CN104226236A - Metal trapping agent and catalytic cracking method - Google Patents
Metal trapping agent and catalytic cracking method Download PDFInfo
- Publication number
- CN104226236A CN104226236A CN201310236838.6A CN201310236838A CN104226236A CN 104226236 A CN104226236 A CN 104226236A CN 201310236838 A CN201310236838 A CN 201310236838A CN 104226236 A CN104226236 A CN 104226236A
- Authority
- CN
- China
- Prior art keywords
- metal traps
- oxide
- porous aluminum
- magnesia
- aluminium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a metal trapping agent and a catalytic cracking method, a method for preparing the metal trapping agent comprises the following steps: 1)mixing small-hole alumina, deionized water and acid and pulping to obtain a first slurry; 2)contacting the first slurry and magnesium hydroxide and/or magnesium oxide to obtain a second slurry; 3)contacting the second slurry and large-hole alumina to obtain a third slurry; 4)performing spray drying on the third slurry, and roasting to obtain a solid; and 5)contacting the solid and a water-soluble magnesium source solution, drying a contacted mixture or roasting without drying. The provided metal trapping agent has good metal trapping effect, and is used for high vanadium heavy oil catalytic cracking, can alleviate the destroy of vanadium to a cracking catalyst, can increase the liquid product yield, and reduces the dry gas and coke yield.
Description
Technical field
The present invention relates to a kind of metal traps, and a kind of catalyst cracking method.
Background technology
The constantly soaring of crude oil price has increased considerably the processing cost of refinery, at present, catalytic cracking is the important means of refinery heavy oil processing, in order to reduce costs to make maximizing the benefits, and poor oil can be used to carry out processing realizing by deep processing mink cell focus.
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 DEG C, mainly concentrates in residual oil, but because of its volatility comparatively strong, also can enter in catalytic cracking cut.Non-porphyrin metal compound may be the compound that the relative molecular weight together with molecular association large with 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 Small molecular will be released.Vanadium to the pollution of catalytic cracking catalyst mainly vanadium irreversible destruction is caused to catalyst.Experiment shows, vanadium poising agent depositing 1000 μ g/g is enough to cause damage to zeolite, worsens product slates.
Usually metal traps is used to carry out the trapping of heavy metal, to reduce heavy metal (as vanadium) to the destruction of Cracking catalyst at present.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%, the Al of (b) 30-60w%
2o
3and the rare earth of (c) 10-30w%, rare earth is selected from lanthanum-oxides and/or neodymium oxides, wherein, and at least part of MgO and Al
2o
3define Mg-Al spinelle.
CN1148256C discloses a kind of composition and method of making the same containing magnesium aluminate spinel, said composition contains the magnesia of the heavy % of 25-30, the aluminium oxide of the heavy % of 60-70 and the rare-earth oxide except cerium of the heavy % of 5-15, wherein, magnesium and aluminium form spinel structure, the content of free magnesium weighs % lower than 5 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 a kind of metal traps with excellent metal trapping performance on the basis of existing technology.
For realizing aforementioned object, on the one hand, the invention provides a kind of metal traps, wherein, this metal traps prepares as follows:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) solid is obtained by carrying out roasting after described 3rd slurries spraying dry;
(5) described solid is contacted with water soluble magnesium source solution, by dry for the mixture after contact or moist after carry out roasting;
Wherein, with the pore volume in 2-100nm hole for 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%.
