CN104907103A - Preparation method of spherical alumina carrier - Google Patents
Preparation method of spherical alumina carrier Download PDFInfo
- Publication number
- CN104907103A CN104907103A CN201410090695.7A CN201410090695A CN104907103A CN 104907103 A CN104907103 A CN 104907103A CN 201410090695 A CN201410090695 A CN 201410090695A CN 104907103 A CN104907103 A CN 104907103A
- Authority
- CN
- China
- Prior art keywords
- preparation
- wet cake
- spherical alumina
- alumina
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a preparation method of a spherical alumina carrier with low compost ratio and large pore volume. A Pt-Sn-K/Al2O3 catalyst prepared from the carrier is suitable for a light alkane dehydrogenation reaction. The preparation method comprises the following steps: preparing alumina sol A by a hydrochloric acid reflux method, preparing wet cake B by an aqueous ammonia precipitation method, mixing the alumina sol A and the wet cake B to prepare mixed alumina sol, mixing the mixed alumina sol with a hexamethylenetetramine solution, carrying out oil-column shaping, aging, drying and roasting to prepare the spherical alumina carrier. The prepared spherical alumina carrier prepared by the preparation method has physical chemical characteristics of low compost ratio, large pore volume, high strength and proper specific surface area, and meets carrier requirements of a light alkane dehydrogenation catalyst. In comparison with a catalyst prepared from an alumina carrier prepared by a conventional method, a catalyst prepared from the spherical alumina carrier prepared by the above method has more excellent light alkane dehydrogenation activity and stability.
Description
Technical field
The present invention relates to a kind of low heap than the preparation method of, large pore volume spherical alumina support and application, the Pt-Sn-K/Al prepared with this carrier
2o
3catalyst is applicable to dehydrogenating low-carbon alkane reaction.
Background technology
Low-carbon alkanes catalytic cracking alkene is the hot subject of petrochemical industry always, and wherein the corresponding alkene of dehydrogenating low-carbon alkane system has become one of emphasis of petrochemical technology research and development.C
3-C
4alkene does not have natural origin, and resource is seriously deficient, mainly from the accessory substance of naphtha steam cracking device and fluidized catalytic cracker.Along with C
3-C
4the exploitation of olefin downstream product, its output cannot meet people's demand growing to it.The main path of low-carbon alkene source growth has been become at present by the corresponding alkene of dehydrogenating low-carbon alkane system.Pt-Sn/Al
2o
3dehydrogenation has been successfully applied in dehydrogenating low-carbon alkane industrial process.The ball-aluminium oxide that this catalyst adopts oil-drop method to prepare mostly is carrier.The process route that oil-drop method prepares spherical alumina support mainly contains: 1. make Alumina gel with hydrochloric acid digestion metallic aluminium, obtain spherical alumina support through forming oil column.The spherical alumina support intensity that this technique obtains is higher.2. aluminium salt or aluminate forming oil column after precipitation, peptization obtains spherical alumina support.The spherical alumina support steady quality that this technique obtains, cost are lower.3. aluminium alcoholates salt forming oil column after hydrolysis, condensation obtains spherical alumina support.This technique is seldom used in industrial processes because cost is higher.United States Patent (USP) 2620314 discloses makes Alumina gel with hydrochloric acid digestion metallic aluminium, and, washing aging through forming oil column, high pressure, drying, roasting, steam reaming obtain the method for ball-aluminium oxide.Chinese patent 92109379.9 discloses with aluminium salt or aluminate for raw material makes Alumina gel through neutralization, acidification, then through forming oil column, aging, washing, the method that dry, roasting obtains ball-aluminium oxide.But very fast, the less stable of catalyst inactivation in dehydrogenating low-carbon alkane application process of preparing of obtained alumina support, therefore researches and develops novel oxidized alumina supporter preparation method and has very important significance in dehydrogenating low-carbon alkane industrial process in conventional manner.
Summary of the invention
The object of this invention is to provide a kind of preparation method and application of spherical alumina support.
The present invention adopts hydrochloric acid reflux legal system to prepare wet cake B for Alumina gel A and ammonia water precipitating respectively, then Alumina gel A and wet cake B are mixed obtained aluminum mixture colloidal sol, then obtain spherical alumina support through forming oil column, aging, dry, roasting after mixing with hexamethylenetetramine solution.
