CN103861605B - A kind of hydrogenation activity guard catalyst and preparation and application thereof - Google Patents
A kind of hydrogenation activity guard catalyst and preparation and application thereof Download PDFInfo
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- CN103861605B CN103861605B CN201210537474.0A CN201210537474A CN103861605B CN 103861605 B CN103861605 B CN 103861605B CN 201210537474 A CN201210537474 A CN 201210537474A CN 103861605 B CN103861605 B CN 103861605B
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Abstract
A kind of hydrogenation activity guard catalyst and preparation and application thereof; described hydrogenation activity guard catalyst contains alumina support and the hydrogenation active metals component of boracic; wherein; described carrier has structure of double peak holes; characterize with mercury injection method; the pore volume of described carrier is 0.9-1.2 ml/g, and specific surface area is 50-300 rice2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。The preparation of described carrier includes the modifier P2 of hydrated alumina P1 and the P1 containing boehmite being mixed and introducing boron-containing compound in the mixture, aftershaping, dry and roasting, the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of the hydrated alumina P1 containing boehmite, DI2Sour peptization index for the modifier P2 of described P1。Compared with prior art, hydrogenation activity guard catalyst provided by the invention has good HDM activity simultaneously。
Description
Technical field
The present invention relates to a kind of hydrogenation activity guard catalyst and preparation and application thereof。
Background technology
Along with the aggravation of crude oil heaviness, in poor quality trend, crude oil difficulty of processing strengthens, light oil yield reduces, and the demand of high grade light-end products is being continuously increased by market, and environmental regulation also increasingly tends to strict。At present, the processing of heavy oil especially residual oil and make full use of and just become the staple of conversation that whole world Oil Refining Industry is paid close attention to, and residual hydrogenation technology is a kind of widely used processing technique in processing of heavy oil technique, the economic and environment-friendly moldeed depth process technology being well recognized as。Containing metal impurities and solid impurities such as substantial amounts of Ni, V, Fe, Ca in residual oil, if this partial impurities can not effectively be removed, downstream hydrogenation catalyst can be had a negative impact, it is easy to make downstream catalyst inactivate。One of effective way solving this problem is to have the protective agent of hydrogenation activity in the filling of hydrogenation catalyst top, and therefore exploitation metal removal activity protective agent high, that appearance metal ability is strong is one of key technology of heavy-oil hydrogenation process。In prior art, the disclosed example about hydrogenation activity guard catalyst and preparation method thereof includes:
CN101890381A discloses a kind of hydrotreating guard catalyst for residual oil and application thereof。This catalyst pore volume is big, and aperture is big, and porosity is high, reasonable pore distribution, and outer surface orifice is relatively big, and duct penetrability is good, and more than 1000nm contains more than 36% in duct。
CN00124903.7 discloses a kind of hydrogenation protecting catalyst; this catalyst contains a kind of alumina support and load molybdenum on the alumina support and/or tungsten and nickel and/or cobalt; wherein; total ammonia integral heat of adsorption of described alumina support is not more than 25 joule/gram, and the percent that ammonia differential heat of adsorption accounts for total ammonia integral heat of adsorption more than the ammonia integral heat of adsorption of 100 kj/mol is not more than 10%。
Patent CN98111379.6 discloses a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carrier is ultra-large aperture, and aperture is the bimodal hole of 0.1-30 μm, and catalyst pore volume is 0.1-0.8ml/g, specific surface 0.1-20m2/ g, containing VI B race metallic element 6.65m%-20.0m% and/or VIII race metallic element 8.7m1% ,-26.13m%。Preparation method is to adopt the granule method of piling up to prepare alumina support, then adopts containing molybdenum solution and solution containing nickel equivalent impregnation, and the catalyst after dipping, at 100-120 DEG C of dry 2-5h, configures roast 2-5h at 500-550 DEG C。
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new hydrogenation activity guard catalyst, the preparation method of this hydrogenation activity guard catalyst and application。
The present invention relates to herein below:
1. a hydrogenation activity guard catalyst, alumina support containing boracic and hydrogenation active metals component, wherein, described carrier has structure of double peak holes, characterizes with mercury injection method, and the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface area is 50-300 rice2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。
2., according to the hydrogenation activity guard catalyst described in 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume。
3., according to the hydrogenation activity guard catalyst described in 1, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 0.1-8 weight %。