Again on the one hand, the invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, is contacted by heavy oil feedstock with containing metal traps with the catalyst mixture of 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, metal traps provided by the invention is used for high vanadium RFCC, can slows down the destruction of vanadium to Cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Such as when vanadium trapping agent provided by the invention mixes by weight for 8:92 with industrial cracking catalyst, on catalyst mixture, Ni content is about 2200ppm, content of vanadium is when being about 4500ppm, with be used alone compared with industrial cracking catalyst, heavy oil yield is reduced to 10.65 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.57 % by weight by 71.60 % by weight, dry gas selectivity is down to 0.0337 by 0.0358, and coke selectivity is down to 0.1720 by 0.1910.As can be seen here, heavy oil transformation more effectively can be become high-value product by metal traps provided by the invention.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is 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 detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the pore size distribution figure of macroporous aluminium oxide A used in the present invention, little porous aluminum oxide A;
Fig. 2 be the metal traps A1 prepared according to the method for embodiment 1 fresh state (being called fresh dose in figure) and in 800 DEG C, hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 100% steam atmosphere pore size distribution figure;
Fig. 3 be the metal traps B1 prepared according to the method for comparative example 1 fresh state (being called fresh dose in figure) and in 800 DEG C, hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 100% steam atmosphere pore size distribution figure;
Fig. 4 is the metal traps A1 for preparing according to the method for embodiment 1 and the XRD spectra of metal traps B1 prepared according to the method for comparative example 1;
Fig. 5 is the UV-vis spectrogram of VO-OEP cyclohexane solution;
Fig. 6 is the invariance curve of VO-OEP cyclohexane solution concentration and ultraviolet absorptivity;
Fig. 7 is the ultraviolet absorptivity curve of the VO-OEP cyclohexane solution after adopting metal traps A2 absorption;
Fig. 8 is the ultraviolet absorptivity curve of the VO-OEP cyclohexane solution after adopting industrial catalyst C absorption.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of metal traps, wherein, this metal traps prepares as follows:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) solid is obtained by carrying out roasting after described 3rd slurries spraying dry;
(5) described solid is contacted with water soluble magnesium source solution, by dry for the mixture after contact or moist after carry out roasting;
Wherein, with the pore volume in 2-100nm hole for 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, with the pore volume in 2-100nm hole for 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, with the pore volume in 2-100nm hole for 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%, with the volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 60-100nm hole is preferably 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 the hole that aperture is more than or equal to 5nm and 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 the hole that aperture is more than or equal to 2nm and is less than or equal to 100nm.
In the present invention, the BET specific surface 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 (also known as pore volume distribution), aperture, pore volume adopt low-temperature nitrogen adsorption method to measure (see " Petrochemical Engineering Analysis method (RIPP test method) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).
Described macroporous aluminium oxide of the present invention and described little porous aluminum oxide also have detailed introduction in Chinese patent CN101745417B.The present invention quotes for illustration of the present invention in the lump at this.
According to metal traps of the present invention, the described macroporous aluminium oxide and the little porous aluminum oxide that meet application claims can be obtained by synthesis, also can be commercially available, the present invention to this without particular/special requirement.
According to metal traps of the present invention, object of the present invention can be well realized according to preceding solution of the present invention, in preparation process, the range of choices of various material consumption is wider, for the present invention, preferably, in magnesia, the consumption weight ratio in described magnesium hydroxide and/or magnesia and water soluble magnesium source is 5-10:1.
According to metal traps of the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, in preparation process, the range of choices of various material consumption is wider as previously mentioned, for the present invention, total consumption in preferred described magnesium hydroxide and/or magnesia and water soluble magnesium source makes the magnesia containing 5-95 % by weight in the metal traps prepared.
According to metal traps of the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, in preparation process, the range of choices of various material consumption is wider as previously mentioned, for the present invention, the consumption of preferred described macroporous aluminium oxide and little porous aluminum oxide makes to contain 10-90 % by weight in the aluminium oxide in the metal traps prepared, the macroporous aluminium oxide of preferred 15-85 % by weight and 10-90 % by weight, the little porous aluminum oxide of preferred 15-85 % by weight, and total consumption of described macroporous aluminium oxide and little porous aluminum oxide makes the total content of macroporous aluminium oxide and little porous aluminum oxide in the metal traps prepared be 5-95 % by weight.
According to metal traps of the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (1), the range of choices of the condition of mixed pulp is wider, specifically can carry out with reference to prior art, the consumption for acid in preferred steps of the present invention (1) makes the pH value of the first slurries be 1-3.0; The consumption of step (1) medium and small porous aluminum oxide and deionized water makes the solid content of the first slurries be 8-20 % by weight.
According to metal traps of the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (2), the range of choices of the condition of contact is wider, for the present invention, described in preferred steps (2), the condition of contact comprises: temperature is 0-70 DEG C, is preferably 15-60 DEG C; Time is more than 15min, is preferably 15-90min.
