CN103055952A - Residual oil hydrotreating catalyst supporter and preparation method thereof - Google Patents
Residual oil hydrotreating catalyst supporter and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a residual oil hydrotreating catalyst supporter and a preparation method thereof. The catalyst supporter is composed of aluminum oxide and mesoporous molecular sieve, wherein the mesoporous molecular sieve accounts for 4.5-9.5 wt% of the supporter. In the catalyst supporter preparation process, a proper amount of alkaline nitrogen-containing compound is added into the raw materials quasi-boehmite, aluminum oxide powder and mesoporous molecular sieve; and due to the actions of blending and sintering, the prepared catalyst supporter has large specific area, large pore size and proper pore structure, reduces the diffusion restriction of the reactants, is suitable for catalyzing macromolecule-participated reactions, and has proper acid value and improved wear resistance. The catalyst supporter is suitable for preparing a boiling bed hydrotreating catalyst. In the residual oil boiling bed hydrotreating process, the catalyst still maintains the desulfurization activity on the premise of enhancing the hydrogenation demetallization and deasphaltenizing activities.
Description
Technical field
The present invention relates to a kind of catalyst for hydrotreatment of residual oil carrier and preparation method thereof, more specifically say about a kind of boiling bed residual oil hydrogenation diasphaltene, demetalization or desulphurization catalyst carrier and preparation method thereof.
Background technology
The demand of distillate increases year by year in the world wide, but because light crude oil output is limited, so distillate output can't satisfy present requirements.But the output of mink cell focus or residual oil constantly increases, and for satisfying the demand of distillate, is necessary these inferior feedstock oil is converted into the large distillate product of demand, has therefore promoted the development of residual hydrogenation modification technology.The residual hydrogenation modification technology mainly contains fixed bed, moving bed, boiling bed hydrogenation technique, although wherein fixed bed hydrogenation technique technology is ripe, but strict to metal in the raw material and carbon residue content restriction, its restricted application, boiling bed hydrogenation technique is strong to adaptability to raw material, and processing scheme is flexible, can the higher decompression residuum of processing metal impurity content, its catalyst can add row online, is conducive to realize the catalyst long-term operation.
In the boiling bed hydrogenation process, catalyst is in fluidized state at inside reactor, and collision and rubbing machine can be more, easily broken and wearing and tearing.Therefore, in the preparation boiling bed hydrogenation catalyst, the impact of the factors such as the mechanical strength of needs consideration catalyst self, abrasion index it has been generally acknowledged that grain shape is that tiny sphere is more suitable, and adds a certain amount of wear-resistant component at preparatory phase.
The hydrocarbon component that contains Various Complex in the residual oil, and a large amount of sulphur, nitrogen and metal (mainly being nickel and vanadium), and these impurity mostly are present in the large molecule of armaticity (resin and asphalt), want to remove this type of impurity, just need to carry out to this quasi-molecule the conversion (hydrogenation is saturated, open loop and hydrogenolysis) of appropriateness, so this type of catalyst except having larger aperture and pore volume, also will have suitable specific area and surface acid intensity.
Ware and Wei(J.Catal.1985,93, studies show that 135-151) adopts the different admixture of characteristic electron difference or acidity as the conditioning agent of acid carrier, and admixture is mainly alkali metal or alkaline-earth metal.Further regulate catalyst surface acidity by admixture, the ratio of hydrogenation and hydrogenolysis in the change catalyst.
The people such as Rayo (Petro. Sci. Tech.2007,25,215-230) a small amount of zeolite molecular sieve is mixed in the alumina support, find that molecular sieve can provide the acidity of appropriateness to help to improve the HDM performance of catalyst, simultaneously because most metal impurities all combine with asphalitine, so the conversion ratio of feedstock oil studies on asphaltene also increases.