4., according to the hydrogenation activity guard catalyst described in 3, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 1-6 weight %。
5., according to the hydrogenation activity guard catalyst described in 4, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 2-5 weight %。
6. according to the hydrogenation activity guard catalyst described in 1; it is characterized in that; described hydrogenation active metals component is selected from least one metal component of group VIII and at least one metal component of group VIB; count with oxide and with catalyst for benchmark; the content of described VIII race's metal component more than 0 to less than or equal to 0.8 weight %, the content of metal component of group VIB more than 0 to less than or equal to 4 weight %。
7. according to the hydrogenation activity guard catalyst described in 6; it is characterized in that; described metal component of group VIII is selected from cobalt and/or nickel; metal component of group VIB is selected from molybdenum and/or tungsten; count with oxide and with catalyst for benchmark; the content of described VIII race's metal component is 0.1-0.6 weight %, and the content of metal component of group VIB is 1.5-3.5 weight %。
8. the preparation method according to the hydrogenation activity guard catalyst described in 1; including preparing carrier the component of load hydrogenation active metals on this carrier; wherein; the preparation of described carrier includes being mixed by the modifier P2 of hydrated alumina P1 and the P1 containing boehmite and introducing boron-containing compound in the mixture; aftershaping, dry and roasting, wherein, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80; the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For having the sour peptization index of the hydrated alumina P1 of boehmite, DI2Sour peptization index for the modifier P2 of the hydrated alumina P1 containing boehmite。
9. according to the method described in 8, it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70-95:5-25。
10., according to the method described in 8, it is characterised in that count with oxide and with described carrier for benchmark, the introduction volume of described boron-containing compound makes the content of boron in final carrier be 0.1-6 weight %。
11. according to the method described in 10, it is characterised in that count with oxide and with described carrier for benchmark, the introduction volume of described boron-containing compound makes the content of boron in final carrier be 0.3-4 weight %。
12. according to the method described in 8, it is characterised in that the k value of described P2 is 0 to less than or equal to 0.6。
13. according to the method described in 8 or 9, it is characterised in that the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, can and bore dia 8-30nm。
14. according to the method described in 13, it is characterised in that the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, can and bore dia 10-25nm。
15. according to the method described in 8,9 or 12 any one, it is characterised in that described P2 is the particulate matter of 80-300 order。
16. according to the method described in 15, it is characterised in that described P2 is the particulate matter of 100-200 order。
17. according to the method described in 8, it is characterised in that described dry condition includes: temperature is 40-350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500。
18. according to the method described in 17, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is that roasting time is 2-6 hour to less than or equal to 1000 DEG C more than 800。
19. according to the method described in 8, it is characterized in that, it is by described hydrated alumina P1 molding containing boehmite, dry by one of P1 method being modified as P2, afterwards it all or part of is ground, sieves, obtaining powder body thing is P2, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are article shaped roastings method one obtained, and sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, it all or part of are ground afterwards, sieve, and obtaining powder body thing is P2；Hydrated alumina P1 containing boehmite is dodged to do by the three of method, and dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C, and obtaining powder body thing is P2；The four of method be by one of method, method two and the modifier that obtains with the three of method in one or more be mixed to get。
20. according to the method described in 19, it is characterised in that the dry condition in described method one includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is 0.1-6 hour；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour。
21. according to the method described in 19 or 20, it is characterised in that described P2 is the particulate matter of 80-300 order in P1 modifier。
22. according to the method described in 21, it is characterised in that described P2 is the particulate matter of 100-200 order in P1 modifier。
