CN104338536B

CN104338536B - A kind of hydrogenation activity guard catalyst and preparation and application thereof

Info

Publication number: CN104338536B
Application number: CN201310334167.7A
Authority: CN
Inventors: 孙淑玲; 杨清河; 刘佳; 胡大为; 曾双亲; 邵志才
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-08-02
Filing date: 2013-08-02
Publication date: 2016-12-28
Anticipated expiration: 2033-08-02
Also published as: CN104338536A

Abstract

A kind of hydrogenation activity guard catalyst and preparation and application thereof; this catalyst contains alumina support and hydrogenation active metals component; described hydrogenation active metals component is selected from least one metal component of group VIII and at least one Group VB metal component; count and on the basis of catalyst by oxide; the content of described metal component of group VIII is to less than or equal to 0.8 weight % more than 0; the content of Group VB metal component is to less than or equal to 5 weight % more than 0; characterize with mercury injection method; the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 100 400 meters²/ gram, described carrier is bimodal pore distribution at a diameter of 5 20nm and a diameter of 100 300nm, and wherein, the pore volume in a diameter of 5 20nm holes accounts for the 30 50% of total pore volume, and the pore volume in a diameter of 100 300nm holes accounts for the 15 35% of total pore volume.Compared with prior art, the hydrogenation protecting catalyst that the present invention provides has preferable HDM activity simultaneously.

Description

A kind of hydrogenation activity guard catalyst and preparation and application thereof

Technical field

The present invention relates to a kind of hydrogenation activity guard catalyst and preparation and application thereof.

Background technology

Along with crude oil heaviness, the aggravation of 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 again by market, and environmental regulation the most increasingly tends to strict.At present, heavy oil is especially The processing of 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 processing of heavy oil work A kind of widely used processing technique in skill, the economic and environment-friendly moldeed depth process technology being well recognized as.Containing substantial amounts of in residual oil The metal impurities such as Ni, V, Fe, Ca and solid impurity, if this partial impurities can not effectively be removed, can urge downstream hydrogenation Agent has a negative impact, it is easy to make downstream catalyst inactivate.One of effective way solving this problem is to urge at hydrogenation The filling of agent top has the protective agent of hydrogenation activity, and therefore exploitation metal removal activity protective agent high, that appearance metal ability is strong is One of key technology that heavy-oil hydrogenation processes.In prior art, disclosed about hydrogenation activity guard catalyst and preparation side thereof The example of method includes:

CN101890381A discloses a kind of hydrotreating guard catalyst for residual oil and application thereof.This catalyst pore volume is big, aperture Greatly, porosity is high, reasonable pore distribution, and outer surface orifice is relatively big, and duct penetrability is good, more than 1000nm contain in duct 36% with On.

CN00124903.7 discloses a kind of hydrogenation protecting catalyst, and 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 little In 25 joule/gram, ammonia differential heat of adsorption accounts for the percentage of total ammonia integral heat of adsorption more than the ammonia integral heat of adsorption of 100 kj/mol Number is not more than 10%.

Patent CN98111379.6 discloses a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carrier is super large Aperture, 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 use granule The method of piling up prepares alumina support, then uses containing molybdenum solution and solution containing nickel equivalent impregnation, and the catalyst after dipping is at 100- 120 DEG C of dry 2-5h, configure 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 protection of this hydrogenation activity The preparation method of catalyst and application.

The present invention relates to herein below:

1. a hydrogenation activity guard catalyst, containing alumina support and hydrogenation active metals component, described hydrogenation is lived Property metal component selected from least one metal component of group VIII and at least one Group VB metal component, in terms of oxide and to urge On the basis of agent, the content of described metal component of group VIII is to less than or equal to 0.8 weight %, Group VB metal component more than 0 Content be to less than or equal to 5 weight % more than 0, characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, than Surface area is 100-400 rice²/ gram, described carrier is bimodal pore distribution at a diameter of 5-20nm and a diameter of 100-300nm, its In, the pore volume in a diameter of 5-20nm hole accounts for the 30-50% of total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for total pore volume 15-35%.

2. according to the catalyst described in 1, it is characterised in that described metal component of group VIII is selected from nickel and/or cobalt, Group VB Metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, and the content of described metal component of group VIII is 0.1-0.7 weight %, the content of Group VB metal component is 1-4 weight %；The pore volume of described carrier is 0.7-1.3 ml/g, Specific surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, a diameter of 100- The pore volume in 300nm hole accounts for the 20-40% of total pore volume.

3. according to the hydrogenation protecting catalyst described in 2, it is characterised in that count and on the basis of catalyst by oxide, institute The content stating metal component of group VIII is 0.2-0.6 weight %, and the content of Group VB metal component is 1.5-3.5 weight %.