Concrete steps comprise:
(1) purity is greater than the aluminium foil of 99.9% to mix by Al/Cl mol ratio 1 ~ 3 with the hydrochloric acid of mass fraction 5 ~ 25%, reacts under 85 ~ 100 DEG C of conditions and dissolve completely to aluminium foil, obtain Alumina gel A;
(2) mixed than 0.5 ~ 1 by liquor capacity by the ammoniacal liquor of the aluminum trichloride solution of mass concentration 25 ~ 50g/L with mass fraction 5 ~ 15%, reacting to pH under 65 ~ 85 DEG C of conditions is 7.5 ~ 9, obtains wet cake B.
(3) wet cake B and Alumina gel A is pressed B/A mass ratio 0.5 ~ 4 to mix, be stirred well to the complete peptization of wet cake B, obtain aluminum mixture colloidal sol.
(4) above-mentioned aluminum mixture colloidal sol being mixed with the hexamethylenetetramine solution of mass fraction 25 ~ 45%, being instilled balling-up in 80 ~ 120 DEG C of oils column with dripping ball device.Wherein hexamethylenetetramine adds by 10 ~ 60wt.% of alumina content.
(5) from oil column, isolate bead and be transferred to aging still, aging 6 ~ 20h under 100 ~ 180 DEG C of conditions.Again through 100 ~ 150 DEG C of drying 2 ~ 8h, 500 ~ 800 DEG C of roasting 4 ~ 12h, obtain spherical alumina support.
The present invention obtains catalyst for dehydrogenation of low-carbon paraffin prepared by spherical alumina support and consists of: Pt0.3 ~ 0.6wt.%, Sn0.3 ~ 3.0wt.%, K0.3 ~ 1.5wt.%, all the other are Al
2o
3.
The preparation method of catalyst of the present invention comprises:
(1) alumina support is placed in vacuum impregnation device, carries out vacuumizing process;
(2) by chloroplatinic acid, stannous chloride, Klorvess Liquid Homogeneous phase mixing, maceration extract is made;
(3) alumina support be impregnated in above-mentioned maceration extract, after 120 DEG C of dryings, 650 DEG C of roastings and hydrogen reducing, obtain catalyst for dehydrogenation of low-carbon paraffin.
Spherical alumina support of the present invention has the feature of low heap ratio, large pore volume; Obtain catalyst prepared by alumina support with conventional method to compare, the present invention obtains catalyst prepared by spherical alumina support and has the active and stability of more excellent dehydrogenating low-carbon alkane.
Accompanying drawing explanation
Fig. 1 is catalyst for dehydrogenation of low-carbon paraffin reactivity and the graph of a relation of time of preparation in the embodiment of the present invention 4 and embodiment 5.
Detailed description of the invention
The present invention is described in detail below by embodiment and accompanying drawing.
Embodiment 1
Take the aluminium foil of 30g purity 99.9wt% in the hydrochloric acid solution of 250g mass fraction 10%, make it dissolve completely under 95 DEG C of conditions, obtain Alumina gel A.
Take the above-mentioned Alumina gel A of 50g, add the hexamethylenetetramine solution of 16.5g mass fraction 40%, (it consists of: C to mix rear instillation 100 DEG C of mineral oil
1011.75wt.%, C
1129.45wt.%, C
1232.34wt.%, C
1326.36wt.%, C
140.10wt.%) balling-up in oil column.After 4h, bead is moved to aging still 140 DEG C of aging 8h, then obtain hydrochloric acid reflux method spherical alumina support after 120 DEG C of dry 4h, 750 DEG C of roasting 12h.
Embodiment 2
Taking the aluminum trichloride solution of 1L mass concentration 40g/L, by being 8 to pH in the ammoniacal liquor of mass fraction 10% instillation aluminum trichloride solution under 85 DEG C of conditions, after suction filtration, obtaining wet cake B.
Take the above-mentioned wet cake B of 50g, add Alumina gel A obtained in 50g embodiment 1, be stirred well to the complete peptization of wet cake B, obtain aluminum mixture colloidal sol.