23. according to the method described in 8, it is characterized in that, the described method in supported on carriers hydrogenation active metals component is infusion process, including the solution of the preparation compound containing hydrogenation active metals and use this solution impregnating carrier, it is dried afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one group VIB and the metal component of at least one VIIIth race, count with oxide and with catalyst for benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of group VIB in final catalyst more than 0 to less than or equal to 4 weight % in the concentration of described solution and the consumption of described solution, the content of the metal component of described VIIIth race more than 0 to less than or equal to 0.8 weight %；Described drying condition includes: temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour。
24. according to the method described in 23, it is characterized in that, the metal component of described group VIB is selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, count with oxide and with catalyst for benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of vib in final catalyst be 1.5-3.5 weight % in the concentration of described solution and the consumption of described solution, and the content of the metal component of the VIIIth race is 0.1-0.6 weight %；Described drying condition includes: temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting condition includes: temperature is 360-450 DEG C, and the time is 2-6 hour。
25. hydrogenation activity guard catalyst described in any one application in hydrocarbon oil hydrogenation processes in aforementioned 1-7。
According to hydrogenation activity guard catalyst provided by the invention, require that carrier therein can be made into various easily operated article shaped depending on difference, for instance spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.)。Wherein, it is conventional method by the modifier P2 of described hydrated alumina P1 and the P1 containing the boehmite method mixed, for instance, P1 and the P2 of powder body is put into mixing in stirring-type batch mixer according to ingredient proportion。The method introducing boron-containing compound in described P1 and P2 mixture is conventional method, such as, in a concrete embodiment preparing carrier, the method introducing boron-containing compound in the mixture of the modifier P2 of described hydrated alumina P1 and the P1 containing boehmite is that boron-containing compound is configured to aqueous solution, this aqueous solution is mixed into while described P1 and P1 mixes or again this aqueous solution is mixed into after described P1 and P1 mixes, aftershaping, dry and roasting。Described boron-containing compound can be one or more in the water soluble compound of arbitrary boron。Such as, the one in boric acid and sodium borate and mixture thereof。
Described molding carries out according to a conventional method, for instance, a kind of method in spin, tabletting and extruded moulding or the combination of several method。When molding, for instance extruded moulding, for ensureing that described molding is smoothed out, it is possible to add in described mixture water, extrusion aid and/or adhesive, containing or without expanding agent, then extrusion molding, be dried afterwards and roasting。Described extrusion aid, the kind of peptizer and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, described peptizer can be mineral acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant。Synthetic cellulose therein is preferably one or more in hydroxymethyl cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in Polyethylene Glycol, poly-propanol, polyvinyl alcohol, and surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof, molecular weight are the propenyl copolymer of 200-10000 and one or more in maleic acid copolymer。
After sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina containing boehmite adds nitric acid by certain acid aluminum ratio, by the hydrated alumina containing boehmite of peptization with Al within certain response time2O3The percent of meter, DI=(1-W2/W1) × 100%, W1And W2Respectively intend before thin water aluminum and acid reaction and with acid reaction after with Al2O3The weight of meter。
The mensuration of DI includes: the (1) calcination base content (calcination base (also referred to as butt) content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight ratio front with burning after its burning) of the mensuration hydrated alumina containing boehmite, is calculated as a；(2) weigh the hydrated alumina W containing boehmite with analytical balance0Gram, W0Amount meet with Al2O3The W of meter1It is 6 grams of (W1/a=W0), weigh deionized water W gram, W=40.0-W0, under stirring, the hydrated alumina containing boehmite weighed and deionized water are added mixing in beaker；With 20mL pipet pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), the lower reaction of stirring 8 minutes；(4) being centrifuged step (3) reacted serosity in centrifuges separating, inserted by precipitate in the crucible weighed, afterwards, it is dry 4 hours in 125 DEG C, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W2Gram；(5) according to formula DI=(1-W2/W1) × 100% calculates and obtains。
The described hydrated alumina P1 containing boehmite can be boehmite prepared by any prior art, can also be boehmite and the mixture of other hydrated alumina, one or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide of other hydrated alumina described。In a preferred embodiment, characterizing with X diffraction, in the described hydrated alumina containing boehmite, boehmite content is not less than 50%, is more preferably not less than 60%。
