance with the present invention, can realize object of the present invention according to aforementioned techniques scheme, optional a wider range of the condition of contact described in step (3), it can be conventional loading condition, for the present invention, described in preferred steps (3), the condition of contact comprises: temperature is 10-60 ℃, and the time is 2-20min.
Preparation in accordance with the present invention, can realize object of the present invention according to aforementioned techniques scheme, for the present invention, in the metal traps that in magnesium hydroxide and/or magnesium oxide described in preferred steps (2) and step (3), total consumption in water soluble magnesium source makes to prepare, contain magnesium oxide 5-95 % by weight.
Preparation in accordance with the present invention, optional a wider range of the kind of described aluminium hydroxide and/or aluminum oxide, what this area routine was used can all be can be used for the present invention by the aluminium hydroxide of sour peptization and/or aluminum oxide, for the present invention, preferred described aluminium hydroxide and/or aluminum oxide are selected from gibbsite, surge aluminium stone, promise diaspore, diasporite, boehmite, pseudo-boehmite, ρ-aluminum oxide, χ-aluminum oxide, η-aluminum oxide, gama-alumina, κ-aluminum oxide, one or more in δ-aluminum oxide and θ-aluminum oxide, wherein preferred described aluminium hydroxide and/or aluminum oxide are pseudo-boehmite.
Preparation in accordance with the present invention, optional a wider range of the kind in described water soluble magnesium source, water soluble magnesium source that can be water-soluble all can be used for the present invention, for the present invention, preferred described water soluble magnesium source is selected from water-soluble magnesium salt, as being selected from one or more in magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium chlorate and magnesium acetate etc.
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 be in the mixed pulp of step (1) and/or step (2) will in described the first slurries and magnesium hydroxide and/or magnesian contact process, introduce the 3rd material, more specifically, the mixed pulp of step of the present invention (1) and/or step (2) described the first slurries are carried out with magnesium hydroxide and/or magnesian contact under the 3rd material exists, described the 3rd material is clay, except described magnesium oxide, described aluminum oxide, described magnesium hydroxide, one or more in the heat-resistant inorganic oxide of described water soluble magnesium source and described aluminium hydroxide and/or the presoma of heat-resistant inorganic oxide.
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 a 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 silicon sol, water glass, aluminium colloidal sol and silicon-aluminum sol.
A preferred embodiment of the invention, the oxide compound of the magnesium oxide that contains 5-60 % by weight in the metal traps that the consumption of total consumption in preferred described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source, described aluminium hydroxide and/or aluminum oxide, the consumption of described the 3rd material make to prepare, the aluminum oxide of 10-95 % by weight and described the 3rd material of equal amount.
Preparation in accordance with the present invention, described spraying is dry, dry method all can be carried out with reference to prior art, the present invention to this without particular requirement.
The invention provides a kind of metal traps preparing according to preparation method of the present invention.The metal traps preparing according to the aforesaid preparation method of the present invention has the advantages such as tap density height, and under preferable case, the tap density of the metal traps preparing according to preparation method of the present invention is 0.85-1.2g/cm
3, be preferably 0.87-1.13g/cm
3.
The invention provides the application of metal traps of the present invention in catalytic cracking.
Metal traps of the present invention is particularly suitable for using in fluidized-bed reactor.
The index that resistance to wears of metal traps provided by the invention and catalytic cracking catalyst, size-grade distribution are suitable, under preferable case, the tap density of described metal traps is a little more than catalytic cracking catalyst, metal traps of the present invention can with Primary Catalysts physical mixed after add catalytic cracking unit, also can add separately catalytic cracking unit, in device, mix with catalytic cracking catalyst.In the present invention, the weight ratio of metal traps and catalytic cracking catalyst can be generally 1:4-99, is preferably 1:5.7-99, more preferably 1:6-32.
Metal traps provided by the invention has good metal trapping effect, for example, adopt metal traps provided by the invention for high vanadium heavy oil fluid catalytic cracking, can slow down the destruction of vanadium to cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Particularly, when metal traps provided by the invention and industrial cracking catalyst are by weight mixing for 12:88, when on catalyst mixture, Ni content is about 3000ppm, content of vanadium and is about 4000ppm, compared with independent use industrial cracking catalyst, heavy oil yield is reduced to 10.53 % by weight by 12.45 % by weight, total liquid product yield is increased to 73.92 % by weight by 70.78 % by weight, and dry gas selectivity is down to 0.0353 by 0.0439, and coke selectivity is down to 0.1785 by 0.1920.