Added in above-mentioned aluminum mixture colloidal sol by the hexamethylenetetramine solution of 22.5g mass fraction 40%, (it consists of: C to mix rear instillation 100 DEG C of mineral oil
1011.75wt.%, C
1129.45wt.%, C
1232.34wt.%, C
1326.36wt.%, C
140.10wt.%) balling-up in oil column.After 4h, bead is moved to aging still 140 DEG C of aging 8h, then obtain mixing method spherical alumina support after 120 DEG C of dry 4h, 750 DEG C of roasting 12h.
The physico-chemical property of this spherical alumina support is: particle diameter 1.5 ~ 2.5mm, bulk density 0.40g/mL, crushing strength 50N/ grain, specific area 164.5m
2/ g, pore volume 1.18cm
3/ g, average pore size 24.5nm.
Embodiment 3
Carry out forming oil column using kerosene as shaping oil, concrete steps are with embodiment 2.
The physico-chemical property of this spherical alumina support is: particle diameter 1.5 ~ 2.5mm, bulk density 0.60g/mL, crushing strength 20N/ grain, specific area 155.0m
2/ g, pore volume 0.55cm
3/ g, average pore size 14.5nm.
In comparative example 2 and embodiment 3, the physico-chemical property of obtained spherical alumina support is known, and the spherical alumina support of preparation in embodiment 2 has the character of lower bulk density, more large pore volume aperture and more high crush strength compared with embodiment 3.
Embodiment 4
Alumina support 10mL obtained in Example 1 is in vacuum impregnation device.After vacuumizing process, the stannous chloride of the chloroplatinic acid of 0.75mL mass concentration 0.02g/mL, 0.75mL mass concentration 0.06g/mL, the potassium chloride mixed solution of 0.75mL mass concentration 0.02g/mL be impregnated on alumina support.Obtained Pt-Sn-K/Al after 120 DEG C of dry 2h, 650 DEG C of roasting 8h and hydrogen reducing 2h
2o
3catalyst Cat-A.
Embodiment 5
Alumina support 10mL obtained in Example 2, concrete steps, with embodiment 4, obtain Pt-Sn-K/Al
2o
3catalyst Cat-B.
Embodiment 6
Fixed bed reactors carry out the evaluation of dehydrogenating low-carbon alkane reactivity worth to catalyst Cat-A and Cat-B obtained in embodiment 4 and embodiment 5.The present embodiment adopts quartz tube type fixed bed reactors, and loaded catalyst is 1.0mL.Reaction evaluating condition is: reaction temperature 580 DEG C, C
4weight (hourly) space velocity (WHSV) 2h
-1, hydrogen-hydrocarbon ratio 1:1, normal pressure.In embodiment 4 and embodiment 5, the dehydrogenation reactivity worth evaluation result of preparation is shown in accompanying drawing.The stability of catalyst is with inactivation Parametric Representation, and in embodiment 4 and embodiment 5, the inactivation parametric results of the dehydrogenation of preparation lists in table 1.
As can be seen from accompanying drawing, after in embodiment 4 and embodiment 5, the low-carbon alkanes initial conversion of dehydrogenation Cat-A and Cat-B of preparation is respectively 53.50% and 54.72%, 168h, conversion ratio is down to 23.81% and 48.65% respectively.In 168h, the inactivation parameter of Cat-A and Cat-B catalyst is respectively 55.50% and 11.09% (table 1).As can be seen here, the dehydrogenating low-carbon alkane activity of the catalyst prepared in embodiment 5 and stability are significantly better than the catalyst of preparation in embodiment 4.
The inactivation parameter of the dehydrogenation of preparation in table 1 embodiment 4 and embodiment 5
The spherical alumina support prepared by the present invention has the physical chemical characteristics of low heap ratio, large pore volume, high strength and suitable specific area, meets the carrier media of catalyst for dehydrogenation of low-carbon paraffin.Obtain catalyst prepared by alumina support with conventional method to compare, the present invention obtains catalyst prepared by spherical alumina support and has the active and stability of more excellent dehydrogenating low-carbon alkane.
Claims (8)
1. a preparation method for spherical alumina support, is characterized in that:
Hydrochloric acid reflux legal system is adopted to prepare aluminium hydroxide wet cake B for Alumina gel A and ammonia water precipitating respectively, then Alumina gel A and wet cake B are mixed obtained aluminum mixture colloidal sol, more shaping in mineral oil, aging, dry after mixing with hexamethylenetetramine solution, roasting obtains spherical alumina support;
Wherein wet cake B and Alumina gel A presses B/A mass ratio 0.5 ~ 4 mixing; Wherein hexamethylenetetramine adds by 10 ~ 60wt.% of alumina content in aluminum mixture colloidal sol.