According to metal traps of the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (3), the range of choices of the condition of contact is wider, for the present invention, described in preferred steps (3), the condition of contact comprises: temperature is 10-60 DEG C, and the time is 20-60min.
According to metal traps of the present invention, object of the present invention can be realized according to preceding solution, described in step (5), the range of choices of the condition of contact is wider, it can be conventional loading condition, for the present invention, described in preferred steps (5), the condition of contact comprises: 10-60 DEG C, the time is 2-20min.
According to metal traps of the present invention, according to needing to introduce the 3rd material in the process of the described metal traps of preparation, particularly such as can the mixed pulp of step (1) and/or step (2) by described first slurries and magnesium hydroxide and/or magnesian contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide and/or step (5) introduced the 3rd material by described solid and water soluble magnesium source solution contact process, also the solid contact that described 3rd material and step (4) and/or step (5) roasting obtain can be introduced by load, for the present invention, the contact of the mixed pulp of preferred steps (1) and/or the contact of step (2) and/or step (3) and/or the contact of step (5) are carried out under the 3rd material exists, wherein, described 3rd material can be clay, except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, one or more in heat-resistant inorganic oxide beyond described water soluble magnesium source and/or the presoma of heat-resistant inorganic oxide, preferred, total consumption of described macroporous aluminium oxide and little porous aluminum oxide, total consumption in described magnesium hydroxide and/or magnesia and water soluble magnesium source, the consumption of described 3rd material makes to contain the macroporous aluminium oxide of 10-95 % by weight and little porous aluminum oxide in the metal traps prepared, the oxide of the magnesia of 5-60 % by weight and described 3rd material of aequum.
According to metal traps of the present invention, described except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, the range of choices of the kind of the heat-resistant inorganic oxide beyond described water soluble magnesium source is wider, meet the conventional heat-resistant inorganic oxide of the prior art of aforementioned claim (usually also referred to as binding agent oxide in this area) and all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide is selected from silica, except described macroporous aluminium oxide, metal oxide outside little porous aluminum oxide and magnesia is (as calcium oxide, titanium oxide, zirconia) in one or more.
According to metal traps of the present invention, the range of choices of the kind of described clay is wider, the clay that this area is commonly used all can be used for the present invention, for the present invention, preferred described clay be selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite one or more, more preferably described clay to be selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
According to metal traps of the present invention, the range of choices of the kind of described heat-resistant inorganic oxide presoma except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, described water soluble magnesium source is wider, the heat-resistant inorganic oxide presoma (this area is also referred to as binding agent) that this area meeting aforementioned claim is commonly used all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide presoma be selected from Ludox, waterglass, boehmite, Alumina gel and silicon-aluminum sol one or more.
According to metal traps of the present invention, the method for described spraying dry, drying, roasting and condition all can refer to prior art and carry out, and the present invention, is not described in detail at this without particular/special requirement this.
Metal traps of the present invention has good metal trapping effect, metal traps provided by the invention is used for high vanadium RFCC, can slows down the destruction of vanadium to Cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Such as when vanadium trapping agent provided by the invention mixes by weight for 8:92 with industrial cracking catalyst, on catalyst mixture, Ni content is about 2200ppm, content of vanadium is when being about 4500ppm, with be used alone compared with industrial cracking catalyst, heavy oil yield is reduced to 10.65 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.57 % by weight by 71.60 % by weight, dry gas selectivity is down to 0.0337 by 0.0358, and coke selectivity is down to 0.1720 by 0.1910.As can be seen here, heavy oil transformation more effectively can be become high-value product by metal traps provided by the invention.
The invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, contacted with the catalyst mixture of catalytic cracking catalyst with containing metal traps by heavy oil feedstock, 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, is more preferably 1:6-32.
According to catalyst cracking method of the present invention, the catalytic cracking condition that described catalytic cracking condition can be commonly used for this area, the present invention, is not described in detail at this without particular/special requirement this.
Below by embodiment, the present invention is further described, but not thereby limiting the invention.