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, the tap density of preferred described metal traps is higher than the tap density of catalytic cracking catalyst, and more preferably the difference of the tap density of metal traps and catalytic cracking catalyst is 0.1-0.55g/cm
3, be preferably 0.15-0.4g/cm
3.Infer in the time that the tap density of metal traps is greater than catalytic cracking catalyst, for example, while in use entering upstriker reactor (riser tube) from the metal traps of revivifier and catalytic cracking catalyst, metal traps is compared with catalytic cracking catalyst, can preferentially contact stock oil (for example, containing vanadium raw materials oil), thereby be conducive to trapping metals compound, can improve thus metal trapping ability.
According to catalyst cracking method of the present invention, preferred described contact is carried out at the fluidized-bed reactor for catalytic cracking reaction and/or transport bed reactor, and described heavy oil feedstock is from the bottom feed of described reactor.The metal traps that so can better realize high-bulk-density of the present invention preferentially contacts with heavy oil feedstock, thereby improves metal trapping effect.
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 particular requirement 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, agent-oil ratio refers to the mass ratio of catalyzer and stock 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 catalyzer 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 pseudo-boehmite provides (solid content is 60.8 % by weight) by Shandong Aluminum Plant, and magnesium oxide effluent Bei Meishen Chemical Co., Ltd. provides.Commercial catalysts C(trade mark COKC, bulk density is 0.72g/cm
3) provided by Sinopec Shandong catalyzer branch office, in comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In each embodiment, abrasion index and tap 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.
Embodiment 1-10 is for illustrating the preparation process of metal traps provided by the invention.
Embodiment 1
The present embodiment is for illustrating the preparation process of metal traps provided by the invention.
(1) by pseudo-boehmite 280g(with Al
2o
3meter) add in deionized water, after being uniformly dispersed, add hydrochloric acid, contact and obtain the first slurries after 30 minutes, the solid content of the first slurries is 15 % by weight, pH is 1.2;
(2) the MgO slurries (containing MgO 640g) that then add deionized water to disperse, temperature is controlled at 55 ℃, contacts and obtains the second slurries after 60 minutes, and the solid content of the second slurries is 28 % by weight, and pH value is 9.8; Described the second slurries are carried out to spray drying forming and obtain microspheres with solid, wherein, the microballoon of particle diameter in 0-149 micrometer range accounts for 92 volume %, and the microballoon of particle diameter in 0-40 micrometer range is 20 volume %, and microsphere average grain diameter (APS) is 70 microns;
(3) under normal temperature (10-40 ℃), described solid 920g is contacted to 10min with water soluble magnesium source solution (character is in table 1) of 0.35L, the mixture after contact is dried to 4 hours at 120 ℃, then carry out roasting, the condition of roasting is 600 ℃/2h, obtains metal traps A1.Formula, preparation parameter, tap density and the abrasion index of A1 are listed in table 1.The XRD spectra of A1 is shown in Fig. 1, as seen from Figure 1, contains magnesia-alumina spinel structure in metal traps, and in metal traps, at least part of magnesium oxide and aluminum oxide have generated magnesium-aluminium spinel.
Embodiment 2-10
Embodiment 2-10 is for illustrating the preparation process of metal traps provided by the invention.
Prepare metal traps A2-A10 according to the method for embodiment 1, different is that formula, preparation parameter, tap density and abrasion index are listed in table 1.
Comparative example 1
This comparative example is for illustrating the preparation process of contrast metal traps B1.
Prepare according to the disclosed ordinary method of US5057205A the metal traps that contains spinel structure, detailed process is as follows:
SB powder (is contained to Al
2o
3560g) add in deionized water, add formic acid peptization after being uniformly dispersed, obtain the first slurries after 30 minutes, the pH value that records the first slurries is 3.3;
Then the MgO slurries (containing MgO 440g) that add 1046g deionized water to disperse keep obtaining the second slurries after 60 minutes at 75 ℃, and the pH value that records the second slurries is 9.1; By after the second slurries spray drying forming, direct roasting, roasting condition is 730 ℃/3h; Then the sample after roasting is sieved, choose the particle that particle diameter is 20-40 μ m, obtain metal traps B1; Formula, preparation parameter, tap density and the abrasion index of B1 are listed in table 2, and the XRD spectra of B1 is shown in Fig. 1, as seen from Figure 1, contain magnesia-alumina spinel structure in metal traps B1, and magnesium oxide and aluminum oxide have generated magnesium-aluminium spinel at least partly.
