CN105709711B - A kind of preparation method of alumina support - Google Patents
A kind of preparation method of alumina support Download PDFInfo
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- CN105709711B CN105709711B CN201410724075.4A CN201410724075A CN105709711B CN 105709711 B CN105709711 B CN 105709711B CN 201410724075 A CN201410724075 A CN 201410724075A CN 105709711 B CN105709711 B CN 105709711B
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Abstract
The present invention discloses a kind of preparation method of alumina support, including following process：（1）A certain amount of boehmite dry glue powder is weighed, in right amount containing the above-mentioned boehmite dry glue powder of the aqueous solution of polyalcohol and/or glucide dipping；（2）By step（1）Resulting material carries out hydro-thermal charing process；（3）By step（2）The mixed solution of material extruding, dried carrier unsaturation spray impregnation of phosphoric acid and ammonium oxalate, the carrier after dipping are sealed heat treatment, and treated carrier is through drying, the obtained alumina support of roasting.Alumina support prepared by this method has large hole appearance and aperture, and in alumina support radially in uneven distribution, which is suitable for preparing the fields such as weight, residuum hydrogenating and metal-eliminating catalyst macropore.
Description
Technical field
The present invention relates to a kind of preparation methods of alumina support, relate in particular to a kind of with large hole appearance, aperture
Alumina support preparation method.
Background technology
At present, in the production process of mink cell focus hydrodemetallization, since feedstock oil contains a certain amount of vanadium, sulphur, arsenic, nickel
Impurity are waited, easily form deposition, so as to the duct of blocking catalyst, catalyst activity are caused to decline or even inactivate rapidly, are influenced
Commercial Application.Hold with large hole and the catalyst of larger bore dia holds metal and appearance coke formation is strong, catalyst can be slowed down
The service cycle for inactivating, making catalyst extends.The pore structure of catalyst is determined by the carrier for forming catalyst, therefore, prepares tool
Large hole is held and the carrier of larger bore dia is to prepare residual oil, especially prepare and add for the higher decompression residuum of tenor
The key of hydrogen catalyst for demetalation.
CN1160602A disclose a kind of macropore alumina supporter for being suitable as Hydrodemetalation catalyst carrier and its
Preparation method.The preparation method of the macropore alumina supporter includes boehmite dry glue powder to be mixed with water or aqueous solution,
Plastic is kneaded into, obtained plastic is extruded into bar on banded extruder, drying simultaneously roasts to obtain product, its main feature is that,
It is additionally added carbon powder in above process as physics expanding agent and chemical action can occur with boehmite or aluminium oxide
The chemical enlargement agent of phosphorous, silicon or boron compound.Wherein carbon powder dosage is 3-10 weights %（On the basis of the weight of aluminium oxide）.
Alumina support obtained can be used for preparing mink cell focus particularly residuum hydrogenating and metal-eliminating and/or Hydrobon catalyst.
US4448896 is proposed using carbon black as expanding agent.Expanding agent is uniformly mixed with boehmite dry glue powder, to
The aqueous solution of nitric acid kneading 30 minutes that mass fraction is 4.3% is added in said mixture, it is 2.1% then to add in mass fraction
Ammonia spirit kneading 25 minutes, kneading uniformly after extruded moulding, carrier after molding it is fired be made final alumina support.Its
The addition of middle carbon powder is preferably greater than the 20% of activated alumina or its precursor weight.
CN102441436A discloses a kind of preparation method of alumina support.This method prepares the step of alumina support such as
Under：（1）Boehmite dry glue powder and extrusion aid are uniformly mixed, and are then added in and have been dissolved physics expanding agent and chemical enlargement agent
Aqueous solution；（2）By step（1）Resulting material is uniformly mixed, the extruded moulding on banded extruder；（3）By step（2）Resulting material is done
Final alumina support is made in dry, roasting.
In conclusion usually using physics expanding agent and chemical enlargement during prior art preparation macropore alumina supporter
Agent improves the aperture of carrier, and the addition of expanding agent can increase really alumina support macropore content.But in alumina support
Forming process, need to be by kneadings such as boehmite dry glue powder, extrusion aid, peptizing agents into plastic, then extruded moulding, due to squeezing
The presence of pressure process can make the macropore of alumina support itself that part occur to cave in, so as to hold the hole of final carrier and big
Hole content substantially reduces.In addition, the pore structure radial distribution of the alumina support of prior art preparation is substantially coincident, that is, carry
Body surface face has identical pore structure with inside, and the carrier with identical pore structure is generally believed that it is a kind of finger of excellent carrier
One of mark is advantageous really for largely catalysis reaction.But during weight, residuum hydrogenating and metal-eliminating, Ni,
The metals such as V are deposited on a catalyst in the form of sulfide, and the external duct of these deposit blocking catalysts causes to be catalyzed
Agent inactivates.