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.
In the present invention, the solid content of material refers to the weight of material after high-temperature roasting and the weight ratio before roasting, i.e. the water content % of the 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 in comparative example:
Alumina gel is provided (Al2O3 content is 21.5 % by weight) by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, kaolin originates from Chinese Suzhou (solid content is 76.9 % by weight), boehmite is provided (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 embodiments, abrasion index and bulk density adopt RIPP standard method to measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).In catalyst mixture, Ni, V content x-ray fluorescence method measures; The thing of metal traps adopts XRD method to measure mutually.
In embodiment and comparative example, big pore aluminium oxide and aperture Properties of Alumina are in table 1.
Embodiment 1
The present embodiment is for illustration of the preparation process of metal traps provided by the invention.
(1) add in deionized water by little porous aluminum oxide A, 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 the MgO slurries (containing MgO750g) of deionized water dispersion to described first slurries, temperature obtains the second slurries after controlling to contact 60 minutes at the temperature of 55 DEG C, 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 DEG C, contact 15min;
(4) by after described 3rd slurries spray drying forming, roasting direct, roasting condition is 550 DEG C/2h, obtains solid;
(5) under normal temperature (10-40 DEG C), solid described in 920g is contacted 10min with water soluble magnesium source solution (character is in table 2) of 0.35L, by the mixture after contact at 120 DEG C dry 4 hours, then carries out roasting, the condition of roasting is 600 DEG C/2h, obtains metal traps A1;
Wherein, the pore size distribution figure of macroporous aluminium oxide A, little porous aluminum oxide A is shown in Fig. 1, and the formula of A1, preparation parameter and abrasion index are listed in table 2; The XRD spectra of A1 is shown in Fig. 4, and as seen from Figure 4, containing magnesia-alumina spinel structure in metal traps A1, namely in metal traps, at least part of magnesia and aluminium oxide define magnesia-alumina spinel structure;
Wherein, metal traps A1 fresh state and in 800 DEG C, the pore size distribution figure of hydrothermal aging after 17 hours is shown in Fig. 2 under 100% steam atmosphere; Metal traps A1 mesopore after hydrothermal aging remains intact as seen from Figure 2, and provides larger pore volume.
Embodiment 2-8
Example 2-8 is for illustration of the preparation process of metal traps provided by the invention.
Prepare metal traps A2-A8 according to the method for embodiment 1, list in table 2 unlike formula, preparation parameter and abrasion index.
Comparative example 1
This comparative example is for illustration of the preparation process of contrast metal traps B1.
(1) boehmite 250g(is pressed 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, and solid content is 15 % by weight;
(2) then add the MgO slurries (containing MgO750g) of deionized water dispersion to described first slurries, obtain the second slurries contact 60 minutes at 76 DEG C after, 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 DEG C/2h, obtains metal traps B1.The formula of B1, preparation parameter and abrasion index are listed in table 3.The XRD spectra of B1 is shown in Fig. 4, and as seen from Figure 4, containing magnesia-alumina spinel structure in metal traps B1, namely in metal traps, at least part of magnesia and aluminium oxide define magnesia-alumina spinel structure;
Wherein, metal traps B1 fresh state and in 800 DEG C, the pore size distribution figure of hydrothermal aging after 17 hours is shown in Fig. 3 under 100% steam atmosphere; Substantially mesopore is not formed as seen from Figure 3 after metal traps B1 hydrothermal aging.
Comparative example 2-3
According to the method preparation contrast metal traps B2-B3 of comparative example 1, unlike, the formula of B2, B3, preparation parameter and abrasion index are listed in table 3.From abrasion index, only use contrast auxiliary agent B 3 intensity difference of macroporous aluminium oxide, be not suitable for catalytic cracking process.
Comparative example 4
Metal traps B4 is prepared according to the method for embodiment 1, unlike, do not have step (3), and directly added in step (1) together with little porous aluminum oxide by macroporous aluminium oxide, all the other Step By Conditions are all identical, obtain metal traps B4.