(Catal. Today 2008,130 411-420) adds a certain amount of USY molecular sieve to the people such as Rana in aluminium oxide, find that by phenetic analysis structure of double peak holes appears in this catalyst, has suitably improved the conversion ratio of asphaltene in vacuum residues.But because USY molecular sieve large usage quantity and its acidity are stronger, so cracking reaction is stronger on the catalyst, is not suitable for the hydrotreatment reaction.
US4,448,896 disclose the catalyst of a kind of hydrodesulfurization and removing heavy-metal.The specific area of the carrier that this catalyst adopts is 100 ~ 350m
2/ g, the pore volume of pore radius 37.5 ~ 75000 are 0.5 ~ 1.5mL/g, and this pore volume is at least 90% with the ratio of total pore volume, and its pore size distribution locates to occur characteristic peak at pore radius less than 100 and 100 ~ 1000 liang.The preparation method of this carrier be with activated alumina or activated alumina precursor mix with carbon black, moulding and roasting.
CN1103009A discloses a kind of preparation method with the alumina support in bimodal hole.The method is that drying, roasting form with two kinds of aluminium oxide or its precursor and carbon powder, surfactant, peptizing agent and water mixed-formings that pore-size distribution is different.
CN1070418A adopts the catalyst of full kneading method preparation, and take titanium, boron as improver, its initial activity is better, but because acidity is stronger, NH
4-TPD acidity reaches 1.449mmol/g, and carbon deposit speed is fast, and catalysqt deactivation is fast, the life-span is short.
CN101590424A discloses a kind of catalyst used for hydrogenation of distilled oil fraction carrier, be composited by aluminium oxide and mesoporous molecular sieve SBA-15, its aperture be the pore volume of 3 ~ 7nm account for total pore volume 70% ~ 86%.Less according to its aperture of SBA-15/ alumina compound that the method obtains, be not suitable for use in the hydrotreating catalyst of heavy oil or residual oil.CN101058074A discloses a kind of catalyst for hydro-processing heavy distillate carrier, is formed by MCM-41 mesopore molecular sieve and alumina composite, and the aperture is 2.9 ~ 4.5nm, is not suitable for the large molecule turnover duct in the residual oil.
Existing preparation has in the method for catalyst for hydrotreatment of residual oil carrier, when the expanding agents such as employing carbon powder, organic additive, and easy temperature runaway during roasting, temperature control is complicated, the poor stability of product quality; When adopting the USY molecular sieve to improve the asphaltene removal effect, its acidity is stronger, and the catalyst surface cracking reaction is too much; At the aluminium oxide that adopts two kinds of different pore sizes to distribute during as catalyst Precursors, the difficult control of the acidity of preparation rear catalyst, namely in the situation that improve demetalization and diasphaltene difficulty take into account desulphurizing activated.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind ofly have that pore structure is suitable, specific area and the larger residual hydrocracking carried catalyst of pore volume, the invention provides simultaneously that a kind of technique is simple, abrasion are little, yield rate is high, are specially adapted to the preparation method of the catalyst for hydrotreatment of residual oil carrier of boiling bed residual oil HDM, diasphaltene and desulfurization.
Catalyst for hydrotreatment of residual oil carrier provided by the invention is comprised of aluminium oxide and mesopore molecular sieve, and wherein mesopore molecular sieve accounts for the 4.5wt% ~ 9.5wt% of vehicle weight.
The character of described catalyst carrier is as follows: total pore volume is 0.7 ~ 1.8mL/g, and specific area is 200 ~ 410m
2/ g, bore dia are that the shared pore volume of 10 ~ 25nm is 40% ~ 70% of total pore volume, and bore dia is 15%～50% of total pore volume greater than the shared pore volume of 25nm, and acidity is 0.975～1.336mmol/g.
Described mesopore molecular sieve can be one or more among MCM-41, SAPO-36, the SBA-15.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention comprises:
(1) boehmite dry glue powder, alumina powder, mesopore molecular sieve, basic nitrogen compound and shaping assistant are mixed, make plastic;
(2) with the plastic moulding of step (1) gained, then dry, roasting obtains catalyst carrier.