Invention content
For existing technical deficiency, the present invention provides a kind of preparation method of macropore alumina supporter, prepared by this method
Macropore alumina supporter there is large hole to hold and aperture, macropore in alumina support radially in uneven distribution, carrier surface
Macropore content is relatively high, and internal macropore content is relatively low, which is suitable for preparing weight, residuum hydrogenating and metal-eliminating catalyst
The fields of grade.
A kind of preparation method of alumina support, including following process：
（1）A certain amount of boehmite dry glue powder is weighed, in right amount containing the leaching of the aqueous solution of polyalcohol and/or glucide
The above-mentioned boehmite dry glue powder of stain；
（2）By step（1）Resulting material carries out hydro-thermal charing process；
（3）By step（2）Material extruding, the mixing of dried carrier unsaturation spray impregnation of phosphoric acid and ammonium oxalate
The mass ratio of solution, phosphoric acid and ammonium oxalate is 3:1-7:1, the mass concentration of ammonium ion is 0.6%-1.2% in mixed solution, every time
Unsaturation spray impregnation increment is not higher than step（1）The 80% of dried carrier water absorption, the carrier after dipping are sealed heating
Processing, processing pressure are self-generated pressure, and treatment temperature is 120-160 DEG C, and processing time is 6-12 hours, and treated, and carrier passes through
Alumina support is made in dry, roasting.
The method of the present invention step（1）Described in polyalcohol be one in xylitol, sorbierite, mannitol or arabite
Kind is several；The carbohydrate is one or more of glucose, ribose or fructose etc. mixing, polyalcohol and/or carbohydrate object
The mass concentration of matter is 20%-40%.The dosage of polyalcohol and/or glucide is to be totally submerged boehmite dry glue powder,
Dip time is 3-5 hours.
The method of the present invention step（2）Described in hydro-thermal charing process be the heat treatment carried out in sealing device, preferably
Autoclave can be dynamic response kettle or static reaction kettle, preferably static reaction kettle；The heat treatment temperature is 120-
160 DEG C, processing time is 8-16 hours.
The method of the present invention step（3）The mass ratio of phosphoric acid and ammonium oxalate is 4:1-5:1, the quality of ammonium ion in mixed solution
A concentration of 0.8%-1.0%, unsaturated spray impregnation increment is not higher than step every time（1）The 70% of dried carrier water absorption, dipping
Carrier afterwards is sealed heat treatment, and treatment temperature is 130-150 DEG C, and processing time is 8-10 hours.
The method of the present invention step（3）In add in suitable methanol in the forward direction system of heated sealed processing, methanol plus
Enter amount for step（1）The 15wt%-30 wt% of middle boehmite dry glue powder weight.During subsequent heated sealed, methanol
Steam, to being handled under mixed atmosphere carrier, is enhanced inside and outside carrier with the mixed gases volatilized after carrier calcination
Nature difference.
The method of the present invention step（3）Described in unsaturated spray be carried out in two steps.For the first time during unsaturated spray dipping
The dosage of mixed solution is step（1）The 50%-80% of middle boehmite dry glue powder water absorption, preferably 60%-70%.For the second time not
The dosage of mixed solution is step during saturation spray dipping（1）The 20%-50% of middle boehmite dry glue powder water absorption, preferably
30%-40%。
It is shaped to shown in the method for the present invention by the boehmite after charing and suitable sesbania powder, aqueous citric acid solution
The uniform extruded moulding of kneading.
Drying process described in the method for the present invention is 1-10 hours dry generally at 60 DEG C -130 DEG C.The roasting
Process is to be roasted 2-4 hours at 600 DEG C -750 DEG C.