4., according to the preparation method of the hydrogenation activity guard catalyst described in 1, comprise the steps:

(1) prepare carrier, intend thin water aluminum including by hydrated alumina PA and PB containing boehmite with a kind of containing The modifier PC mixing of the hydrated alumina of stone, molding, dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is The κ value of 20-60:20-50:5-50, PC is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For PC aqua oxidation before modified The sour peptization index of aluminum, DI₂Sour peptization index for described PC；

(2) introducing hydrogenation active metals component on the carrier that step (1) obtains, described hydrogenation active metals component is selected from At least one metal component of group VIII and at least one Group VB metal component, count and on the basis of catalyst by oxide, institute State the introduction volume of metal component of group VIII make the content of metal component of group VIII in final catalyst for more than 0 to being less than or equal to 0.8 weight %, the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst be big In 0 to less than or equal to 5 weight %, it is dried afterwards and roasting；

Wherein, the drying condition of described step (1) including: temperature is 40-350 DEG C, and the time is 1-24 hour, roasting condition Including: temperature is that the time is 1-8 hour more than 500 to less than or equal to 1200 DEG C；The drying condition of described step (2) including: temperature Degree is for 100-250 DEG C, and the time is 1-10 hour；Roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour.

5. according to the method described in 4, it is characterised in that the Mixing ratio by weight of described PA and PB and their modifier PC is 20-50:20-50:10-50；Described PC is 0 to less than or equal to 0.6；The drying condition of described step (1) including: temperature is 100- 200 DEG C, the time is 2-12 hour, and roasting condition includes: temperature for more than 800 to less than or equal to 1000 DEG C, roasting time for for 2-6 hour；The drying condition of described step (2) including: temperature is 100-140 DEG C.

6. according to the method described in 4 or 5, it is characterised in that the hole of the described hydrated alumina PA containing boehmite Holding for 0.75-1 ml/g, specific surface is 200-450 rice²/ gram, can and bore dia 3-10nm；Described containing boehmite The pore volume of hydrated alumina PB be 0.9-1.4 ml/g, specific surface is 100-350 rice²/ gram, can and bore dia more than 10 To less than or equal to 30nm.

7. according to the method described in 6, it is characterised in that the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, specific surface is 200-400 rice²/ gram, can and bore dia 5-10nm；Described containing boehmite The pore volume of hydrated alumina PB be 0.95-1.3 ml/g, specific surface is 120-300 rice²/ gram, can and bore dia be more than 10 to less than or equal to 25nm.

8. according to the method described in 4 or 5, it is characterised in that described PC is the particulate matter of 80-300 mesh.

9. according to the method described in 8, it is characterised in that described PC is the particulate matter of 100-200 mesh.

10. according to the method described in 4, it is characterised in that the hydrated alumina containing boehmite is modified as PC's One of method is by described hydrated alumina molding containing boehmite, is dried, and it is completely or partially ground afterwards Mill, screening, described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are method one to be obtained The article shaped roasting arrived, sintering temperature is that roasting time is 1-8 hour, afterwards that it is complete more than 350 to less than or equal to 1400 DEG C Portion or part are ground, sieve；The three of method are to dodge the hydrated alumina containing boehmite to do, and it is big for dodging dry temperature In 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, the two of method and with One or more in the modifier that the three of method obtain are mixed to get.

11. according to the method described in 10, it is characterised in that the condition being dried in described method one includes: temperature is 100-200 DEG C, the time is 2-12 hour；Sintering temperature in the two of method is 500-1200 DEG C, and roasting time is that 0.1-6 is little Time；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 hour.

12. according to the method described in 10 or 11, it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in the particulate matter of 80-300 mesh.

13. according to the method described in 12, it is characterised in that described PC is changing of the hydrated alumina containing boehmite The particulate matter of 100-200 mesh in property thing.

14. according to the method described in 4, it is characterised in that the metal component of described VIIIth race is selected from nickel and/or cobalt, VB The metal component of race is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, the introducing of described metal component of group VIII Amount makes the content of the metal component of group VIII in final catalyst be 0.1-0.7 weight %, drawing of described Group VB metal component Entering amount makes the content of the Group VB metal component in final catalyst be 1-4 weight %.

15. according to the method described in 14, it is characterised in that the introduction volume of described metal component of group VIII makes final catalyst In the content of metal component of group VIII be 0.2-0.6 weight %, the introduction volume of described Group VB metal component makes finally to be catalyzed The content of the Group VB metal component in agent is 1.5-3.5 weight %.

16. according to the method described in 4, it is characterised in that the described method introducing hydrogenation active metals component on carrier For infusion process.

In 17. claim 1-3 hydrogenation activity guard catalyst described in any one in hydrocarbon oil hydrogenation processes should With.