Wherein the described aluminium oxide of step (1) is its precursor roasting gained, sintering temperature is at 650～1100 ℃, time is 1～7 hour, consumption accounts for the 8wt%～20wt% of total alumina weight in the material, and the described mesopore molecular sieve of step (1) can be one or more among MCM-41, SAPO-36, the SBA-15.The described shaping assistant of step (1), those skilled in the art can make one's options according to molding mode, such as adding extrusion aid, peptizing agent etc.The kind of described extrusion aid and consumption all are this area routines, and for example common extrusion aid can be selected from one or more in sesbania powder, starch, the PVOH, and its consumption accounts for the 0.5wt% ~ 6.0wt% of alumina weight in the material.Described peptizing agent is inorganic acid and/or organic acid, can be one or more in nitric acid, acetic acid, citric acid, tartaric acid, the oxalic acid, and its consumption accounts for the 0.5wt% ~ 4.5wt% of alumina weight in the material.The preferred water miscible basic nitrogen compound of basic nitrogen compound described in the step (1), such as in carbonic hydroammonium, ammonium oxalate, the ammonium acetate one or more, its consumption accounts for the 25.5wt% ~ 47.5wt% of alumina weight in the material.
The described moulding of step (2) can be selected suitable forming method according to practical application, and when being used for the boiling bed hydrogenation processing procedure, the general selection made microspheroidal, and diameter is 0.1 ~ 0.7 millimeter.Drying condition described in the step (2) is as follows: 70 ~ 130 ℃ lower dry 2 ~ 6 hours, described roasting condition is as follows: 500 ~ 1000 ℃ of lower roastings 2 ~ 8 hours.
In the catalyst carrier preparation process of the present invention, adopt boehmite, alumina powder, mesopore molecular sieve is raw material, add an amount of basic nitrogen compound, because blending and agglomeration, make the catalyst carrier of making have larger specific area, larger aperture and suitable pore structure, reduce the diffusion restriction of reactant, be fit to the reaction that the large molecule of catalysis participates in, has simultaneously suitable acidity, and improved the abrasion resistance properties of catalyst, be used for boiling bed residual oil hydrotreatment process, improving HDM, keep desulphurizing activated in the time of the diasphaltene activity.
The inventive method adopts the mode Kaolinite Preparation of Catalyst carrier of mechanical mixture, so can be easier, direct, need not to add the auxiliary agent of adjusting catalyst acidity, reduce simultaneously the impact that the carrier hole structure is caused, reduce specific area reduction etc. such as large hole number.
Method provided by the invention is not used the expanding agent of carbon powder, organic additive class, has eliminated the possibility of temperature runaway in the roasting process, and the while flow process is simplified, yield rate is high.
Catalyst for hydrotreatment of residual oil carrier of the present invention can adopt conventional method supported active metal component to make catalyst for hydrotreatment of residual oil, this catalyst can be used for the processes such as boiling bed residual oil HDM, diasphaltene, desulfurization, is particularly suitable for HDM, the diasphaltene reaction of the higher decompression residuum of asphalt content.
The specific embodiment
In the inventive method, specific area, pore volume and pore size distribution are to adopt the low temperature liquid nitrogen determination of adsorption method.Acidity is to adopt NH
3-TPD method is measured.Wt% is mass fraction.
Below in conjunction with embodiment the present invention will be further described.
Agents useful for same is chemically pure reagent among the embodiment except specifying.
Embodiment 1
Boehmite dry glue powder (butt is 80wt%) 850 ℃ of lower roastings 3 hours, is obtained alumina powder.Take by weighing 14.2 gram alumina powders, take by weighing again boehmite dry glue powder 100 grams, MCM-41 molecular sieve 5.1 grams, sesbania powder 1.9 grams, carbonic hydroammonium 28.3 grams, mix an amount of deionized water of rear adding, rare nitric acid mixes, kneading becomes plastic, then makes the about 0.2 millimeter micro-spherical particle of diameter.Spheric granules descended dry 5 hours at 100 ℃, 700 ℃ of lower roastings 3 hours, obtained catalyst carrier A.