The method of the present invention prepares alumina support and specifically has the following advantages：
（1）The present invention is done first with the solution saturation dipping boehmite containing polyalcohol and/or glucide
Rubber powder, then hydro-thermal charing process during extruded moulding, due to the presence of charcoal particle, can play good support
Effect, effectively prevents caving in for boehmite macropore, improves the Kong Rong of carrier；
（2）In the prior art, technical staff does one's utmost to pursue materialization inside and outside aluminium oxide during alumina support is prepared
Property it is consistent.For the pore structure of aluminium oxide, researcher wishes the Kong Rong of aluminium oxide, aperture inside and outside aluminium oxide in equal
Even distribution.Therefore expanding agent is added in by way of kneading in the preparation process of aluminium oxide.With identical physico-chemical property
Aluminium oxide is considered as a kind of important indicator of excellent carrier, facts proved that being strictly advantageous for largely catalysis reaction
's.But the result of study of inventor shows in the preparation process of residual oil catalyst for demetalation, using suitable solution insatiable hunger
With spray oxide impregnation aluminium, uneven modification is carried out to alumina support, to carrying alumina inside and outside physico-chemical property such as Kong Rong, hole
Diameter carries out differential modification, can significantly improve the activity stability of residuum hydrogenating and metal-eliminating catalyst.
Specific embodiment
The effect of method and effect are further illustrated the present invention with reference to embodiment, but is not limited to following implementation
Example.
Example 1
Weigh 100g boehmite dry glue powders（Wenzhou essence crystal alumina Co., Ltd produces, water absorption rate 1.2ml/g）
It is placed in beaker, the xylose alcohol solution that 200mL mass concentrations are 25% is added in into beaker and is impregnated 4 hours.Material after dipping
Filtered, filter cake is transferred in autoclave in 140 DEG C of encapsulation process 10 hours.Treated material is through dry with 5g sesbanias
Powder, appropriate mass concentration be 5% aqueous citric acid solution kneading uniformly, extruded moulding.Strip wet feed after molding is through at 120 DEG C
It is 8 hours dry.Dried carrier is put into spray rolling pot, under rotary state, with carrier of the atomizing type into rolling pot not
Saturation uniformly sprays 80ml containing 1.6 grams of ammonium oxalate, and the solution that 8 grams of phosphoric acid sprays above-mentioned carrier（The matter of ammonium ion in solution
Measure a concentration of 0.6%, the mass ratio of phosphoric acid and ammonium oxalate is 5:1）.Carrier after spraying is placed in autoclave to be added for 130 DEG C in sealing
Then heat 8 hours dries carrier 5 hours in 80 DEG C.Dried carrier continues to be put into spray rolling pot, in rotary state
Under, above-mentioned solution 40ml is uniformly sprayed with carrier of the atomizing type into rolling pot.Carrier after spraying is placed in autoclave in 140
Then DEG C heated sealed 10 hours dries carrier 5 hours in 80 DEG C.It is small that dried carrier roasts 4 at a temperature of 650 DEG C
When alumina support A1 is made.
Example 2
With example 1, the mass ratio for being 40% with mass concentration when only impregnating is 1:The mixing of 1 sorbierite and mannitol
Aqueous solution impregnates 3 hours.The temperature of charing process is 130 DEG C of encapsulation process 14 hours.When spraying phosphoric acid with ammonium oxalate solution, the
Primary spray dipping is with 50ml containing 1.5 grams of ammonium oxalate, the solution unsaturation spray dipping of 10.5 grams of phosphoric acid（In solution ammonium root from
The mass concentration of son is 0.9%, and the mass ratio of phosphoric acid and ammonium oxalate is 7:1）, the temperature of sealing heat treatment for the first time is 120 DEG C,
Processing time is 10 hours, second of spray dipping above-mentioned solution unsaturation spray dippings of 30ml.Second of sealing heat treatment
Temperature for 150 DEG C, processing time is 6 hours, and alumina support A2 of the present invention is made.
Example 3
With example 1, the mass ratio for being 30% with mass concentration when only impregnating is 1:1 glucose and the mixing water of ribose
Solution impregnates 5 hours.The temperature of charing process is 120 DEG C of encapsulation process 16 hours.When spraying phosphoric acid with ammonium oxalate solution, first
Secondary unsaturated spray dipping is with 60ml containing 2.4 grams of ammonium oxalate, the solution unsaturation spray dipping of 7.2 grams of phosphoric acid（Ammonium in solution
The mass concentration of radical ion is 1.2%, and the mass ratio of phosphoric acid and ammonium oxalate is 3:1）, the temperature of sealing heat treatment for the first time is 160
DEG C, processing time is 6 hours, second of spray dipping above-mentioned solution unsaturation spray dippings of 20ml.At second of sealing heat
The temperature of reason is 130 DEG C, and processing time is 12 hours, and alumina support A3 of the present invention is made.