Depending on difference, the hydrogenation activity guard catalyst provided according to the present invention, requires that carrier therein can be made into various being prone to The article shaped of operation, the most spherical, cellular, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).Molding can be pressed Conventional method is carried out, such as, and a kind of method in spin, tabletting and extruded moulding or the combination of several method.When molding, example Such as extruded moulding, for ensureing that described molding is smoothed out, water, extrusion aid and/or gluing can be added in described mixture Agent, with or without expanding agent, then extrusion molding, be dried afterwards and roasting.Described extrusion aid, the kind of peptizer and use Measuring known to those skilled in the art, the most common extrusion aid can be selected from sesbania powder, methylcellulose, starch, poly-second One or more in enol, PVOH, described peptizer can be mineral acid and/or organic acid, and described expanding agent is permissible It is one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose therein is preferably hydroxyl first One or more in base cellulose, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is excellent Electing one or more in Polyethylene Glycol, poly-propanol, polyvinyl alcohol as, surfactant is preferably fat alcohol polyethylene ether, fat Fat alkylolamides and derivant thereof, molecular weight be the one in the propenyl copolymer of 200-10000 and maleic acid copolymer or Several.

In the present invention, described acid peptization index D I refers to the hydrated alumina containing boehmite and containing intending thin water After the hydrated alumina modifier of aluminum stone adds nitric acid by certain acid aluminum ratio, intended by containing of peptization within certain response time The hydrated alumina of boehmite is with Al₂O₃The percent of meter, DI=(1-W₂/W₁) × 100%, W₁And W₂It is respectively containing intending thin water Before the hydrated alumina of aluminum stone and acid reaction and with acid reaction after with Al₂O₃The weight of meter.

The mensuration of DI includes: (1) measure calcination base (also referred to as butt) content of the hydrated alumina containing boehmite (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours, weight weight ratio front with burning after its burning, with Percent represents), it 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, contain the thin water aluminum of plan by weigh The hydrated alumina of stone and deionized water add in beaker and mix；With 20mL pipet pipette 20mL, concentration is the dilute of 0.74N Salpeter solution, joins in the beaker of step (2) by this acid solution, the lower reaction of stirring 8 minutes；(4) by reacted for step (3) Serosity is centrifuged separating in centrifuge, is inserted by precipitate in the crucible weighed, and afterwards, in 125 DEG C, it is dried 4 little Time, 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% is calculated.

On the premise of being enough to make final carrier meet application claims, the present invention is to the described water containing boehmite Close aluminium oxide PA and PB not specially require, can be the boehmite prepared of any prior art, it is also possible to be to intend thin water The mixture of aluminum stone and other hydrated alumina, other hydrated alumina described is selected from a water aluminium oxide, gibbsite And one or more in amorphous hydrated aluminium oxide.

In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite is 0.75-1 Ml/g, specific surface is 200-450 rice²/ gram, can and bore dia 3-10nm, further preferred pore volume is 0.80-0.95 milli Rise/gram, specific surface is 200-400 rice²/ gram, can and bore dia 5-10nm；The described hydrated alumina containing boehmite The preferred pore volume of PB is 0.9-1.4 ml/g, and specific surface is 100-350 rice²/ gram, can and bore dia more than 10 to being less than or equal to 30nm, further preferred pore volume is 0.95-1.3 ml/g, and specific surface is 120-300 rice²/ gram, can and bore dia more than 10 To less than or equal to 25nm.

In the present invention, the pore volume of the hydrated alumina containing boehmite, specific surface area and can and aperture, be by institute State the hydrated alumina containing boehmite after 600 DEG C of roastings 4 hours, BET N2 adsorption characterize and obtain.

In further preferred embodiment, characterize with X diffraction, the described hydrated alumina PA containing boehmite With the boehmite content in PB not less than 50%, more preferably not less than 60%.

Inventors of the present invention have surprisingly found that, carry out being thermally treated resulting in changing by the hydrated alumina containing boehmite Property thing PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, will This modifier and PA and PB mixed-forming, it is dried and after roasting, obtained carrier has obvious bimodal pore distribution.Especially It is at the granule by 80-300 mesh therein, the granule of preferably 100-200 mesh and PA and PB mixed-forming, is dried and after roasting, Obtained by carrier bimodal in each unimodal pore size distribution concentrate especially.Here, the granule of described 80-300 mesh, preferably The granule of 100-200 mesh refers to that described modifier (includes step that is broken or that grind) if desired through sieving, and its screening thing is (under sieve Thing) meet the granule of 80-300 mesh, the particulate matter of preferably 100-200 mesh accounts for the percent (by weight) of total amount not less than 60%, Further preferably not less than 70%.Here the hydrated alumina containing boehmite can any prior art be prepared Boehmite, it is also possible to be boehmite and the mixture of other hydrated alumina, other hydrated alumina described One or more in a water aluminium oxide, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment, Described PC is the modifier of PA and/or PB.

In the present invention, described PA, PB refer in the most described PA, PB mixture with PC with the Mixing ratio by weight of PC The ratio of the most shared parts by weight of PA, PB and PC.Wherein, PA:PB:PC is preferably 20-60:20-50:5-50, further preferably For 30-50:35-50:10-30.