Comparative example 5
Metal traps B5 is prepared according to the method for embodiment 1, unlike, do not have step (5), and in step (1), magnesian consumption is 750g, all the other Step By Conditions are all identical, and the solid that namely step (4) obtains is metal traps B5.
Table 1
Table 2
As can be seen from the data of table 2, metal traps abrasion index of the present invention is low, shows that metal traps abrasion resistance properties of the present invention is good.
Table 3
Test case 1
This test case is for illustration of the absorption property of metal traps A1 of the present invention to vanadium-containing compound.
Adopt octaethyl porphines vanadyl (VO-OEP) (octaethyl porphines vanadyl structure is similar to etioporphyrin (ETIO) vanadyl (ETIO) structure in oil) to be probe molecule, investigate the absorption property of metal traps A1-A8, detailed process is as follows:
With Perkin Elmer UV/VIS spectrometer in 400nm-600nm interval interscan VO-OEP cyclohexane solution (see figure 5), as can be seen from Figure 5 there is highest peak at λ=570nm place.Therefore this wavelength measurement VO-OEP cyclohexane solution is selected, the VO-OEP cyclohexane solution of configuration variable concentrations, absorbance is measured by ultraviolet-uisible spectrophotometer, and it is associated with VO-OEP concentration, Criterion curve, see Fig. 6, Fig. 6 shows that VO-OEP cyclohexane solution concentration and absorbance are good linear relationship.
Then by metal traps A1 dry 3h at 120 DEG C, get the dried sample of 0.1g and be placed in 25mL conical flask, then the VO-OEP cyclohexane solution that 20g mass fraction is 14.04 μ g/g is added, shaken at room temperature, sample every 15min, utilize the VO-OEP absorbance in ultraviolet-visible spectrophotometer working sample, result table 4.
Test case 2-8
Test according to the method for test case 1, unlike, the metal traps of use is A2-A8, the results are shown in Table 4, and wherein after A2 absorption, the ultraviolet absorptivity of VO-OEP cyclohexane solution is shown in Fig. 7.
Test comparison example 1-5
Test according to the method for test case 1, unlike, the sample used be independent industrial catalyst C(wherein, after industrial catalyst C adsorbs, the ultraviolet absorptivity curve of VO-OEP cyclohexane solution is shown in Fig. 8), metal traps B1, metal traps B2, metal traps B4, metal traps B5, the results are shown in Table 4.
Table 4
| Sample number into spectrum | y 0 | A 1 | t 1 | A 1/t 1 |
| A1 | 1.2165 | 12.8225 | 9.8414 | 1.3029 |
| A2 | 1.2835 | 12.7266 | 10.6445 | 1.1956 |
| A3 | 1.1829 | 12.7461 | 10.3782 | 1.2282 |
| A4 | 1.1625 | 12.8911 | 10.1236 | 1.2734 |
| A5 | 0.9912 | 12.9589 | 9.3621 | 1.3842 |
| A6 | 1.2958 | 12.7263 | 10.5937 | 1.2013 |
| A7 | 1.2264 | 12.7832 | 10.4812 | 1.2196 |
| A8 | 1.1351 | 12.8763 | 9.7234 | 1.3243 |
| C | 0.9744 | 12.9606 | 12.3015 | 1.0536 |
| B1 | 2.1419 | 11.8823 | 10.9002 | 1.0901 |
| B2 | 2.2831 | 11.6237 | 10.8622 | 1.0701 |
| B4 | 1.8626 | 12.1542 | 10.8117 | 1.1242 |
| B5 | 1.6314 | 12.4562 | 11.3036 | 1.1020 |
From the absorbance of Fig. 7, Fig. 8 in time change curve can find out that metal traps of the present invention, catalytic cracking catalyst C are to all exponentially type decay of the Adsorption law of VO-OEP, it can use equation y=A
1* exp (-x/t
1)+y
0carry out matching, wherein y represents the concentration of VO-OEP in absorbance or solution, and x represents adsorption time, A
1, t
1for constant.When x levels off to infinity, y
0vO-OEP concentration when being material saturated adsorption in solution, y
0littlely show that material is stronger to VO-OEP adsorption capacity.To fit equation differentiate, obtain Sorption rate equation y ,=(-A
1/ t
1) * exp (-x/t
1), as x=0, (-A
1/ t
1) absolute value be the initial rate of adsorption of material, corresponding y value is the initial concentration of VO-OEP cyclohexane solution.