Get 50 gram catalyst carriers with 150 milliliters of reactive metal salt solution impregnation that contain ammonium molybdate and basic nickel carbonate 2 hours, consumption is by containing MoO in the catalyst
3Be 9.5wt%, NiO is the 3.5wt% meter.Then 100 ℃ lower dry 5 hours, 450 ℃ of lower roastings 3 hours obtain catalyst A.
Embodiment 2
In embodiment 1, change the MCM-41 molecular sieve into 7.0 grams, all the other conditions are constant, obtain catalyst carrier B.
Embodiment 3
In embodiment 1, change the MCM-41 molecular sieve into 3.5 grams, add simultaneously SAPO-36 molecular sieve 3.5 grams, all the other conditions are constant, obtain catalyst carrier C.
Embodiment 4
Take by weighing 14.2 gram alumina powders (with embodiment 1), take by weighing again boehmite dry glue powder 100 grams, MCM-41 molecular sieve 3.5 grams, SAPO-36 molecular sieve 3.5 grams, sesbania powder 0.9 gram, PVOH 1 gram, ammonium oxalate 28.3 grams, mix an amount of deionized water of rear adding, tartaric acid mixes, kneading is taken out after becoming plastic, make micro-spherical particle, about 0.2 millimeter of diameter.Round descended dry 5 hours at 100 ℃, 700 ℃ of lower roastings 3 hours, obtained catalyst carrier D.
Get 50 gram carriers with 150 milliliters of reactive metal salt solution impregnation that contain ammonium molybdate and basic nickel carbonate 2 hours, consumption is by containing MoO in the catalyst
3Be 9.5wt%, NiO is the 3.5wt% meter.Then 100 ℃ lower dry 5 hours, 450 ℃ of lower roastings 3 hours obtain catalyst D.
Embodiment 5
In embodiment 4, change the SAPO-36 molecular sieve into 5.0 grams, all the other conditions are constant, obtain catalyst carrier E.
Embodiment 6
In embodiment 4, change the SAPO-36 molecular sieve into the SBA-15 molecular sieve, all the other conditions are constant, obtain catalyst carrier F.
Embodiment 7
In embodiment 4, change round carrier roasting time into 5 hours, the catalyst soakage time changes 4 hours into, and all the other conditions are constant, obtain catalyst carrier G.
Comparative example 1
In embodiment 1, do not add the MCM-41 molecular sieve, all the other conditions are constant, obtain catalyst carrier A
1
Above-described embodiment and comparative example gained catalyst carrier A～G and A
1Physico-chemical property, see Table 1.
The physico-chemical property of table 1 different catalysts carrier
| Project | A | B | C | D |
| Mesopore molecular sieve content, wt% | 4.5 | 6.1 | 6.1 | 6.1 |
| Specific area, m 2/g | 238 | 259 | 278 | 285 |
| Pore volume, mL/g | 0.72 | 0.76 | 0.95 | 0.84 |
| Pore size distribution, % | ? | ? | ? | ? |
| <10nm | 18 | 18 | 23 | 16 |
| 10～25nm | 49 | 55 | 57 | 64 |
| >25nm | 33 | 27 | 20 | 20 |
| Rate of wear, wt% | 1.3 | 0.8 | 0.9 | 1.1 |
| Acidity, mmol/g | 1.001 | 1.079 | 1.133 | 1.139 |
Table 1 is continuous
| Project | E | F | G | A 1 |
| Mesopore molecular sieve content, wt% | 7.4 | 6.1 | 6.1 | 6.1 |
| Specific area, m 2/g | 337 | 275 | 266 | 147 |
| Pore volume, mL/g | 0.73 | 0.71 | 0.74 | 0.58 |
| Pore size distribution, % | ? | ? | ? | ? |
| <10nm | 19 | 35 | 12 | 13 |
| 10～25nm | 56 | 47 | 64 | 39 |
| >25nm | 25 | 18 | 24 | 48 |
| Rate of wear, wt% | 1.0 | 0.7 | 0.9 | 2.2 |
| Acidity, mmol/g | 1.278 | 1.246 | 1.189 | 0.865 |
Embodiment 10
Under the same process condition, on NH-1 type fluid bed abrasion instrument to catalyst A, D, A
1Estimate, on the ebullated bed middle-scale device above-mentioned catalyst is estimated simultaneously, estimate feedstock oil character and see Table 2 with the evaluation process conditions, evaluation result sees Table 3.