In the present invention, described PC conveniently can be obtained by following method:

Hereinafter, the method illustrating to obtain PC with described PA and PB for initiation material.

(1) based on being dried to obtain PC, including by hydrated alumina PA and/or PB containing boehmite according to a conventional method During regular oxidation alumina supporter is prepared in molding, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped exists Dry, the tailing (being referred to as traditionally being dried waste material) of integer process by-product, mills this tailing, sieves and obtain PC.

(2) obtain based on roasting, become according to a conventional method including by hydrated alumina PA and/or PB containing boehmite During regular oxidation alumina supporter prepared by type, the tailing (being referred to as roasting waste material traditionally) of fired by-product, such as, become in spin In type, spheroidal particle is the tailing of by-product in roasting process, is milled by this tailing, sieves and obtain PC；Or directly will PA and/or PB dodges and dry obtains, and when directly dodging dry by PA and/or PB, flash-off time is preferably 0.05-1 hour, further preferably For 0.1-0.5 hour.

(3) two or more be mixed to get in the modifier PC obtained based on preceding method.Obtain when using mixed method When obtaining C, the mixed proportion of the modifier PC respectively obtaining aforementioned several method does not limit.

The hydrogenation protecting catalyst provided according to the present invention, wherein, described hydrogenation active metals component the preferably the VIIIth race gold Belonging to component is cobalt and/or nickel, and the metal component of Group VB is vanadium and/or niobium, counts and on the basis of catalyst by oxide, described The content of metal component of group VIII is to less than or equal to 0.8 weight % more than 0, preferably 0.1-0.7 weight %, more preferably 0.2-0.6 weight %, the content of described Group VB metal component is to less than or equal to 4 weight % more than 0, preferably 1-4 weight %, More preferably 1.5-3.5 weight %.

On the premise of being enough to be carried on described carrier described hydrogenation active metals component, the present invention is to described negative Support method is not particularly limited, and preferred method is infusion process, including the dipping solution of the preparation compound containing described metal, it Afterwards with the carrier described in this solution impregnation.Described dipping method is conventional method, for example, it may be excess immersion stain, hole satisfy With method infusion process.The described one being selected from the soluble compound in them containing the metal component compound selected from V B race Or several, for example, it is possible to selected from such as the one or several in vanadic anhydride, ammonium vanadate, ammonium metavanadate, Sulfovanadic acid, vanada polyacid Kind, ammonium metavanadate preferably wherein, ammonium vanadate.The described solubility being selected from them containing the compound selected from VIII race's metal component One or more in compound, in the soluble complexes of cobalt nitrate, cobaltous acetate, basic cobaltous carbonate, cobaltous chloride and cobalt One or more, preferably cobalt nitrate, basic cobaltous carbonate；Nickel nitrate, nickel acetate, basic nickel carbonate, Nickel dichloride. and nickel solvable One or more in property complex, preferably nickel nitrate, basic nickel carbonate.

The catalyst provided according to the present invention, it is also possible to provide catalyst performance maybe can change containing any present invention that do not affects The addO-on therapy of the catalytic performance of the catalyst that rare book invention provides.As the addO-on therapy such as phosphorus can be contained, in terms of oxide also On the basis of catalyst, the content of described addO-on therapy is less than 10 weight %, preferably 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；Permissible It is that the compound containing components such as described phosphorus and the compound containing hydrogenation active metals component are configured to leaching after mixed solution Carrier described in stain；Can also is that and after the compound containing components such as phosphorus is individually prepared solution, impregnate described carrier roasting.When When the addO-on therapy such as phosphorus and hydrogenation active metals introduce described carrier respectively, first with containing described addO-on therapy compound Solution impregnation described in carrier roasting, the most again by the solution impregnation containing hydrogenation active metals component composition.Wherein, institute Stating sintering temperature and be 400-600 DEG C, preferably 420-500 DEG C, roasting time is 2-6 hour, preferably 3-6 hour.

According to hydrocarbon ils provided by the present invention (including residual oil) hydrotreating method, anti-to the hydrotreating of described hydrocarbon ils Answering condition to be not particularly limited, in a preferred embodiment, described hydrotreating reaction condition is: reaction temperature 300-550 DEG C, further preferred 330-480 DEG C, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 is little Time^-1, further preferred 0.15-2 hour^-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.

The device of described hydrogenation reaction can any be enough to make described raw oil at hydrotreating reaction conditions with institute State in the catalytic reactor of catalyst and carry out, such as, anti-at described fixed bed reactors, moving-burden bed reactor or ebullated bed Answer in device and carry out.

According to the conventional method in this area, described hydrotreating catalyst before the use, generally can exist at hydrogen Under, at a temperature of 140-370 DEG C, carrying out presulfurization with sulfur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device Also can be In-situ sulphiding in device, the active metal component it loaded is converted into metal sulfide component.