As can be seen from the data of table 4, compared with Cracking catalyst, metal traps of the present invention is lower slightly to VO-OEP saturated extent of adsorption, but the rate of adsorption is faster, therefore for the moment finish contact process of FCC process, the rate of adsorption is even more important, and namely metal traps of the present invention is very suitable for FCC catalytic cracking process; And compare with B5 with contrast metal traps B1, B2, B4, metal traps provided by the invention all has advantage to the saturated extent of adsorption of VO-OEP and the rate of adsorption, and namely metal traps of the present invention can trap the vanadium-containing compound in feedstock oil sooner, more.
Embodiment 9
Embodiment 9 is used for the Catalytic Cracking Performance of catalytic cracking for illustration of the heavy metal-polluted dyeing method of metal traps and industrial cracking catalyst mixture and metal traps of the present invention.
First the solid content of analytical industry Cracking catalyst C and metal traps A1 provided by the invention, then catalyst mixture is obtained with butt metering physical mixed, catalyst mixture first carries out cyclic polluting (to deposit Ni and V) on circulation aging equipment, (the content namely calculated of amount in theory of Ni, V on catalyst mixture after cyclic polluting, actually have a little error, but do not affect result of the present invention) in table 6, wherein
Cycle is polluted step and is comprised: catalyst mixture passes through meter Xie Er infusion process (see document: R.Mitchell Bruce, Ind.Eng.Chem.Prod.Res.Dev., 19 (1980) 209-213.) introduce heavy metal (Ni and V) after, then the catalyst mixture introduced after heavy metal is loaded in D-100 device (small fixed flowing bed), D-100 device processes as follows:
A () in a nitrogen atmosphere, with the heating rate of 20 DEG C/min, is heated to 600 DEG C;
B (), with the heating rate of 1.5 DEG C/min, after being heated to 780 DEG C, constant temperature, at 780 DEG C, changes process atmosphere in thermostatic process as follows:
(i) with the nitrogen (wherein, the propylene containing 5 volume % in nitrogen) containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes,
(ii) with the nitrogen (pure nitrogen gas, without propylene) containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes,
(iii) to contain the air of 40 volume % (containing 4000 μm of ol/mol SO
2), the atmosphere process of the steam of 60 volume % 10 minutes,
(iv) with the nitrogen containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes; Then press aforementioned sequence again repetitive cycling step (i)-(iv) respectively once then repeat step (i), end loop pollutes step;
Then carry out aging step: the catalyst mixture after cyclic polluting at 788 DEG C, in containing the atmosphere of the steam of 80 volume % and the air of 20 volume % aging 8 hours;
Then on ACE device, investigate the catalytic performance of the catalyst mixture after cyclic polluting-aging, wherein, feedstock oil enters in reactor bottom and contacts with catalyst mixture, wherein, raw materials used oil nature in table 5, appreciation condition and the results are shown in Table 6.
Comparative example 6-9
Comparative example 6-9 is used for the Catalytic Cracking Performance of catalytic cracking for illustration of the heavy metal-polluted dyeing method of comparative catalyst's mixture and contrast metal traps.
According to the method for embodiment 9 carry out metallic pollution and and catalytic cracking, catalyst mixture after the metal traps B5 that the metal traps B4 that the metal traps B1, the comparative example 4 that provide for independent industrial catalyst C, comparative example 1 unlike the catalyst mixture adopted provide, comparative example 5 provide and industrial catalyst C by weight physical mixed, to pollute on rear catalyst mixture Ni, V content in table 6, appreciation condition and the results are shown in Table 6.