Example 4
With example 1, the mass ratio for being 20% with mass concentration when only impregnating is 1:1 arabite and fructose it is mixed
Heshui solution impregnates 4 hours.The temperature of charing process is 150 DEG C of encapsulation process 12 hours.When spraying phosphoric acid with ammonium oxalate solution,
For spray dipping with 70ml containing 1.9 grams of ammonium oxalate, the solution unsaturation of 7.6 grams of phosphoric acid sprays dipping for the first time（Ammonium root in solution
The mass concentration of ion is 0.8%, and the mass ratio of phosphoric acid and ammonium oxalate is 4:1）, during heat treatment, 15 grams of first are added in autoclave
During heat treatment, 20 grams of methanol are added in autoclave for alcohol, second spray dipping 50ml above-mentioned solution unsaturation spray dippings,
Alumina support A4 of the present invention is made.
Example 5
With example 1, the sorbitol aqueous solution that mass concentration is 35% when only impregnating impregnates 5 hours.The temperature of charing process
It spends for 160 DEG C of encapsulation process 8 hours, when spray phosphoric acid is with ammonium oxalate solution, spray dipping contains ammonium oxalate 2.7 with 75ml for the first time
Gram, the solution unsaturation spray dipping of 16.2 grams of phosphoric acid（The mass concentration of ammonium ion is 1.1% in solution, phosphoric acid and oxalic acid
The mass ratio of ammonium is 6:1）, during heat treatment, add in 30 grams of methanol in autoclave, second of spray dipping with the above-mentioned solution of 40ml not
Saturation spray dipping, during heat treatment, adds in 25 grams of methanol, alumina support A5 of the present invention is made in autoclave.
Comparative example 1
With example 1, only the polyalcohol of phase homogenous quantities and/or glucide are added when carrier is molded in a manner of kneading
Enter into carrier and comparative example alumina support A6 is made.
Comparative example 2
With example 1, comparative example carrying alumina is made in the only unused processing containing the material impregnation of polyalcohol and/or carbohydrate of carrier
Body A7.
Comparative example 3
With example 1, comparative example alumina support A8 is made without hydro-thermal charing process in the boehmite after only impregnating.
Comparative example 4
With example 1, the side for only impregnating the phosphoric acid of phase homogenous quantities and ammonium oxalate with isometric saturation after carrier molding
Formula, which once sprays, is made comparative example alumina support A9 in alumina support.
Example 6
This example prepares Hydrodemetalation catalyst C1-C9 using aluminium oxide obtained by examples detailed above and comparative example as carrier, has
Body process is as follows：100 grams of aluminium oxide obtained by weighing examples detailed above and comparative example, uses 150mlMoO3Content is 9.5g/100ml（Molybdenum
Source comes from ammonium molybdate）, NiO contents are 1.2g/100ml（Nickel source comes from nickel chloride）Active metal maceration extract impregnate 5 hours, leaching
Material after stain is filtered, 110 DEG C dry 5 hours, dried material, which roast to be made for 4 hours at a temperature of 650 DEG C, adds hydrogen
Catalyst for demetalation.
Embodiment 7
The present embodiment carries out activity rating, more each catalyst activity to the Hydrodemetalation catalyst of above-mentioned preparation.It is former
Material oil nature and evaluation process conditions are shown in Tables 1 and 2, and the Activity evaluation for operating 200h is shown in Table 3.
Table 1
Table 2
Table 3
| Project | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 |
| It is de-（Nickel+vanadium）Rate, % | 81 | 80 | 79 | 85 | 86 | 55 | 57 | 61 | 63 |
Hydrodemetalation catalyst using the aluminium oxide for preparing of the present invention as carrier it can be seen from 3 data of table have compared with
High hydrodemetallization activity.
Activity rating is carried out to the catalyst obtained by above-described embodiment and comparative example, the Wen Sheng for running 5000h is shown in Table 4.
4 reaction temperature lift-off value of table
Find out from the result of table 4, after reacting 5000 hours, using aluminium oxide prepared by the present invention as the hydrodemetallization of carrier
Catalyst, in order to keep high demetallization per, required reaction temperature increase rate, which is far smaller than, compares what aluminium oxide was prepared for carrier
Hydrodemetalation catalyst, this illustrates that alumina support provided by the invention is suitble to due to heavy resid hydrodemetallization field.