Comparative example 2
This comparative example is for illustrating the preparation process of contrast metal traps B2.
Prepare metal traps B2 according to the method for embodiment 2, different is there is no step (3).
Comparative example 3
Prepare metal traps D3 by the method for disclosed embodiment 1 in Chinese patent CN1148256C, the tap density that records D3 is 0.73g/cm
3, pore volume is 0.41mL/g.
Table 1
Table 2
Embodiment 11-20
Embodiment 11-20 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-A10 provided by the invention, then obtains catalyst mixture with butt metering physical mixed,
Catalyst mixture first carries out cyclic polluting (to deposit Ni and V) on circulation aging equipment, on the catalyst mixture after cyclic polluting Ni, V content in table 4 and table 5, wherein,
Cycle is polluted step and is comprised: catalyst mixture is introduced after heavy metal (Ni and V) by meter Xie Er pickling 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 temperature rise rate of 20 ℃/min, be heated to 600 ℃;
(b) with the temperature rise 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 water vapour of 60 volume % is processed 10 minutes,
(ii) the nitrogen (pure nitrogen gas, without propylene) to contain 40 volume %, the atmosphere of the water vapour 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 water vapour of 60 volume % is processed 10 minutes,
(iv) to contain the nitrogen of 40 volume %, the atmosphere of the water vapour of 60 volume % is processed 10 minutes; Then by aforementioned order again recirculation 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 water vapour 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, stock oil enters with catalyst mixture and contacts in reactor bottom, and wherein, raw materials used oil nature is in table 3, appreciation condition and the results are shown in Table 4 and table 5.
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.
Carry out metallic pollution and catalytic cracking according to the method for embodiment 11-20, the auxiliary agent B 1 that the catalyst mixture that different is adopts provides for independent commercial catalysts C, comparative example 1, the auxiliary agent B that comparative example 2 provides 2 and commercial catalysts C are by weight the catalyst mixture after physical mixed, pollute on rear catalyst mixture Ni, V content in table 4 and table 5, appreciation condition and the results are shown in Table 4 and table 5.
Table 3
| Density (20 ℃)/(g/cm 3) | 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 |
Table 4
In the present invention, transformation efficiency=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/transformation efficiency, dry gas selectivity=dry gas yield/selectivity.
Can find out from the data of table 4, in catalytic cracking catalyst, add metal traps provided by the invention can slow down the destruction of vanadium to catalytic cracking catalyst, improve the selectivity 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
Can find out from the data of table 5, compared with contrast metal traps B1, B2, metal traps provided by the invention has better vanadium trapping ability, can more effectively improve the selectivity of coke and dry gas for catalytic cracking process, increases total liquid product yield.Infer that reason is, B1 is because particle diameter is too little for contrast metal traps, floats on part on reaction bed in fluidized-bed, cannot realize preferentially and contacting with the vanadium compound in raw material, thereby it is poor to cause trapping effect; And the tap density of contrast metal traps B2 is suitable with the tap density of catalytic cracking catalyst, after therefore evenly mixing with cracking catalyst, can not preferentially contact the vanadium compound in raw material in the time of fluidized.And metal traps provided by the invention due to tap density a little more than cracking catalyst the bottom in reaction bed, preferentially contact with the vanadium compound in raw material, thereby improved vanadium trapping effect.
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 above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, 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 (24)
1. a metal traps, is characterized in that, the tap density of described metal traps is 0.85-1.2g/cm
3.
2. metal traps according to claim 1, wherein, the tap density of described metal traps is 0.87-1.13g/cm
3.
3. metal traps according to claim 1 and 2, wherein, contains the magnesium oxide of 5-95 % by weight in described metal traps, the aluminum oxide of 5-95 % by weight, and magnesium oxide and at least partly aluminum oxide formation magnesia-alumina spinel structure at least partly.
4. metal traps according to claim 3, wherein, also contains the 3rd component in described metal traps, described the 3rd component is heat-resistant inorganic oxide and/or the clay except magnesium oxide and aluminum oxide.