It is preferred that the pore volume of the described hydrated alumina P1 containing boehmite be 0.9-1.4 ml/g, specific surface is 100-350 rice2/ gram, can and bore dia 8-30nm, it is more preferable to the pore volume of the described hydrated alumina P1 containing boehmite be 0.95-1.3 ml/g, specific surface is 120-300 rice2/ gram, can and bore dia 10-25nm。
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and can and aperture, be by the described hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain。
Inventors of the present invention have surprisingly found that, hydrated alumina P1 containing boehmite is carried out heat treatment modified, the peptization index of its modifier changes, by this modifier with without heat treated P1 mixed-forming, dry and roasting after, obtained carrier has obvious bimodal pore distribution。Particularly at the granule by 80-300 order therein, it is preferable that the granule of 100-200 order with without after heat treated part mixed-forming, dry and roasting, obtained carrier bimodal in each unimodal pore size distribution concentrate especially。Here, the granule of described 80-300 order, the granule of preferred 100-200 order refers to that described modifier is through sieve (including step that is broken or that grind if desired), its screening thing (siftage) meets the granule of 80-300 order, the particulate matter of preferred 100-200 order accounts for the percent (by weight) of total amount and is not less than 60%, it is preferred that be not less than 70%。
The Mixing ratio by weight of described P1 and P2 refers to the ratio of P1 and P2 shared parts by weight respectively in the mixture of every hundred parts of described P1 and P2。Wherein, the preferred span of parts by weight of P1 is 20-95, more preferably 70-95；The preferred span of parts by weight of P2 is 5-80, more preferably 5-25。
In being embodied as, described P2 conveniently can be obtained by following method:
(1) obtain P2 based on dry, including being prepared in regular oxidation alumina supporter process by the hydrated alumina P1 molding according to a conventional method containing boehmite, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped is at tailing (being called dry waste material traditionally) dry, integer process by-product, this tailing is milled, sieves and obtain P2。
(2) obtain based on roasting, including being prepared in regular oxidation alumina supporter process by the hydrated alumina P1 molding according to a conventional method containing boehmite, the tailing (being called roasting waste material traditionally) of fired by-product, such as, in roller forming, spheroidal particle is the tailing of by-product in roasting process, is milled by this tailing, sieves and obtain P2；Or directly P1 is dodged dry obtaining, when directly dodging dry by P1, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour。
(3) two or more be mixed to get in the modifier P2 obtained based on preceding method。When adopting mixed method to obtain P2, the mixed proportion of the modifier P2 that aforementioned several method is respectively obtained does not limit。
According to hydrogenation activity guard catalyst provided by the invention; wherein; described hydrogenation active metals component is kind known in those skilled in the art and content thereof; preferred VIII race's metal component is cobalt and/or nickel; VI B race metal component is molybdenum and/or tungsten; count with oxide and with catalyst for benchmark; the content of described VIII race's metal component is preferably greater than 0 to less than or equal to 0.8 weight %; more preferably 0.1-0.6 weight %; the content of described VI B race metal component is preferably greater than 0 to less than or equal to 4 weight %, more preferably 1.5-3.5 weight %。
Described hydrogenation active metals component is carried under the premise on described carrier being enough to, described carrying method is not particularly limited by the present invention, preferred method is infusion process, including the dipping solution of the compound prepared containing described metal, afterwards with the carrier described in this solution impregnation。Described dipping method is conventional method, for instance, it is possible to it is excessive immersion stain, hole saturation infusion process。Described is selected from one or more in the soluble compound in them, one or more in molybdenum oxide, molybdate, paramolybdate, it is preferable that molybdenum oxide therein, ammonium molybdate, ammonium paramolybdate containing the metal component compound selected from VI B race；One or more in tungstates, metatungstate, ethyl metatungstate, it is preferable that ammonium metatungstate therein, ethyl ammonium metatungstate。One or more in the described soluble compound being selected from them containing the compound selected from VIII race's metal component, one or more in the soluble complexes of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt, it is preferred to cobalt nitrate, basic cobaltous carbonate；One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel, it is preferred to nickel nitrate, basic nickel carbonate。
According to catalyst provided by the invention, it is also possible to containing any addO-on therapy not affecting the catalytic performance that the present invention provides catalyst performance maybe can improve catalyst provided by the invention。As contained the addO-on therapy such as phosphorus, counting with oxide and with catalyst for benchmark, the content of described addO-on therapy is less than 10 weight %, it is preferred to 0.1-4 weight %。