2., according to preparation method according to claim 1, it is characterized in that:
Hydrochloric acid reflux legal system is for Alumina gel A: the hydrochloric acid of the aluminium foil and mass fraction 5 ~ 25% that purity are more than or equal to 99.9wt.% mixes by Al/Cl mol ratio 1 ~ 3, reacts and dissolves completely to aluminium foil, obtain Alumina gel A under 85 ~ 100 DEG C of conditions.
3., according to preparation method according to claim 1, it is characterized in that:
Ammonia water precipitating prepares wet cake B: mixed than 0.5 ~ 1 by liquor capacity by the ammoniacal liquor of the aluminum trichloride solution of mass concentration 25 ~ 50g/L with mass fraction 5 ~ 15%, and reacting to pH under 65 ~ 85 DEG C of conditions is 7.5 ~ 9, obtains wet cake B after filtration.
4., according to preparation method according to claim 1, it is characterized in that:
Aluminum mixture colloidal sol being mixed with the hexamethylenetetramine solution of mass fraction 25 ~ 45%, being instilled 80 ~ 120 DEG C, preferably balling-up in 90 ~ 110 DEG C of mineral oil oils column with dripping ball device.
5. according to preparation method according to claim 1, it is characterized in that: wherein hexamethylenetetramine better adds by 30 ~ 50wt.% of alumina content.
6. according to the forming method described in claim 1 or 4, it is characterized in that: described mineral oil preferably C
10~ C
13mixing linear paraffin.
7., according to preparation method according to claim 1, it is characterized in that:
From mineral oil oil column, isolate bead and be transferred to aging still, aging 6 ~ 20h under 100 ~ 180 DEG C of conditions; Again through 100 ~ 150 DEG C of drying 2 ~ 8h, 500 ~ 800 DEG C of roasting 4 ~ 12h, obtain spherical alumina support.
8., according to the preparation method described in claim 1 or 7, it is characterized in that:
Obtained spherical alumina support is for the preparation of catalyst for dehydrogenation of low-carbon paraffin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410090695.7A CN104907103A (en) | 2014-03-12 | 2014-03-12 | Preparation method of spherical alumina carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410090695.7A CN104907103A (en) | 2014-03-12 | 2014-03-12 | Preparation method of spherical alumina carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104907103A true CN104907103A (en) | 2015-09-16 |
Family
ID=54076786
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410090695.7A Pending CN104907103A (en) | 2014-03-12 | 2014-03-12 | Preparation method of spherical alumina carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104907103A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014829A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | Phosphorous hydrated alumina composition and formed body and preparation method and catalyst and preparation method thereof |
| CN108295846A (en) * | 2018-02-11 | 2018-07-20 | 四川润和催化新材料股份有限公司 | A kind of alkane dehydrogenating catalyst and preparation method thereof |
| CN109569740A (en) * | 2018-12-29 | 2019-04-05 | 杨斌 | A kind of alumina support and preparation method and application |
| CN111151232A (en) * | 2018-11-08 | 2020-05-15 | 营口市向阳催化剂有限责任公司 | Preparation method of spherical alumina |
| CN113735614A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of spherical alumina |
| CN114602442A (en) * | 2022-03-28 | 2022-06-10 | 福州大学 | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed |
| CN115430423A (en) * | 2022-09-21 | 2022-12-06 | 北京化工大学 | Rare earth doped spherical alumina-based PtSn catalyst and preparation method and application thereof |
-
2014
- 2014-03-12 CN CN201410090695.7A patent/CN104907103A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 訾仲岳等: "氧化铝载体老化温度对长链烷烃脱氢催化剂性能的影响", 《工业催化》 * |
| 马群等: "球形氧化铝制备过程中影响因素的研究", 《无机盐工业》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108014829A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | Phosphorous hydrated alumina composition and formed body and preparation method and catalyst and preparation method thereof |