Table 5
| Density/(g/cm 3(20℃)) | 0.9048 |
| Viscosity (80 DEG C)/(mm 2/s) | 18.54 |
| Viscosity (100 DEG C)/(mm 2/s) | 10.89 |
| Condensation point/DEG C | 38 |
| Aniline point/DEG C | 92.5 |
| Carbon residue/% | 2.8 |
| Refractive power (70 DEG C) | 1.4912 |
| Constituent content/quality % | ? |
| C | 86.09 |
| H | 12.51 |
| S | 0.65 |
| N | 0.28 |
| Boiling range (D1160)/DEG C | ? |
| Initial boiling point | 233 |
| 5% | 295 |
| 10% | 333 |
| 30% | 395 |
| 50% | 429 |
| 70% | 470 |
| 90% | 539 |
Table 6
In the present invention, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield, total liquid yield (also known as total liquid product yield)=yield of gasoline+diesel yield+yield of liquefied gas, coke selectivity=coking yield/conversion ratio, dry gas selectivity=dry gas yield/conversion ratio.
As can be seen from the data of table 6, 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, selective from dry gas, metal traps of the present invention also has the effect of certain anti-nickel contamination.
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 characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.
Claims (12)
1. a metal traps, is characterized in that, this metal traps prepares as follows:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) solid is obtained by carrying out roasting after described 3rd slurries spraying dry;
(5) described solid is contacted with water soluble magnesium source solution, by dry for the mixture after contact or moist after carry out roasting;
Wherein, with the pore volume in 2-100nm hole for 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, in magnesia, the consumption weight ratio in described magnesium hydroxide and/or magnesia and water soluble magnesium source is 5-10:1.
3. metal traps according to claim 1 and 2, wherein, total consumption in described magnesium hydroxide and/or magnesia and water soluble magnesium source makes in the metal traps prepared, containing magnesia 5-95 % by weight.
4. want the metal traps in 1-3 described in any one according to right, wherein, the consumption of described macroporous aluminium oxide and little porous aluminum oxide makes containing the macroporous aluminium oxide of 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight in the aluminium oxide in the metal traps prepared, and total consumption of described macroporous aluminium oxide and little porous aluminum oxide makes the total content of macroporous aluminium oxide and little porous aluminum oxide in the metal traps prepared be 5-95 % by weight.
5. according to the metal traps in claim 1-4 described in any one, wherein,
In step (1), the consumption of acid makes the pH value of the first slurries be 1-3.0;
The consumption of step (1) medium and small porous aluminum oxide and deionized water makes the solid content of the first slurries be 8-20 % by weight.
6. according to the metal traps in claim 1-5 described in any one, wherein, described in step (2), the condition of contact comprises: temperature is 0-70 DEG C, and the time is more than 15min.
7. according to the metal traps in claim 1-6 described in any one, wherein, described in step (3), the condition of contact comprises: temperature is 10-60 DEG C, and the time is 2-20min.
8. according to the metal traps in claim 1-7 described in any one, wherein, the contact of the mixed pulp of step (1) and/or the contact of step (2) and/or step (3) and/or the contact of step (5) are carried out under the 3rd material exists, described 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, described water soluble magnesium source and/or the presoma of heat-resistant inorganic oxide.
9. metal traps according to claim 8, wherein, total consumption in total consumption of described macroporous aluminium oxide and little porous aluminum oxide, described magnesium hydroxide and/or magnesia and water soluble magnesium source, the consumption of described 3rd material make to contain the macroporous aluminium oxide of 10-95 % by weight and little porous aluminum oxide in the metal traps prepared, the oxide of the magnesia of 5-60 % by weight and described 3rd material of aequum.
10. metal traps according to claim 8, wherein, described heat-resistant inorganic oxide except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, described water soluble magnesium source is selected from silica, one or more in the metal oxide except described macroporous aluminium oxide, little porous aluminum oxide and magnesia; Described heat-resistant inorganic oxide presoma except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, described water soluble magnesium source be selected from Ludox, waterglass, boehmite, Alumina gel and silicon-aluminum sol one or more.
11. 1 kinds of catalyst cracking methods, the method comprises: under catalytic cracking condition, contacted with the catalyst mixture of catalytic cracking catalyst with containing metal traps by heavy oil feedstock, it is characterized in that, described metal traps is the metal traps in claim 1-10 described in any one.