When in described catalyst possibly together with addO-on therapy such as phosphorus, the introducing method of described addO-on therapy can be arbitrary method, can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, molding roasting；Can be impregnate described carrier after the compound containing components such as described phosphorus is configured to mixed solution with the compound containing hydrogenation active metals component；Can also is that and after the compound containing components such as phosphorus is individually prepared solution, impregnate described carrier roasting。When the addO-on therapy such as phosphorus introduce described carrier respectively with hydrogenation active metals, it is preferable that first with carrier roasting described in the solution impregnation containing described addO-on therapy compound, afterwards again by the solution impregnation containing hydrogenation active metals component composition。Wherein, described sintering temperature is 400-600 DEG C, it is preferred to 420-500 DEG C, and roasting time is 2-6 hour, it is preferred to 3-6 hour。
According to hydrocarbon ils provided by the present invention (including residual oil) hydrotreating method, the reaction condition of the hydrotreatment of described hydrocarbon ils is not particularly limited, in a preferred embodiment, described hydrotreatment reaction condition is: reaction temperature 300-550 DEG C, it is preferred that 330-480 DEG C, hydrogen dividing potential drop 4-20 MPa, it is preferred that 6-18 MPa, volume space velocity 0.1-3.0 hour-1, it is preferred that 0.15-2 hour-1, hydrogen to oil volume ratio 200-2500, it is preferred that 300-2000。
The device of described hydrogenation reaction can make described raw oil carry out with the catalytic reactor of described catalyst at hydrotreating reaction conditions any being enough to, for instance, at described fixed bed reactors, moving-burden bed reactor or carry out in fluidized bed reactor。
According to the conventional method in this area, described hydrotreating catalyst is before the use, generally can be in presence of hydrogen, presulfurization is carried out with sulfur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can carry out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component。
Catalyst provided by the invention can be used alone, it is also possible to using with the combination of other catalyst, this catalyst is particularly suitable for heavy oil particularly poor residuum and carries out hydrotreatment, in order to provide qualified raw oil for subsequent technique (such as catalytic cracking process)。Compared with the Hydrogenation active protective agent that prior art provides, Hydrogenation active protective agent provided by the invention has good HDM activity while having GPF (General Protection False agent function。
Detailed description of the invention
The present invention will be further described for the following examples, but should therefore understands that be not limitation of the invention。
Agents useful for same in example, except as expressly described, is chemically pure reagent。
The boehmite used below in an example includes:
P1-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters2/ gram, can and bore dia 15.8nm。Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 15.8)。
P1-2: (pore volume is 1.1 mls/g to the dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 meters2/ gram, can and bore dia 12nm。Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weight %, and surplus is amorphous alumina, DI value 17.2)。
Embodiment 1-5 illustrates modifier P2 of described P1 preparing carrier of the present invention and preparation method thereof。
Embodiment 1
Weigh 1000 grams of P1-1, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar in 120 DEG C dry 4 hours, obtain dried strip, by dried strip shaping, sieve, the length dried strip material (being commonly referred to as industrially drying bar waste material) less than 2mm is milled, sieves, take wherein 100～200 mesh sieves and divide, obtain the modifier P2A of P1-1。The k value of P2A is in Table 1。
Embodiment 2
Weigh 1000 grams of P1-1, dodge dry 6 minutes in 240 DEG C, obtain the modifier P2B of P1-1。The k value of P2B is in Table 1。
Embodiment 3
The each 200 grams of Homogeneous phase mixing of P2B that the P2A obtain embodiment 1 and embodiment 2 obtain, obtain the modifier P2C of P1-1。The k value of P2C is in Table 1。
Embodiment 4
Weigh 1000 grams of P1-2, add the aqueous solution 1440 milliliters containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm。Wet bar in 120 DEG C dry 4 hours, 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the length carrier strip material less than 2mm (being commonly referred to as industry carrier waste material) is milled, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier P2D of P1-2。The k value of P2D is in Table 1。
Embodiment 5
Weigh 1000 grams of P1-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier P2E of P1-2。The k value of P2E is in Table 1。
Table 1
| Embodiment | Raw material | k |
| 1 | P2A | 0.5 |
| 2 | P2B | 0.4 |
| 3 | P2C | 0.4 |
| 4 | P2D | 0 |
| 5 | P2E | 0.3 |
Embodiment 6-13 illustrates the preparation method preparing carriers for catalysts of the present invention。The preparation method that comparative example 1-2 illustrates conventional catalyst carrier。
Embodiment 6
