CN104338562B - A kind of Bimodal-pore alumina support and preparation method thereof - Google Patents
A kind of Bimodal-pore alumina support and preparation method thereof Download PDFInfo
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Abstract
A kind of Bimodal-pore alumina support and preparation method thereof, characterizes with mercury injection method, and the pore volume of described carrier is 0.6 1.4 mls/g, and specific surface area is 80 400 meters2/ gram, the pore volume in a diameter of 5 20nm holes accounts for the 30 60% of total pore volume, and the pore volume in a diameter of 100 300nm holes accounts for the 15 45% of total pore volume.The preparation method of this carrier includes: the modifier PC of hydrated alumina PA and PB containing boehmite with a kind of hydrated alumina containing boehmite is mixed, molding, be dried and roasting, wherein, the Mixing ratio by weight of described PA, PB and PC is 20 60:20 50:5 50, the κ value of PC is 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1For the sour peptization index of PC hydrated alumina before modified, DI2Sour peptization index for described PC.What the present invention provided has Bimodal-pore alumina support and can use as adsorbent and catalyst carrier.
Description
Technical field
The present invention relates to a kind of alumina support and preparation method thereof, carry more specifically to a kind of bimodal porous aluminum oxide
Body and preparation method 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 hetero atoms such as Ni, V, Fe, Ca, S, N, these hetero atoms are mostly present in the macromolecular compound such as colloid, asphalitine, by often
Hydrogenation catalyst prepared by carrier prepared by rule method suffers from spreading control, and this part macromole impurity made can not obtain
Effectively removing, thus affect the heteroatomic removing of Ni, V, Fe, Ca, S, N etc. in residual oil.Solve this problem effective way it
One is the pore structure improving hydrogenation catalyst so that catalyst has structure of double peak holes, and wherein macropore is used for providing to macromole
Diffusion admittance, mesopore is used for carrying out catalytic reaction.
Patent CN1727063A discloses the preparation method of a kind of alumina supporter, and the method includes water
Close aluminium oxide mix with aluminium carbonate ammonium, molding roasting, wherein the Mixing ratio by weight of hydrated alumina and aluminium carbonate ammonium is 20-
90:10-80, sintering temperature is 450-1000 DEG C, and roasting time is 1-8 hour.The alumina support that this invention provides has double
Peak pore structure, and pore volume is relatively big, can use as adsorbent and catalyst carrier.
Patent CN1188216C discloses the preparation method of a kind of alumina support, and the method is by two kinds of thin water of different plans
Aluminum stone dry glue powder uniformly mixes, then carry out peptization, molding, be dried, roasting prepare Bimodal-pore alumina support.Wherein the first
The pore volume of boehmite is between 0.85mL/g-1.50mL/g, and additional proportion accounts for the Al that feeds intake2O35 weight %-50 weight %；The
The pore volume of two kinds of boehmites is between 0.50mL/g-0.80mL/g.Alumina support bore dia prepared by the present invention is respectively
In the range of concentrating on 6nm-35nm and 100nm-2000nm.Alumina support prepared by the method can be protected as producing heavy-oil hydrogenation
Protect the carrier of the course of reaction catalyst that agent, catalyst for demetalation and diffusion control.
Patent CN1047957C discloses the preparation method of a kind of Bimodal-pore alumina support, and the method is by two kinds or two kinds
Boehmite dry glue powder prepared by above different material route methods uniformly mixes, and then carries out peptization, molding, is dried and roasting
Burning processes and prepares and have the alumina support of structure of double peak holes, and the method is simple and easy to do, and products obtained therefrom large and small boring ratio example can be
Regulation in a big way.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new alumina support with structure of double peak holes and system
The method of this carrier standby.
The present invention relates to herein below:
1. a Bimodal-pore alumina support, characterizes with mercury injection method, and the pore volume of described carrier is 0.6-1.4 ml/g, than
Surface area is 80-400 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30-60% of total pore volume, a diameter of 100-300nm hole
Pore volume account for the 15-45% of total pore volume.
2. according to the carrier described in 1, it is characterised in that the pore volume of described carrier is 0.7-1.3 ml/g, specific surface area
For 100-300 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 35-50% of total pore volume, the hole in a diameter of 100-300nm hole
Volume accounts for the 20-40% of total pore volume.
3. according to the preparation method of carrier described in 1, including by hydrated alumina PA and PB and containing boehmite
Plant containing the modifier PC mixing of hydrated alumina of boehmite, molding, be dried and roasting, wherein, described PA, PB and PC
The κ value that Mixing ratio by weight is 20-60:20-50:5-50, PC be 0 to less than or equal to 0.9, described κ=DI2/DI1, DI1Change for PC
The sour peptization index of the hydrated alumina before property, DI2Sour peptization index for described PC.
4. according to the method described in 3, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:
10-30。
5. according to the method described in 3, it is characterised in that the k value of described PC is 0 to less than or equal to 0.6.
6. according to the method described in 3 or 4, 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 3,4 or 5 any one, 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 3, it is characterised in that described dry condition includes: temperature is 40-350 DEG C, the time
For 1-24 hour, the condition of described roasting included: temperature is that the time is 1-8 hour to less than or equal to 1200 DEG C more than 500.
11. according to the method described in 10, it is characterised in that described dry condition includes: temperature is 100-200 DEG C, time
Between be 2-12 hour, the condition of described roasting includes: temperature for more than 800 to less than or equal to 1000 DEG C, roasting time is 2-6
Hour.
12. according to the method described in 3, 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.
13. according to the method described in 12, 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.
14. according to the method described in 14, it is characterised in that described PC is changing of the hydrated alumina containing boehmite
The particulate matter of 80-300 mesh in property thing.
15. according to the method described in 14, 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.