The catalyst that the present invention provides can be used alone, it is also possible to is applied in combination with other catalyst, and this catalyst is special It is not suitable for heavy oil particularly poor residuum and carries out hydrotreating, in order to provide for subsequent technique (such as catalytic cracking process) and close The raw oil of lattice.Compared with the Hydrogenation active protective agent that prior art provides, the Hydrogenation active protective agent that the present invention provides is at tool There is while having GPF (General Protection False agent function preferable HDM activity.

Detailed description of the invention

The present invention will be further described for the following examples, but should be 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:

(pore volume is 0.9 ml/g to the dry glue powder that PA-1: Chang Ling catalyst branch company produces, and specific surface is 280 meters²/ gram, Can and bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, surplus For amorphous alumina, DI value 34.6).

(pore volume is 0.9 ml/g to the dry glue powder of PA-2: Zibo limited production of neat cyclopentadienyl catalyst, and specific surface is 290 meters²/ Gram, can and bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 weight %, Surplus is amorphous alumina, DI value 33.2).

(pore volume is 1.2 mls/g to the dry glue powder that PB-1: 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 %, remaining Amount is amorphous alumina, DI value 15.8).

(pore volume is 1.1 mls/g to the dry glue powder that PB-2: Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 Rice²/ gram, can and bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 weights Amount %, surplus is amorphous alumina, DI value 17.2).

Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.

Embodiment 1

Weigh 1000 grams of PA-1, add the aqueous solution 1000 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains dried strip, By dried strip shaping, sieve, the length dried strip material (commonly referred to as industrially drying bar waste material) less than 2mm milled, Sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-A1 of PA-1.The k value of PC-A1 is shown in Table 1.

Embodiment 2

Weigh 1000 grams of PA-1, add the aqueous solution 1000 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, 800 DEG C of roastings 4 Hour, obtain carrier, by carrier strip shaping, sieve, by the length carrier strip material less than 2mm, (commonly referred to as industry carrier gives up Material) mill, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-A2 of PA-1.The k value of PC-A2 is shown in Table 1.

Embodiment 3

Weigh 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.The k value of PC-A3 is shown in Table 1。

Embodiment 4

The each 200 grams of uniform mixing of PC-A3 that PC-A1 embodiment 1 obtained and embodiment 3 obtain, obtain PA-1 and PA- The modifier PC-A4 of 2.The k value of PC-A4 is shown in Table 1.

Embodiment 5

Weigh 1000 grams of PB-1, add the aqueous solution 1440 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, 1200 DEG C of roastings 4 Hour, obtain carrier, by carrier strip shaping, sieve, by the length carrier strip material less than 2mm, (commonly referred to as industry carrier gives up Material) mill, sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-B1 of PB-1.The k value of PC-B1 is shown in Table 1.

Embodiment 6

Weigh 1000 grams of PB-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier PC-B2 of PB-2.The k value of PC-B2 is shown in Table 1。

Embodiment 7

Weigh 1000 grams of PB-2, add the aqueous solution 1440 containing 10 milliliters of nitric acid (Tianjin chemical reagent three factory product) afterwards Milliliter, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.Wet bar is dried 4 hours in 120 DEG C, obtains dried strip, By dried strip shaping, sieve, the length dried strip material (commonly referred to as industrially drying bar waste material) less than 2mm milled, Sieve, take wherein 100～200 mesh sieves and divide, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is shown in Table 1.

Embodiment 8

The each 200 grams of uniform mixing of PC-B2 that PC-B1 embodiment 5 obtained and embodiment 6 obtain, obtain PB-1 and PB- The modifier PC-B4 of 2.The k value of PC-B4 is shown in Table 1.

Embodiment 9

150 grams of PC-B3 that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain uniformly mix, obtain PA-1 and The modifier PC-B5 of PB-2.The k value of PC-B5 is shown in Table 1.

Embodiment 10

The each 150 grams of uniform mixing of PC-B1 that PC-A3 embodiment 3 obtained and embodiment 5 obtain, obtain PA-2 and PB- The modifier PC-B6 of 1.The k value of PC-B6 is shown in Table 1.

Table 1

Embodiment	Raw material	DI	k
				1	PC-A1	10.0	0.29
2	PC-A2	0.9	0.02
				3	PC-A3	3.6	0.11
4	PC-A4	6.7	0.20
				5	PC-B1	0	0
6	PC-B2	2.1	0.12
				7	PC-B3	5.3	0.31
8	PC-B4	1.0	0.06
				9	PC-B5	7.0	0.29
10	PC-B6	1.6	0.07

Bimodal hole carrier that the embodiment 11-18 explanation present invention provides and preparation method thereof.Comparative example 1-4 explanation routine is urged Agent carrier and preparation method thereof.