Weigh 800 grams of P1-1, after 200 grams of raw material P2A Homogeneous phase mixing prepared with embodiment 1, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 2.4g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z1。The character of carrier Z1 is listed in table 2。
Embodiment 7
Weigh 200 grams of P1-1, after 800 grams of raw material P2B Homogeneous phase mixing prepared with embodiment 2, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 2.4g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z2。The character of carrier Z2 is listed in table 2。
Embodiment 8
Weigh 500 grams of P1-1, after 500 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing (nitric acid Tianjin chemical reagent three factory product) 10 milliliters, boric acid aqueous solution 1440 milliliters containing diboron trioxide 2.4g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtains carrier Z3。The character of carrier Z3 is listed in table 2。
Comparative example 1
Weigh 1000 grams of P1-1, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 2.4g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ1。The character of carrier DZ1 is listed in table 2。
Embodiment 9
Weigh 800 grams of P1-2, after 200 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 14g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z4。The character of carrier Z4 is listed in table 2。
Embodiment 10
Weigh 900 grams of P1-1, after 100 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 14g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z5。The character of carrier Z5 is listed in table 2。
Embodiment 11
Weigh 850 grams of P1-2, after 150 grams of raw material P2C Homogeneous phase mixing prepared with embodiment 3, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 14g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, obtains carrier Z6。The character of carrier Z6 is listed in table 2。
Comparative example 2
Weigh 1000 grams of P1-2, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 14g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ2。The character of carrier DZ2 is listed in table 2。
Embodiment 12
Weigh 900 grams of P1-2, after 100 grams of raw material P2D Homogeneous phase mixing prepared with embodiment 4, add containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), boric acid aqueous solution 1440 milliliters containing diboron trioxide 28g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier Z7。The character of carrier Z7 is listed in table 2。
Embodiment 13
Weigh 850 grams of P1-2, after 150 grams of raw material P2E Homogeneous phase mixing prepared with embodiment 5, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, boric acid aqueous solution 1440 milliliters containing diboron trioxide 28g, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier Z8。The character of carrier Z8 is listed in table 2。
Comparative example 3
According to the method that patent CN1782031A embodiment 9 provides, plunger type bar extruder is extruded into the Raschig ring shape bar of external diameter 2.5mm, internal diameter 1.0mm。Wet bar dries 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ3。The character of carrier DZ3 is listed in table 2。
Table 2
By the result of table 2 it will be seen that compared with conventional method, provider's method of the present invention the alumina support prepared has obvious structure of double peak holes。
Embodiment 14-19 illustrates Catalysts and its preparation method provided by the invention。
Embodiment 14
Take 200 grams of carrier Z1, with 220 milliliters containing MoO328.6 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C1。The composition of C1 is listed in table 3。
Embodiment 15
Take 200 grams of carrier Z2, with 220 milliliters containing WO328.6 g/l, the ammonium metatungstate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C2。The composition of C2 is listed in table 3。
Embodiment 16
Take 200 carrier Z3, with 220 milliliters containing MoO325 g/l, the ammonium molybdate of NiO3 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C3。The composition of C3 is listed in table 3。
Embodiment 17
Take 200 grams of carrier Z4, with 220 milliliters containing MoO325 g/l, the ammonium molybdate of CoO3 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C4。The composition of C4 is listed in table 3。
Embodiment 18
Take 200 grams of carrier Z5, with 220 milliliters containing MoO319.0 g/l, the ammonium molybdate of NiO2 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C5。The composition of C5 is listed in table 3。
Embodiment 19
Take 200 grams of carrier Z8, with 220 milliliters containing WO319.0 g/l, the ammonium metatungstate of NiO2 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C6。The composition of C6 is listed in table 3。
Contrast row 4
Take 200 grams of carrier DZ1, with 220 milliliters containing MoO328.6 g/l, the ammonium molybdate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC1。The composition of DC1 is listed in table 3。
Contrast row 5
Take 200 grams of carrier DZ1, with 220 milliliters containing WO328.6 g/l, the ammonium metatungstate of NiO5 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC2。The composition of DC2 is listed in table 3。
Comparative example 6
Take 200 grams of carrier DZ2, with 220 milliliters containing MoO325 g/l, the ammonium molybdate of NiO3 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC3。The composition of DC3 is listed in table 3。
Comparative example 7