| CN108014829B (en) * | 2016-10-28 | 2020-07-28 | 中国石油化工股份有限公司 | Phosphorus-containing hydrated alumina composition, molded body and preparation method thereof, and catalyst and preparation method thereof |
| CN108295846A (en) * | 2018-02-11 | 2018-07-20 | 四川润和催化新材料股份有限公司 | A kind of alkane dehydrogenating catalyst and preparation method thereof |
| CN111151232A (en) * | 2018-11-08 | 2020-05-15 | 营口市向阳催化剂有限责任公司 | Preparation method of spherical alumina |
| CN109569740A (en) * | 2018-12-29 | 2019-04-05 | 杨斌 | A kind of alumina support and preparation method and application |
| CN113735614A (en) * | 2020-05-29 | 2021-12-03 | 中国石油化工股份有限公司 | Preparation method of spherical alumina |
| CN113735614B (en) * | 2020-05-29 | 2023-01-13 | 中国石油化工股份有限公司 | Preparation method of spherical alumina |
| CN114602442A (en) * | 2022-03-28 | 2022-06-10 | 福州大学 | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed |
| CN114602442B (en) * | 2022-03-28 | 2023-01-10 | 福州大学 | Preparation method of low-carbon alkane dehydrogenation catalyst for moving bed |
| CN115430423A (en) * | 2022-09-21 | 2022-12-06 | 北京化工大学 | Rare earth doped spherical alumina-based PtSn catalyst and preparation method and application thereof |
| CN115430423B (en) * | 2022-09-21 | 2024-03-29 | 北京化工大学 | Rare earth doped spherical alumina-based PtSn catalyst, and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104907103A (en) | Preparation method of spherical alumina carrier | |
| CN1130265C (en) | Catalyst capable of using on carrier in organic compound conversion reaction | |
| US10307737B2 (en) | Transition metal-noble metal complex oxide catalyst for dehydrogenation prepared by one-pot synthesis and use thereof | |
| CN105214657B (en) | A kind of catalyst for manufacturing olefin by low-carbon alkane dehydrogenation and preparation method thereof | |
| RU2329099C1 (en) | Highly active isomerisation catalyst and isomerisation method | |
| CN105268459B (en) | A kind of catalyst for dehydrogenation of low-carbon paraffin of sulfur-bearing and preparation method thereof | |
| JP6653715B2 (en) | Support for selectively synthesizing high-quality kerosene fraction from synthesis gas, its catalyst, and method for its preparation | |
| CN106582629B (en) | A kind of catalyst of preparing propylene by dehydrogenating propane and its preparation method and application | |
| CN108295846A (en) | A kind of alkane dehydrogenating catalyst and preparation method thereof | |
| CN109894122A (en) | A kind of FCC gasoline Hydrobon catalyst and preparation method thereof | |
| CN108250010A (en) | A kind of selection method of hydrotreating of methanol-to-olefins product | |
| CN104588008A (en) | Saturated alkane dehydrogenation catalyst and preparation method thereof | |
| CN101745407B (en) | Solid super acidic catalyst and preparation method thereof | |
| CN109420504A (en) | A kind of catalytic cracking gasoline hydrodesulfurization catalyst and preparation method | |
| CN108863706A (en) | A kind of selection method of hydrotreating of the C-4-fraction containing alkynes | |
| CN109395772A (en) | A kind of isomerization catalyst and its preparation method and application | |
| CN107537587A (en) | The processing method of catalyst | |
| CN108865243B (en) | Pre-hydrogenation treatment method of carbon tetra-alkylation raw material | |
| CN113289673B (en) | Isomerization catalyst and preparation method and application thereof | |
| CN102372548A (en) | Method for preparing low-carbon olefin through methanol dehydration | |
| CN109529811A (en) | Alumina support, salic carried catalyst preparation method and catalyst application | |
| JP2567260B2 (en) | Method for producing hydrotreating catalyst from hydrogel | |
| KR102478028B1 (en) | Transition Metal-Noble Metal Complex Oxide Catalysts Prepared by One-Pot for Dehydrogenation and Use Thereof | |
| CN1185325C (en) | Method for isomerization of hydrocarbon, andsolid acid catalyst and isomerization device for use therein | |
| TW201914688A (en) | Method for producing ethylene from ethanol raw material having a higher ethanol conversion rate and higher ethylene selectivity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150916 |