Embodiment 11

Weighing each 400 grams of PA-1 and PB-1, after the 200 grams of raw material PC-A2 prepared with embodiment 2 uniformly mix, addition contains The aqueous solution 1300 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), is extruded into external diameter φ on double screw banded extruder The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, is carried Body Z1.The character of carrier Z1 is listed in table 2.

Embodiment 12

Weigh 300 grams of PA-2,200 grams of PB-2, after the 500 grams of raw material PC-B2 prepared with embodiment 6 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 900 DEG C of roastings of this article shaped 3 hours, is carried Body Z2.The character of carrier Z2 is listed in table 2.

Embodiment 13

Weigh 500 grams of PA-2,300 grams of PB-2, after the 200 grams of raw material PC-B4 prepared with embodiment 8 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1300 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 950 DEG C of roastings of this article shaped 3 hours, is carried Body Z3.The character of carrier Z3 is listed in table 2.

Comparative example 1

Weigh 500 grams of PA-2,500 grams of PB-2, uniformly add the product in nitric acid Tianjin chemical reagent three factory after mixing) 10 millis The aqueous solution 1300 milliliters risen, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.It is little that wet bar is dried 4 in 120 DEG C Time, obtain article shaped, by 900 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ1.The character of carrier DZ1 is listed in table 2.

Comparative example 2

Weigh 400 grams of PA-1,600 grams of PB-1, uniformly add the product in nitric acid Tianjin chemical reagent three factory after mixing) 10 millis The aqueous solution 1300 milliliters risen, is extruded into the butterfly bar of external diameter φ 1.4mm on double screw banded extruder.It is little that wet bar is dried 4 in 120 DEG C Time, obtain article shaped, by 950 DEG C of roastings of this article shaped 3 hours, obtain carrier DZ2.The character of carrier DZ2 is listed in table 2.

Embodiment 14

Weigh 250 grams of PA-1,500 grams of PB-1, after the 250 grams of raw material PC-B5 prepared with embodiment 9 uniformly mix, add Containing the aqueous solution 1300 milliliters of 10 milliliters of nitric acid (Tianjin chemical reagent three factory product), double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 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 15

Weigh 350 grams of PA-2,350 grams of PB-2, after the 300 grams of raw material PC-B6 prepared with embodiment 10 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 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 16

Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-B1 prepared with embodiment 5 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, is carried Body Z6.The character of carrier Z6 is listed in table 2.

Embodiment 17

Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-A4 prepared with embodiment 4 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, is carried Body Z7.The character of carrier Z76 is listed in table 2.

Embodiment 18

Weigh 200 grams of PA-1,600 grams of PB-1, after the 200 grams of raw material PC-A2 prepared with embodiment 2 uniformly mix, add Containing nitric acid Tianjin chemical reagent three factory product) aqueous solution 1440 milliliters of 10 milliliters, double screw banded extruder is extruded into external diameter φ The butterfly bar of 1.4mm.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 850 DEG C of roastings of this article shaped 3 hours, is carried Body Z8.The character of carrier Z8 is listed in table 2.

Comparative example 3

The method provided according to patent CN1782031A embodiment 7, is extruded into external diameter φ 1.4mm's on plunger type bar extruder Butterfly bar.Wet bar is dried 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.

Comparative example 4

The method provided according to patent CN1120971A embodiment 1, is extruded into external diameter φ 1.4mm's on plunger type bar extruder Butterfly bar.Wet bar is dried 4 hours in 120 DEG C, obtains article shaped, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ3. The character of carrier DZ3 is listed in table 2.

Comparative example 5

Weigh 200 grams of PA-1,800 grams of PB-2, add the product in nitric acid Tianjin chemical reagent three factory) aqueous solution of 10 milliliters 1300 milliliters, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar is dried 4 hours in 120 DEG C, is become Type thing, by 1000 DEG C of roastings of this article shaped 3 hours, obtains carrier DZ5.The character of carrier DZ5 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 There is obvious structure of double peak holes.

Catalyst that the embodiment 19-24 explanation present invention provides and preparation method thereof.

Embodiment 19

Take 200 grams of carrier Z1, with 220 milliliters containing V₂O₅28.6 grams per liters, the ammonium metavanadate of NiO5 grams per liter and nickel nitrate mixing Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst C1.The composition of C1 It is shown in Table 3.

Embodiment 20

Take 200 grams of carrier Z2, with 220 milliliters containing V₂O₅28.6 grams per liters, the ammonium metavanadate of CoO5 grams per liter and cobalt nitrate mixing Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst C2.The composition of C2 It is shown in Table 3.

Embodiment 21

Take 200 carrier Z3, with 220 milliliters containing V₂O₅25 grams per liters, the ammonium metavanadate of NiO3 grams per liter 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 In table 3.

Embodiment 22

Take 200 grams of carrier Z4, with 220 milliliters containing V₂O₅25 grams per liters, the ammonium metavanadate of CoO3 grams per liter and cobalt nitrate mixing are molten Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst C4.The composition row of C4 In table 3.