Take 200 grams of carrier DZ2, with 220 milliliters containing MoO325 g/l, the ammonium molybdate of CoO3 g/l and cobalt nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC4。The composition of DC4 is listed in table 3。
Comparative example 8
Take 200 grams of carrier DZ3, with 220 milliliters containing MoO319.0 g/l, the ammonium molybdate of NiO2 g/l and nickel nitrate mixed solution impregnate 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC5。The composition of DC5 is listed in table 3。
Table 3
In catalyst, the content of each metal component is value of calculation。
Embodiment 20-25
Embodiment 20-25 illustrates demetallization per and the desulfurization degree of hydrogenation protecting catalyst provided by the invention。
With the normal slag of Yi Chong for raw material (raw oil character is in Table 4), 100 milliliters of small fixed reactors are evaluated protective agent。
Catalyst C1, C2, C3, C4, C5 and C6 are broken into the granule of diameter 2-3 millimeter, and catalyst loading amount is 100 milliliters。Reaction condition is: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPas, liquid hourly space velocity (LHSV) are 0.7 hour-1, hydrogen to oil volume ratio is 1000, sample analysis after reacting 200 hours。Inductive coupling plasma emission spectrograph (ICP-AES) is adopted to measure the content (instrument is U.S.'s PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90) of metal in oil before and after hydrotreatment。Calculate metal removal rate according to the following formula:
Raw oil character is listed in table 4, and evaluation result is listed in table 5。
Comparative example 9-13
According to the method evaluation catalyst DC1 of embodiment 20-25, DC2, DC3, DC4 and DC5 demetallization per, result is in Table 5.
Table 4
| Raw oil title | The normal slag of Yi Chong |
| Density (20 DEG C), kg/m3 | 0.966 |
| Mean molecule quantity | 452 |
| Ni, μ g/g | 47.7 |
| V, μ g/g | 133 |
| Fe, μ g/g | 8.4 |
| Ca, μ g/g | 29.5 |
Table 5 protective agent evaluation result
Being can be seen that compared with existing catalyst by the data of table 5, hydrogenation protecting agent provided by the invention has higher demetallization per。
Claims (25)
1. a hydrogenation activity guard catalyst, alumina support containing boracic and hydrogenation active metals component, wherein, described carrier has structure of double peak holes, characterizes with mercury injection method, and the pore volume of described carrier is 0.95-1.2 ml/g, and specific surface area is 50-300 rice2/ gram, diameter is the 55-80% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 10-35% that the pore volume in 300-500nm hole accounts for total pore volume。
2. hydrogenation activity guard catalyst according to claim 1, it is characterised in that the pore volume of described carrier is 0.95-1.15 ml/g, specific surface area is 80-200 rice2/ gram, diameter is the 60-75% that the pore volume in 10-30nm hole accounts for total pore volume, and diameter is the 15-30% that the pore volume in 300-500nm hole accounts for total pore volume。
3. hydrogenation activity guard catalyst according to claim 1, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 0.1-8 weight %。
4. hydrogenation activity guard catalyst according to claim 3, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 1-6 weight %。
5. hydrogenation activity guard catalyst according to claim 4, it is characterised in that count with oxide and with carrier for benchmark, the content of described boron is 2-5 weight %。
6. hydrogenation activity guard catalyst according to claim 1; it is characterized in that; described hydrogenation active metals component is selected from least one metal component of group VIII and at least one metal component of group VIB; count with oxide and with catalyst for benchmark; the content of described VIII race's metal component more than 0 to less than or equal to 0.8 weight %, the content of metal component of group VIB more than 0 to less than or equal to 4 weight %。
7. hydrogenation activity guard catalyst according to claim 6; it is characterized in that; described metal component of group VIII is selected from cobalt and/or nickel; metal component of group VIB is selected from molybdenum and/or tungsten; count with oxide and with catalyst for benchmark; the content of described VIII race's metal component is 0.1-0.6 weight %, and the content of metal component of group VIB is 1.5-3.5 weight %。
8. the preparation method of hydrogenation activity guard catalyst according to claim 1; including preparing carrier the component of load hydrogenation active metals on this carrier; wherein; the preparation of described carrier includes being mixed by the modifier P2 of hydrated alumina P1 and the P1 containing boehmite and introducing boron-containing compound in the mixture; aftershaping, dry and roasting, wherein, the Mixing ratio by weight of described P1 and P2 is 20-95:5-80; the κ value of P2 is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of the hydrated alumina P1 containing boehmite, DI2Sour peptization index for the modifier P2 of the hydrated alumina P1 containing boehmite。
9. method according to claim 8, it is characterised in that the Mixing ratio by weight of described P1 and P2 is 70-95:5-25。
10. method according to claim 8, it is characterised in that count with oxide and with described carrier for benchmark, the introduction volume of described boron-containing compound makes the content of boron in final carrier be 0.1-6 weight %。