Claims (10)
1. a kind of preparation method of alumina support, it is characterised in that：Including following process：
（1）A certain amount of boehmite dry glue powder is weighed, in right amount containing on the aqueous solution of polyalcohol and/or glucide dipping
State boehmite dry glue powder；
（2）By step（1）Resulting material carries out hydro-thermal charing process；
（3）By step（2）Material extruding, the mixing of dried carrier unsaturation spray impregnation of phosphoric acid and ammonium oxalate are molten
The mass ratio of liquid, phosphoric acid and ammonium oxalate is 3:1-7:1, the mass concentration of ammonium ion is 0.6%-1.2% in mixed solution, every time not
Saturation spray impregnation increment is not higher than step（1）The 80% of middle boehmite dry glue powder water absorption, the carrier after dipping are sealed
Heat treatment, processing pressure are self-generated pressure, and treatment temperature is 120-160 DEG C, and processing time is 6-12 hours, and treated carries
Alumina support is made through drying, roasting in body；
Wherein, step（3）Described in unsaturated spray dipping be carried out in two steps, mixed during unsaturated spray dipping for the first time molten
The dosage of liquid is step（1）The 50%-80% of middle boehmite dry glue powder water absorption, second of unsaturated spray mix when impregnating
The dosage of solution is step（1）The 20%-50% of middle boehmite dry glue powder water absorption.
2. according to the method described in claim 1, it is characterized in that：Step（1）Middle polyalcohol is xylitol, sorbierite, sweet dew
One or more of alcohol or arabite.
3. according to the method described in claim 1, it is characterized in that：Step（1）Middle carbohydrate is in glucose, ribose or fructose
It is one or more of.
4. according to the method described in claim 1, it is characterized in that：Step（1）The quality of middle polyalcohol and/or glucide is dense
It spends for 20%-40%, the dosage of the aqueous solution of polyalcohol and/or glucide is soaked for boehmite dry glue powder is totally submerged
The stain time is 3-5 hours.
5. according to the method described in claim 1, it is characterized in that：Step（2）Middle hydro-thermal charing process is in sealing device
The heat treatment of progress, heat treatment temperature are 120-160 DEG C, and processing time is 8-16 hours.
6. according to the method described in claim 1, it is characterized in that：Step（3）The mass ratio of middle phosphoric acid and ammonium oxalate is 4:1-
5:1, the mass concentration of ammonium ion is 0.8%-1.0% in mixed solution, and unsaturated spray impregnation increment is not higher than step every time（1）In
The 70% of boehmite dry glue powder water absorption, dipping post-processing temperature are 130-150 DEG C, and processing time is 8-10 hours.
7. according to the method described in claim 1, it is characterized in that：Step（3）In in the forward direction system of heated sealed processing
Suitable methanol is added in, the addition of methanol is step（1）The 15wt%-30 wt% of middle boehmite dry glue powder weight.
8. according to the method described in claim 1, it is characterized in that：The dosage of mixed solution when unsaturated spray impregnates for the first time
For step（1）The 60%-70% of middle boehmite dry glue powder water absorption, the use of mixed solution when second of unsaturated spray impregnates
It measures as step（1）The 30%-40% of middle boehmite dry glue powder water absorption.
9. according to the method described in claim 1, it is characterized in that：Step（3）In be shaped to the boehmite after charing
With suitable sesbania powder, the uniform extruded moulding of aqueous citric acid solution kneading.
10. according to the method described in claim 1, it is characterized in that：Step（3）Middle drying process is to be done at 60 DEG C -130 DEG C
1-10 hours dry, roasting process is to be roasted 2-4 hours at 600 DEG C -750 DEG C.
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| CN107983326B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst forming carrier |
| CN107983405B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN107983404B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Hydrogenation catalyst forming carrier |
| CN109718797B (en) * | 2017-10-27 | 2021-08-06 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN112718013A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation and application thereof |
| CN111617734B (en) * | 2020-05-27 | 2022-07-05 | 青岛华世洁环保科技有限公司 | Color-changeable amine deodorization material |
| CN111617735B (en) * | 2020-05-27 | 2022-07-05 | 青岛华世洁环保科技有限公司 | Amine odor removal material |
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| CN102441436A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102861619A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing alumina supporter with high specific surface area |
| CN102861615A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina carrier |
| CN103785479A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof |
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| JPH0295443A (en) * | 1988-09-30 | 1990-04-06 | Nippon Oil Co Ltd | Catalyst for hydrogenation treatment of residual oil |
| CN102441436A (en) * | 2010-10-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method for alumina carrier |
| CN102861619A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing alumina supporter with high specific surface area |
| CN102861615A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Preparation method of macroporous alumina carrier |
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