Embodiment 23

Take 200 grams of carrier Z5, with 220 milliliters containing V₂O₅19.0 grams per liters, the ammonium metavanadate of NiO2 grams per liter and nickel nitrate mixing Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst C5.The composition of C5 It is shown in Table 3.

Embodiment 24

Take 200 grams of carrier Z8, with 220 milliliters containing V₂O₅19.0 grams per liters, the ammonium metavanadate of NiO2 grams per liter and nickel nitrate mixing Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst C6.The composition of C6 It is shown in Table 3.

Contrast row 6

Take 200 grams of carrier DZ1, with 220 milliliters containing V₂O₅28.6 grams per liters, the ammonium metavanadate of NiO5 grams per liter and nickel nitrate are mixed Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC1.DC1's Composition is shown in Table 3.

Contrast row 7

Take 200 grams of carrier DZ2, with 220 milliliters containing WO₃28.6 grams per liters, the ammonium metatungstate of NiO5 grams per liter and nickel nitrate are mixed Close solution impregnation 1 hour, dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC2.DC2's Composition is shown in Table 3.

Comparative example 8

Take 200 grams of carrier DZ3, with 220 milliliters containing V₂O₅25 grams per liters, the ammonium metavanadate of NiO3 grams per liter and nickel nitrate mixing Solution impregnation 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst DC3.The group of DC3 One-tenth is shown in Table 3.

Comparative example 9

Take 200 grams of carrier DZ4, with 220 milliliters containing MoO₃25 grams per liters, the ammonium molybdate of CoO3 grams per liter and cobalt nitrate mixing are molten Immersion stain 1 hour, dries 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtains hydrogenation activity guard catalyst DC4.The composition of DC4 It is shown in Table 3.

Table 3

In catalyst, the content of each metal component is value of calculation.

Embodiment 25-30

The demetallization per of the hydrogenation protecting catalyst that the embodiment 25-30 explanation present invention provides and desulfurization degree.

With the normal slag of Yi Chong as raw material (raw oil character is shown in Table 4), 100 milliliters of small fixed reactors are evaluated protection 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 millis Rise.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.Before and after using inductive coupling plasma emission spectrograph (ICP-AES) to measure hydrotreating In oil, (instrument is U.S.'s PE company PE-5300 type plasma quantometer to the content of metal, and concrete grammar is shown in petrochemical industry Analysis method RIPP124-90).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 below.

Comparative example 10-13

Method according to embodiment 25-30 evaluates the demetallization per of catalyst DC1, DC2, DC3 and DC4, the results are shown 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

Be can be seen that compared with existing catalyst by the data of table 5, the hydrogenation protecting agent that the present invention provides has higher Demetallization per.

Claims

1. a hydrogenation activity guard catalyst, containing alumina support and hydrogenation active metals component, described hydrogenation activity gold Belong to component and be selected from least one metal component of group VIII and at least one Group VB metal component, in terms of oxide and with catalyst On the basis of, the content of described metal component of group VIII is to less than or equal to 0.8 weight %, containing of Group VB metal component more than 0 Amount is to less than or equal to 5 weight % more than 0, characterizes with mercury injection method, and the pore volume of described carrier is 0.6-1.4 ml/g, specific surface Amass as 100-400 rice²/ gram, described carrier is bimodal pore distribution at a diameter of 5-20nm and a diameter of 100-300nm, wherein, directly Footpath is the 30-50% that the pore volume in 5-20nm hole accounts for total pore volume, and the pore volume in a diameter of 100-300nm hole accounts for the 15-of total pore volume 35%.

Hydrogenation activity guard catalyst the most according to claim 1, it is characterised in that described metal component of group VIII is selected from Nickel and/or cobalt, Group VB metal component is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described VIIIth race's gold The content belonging to component is 0.1-0.7 weight %, and the content of Group VB metal component is 1-4 weight %；The pore volume of described carrier is 0.7-1.3 ml/g, specific surface area is 100-300 rice²/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-of total pore volume 50%, the pore volume in a diameter of 100-300nm hole accounts for the 20-35% of total pore volume.

Hydrogenation activity guard catalyst the most according to claim 2, it is characterised in that in terms of oxide and with catalyst be Benchmark, the content of described metal component of group VIII is 0.2-0.6 weight %, and the content of Group VB metal component is 1.5-3.5 weight Amount %.