The carrier provided according to the present invention, can be made into various easily operated article shaped, the most spherical, honeybee depending on different requirement
Nest shape, nest like, tablet or bar shaped (Herba Trifolii Pratentis, butterfly, cylinder etc.).Molding can be carried out according to a conventional method, such as, spin,
A kind of method in tabletting and extruded moulding or the combination of several method.When molding, such as extruded moulding, for ensureing described one-tenth
Type is smoothed out, and can add water, extrusion aid and/or adhesive, with or without expanding agent in described mixture, then squeezes
Go out molding, be dried afterwards and roasting.Public affairs that described extrusion aid, the kind of peptizer and consumption are those skilled in the art
Knowing, the most common extrusion aid can be selected from the one or several in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH
Kind, described peptizer can be mineral acid and/or organic acid, and described expanding agent can be starch, synthetic cellulose, polymeric alcohol
With one or more in surfactant.Synthetic cellulose therein is preferably hydroxymethyl cellulose, methylcellulose, ethyl
One or more in cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably Polyethylene Glycol, poly-propanol, poly-second
One or more in enol, surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivant thereof, molecular weight
For one or more in the propenyl copolymer of 200-10000 and maleic acid copolymer.
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.
With prior art provide there is Bimodal-pore alumina support compared with, the present invention provide there is bimodal porous aluminum oxide
The bimodal of carrier concentrates on 5nm-20nm and 100nm-300nm.Can use as adsorbent and catalyst carrier.Especially as
Carrier is for preparing hydrogenation protecting agent and the catalyst such as depitching matter, demetalization hydrotreating of processing of heavy oil.
Detailed description of the invention
The present invention will be further described for example below, but should be therefore understands that be not limitation of the invention.
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.
Claims (15)
1. a Bimodal-pore alumina support, characterizes with mercury injection method, and the pore volume of described carrier is 0.6-1.4 ml/g, specific surface
Amass as 80-400 rice2/ gram, the pore volume in a diameter of 5-20nm hole accounts for the 30-60% of total pore volume, a diameter of 100-300nm hole
Pore volume accounts for the 15-45% of total pore volume.
Carrier the most according to claim 1, it is characterised in that the pore volume of described carrier is 0.7-1.3 ml/g, compares table
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 100-300nm hole
Pore volume account for the 20-40% of total pore volume.
The most according to claim 1, the preparation method of carrier, including by hydrated alumina PA and PB containing boehmite
Mix with the modifier PC of a kind of hydrated alumina containing boehmite, molding, be dried and roasting, wherein, described PA, PB
It is 0 to less than or equal to 0.9 with the κ value that Mixing ratio by weight is 20-60:20-50:5-50, PC of PC, described κ=DI2/DI1, DI1
For the sour peptization index of PC hydrated alumina before modified, DI2Sour peptization index for described PC.
Method the most according to claim 3, it is characterised in that the Mixing ratio by weight of described PA, PB and PC is 30-50:35-
50:10-30.
Method the most according to claim 3, it is characterised in that the k value of described PC is 0 to less than or equal to 0.6.
6. according to the method described in claim 3 or 4, it is characterised in that the described hydrated alumina PA containing boehmite
Pore volume be 0.75-1 ml/g, specific surface is 200-450 rice2/ gram, most probable bore dia 3-10nm；Described containing intending thin water
The pore volume of the hydrated alumina PB of aluminum stone is 0.9-1.4 ml/g, and specific surface is 100-350 rice2/ gram, most probable bore dia is big
In 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 is 200-400 rice2/ gram, most probable bore dia 5-10nm；Described containing intending thin water
The pore volume of the hydrated alumina PB of aluminum stone is 0.95-1.3 ml/g, and specific surface is 120-300 rice2/ gram, most probable bore dia
More than 10 to less than or equal to 25nm.
8. according to the method described in claim 3,4 or 5 any one, it is characterised in that described PC is the granule of 80-300 mesh
Thing.
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 3, it is characterised in that described dry condition includes: temperature is 40-350 DEG C,
Time is 1-24 hour, and the condition of described roasting includes: temperature is that the time is that 1-8 is little to less than or equal to 1200 DEG C more than 500
Time.
11. methods according to claim 10, 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 to less than or equal to 1000 DEG C more than 800
For 2-6 hour.
12. methods according to claim 3, 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
With one or more in the modifier obtained with the three of method are mixed to get.
13. methods according to claim 12, 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；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.
14. methods according to claim 13, it is characterised in that described PC is the hydrated alumina containing boehmite
Modifier in the particulate matter of 80-300 mesh.
15. methods according to claim 14, it is characterised in that described PC is the hydrated alumina containing boehmite
Modifier in the particulate matter of 100-200 mesh.
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| CN109603791B (en) * | 2018-11-20 | 2021-11-30 | 中国石油天然气股份有限公司 | Sulfur recovery catalyst for low-temperature Claus process and preparation method thereof |
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| CN1047957C (en) * | 1994-10-19 | 2000-01-05 | 中国石油化工总公司抚顺石油化工研究院 | Prepn of alumina supporter |
| CN100586569C (en) * | 2004-06-29 | 2010-02-03 | 中国石油化工股份有限公司 | Great pore volume formed aluminium oxide carrier and its preparing method |
| CN1332762C (en) * | 2004-07-29 | 2007-08-22 | 中国石油化工股份有限公司 | Method for preparing alumina supporter in structure of double peak holes |
| JP4916157B2 (en) * | 2005-10-28 | 2012-04-11 | 日揮触媒化成株式会社 | Alumina support for hydrodemetallation catalyst, production method thereof, and hydrodemetallation catalyst using the same |
| CN101450327B (en) * | 2007-11-29 | 2010-08-25 | 南化集团研究院 | Process for preparing alumina carrier |
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