5. metal traps according to claim 4, wherein, described heat-resistant inorganic oxide is selected from one or more in silicon-dioxide, metal oxide except magnesium oxide and aluminum oxide; Described clay is selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
6. according to the metal traps described in claim 4 or 5, wherein, in described metal traps, contain magnesium oxide, the aluminum oxide of 10-95 % by weight and described the 3rd component of equal amount of 5-60 % by weight.
7. a preparation method for metal traps, the method comprises:
(1) aluminium hydroxide and/or 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 magnesium oxide, described the second slurries are sprayed to be dried obtains solid;
(3) described solid is contacted with water soluble magnesium source solution, by dry the mixture after contact or moist after carry out roasting.
8. preparation method according to claim 7, wherein, in magnesium oxide, the consumption weight ratio in described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source is 5-10:1.
9. according to the preparation method described in claim 7 or 8, wherein,
It is 1-3.5 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 middle aluminium hydroxide of step (1) and/or aluminum oxide and deionized water makes the solid content of the first slurries, and the aluminum oxide that contains 5-95 % by weight in the metal traps that makes to prepare.
10. according to the preparation method described in any one in claim 7-9, wherein, described in step (2), the condition of contact comprises: temperature is 0-70 ℃, and the time is more than 15min.
11. preparation methods according to any one of claims of claim 7-10, wherein, described in step (3), the condition of contact comprises: temperature is 10-60 ℃, and the time is 2-20min.
12. according to the preparation method described in any one in claim 7-11, wherein, in the metal traps that total consumption in described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source makes to prepare, contains magnesium oxide 5-95 % by weight.
13. according to the preparation method described in any one in claim 7-12, wherein, described aluminium hydroxide and/or aluminum oxide are selected from one or more in gibbsite, surge aluminium stone, promise diaspore, diasporite, boehmite, pseudo-boehmite, ρ-aluminum oxide, χ-aluminum oxide, η-aluminum oxide, gama-alumina, κ-aluminum oxide, δ-aluminum oxide and θ-aluminum oxide.
14. according to the preparation method described in any one in claim 7-13, and wherein, described water soluble magnesium source is selected from one or more in magnesium chloride, magnesium chlorate, magnesium nitrate, magnesium sulfate and magnesium acetate.
15. according to the preparation method described in any one in claim 7-14, wherein, the mixed pulp of step (1) and/or step (2) described the first slurries and magnesium hydroxide and/or magnesian contact under the 3rd material exists are carried out, described the 3rd material is clay, one or more in the presoma of heat-resistant inorganic oxide except described magnesium oxide, described aluminum oxide, described magnesium hydroxide, described water soluble magnesium source and described aluminium hydroxide and/or heat-resistant inorganic oxide.
16. preparation methods according to claim 15, wherein, described heat-resistant inorganic oxide presoma is selected from one or more in silicon sol, water glass, aluminium colloidal sol and silicon-aluminum sol.
17. preparation methods according to claim 15, the oxide compound of magnesium oxide, the aluminum oxide of 10-95 % by weight and described the 3rd material of equal amount that contains 5-60 % by weight in the metal traps that wherein, the consumption of the consumption of total consumption in described magnesium hydroxide and/or magnesium oxide and water soluble magnesium source, described aluminium hydroxide and/or aluminum oxide, described the 3rd material makes to prepare.
18. 1 kinds of metal traps that prepared by the preparation method described in any one in claim 7-17, the tap density of described metal traps is 0.85-1.2g/cm
3, be preferably 0.87-1.13g/cm
3.
The application of metal traps in 19. claim 1-6 and claim 18 described in any one in catalytic cracking.
20. 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 1-6 and claim 18.
21. methods according to claim 20, wherein, in described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99.
22. according to the method described in claim 20 or 21, and wherein, the tap density of described metal traps is higher than the tap density of catalytic cracking catalyst.
23. methods according to claim 22, wherein, the difference of the tap density of metal traps and catalytic cracking catalyst is 0.1-0.55g/cm
3.
24. according to the method described in any one in claim 18-20, and wherein, described contact is carried out at the fluidized-bed reactor for catalytic cracking reaction and/or transport bed reactor, and described heavy oil feedstock is from the bottom feed of described reactor.
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| CN109513420B (en) * | 2017-09-19 | 2021-09-07 | 中国石油化工股份有限公司 | Metal trapping agent, preparation method thereof and catalytic cracking method |
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