The preparation method of hydrogenation activity guard catalyst the most according to claim 1, comprises the steps:

(1) prepare carrier, including by hydrated alumina PA and PB containing boehmite with a kind of containing boehmite The modifier PC mixing of hydrated alumina, molding, dry and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20- The κ value of 60:20-50:5-50, PC is 0 to less than or equal to 0.9, described κ=DI₂/DI₁, DI₁For PC hydrated alumina before modified Sour peptization index, DI₂Sour peptization index for described PC；

(2) introducing hydrogenation active metals component on the carrier that step (1) obtains, described hydrogenation active metals component is selected from least A kind of metal component of group VIII and at least one Group VB metal component, count and on the basis of catalyst by oxide, and described the The introduction volume of VIII race's metal component makes the content of the metal component of group VIII in final catalyst be to less than or equal to 0.8 more than 0 Weight %, the introduction volume of described Group VB metal component makes the content of the Group VB metal component in final catalyst for more than 0 To less than or equal to 5 weight %, it is dried afterwards and roasting；

Wherein, the drying condition of described step (1) including: temperature is 40-350 DEG C, and the time is 1-24 hour, roasting condition bag Include: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500；The drying condition of described step (2) including: temperature For 100-250 DEG C, the time is 1-10 hour；Roasting condition includes: temperature is 360-500 DEG C, and the time is 1-10 hour.

Method the most according to claim 4, it is characterised in that the weight mixing of described PA and PB and their modifier PC Ratio is 20-50:20-50:10-50；The κ value of described PC is 0 to less than or equal to 0.6；The drying condition of described step (1) including: Temperature is 100-200 DEG C, and the time is 2-12 hour, and roasting condition includes: temperature is to less than or equal to 1000 DEG C more than 800, roasts The burning time is 2-6 hour；The drying condition of described step (2) including: temperature is 100-140 DEG C.

6. according to the method described in claim 4 or 5, it is characterised in that the described hydrated alumina PA containing boehmite Pore volume be 0.75-1 ml/g, specific surface area is 200-450 rice²/ gram, most probable bore dia 3-10nm；Described thin containing intending The pore volume of the hydrated alumina PB of diaspore is 0.9-1.4 ml/g, and specific surface area is 100-350 rice²/ gram, most probable hole is straight Footpath is more than 10 to less than or equal to 30nm.

Method the most according to claim 6, it is characterised in that the hole of the described hydrated alumina PA containing boehmite Holding for 0.80-0.95 ml/g, specific surface area is 200-400 rice²/ gram, most probable bore dia 5-10nm；Described thin containing intending The pore volume of the hydrated alumina PB of diaspore is 0.95-1.3 ml/g, and specific surface area is 120-300 rice²/ gram, most probable hole Diameter is more than 10 to less than or equal to 25nm.

8. according to the method described in claim 4 or 5, it is characterised in that described PC is the particulate matter of 80-300 mesh.

Method the most according to claim 8, it is characterised in that described PC is the particulate matter of 100-200 mesh.

Method the most according to claim 4, it is characterised in that the hydrated alumina containing boehmite is modified as One of method of PC is by described hydrated alumina molding containing boehmite, is dried, and it is completely or partially entered afterwards Row grinds, screening, and described dry condition includes: temperature is 40-350 DEG C, and the time is 1-24 hour；The two of method are by method The article shaped roasting that one obtains, sintering temperature is that roasting time is 1-8 hour more than 350 to less than or equal to 1400 DEG C, afterwards will It is completely or partially ground, sieves；The three of method are to dodge the hydrated alumina containing boehmite to do, and dodge dry temperature For more than 150 to less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour；The four of method be by one of method, the two of method It is mixed to get with several in the three of the method modifiers obtained.

11. methods according to claim 10, it is characterised in that the condition being dried in described method one includes: temperature For 100-200 DEG C, the time is 2-12 hour；Sudden strain of a muscle in the three of method is done temperature and is 200-1000 DEG C, and flash-off time is 0.1-0.5 Hour.

12. according to the method described in claim 10 or 11, it is characterised in that described PC is the hydration oxygen containing boehmite Change the particulate matter of 80-300 mesh in the modifier of aluminum.

13. methods according to claim 12, it is characterised in that described PC is the hydrated alumina containing boehmite Modifier in the particulate matter of 100-200 mesh.

14. methods according to claim 4, it is characterised in that the metal component of described VIIIth race is selected from nickel and/or cobalt, The metal component of Group VB is selected from vanadium and/or niobium, counts and on the basis of catalyst by oxide, described metal component of group VIII Introduction volume makes the content of the metal component of group VIII in final catalyst be 0.1-0.7 weight %, described Group VB metal component Introduction volume make the content of the Group VB metal component in final catalyst be 1-4 weight %.

15. methods according to claim 14, it is characterised in that the introduction volume of described metal component of group VIII makes finally to urge The content of the metal component of group VIII in agent is 0.2-0.6 weight %, and the introduction volume of described Group VB metal component makes finally The content of the Group VB metal component in catalyst is 1.5-3.5 weight %.

16. methods according to claim 4, it is characterised in that described introduce hydrogenation active metals component on carrier Method is infusion process.

Hydrogenation activity guard catalyst described in any one application in hydrocarbon oil hydrogenation processes in 17. claim 1-3.