12. methods according to claim 11, wherein, in described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236838.6A CN104226236B (en) | 2013-06-14 | 2013-06-14 | Metal traps and catalyst cracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310236838.6A CN104226236B (en) | 2013-06-14 | 2013-06-14 | Metal traps and catalyst cracking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104226236A true CN104226236A (en) | 2014-12-24 |
| CN104226236B CN104226236B (en) | 2016-12-28 |
Family
ID=52215662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310236838.6A Active CN104226236B (en) | 2013-06-14 | 2013-06-14 | Metal traps and catalyst cracking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104226236B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1491188A (en) * | 2001-02-09 | 2004-04-21 | ŵ�����˹ɷ�����˾ | Doped anionic clays |
| CN101583696A (en) * | 2006-12-06 | 2009-11-18 | 哥伦比亚国家石油股份有限公司 | Vanadium traps for catalytic cracking processes and preparation thereof |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
-
2013
- 2013-06-14 CN CN201310236838.6A patent/CN104226236B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1491188A (en) * | 2001-02-09 | 2004-04-21 | ŵ�����˹ɷ�����˾ | Doped anionic clays |
| CN101583696A (en) * | 2006-12-06 | 2009-11-18 | 哥伦比亚国家石油股份有限公司 | Vanadium traps for catalytic cracking processes and preparation thereof |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李晓等: "镁铝尖晶石作为催化裂化双功能助剂的研究", 《石油学报(石油加工)》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104226236B (en) | 2016-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103785346B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| Subhan et al. | Acidic sites and deep desulfurization performance of nickel supported mesoporous AlMCM-41 sorbents | |
| Rashidi et al. | Adsorptive desulfurization and denitrogenation of model fuel using HPW and NiO-HPW modified aluminosilicate mesostructures | |
| Tian et al. | The study of thiophene adsorption onto La (III)-exchanged zeolite NaY by FT-IR spectroscopy | |
| Al-Ghouti et al. | New adsorbents based on microemulsion modified diatomite and activated carbon for removing organic and inorganic pollutants from waste lubricants | |
| CN104226234B (en) | Metal traps and catalyst cracking method | |
| US7087156B2 (en) | Process for removal of nitrogen containing contaminants from gas oil feedstreams | |
| Nair et al. | The role of surface acidity in adsorption of aromatic sulfur heterocycles from fuels | |
| Saucier et al. | Comparison of a homemade bacuri shell activated carbon with carbon nanotubes for food dye removal | |
| CN105126928A (en) | Preparation method of modified mesoporous silicon-aluminum material | |
| CN108452837A (en) | A kind of catalytic cracking catalyst | |
| Silva et al. | Influence of the chemical composition of silica–alumina adsorbents in sulfur and nitrogen compounds removal from hydrotreated diesel | |
| FI79249B (en) | FOER HOEGOKTANIGA BENSINPRODUKTER AVSEDDA KATALYSATORER FOER KATALYTISK KRACKNING. | |
| Al-Ghouti et al. | Minimisation of organosulphur compounds by activated carbon from commercial diesel fuel: Mechanistic study | |
| Escobar et al. | Interaction between Ni and V with USHY and rare earth HY zeolite during hydrothermal deactivation | |
| CN108452833A (en) | A kind of catalytic cracking catalyst | |
| CN103789013B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| CN107344720B (en) | A kind of Y type molecular sieve and preparation method thereof | |
| Liu et al. | Vanadium contamination on the stability of zeolite USY and efficient passivation by La2O3 for cracking of residue oil | |
| CN104556081A (en) | Modified kaolin as well as preparation method and application thereof | |
| RU2516847C1 (en) | Catalytic additive for octane improvement in cat-cracked petrol and method of its manufacturing | |
| Zanjanchi et al. | Modification of MCM‐41 with Anionic Surfactant: A Convenient Design for Efficient Removal of Cationic Dyes from Wastewater | |
| RU2473385C1 (en) | Micropsherical catalyst for oil fractions cracking and method of its making | |
| CN104226235A (en) | Metal trapping agent and catalytic cracking method | |
| CN104226236A (en) | Metal trapping agent and catalytic cracking method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |