CN105521779A - Method for preparing low-carbon alkane dehydrogenation catalyst - Google Patents
Method for preparing low-carbon alkane dehydrogenation catalyst Download PDFInfo
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- CN105521779A CN105521779A CN201410563587.7A CN201410563587A CN105521779A CN 105521779 A CN105521779 A CN 105521779A CN 201410563587 A CN201410563587 A CN 201410563587A CN 105521779 A CN105521779 A CN 105521779A
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Abstract
The invention discloses a method for preparing a low-carbon alkane dehydrogenation catalyst. The method comprises the following steps: 1) dropping ammoniacal liquor into a ZnCl2 aqueous solution to obtain white Zn(OH)2 precipitate, fully stirring the precipitate and dissolving the precipitate, adding water for dilution to obtain a Zn(NH3)4Cl2 solution, adding a platinum-containing compound, fully stirring the material and heating the material to obtain an impregnation liquid; and 2) impregnating a carrier by the impregnation liquid obtained in the step 1), drying the carrier and calcining the carrier to obtain the low-carbon alkane dehydrogenation catalyst. Through a complexation co-impregnation method, Pt and Zn are loaded on the surface of the carrier, and the low-carbon alkane dehydrogenation catalyst with good dehydrogenation activity is prepared.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin.
Background technology
The exploitation of North America shale gas has caused Gas Prices declining to a great extent relative to crude oil price, and condensed liquids a large amount of in shale gas (NGLs) output also increases rapidly.Be rich in the low-carbon alkanes such as ethane, propane, butane in shale gas condensed liquid, ethane can produce ethene as cracking stock, therefore only can not the demand that increases fast of propylene by FCC technology.The effective way addressed this problem by the dehydrogenating low-carbon alkane preparing low-carbon olefins in natural gas (conventional gas, shale gas, coal bed gas, combustible ice etc.).And day by day deficient along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material sources from the simple oil that relies on, also becomes a kind of trend gradually.In recent years, the technology that dehydrogenating propane produces propylene achieved large development, and particularly the technical development of dehydrogenating propane (PDH) propylene processed is very fast, has become the third-largest propylene production.
At present, dehydrogenating low-carbon alkane technology mainly comprises: anaerobic dehydrogenation and the large class of aerobic dehydrogenation two.Again based on Pt system noble metal dehydrogenation technology and Cr system De-hydrogen Technology in anaerobic dehydrogenation technology.Anaerobic dehydrogenation technology main in the world comprises: the Oleflex technique of Uop Inc., the Catofin technique of ABB Lu Musi company, the Star technique of Kang Fei (Uhde) company, the FBD-4 technique of Snamprogetti/Yarsintz company, the PDH technique etc. of Lin De/BASF AG.The leading technology adopted in new device has wherein been become with Catofin and Oleflex technique.Catalyst used in Oleflex technique is Pt system noble metal catalyst, and catalyst used in Catafin technique is Cr system dehydrogenation.Aerobic De-hydrogen Technology there is no industrialization example.
In anaerobic dehydrogenation field, Pt is as the dehydrogenation active component of generally acknowledging, studied for many years by countries in the world, the selection of its co catalysis component is also studied widely.Sn is a kind of the most frequently used auxiliary agent be introduced in Pt system dehydrogenation catalyst systems, produces act synergistically in dehydrogenation reaction with Pt, improves the activity of Pt system dehydrogenation.Except Sn, the metals such as In, Zn, La, Ce, Fe, K, Ca are also often added in Pt system dehydrogenation.
CN97104462.7 discloses a kind of Pt system dehydrogenation.The aluminium oxide that this catalyst distributes with diplopore is for carrier, the aqueous solution of chloroplatinic acid, salt aqueous acid, the aqueous solution of stannous chloride, the aqueous solution of potassium chloride joined and make maceration extract in the aqueous solution of ethanol and carry out impregnated carrier, drying, roasting obtain catalyst.The open source literature report that this catalyst is relevant also comprises: " petroleum journal " the 1st volume the 3rd phase in 1980, " catalysis journal " the 8th volume the 4th phase in 1987, " catalysis journal " the 18th volume the 2nd phase, Chinese patent CN87101513A in 1997 etc.
" Ca is to PtSn/MgAl in " Journal of Molecular Catalysis " (1998, the 12nd volume, the 3rd phase)
2o
4the impact of structure and dehydrogenating propane performance " in disclose a kind of preparation method of dehydrogenation, by the ethanolic solution of chloroplatinic acid, stannous chloride and calcium nitrate dipping magnesia alumina spinel carrier, obtain dehydrogenation by super-dry, roasting.
CN92114525.X discloses a kind of preparation method of noble metal dehydrogenation catalyst, and chloroplatinic acid, stannous chloride, sodium chloride, hydrochloric acid, mixing of second alcohol and water are made maceration extract, and oxide impregnation alumina supporter makes Pt system dehydrogenation.
CN94104910.8 and CN94104914.0 also discloses a class and uses the metal promoter of organic coordination compound form to carry out the method for modulation noble metal dehydrogenation catalyst.This metal promoter is at least one in germanium, tin, lead, iron, titanium and chromium, and the organic coordination compound of this metal is carbonyl-complexes, many ketone complex and alkyl compound.But in such catalyst preparation process Pt and Sn be step load on carrier, not do not form complex form.
" Zn is to Pt-Sn/Al in " SCI " (2006, the 27th volume, the 8th phase)
2o
3the impact of the activated state of Sn and dehydrogenating propane reaction in catalyst " in disclose Pt-Sn/Al
2o
3catalyst adds Zn as the impact of auxiliary agent in dehydrogenating propane reaction.Research shows that the introducing of Zn can suppress Sn component to be reduced under the reducing conditions, and can improve conversion of propane and Propylene Selectivity.In this article Zn be with by carrier at Zn (NO
3)
26H
2flood in the aqueous solution of O, be carried on carrier by mode that is dry, roasting, and then total immersion stain supporting Pt and Sn component.
CN200610150591.6 discloses the preparation method of a kind of Pt system dehydrogenation, and the ethanolic solution of the mixing containing cerium or zinc and tin and carrier are carried out incipient impregnation by the method, by dry, roasting.By above-mentioned product dip loading active component Pt, obtain final catalyst by dry, roasting.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin, by complexing total immersion method, Pt and Zn is carried on carrier surface, prepare a kind of catalyst for dehydrogenation of low-carbon paraffin with good dehydrogenation activity.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, comprises following content:
(1) ammoniacal liquor is dropwise added to ZnCl
2in the aqueous solution, obtain white Zn (OH)
2precipitation, dropwises, and fully stirs and precipitation is dissolved, be diluted with water, obtain Zn (NH
3)
4cl
2solution, then add containing platinum compounds, at 50 ~ 70 DEG C of temperature, preferably 55 ~ 60 DEG C, fully stir, make maceration extract;
(2) with the impregnation fluid carrier that step (1) obtains, dry, roasting, obtains catalyst for dehydrogenation of low-carbon paraffin.
In the inventive method, ZnCl
2the mass concentration of the aqueous solution is 1% ~ 30%, preferably 5% ~ 20%; The mass concentration of ammoniacal liquor is 1% ~ 25%, preferably 5% ~ 20%.
In the inventive method, Zn in described maceration extract
2+with NH
4 +mol ratio be 1:4 ~ 1:5.
In the inventive method, Zn in described maceration extract
2+mass concentration be 0.0005g/ml ~ 0.03g/ml, preferred 0.001g/ml ~ 0.02g/ml.
In the inventive method, described Zn (NH
3)
4cl
2the volume of solution and the volume ratio of carrier to be impregnated are 1:1 ~ 3:1.
In the inventive method, described is chloroplatinic acid or CDCP containing platinum compounds, and preferred CDCP, in maceration extract, the mass concentration of Pt is 0.0001g/ml ~ 0.02g/ml, preferred 0.0002g/ml ~ 0.015g/ml.
In the inventive method, described carrier is the γ-Al containing Sn
2o
3for carrier, namely introduce the material containing Sn when aluminium oxide plastic, then make carrier, concrete grammar is known for the skilled in the art; Wherein carrier can be spherical, bar shaped, the suitable shape such as microballoon or abnormity, and particle equivalent diameter is generally 0.2 ~ 4mm, and preferred particle size is 0.5 ~ 2mm.
In the inventive method, described dip time is 1 ~ 20 hour, preferably 3 ~ 10 hours; Drying condition is 100 ~ 130 DEG C, 10 ~ 24 hours drying times; Sintering temperature is 450 ~ 550 DEG C, preferably 480 DEG C ~ 520 DEG C; Roasting time is 3 ~ 12 hours, preferably 4 ~ 6 hours.
Catalyst for dehydrogenation of low-carbon paraffin prepared by the inventive method, with the γ-Al of skeleton containing Sn
2o
3for carrier, Pt is dehydrogenation active component, and Zn is co catalysis component, accounts for the mass percentage of carrier in metal simple-substance: Sn is 0.1% ~ 5%, Pt be 0.1% ~ 2%, Zn is 0.5% ~ 4%.
In the inventive method, in the process of preparation maceration extract, first Zn forms complex with the amino molecule in solution and chlorion, then add under the condition of heating water bath containing Pt compound, it is the complex of part that Pt and Zn is formed jointly with ammonia, support on carrier by the mode of dipping, roasting again, form the cluster of Pt and Zn close to each other at carrier surface.In dehydrating alkanes reaction, this Pt-Zn cluster close to each other produces concerted catalysis effect, has more excellent alkane conversion and olefine selective.
Detailed description of the invention
Describe technical scheme of the present invention in detail below in conjunction with embodiment, but the invention is not restricted to following examples.
embodiment 1
Preparation is containing the γ-Al of Sn
2o
3carrier: after the aluminum trichloride solution of a certain amount of 0.98M and the mixing of 0.01M butter of tin solution, add a certain amount of 8% ammoniacal liquor, mix in neutralizing tank at 60 ~ 80 DEG C, control ph 7.0 ~ 9.0, filter, washing, after acidifying, balling-up of pressurizeing in oil ammonia column, through super-dry, aging, 650 ~ 750 DEG C of roastings 4 hours, obtain the ball-type aluminium oxide containing Sn1.5wt% that particle diameter is 1.5mm.
Preparation maceration extract: by 1.08gZnCl
2be dissolved in 20ml deionized water, and drip the ammoniacal liquor 6ml that mass concentration is 25% wherein, dropwise rear abundant stirring, the white precipitate of generation is dissolved completely.Add deionized water and be diluted to 100ml.Taking 0.2g CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.
Measure 50ml contain the ball-type alumina support of 1.5wt%Sn and claim its quality to be about 26g.Be placed in Rotary Evaporators, vacuumize 30min.Sucked by maceration extract in Rotary Evaporators, close vavuum pump, keep bath temperature to be 60 DEG C, normal pressure floods 6 hours.
Then bath temperature is risen to 80 DEG C, catalyst vacuum is drained in rear immigration beaker, be placed in dry 15 hours of the baking oven of 110 DEG C.Then catalyst is moved in Muffle furnace, 500 DEG C of roastings 5 hours.In this catalyst, each metal simple-substance accounts for the percentage by weight of carrier and is: Pt0.5wt%, Sn1.5wt%, Zn2wt%.This catalyst is denoted as A.
comparative example 1
The Pt system dehydrogenation that the method preparation disclosed according to patent CN200910011770.5 is carrier with the aluminium oxide containing Sn, then with the solution impregnating catalyst containing zinc nitrate, then obtains final catalyst through super-dry, roasting.Drying, roasting condition are with embodiment 1.In this catalyst, each metal simple-substance accounts for the percentage by weight of carrier and is: Pt0.5wt%, Sn1.5wt%, Zn2wt%.This catalyst is denoted as B1.
comparative example 2
According to the method Kaolinite Preparation of Catalyst that patent CN200610150591.6 discloses.In this catalyst, each metal simple-substance accounts for the percentage by weight of carrier and is: Pt0.5wt%, Sn1.5wt%, Zn2wt%.This catalyst is denoted as B2.
embodiment 2
The preparation of catalyst carrier is with embodiment 1.
Preparation maceration extract: by the ZnCl of 3.38g
2be dissolved in 20ml deionized water, and drip the ammoniacal liquor 31ml that mass concentration is 15% wherein, dropwise rear abundant stirring, the white precipitate of generation is dissolved completely.Add deionized water and be diluted to 150ml.Taking 0.58g CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.
Measure 100ml contain the ball-type alumina support of 1.5wt%Sn and claim its quality to be about 54g.Be placed in Rotary Evaporators, vacuumize 30min.Sucked by maceration extract in Rotary Evaporators, close vavuum pump, keep bath temperature to be 70 DEG C, normal pressure floods 6 hours.
Then bath temperature is risen to 80 DEG C, catalyst vacuum is drained in rear immigration beaker, be placed in dry 10 hours of the baking oven of 120 DEG C.Then catalyst is moved in Muffle furnace, 510 DEG C of roastings 5 hours.In this catalyst, each metal simple-substance accounts for the percentage by weight of carrier and is: Pt0.7wt%, Sn1.5wt%, Zn3wt%.This catalyst is denoted as C.
embodiment 3
The preparation of catalyst carrier is with embodiment 1.
Preparation maceration extract: by the ZnCl of 4.5g
2be dissolved in 25ml deionized water, and drip the ammoniacal liquor 28ml that mass concentration is 20% wherein, dropwise rear abundant stirring, the white precipitate of generation is dissolved completely.Add deionized water and be diluted to 200ml.Taking 1g CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.
Measure 100ml contain the ball-type alumina support of 3wt%Sn and claim its quality to be about 54g.Be placed in Rotary Evaporators, vacuumize 30min.Sucked by maceration extract in Rotary Evaporators, close vavuum pump, keep bath temperature to be 70 DEG C, normal pressure floods 6 hours.
Then bath temperature is risen to 80 DEG C, catalyst vacuum is drained in rear immigration beaker, be placed in dry 10 hours of the baking oven of 120 DEG C.Then catalyst is moved in Muffle furnace, 500 DEG C of roastings 5 hours.In this catalyst, each metal simple-substance accounts for the percentage by weight of carrier and is: Pt1.2wt%, Sn3wt%, Zn4wt%.This catalyst is denoted as D.
embodiment 4
Get catalyst prepared by above embodiment and comparative example and carry out conventional hydrothermal dechlorination, and carry out dehydrogenating propane evaluation experimental in micro-reactor.
Hydro-thermal dechlorination condition: in fixed bed hydro-thermal dechlorination reaction device, passes through beds 5 hours with 100% steam at 540 DEG C.Water inlet air speed is 1h
-1.
The activation condition of catalyst: with the hydrogen of 100%, 500 DEG C of constant temperature 2 hours.The volume space velocity of reducing gases is 3000h
-1.
The passivating conditions of catalyst: the mass velocity 1200h of the mixed gas of hydrogen sulfide and nitrogen
-1, volume ratio is 1:5, temperature 500 DEG C, passivation time 1 hour.
Appreciation condition: catalyst volume 6.0ml, volume space velocity is 1000h
-1, reaction pressure normal pressure, reaction temperature is 600 DEG C, hydrogen: the volume ratio of propane is 1:1.Initial and the propane one way molar yield of 30 hours of catalyst and Propylene Selectivity list in table 1.
Table 1 embodiment and comparative example evaluating catalyst result.
From reaction result, adopt the Pt-Sn-Zn/ γ-Al that complexing total immersion legal system is standby
2o
3dehydrogenation has better dehydrogenation activity and olefine selective.
Claims (10)
1. a preparation method for catalyst for dehydrogenation of low-carbon paraffin, is characterized in that comprising following content: ammoniacal liquor is dropwise added to ZnCl by (1)
2in the aqueous solution, obtain white Zn (OH)
2precipitation, dropwises, and fully stirs and precipitation is dissolved, be diluted with water, obtain Zn (NH
3)
4cl
2solution, then add containing platinum compounds, at 50 ~ 70 DEG C of temperature, fully stir, make maceration extract; (2) with the impregnation fluid carrier that step (1) obtains, dry, roasting, obtains catalyst for dehydrogenation of low-carbon paraffin.
2. in accordance with the method for claim 1, it is characterized in that: ZnCl
2the mass concentration of the aqueous solution is 1% ~ 30%, and the mass concentration of ammoniacal liquor is 1% ~ 25%.
3. in accordance with the method for claim 1, it is characterized in that: Zn in described maceration extract
2+with NH
4 +mol ratio be 1:4 ~ 1:5.
4. in accordance with the method for claim 1, it is characterized in that: Zn in described maceration extract
2+mass concentration be 0.0005g/ml ~ 0.03g/ml.
5. in accordance with the method for claim 1, it is characterized in that: described Zn (NH
3)
4cl
2the volume of solution and the volume ratio of carrier to be impregnated are 1:1 ~ 3:1.
6. in accordance with the method for claim 1, it is characterized in that: described is chloroplatinic acid or CDCP containing platinum compounds, and in maceration extract, the mass concentration of Pt is 0.0001g/ml ~ 0.02g/ml.
7. in accordance with the method for claim 1, it is characterized in that: described carrier is the γ-Al containing Sn
2o
3for carrier.
8. in accordance with the method for claim 1, it is characterized in that: described dip time is 1 ~ 20 hour.
9. in accordance with the method for claim 1, it is characterized in that: drying condition is 100 ~ 130 DEG C, 10 ~ 24 hours drying times; Sintering temperature is 450 ~ 550 DEG C, and roasting time is 3 ~ 12 hours.
10. according to catalyst for dehydrogenation of low-carbon paraffin prepared by the method described in the arbitrary claim of claim 1 ~ 10, it is characterized in that: with the γ-Al of skeleton containing Sn
2o
3for carrier, Pt is dehydrogenation active component, and Zn is co catalysis component, accounts for the mass percentage of carrier in metal simple-substance: Sn is 0.1% ~ 5%, Pt be 0.1% ~ 2%, Zn is 0.5% ~ 4%.
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| CN107961783A (en) * | 2017-11-22 | 2018-04-27 | 航天长征化学工程股份有限公司 | Catalyst for synthesizing low-carbon olefin |
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| CN110114143A (en) * | 2016-12-22 | 2019-08-09 | 三井化学株式会社 | The manufacturing method of Porous formed body, the manufacturing method of alpha-olefin dimerization catalyst, the manufacturing method of alpha-olefin dimer, Porous formed body and alpha-olefin dimerization catalyst |
| CN110496636A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496637A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496617A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN111408370A (en) * | 2019-01-08 | 2020-07-14 | 天津大学 | Supported PtZn intermetallic alloy catalyst and preparation method and application thereof |
| CN113385172A (en) * | 2020-03-11 | 2021-09-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene by ethane hydrogen dehydrogenation and preparation and application thereof |
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| CN110496617A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
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| CN110496637B (en) * | 2018-05-17 | 2021-10-19 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
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| CN113385172A (en) * | 2020-03-11 | 2021-09-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene by ethane hydrogen dehydrogenation and preparation and application thereof |
| CN113385172B (en) * | 2020-03-11 | 2022-08-30 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethylene by ethane hydrogen dehydrogenation and preparation and application thereof |
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