11. method according to claim 10, it is characterised in that count with oxide and with described carrier for benchmark, the introduction volume of described boron-containing compound makes the content of boron in final carrier be 0.3-4 weight %。
12. method according to claim 8, it is characterised in that the k value of described P2 is 0 to less than or equal to 0.6。
13. method according to claim 8 or claim 9, it is characterised in that the pore volume of the described hydrated alumina P1 containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, can and bore dia 8-30nm。
14. method according to claim 13, it is characterised in that the pore volume of the described hydrated alumina P1 containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, can and bore dia 10-25nm。
15. according to Claim 8, the method described in 9 or 12 any one, it is characterised in that described P2 is the particulate matter of 80-300 order。
16. method according to claim 15, it is characterised in that described P2 is the particulate matter of 100-200 order。
17. method according to claim 8, it is characterised in that described dry condition includes: temperature is 40-350 DEG C, the time is 1-24 hour, and the condition of described roasting includes: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500。
18. method according to claim 17, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, the time is 2-12 hour, and the condition of described roasting includes: temperature is that roasting time is 2-6 hour to less than or equal to 1000 DEG C more than 800。
19. method according to claim 8, it is characterized in that, it is by described hydrated alumina P1 molding containing boehmite, dry by one of P1 method being modified as P2, afterwards it all or part of is ground, sieves, obtaining powder body thing is P2, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are article shaped roastings method one obtained, and sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, it all or part of are ground afterwards, sieve, and obtaining powder body thing is P2；Hydrated alumina P1 containing boehmite is dodged to do by the three of method, and dodging dry temperature is that flash-off time is 0.05-1 hour more than 150 to less than or equal to 1400 DEG C, and obtaining powder body thing is P2；The four of method be by one of method, method two and the modifier that obtains with the three of method in one or more be mixed to get。
20. method according to claim 19, it is characterised in that the dry condition in described method one includes: temperature is 100-200 DEG C, and the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is 0.1-6 hour；The dry temperature of sudden strain of a muscle in the three of method is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour。
21. the method according to claim 19 or 20, it is characterised in that described P2 is the particulate matter of 80-300 order in P1 modifier。
22. method according to claim 21, it is characterised in that described P2 is the particulate matter of 100-200 order in P1 modifier。
23. method according to claim 8, it is characterized in that, the described method in supported on carriers hydrogenation active metals component is infusion process, including the solution of the preparation compound containing hydrogenation active metals and use this solution impregnating carrier, it is dried afterwards, roasting or not roasting, described hydrogenation active metals component is selected from the metal component of at least one group VIB and the metal component of at least one VIIIth race, count with oxide and with catalyst for benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of group VIB in final catalyst more than 0 to less than or equal to 4 weight % in the concentration of described solution and the consumption of described solution, the content of the metal component of described VIIIth race more than 0 to less than or equal to 0.8 weight %；Described drying condition includes: temperature is 100-250 DEG C, and the time is 1-10 hour；Described roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour。
24. method according to claim 23, it is characterized in that, the metal component of described group VIB is selected from molybdenum and/or tungsten, the metal component of the VIIIth race is selected from cobalt and/or nickel, count with oxide and with catalyst for benchmark, the described compound containing hydrogenation active metals makes the content of the metal component of vib in final catalyst be 1.5-3.5 weight % in the concentration of described solution and the consumption of described solution, and the content of the metal component of the VIIIth race is 0.1-0.6 weight %；Described drying condition includes: temperature is 100-140 DEG C, and the time is 1-6 hour；Described roasting condition includes: temperature is 360-450 DEG C, and the time is 2-6 hour。
25. the application that the hydrogenation activity guard catalyst according to any one in claim 1-7 is in hydrocarbon oil hydrogenation processes。
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| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
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| CN1488441A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Method for preparing alumina supporter |
| CN1782031A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Slag oil hydro-demetallization catalyst and its preparing method |
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