Table 2 feedstock oil character and process conditions
| Feedstock oil character | ? | Process conditions | ? |
| Density (20 ℃), kg/m 3 | 983 | Reaction pressure, MPa | 14 |
| Sulphur, wt% | 2.8 | Liquid hourly space velocity (LHSV), h -1 | 1.0 |
| Nitrogen, μ g/g | 4899 | Reaction temperature, ℃ | 400 |
| Carbon residue, wt% | 15.2 | Hydrogen to oil volume ratio | 900:1 |
| Nickel+vanadium, μ g/g | 247.8 | The duration of runs, h | 300 |
Illustrate: estimating with feedstock oil is Iranian decompression residuum, 520 ℃ of boiling ranges
+
Table 3 catalyst A, D and A
1Evaluation result
| Catalyst | A | D | A 1 |
| Rate of wear, wt% | 1.3 | 1.1 | 2.2 |
| Demetallization per, wt% | 88.5 | 91.1 | 80.1 |
| Desulfurization degree, wt% | 61.1 | 64.7 | 55.5 |
Illustrate: (1) attrition of catalyst rate=(powder quality of generation/reaction procatalyst quality) * 100%;
(2) adopt plasma emission spectrum (AES/ICP) method to measure the content that generates nickel, vanadium in the oil, and calculate demetallization per, be i.e. total demetallization per=[1-(generates the content sum of nickel, vanadium in the content sum/raw material of nickel, vanadium in the oil)] * 100%.
As seen from Table 3, the performance of catalyst of the present invention is better than the comparative catalyst, and especially rate of wear obviously is better than not adding the catalyst of mesopore molecular sieve.The performance of catalyst of the present invention is better than the comparative catalyst, has improved especially simultaneously HDM and desulphurizing activated.Because most metals component and asphalitine are combined closely in the residual oil, so when improving metal removal activity, hydrogenation diasphaltene activity also can increase.
Claims (10)
1. a catalyst for hydrotreatment of residual oil carrier is comprised of aluminium oxide and mesopore molecular sieve, and wherein mesopore molecular sieve accounts for the 4.5wt% ~ 9.5wt% of vehicle weight.
2. according to catalyst carrier claimed in claim 1, it is characterized in that the character of described catalyst carrier is as follows: total pore volume is 0.7 ~ 1.8mL/g, and specific area is 200 ~ 410m
2/ g, bore dia are that the shared pore volume of 10 ~ 25nm is 40% ~ 70% of total pore volume, and bore dia is 15%～50% of total pore volume greater than the shared pore volume of 25nm, and acidity is 0.975～1.336mmol/g.
3. according to catalyst carrier claimed in claim 1, it is characterized in that described mesopore molecular sieve is one or more among MCM-41, SAPO-36, the SBA-15.
4. according to catalyst carrier claimed in claim 1, it is characterized in that described catalyst carrier is microspheroidal, diameter is 0.1 ~ 0.7 millimeter.
5. the preparation method of the arbitrary described catalyst carrier of claim 1 ~ 4 comprises:
(1) boehmite dry glue powder, alumina powder, mesopore molecular sieve, basic nitrogen compound and shaping assistant are mixed, make plastic; The described alumina powder of step (1) is its precursor roasting gained, sintering temperature is at 650～1100 ℃, time is 1～7 hour, and consumption accounts for the 8wt%～20wt% of total alumina weight in the material, and the consumption of described basic nitrogen compound accounts for the 25.5wt% ~ 47.5wt% of alumina weight in the material;
(2) with the plastic moulding of step (1) gained, then dry, roasting obtains catalyst carrier.
6. in accordance with the method for claim 5, it is characterized in that basic nitrogen compound described in the step (1) is one or more in carbonic hydroammonium, ammonium oxalate, the ammonium acetate.
7. in accordance with the method for claim 5, it is characterized in that the drying condition described in the step (2) is as follows: 70 ~ 130 ℃ lower dry 2 ~ 6 hours, described roasting condition is as follows: 500 ~ 1000 ℃ of lower roastings 2 ~ 8 hours.
8. in accordance with the method for claim 5, it is characterized in that the described shaping assistant of step (1) is one or both in extrusion aid, the peptizing agent.
9. in accordance with the method for claim 8, it is characterized in that described extrusion aid is selected from one or more in sesbania powder, starch, the PVOH, its consumption accounts for the 0.5wt% ~ 6.0wt% of alumina weight in the material.
10. in accordance with the method for claim 8, it is characterized in that described peptizing agent is inorganic acid and/or organic acid, its consumption accounts for the 0.5wt% ~ 4.5wt% of alumina weight in the material.
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Cited By (5)
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| CN104449815A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Hydrocarbon-oil hydrotreatment method |
| CN105688973A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Hydrodesulfurization and denitrification catalyst for inferior raw oil and application thereof |
| CN105694955A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Hydrodesulfurization and denitrification method for inferior raw oil |
| CN105689007A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Carrier for hydrodesulfurization and denitrification catalyst for inferior raw oil, and preparation method and application thereof |
| CN108187709A (en) * | 2017-12-22 | 2018-06-22 | 洛阳金达石化有限责任公司 | A kind of preparation method of deep hydrodesulfurizationof catalyst and the application of the catalyst |
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| CN104449815A (en) * | 2013-09-22 | 2015-03-25 | 中国石油化工股份有限公司 | Hydrocarbon-oil hydrotreatment method |
| CN104449815B (en) * | 2013-09-22 | 2016-07-20 | 中国石油化工股份有限公司 | A kind of method for hydrotreating hydrocarbon oil |
| CN105688973A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Hydrodesulfurization and denitrification catalyst for inferior raw oil and application thereof |
| CN105694955A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Hydrodesulfurization and denitrification method for inferior raw oil |
| CN105689007A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Carrier for hydrodesulfurization and denitrification catalyst for inferior raw oil, and preparation method and application thereof |
| CN105694955B (en) * | 2014-11-27 | 2017-07-11 | 中国海洋石油总公司 | A kind of method of inferior feedstock oil hydrogenation desulfurization and denitrogenation |
| CN105688973B (en) * | 2014-11-27 | 2019-01-11 | 中国海洋石油集团有限公司 | A kind of inferior feedstock oil hydrogenation desulfurization and denitrogenation catalyst and its application |
| CN105689007B (en) * | 2014-11-27 | 2019-04-26 | 中国海洋石油集团有限公司 | Inferior feedstock oil hydrogenation desulfurization and denitrogenation carriers for catalysts and its preparation method and application |
| CN108187709A (en) * | 2017-12-22 | 2018-06-22 | 洛阳金达石化有限责任公司 | A kind of preparation method of deep hydrodesulfurizationof catalyst and the application of the catalyst |
| CN108187709B (en) * | 2017-12-22 | 2020-06-19 | 洛阳金达石化有限责任公司 | Preparation method of deep hydrodesulfurization catalyst and application of catalyst |
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