CN105521813A - Method for preparing low-carbon alkane dehydrogenation catalyst - Google Patents
Method for preparing low-carbon alkane dehydrogenation catalyst Download PDFInfo
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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)mixing a ZSM-5 molecular sieve, alumina, sesbania powder and a dilute nitric acid solution, beating the materials, kneading the materials, extruding the materials, drying and performing calcination to obtain a ZSM-5 molecular sieve-doped alumina carrier; 2) impregnating the carrier by using a Sn-containing predecessor solution, drying the carrier and performing calcination on the carrier to obtain the Sn-containing carrier; 3) dropping ammoniacal liquor and adding the material into a ZnCl2 aqueous solution, preparing a Zn(NH3)4C12 solution, adding a platinum-containing compound to prepare an impregnation solution; and 4) performing impregnation on the Sn-containing carrier by using the impregnation solution in the step 4), drying the material, and performing calcination to obtain the low-carbon alkane dehydrogenation catalyst. The prepared low-carbon alkane dehydrogenation catalyst has high alkane conversion rate, alkene selectivity and good stability in a low carbon alkane dehydrogenation reaction.
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.
" 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.
The carrier of dehydrogenation is also studied widely, except industrialized activated alumina and gahnite, aluminosilicate molecular sieves, borosilicate molecular sieve, aluminium silicophosphate molecular sieve, silica, zirconium dioxide, alkali metal etc. are also often used as carrier.In the technology taking aluminosilicate molecular sieves as carrier, ZSM Series Molecules sieve mainly with ten-ring is carrier, as ZSM-5, ZSM-11 etc., active component is by dip loading on carrier, and auxiliary agent is incorporated in colloid by dip loading or in molecular sieve process.As patent CN91106059.6, CN01804051.9, CN200710023431.X, CN200810042177.2, CN200910129614.9, CN201010292066.4 and CN201010588617.1 etc.
Research shows, with ZSM-5 be carrier catalyst on dehydrogenating propane reaction be pass through C
+mechanism is carried out or the transfer of hydride realizes, and therefore the B acid site contiguous with dehydrogenation activity center of catalyst surface is very necessary to the carrying out of dehydrogenation reaction.Because Pt particle diameter is about 1.4 ~ 2.0nm, and the aperture of ZSM-5 molecular sieve is about 0.54 ~ 0.56nm, so when using conventional infusion process to be carried on ZSM-5 molecular sieve by Pt, Pt cannot enter inside, ZSM-5 molecular sieve duct, but is evenly distributed on the outer surface of ZSM-5 crystal grain.But the acid site overwhelming majority of ZSM-5 molecular sieve is distributed in inside, duct, the acid amount of outer surface only accounts for about 3 ~ 5% of total acid content.In addition the modification of the auxiliary agent such as alkali metal, alkaline-earth metal or rare earth metal, makes outer surface only Determining Micro Acid center become less.In addition, during using ZSM-5 molecular sieve as the carrier of dehydrogenation, be present in inside, duct a large amount of at high temperature can increase the generation of the side reaction such as alkane cracking, polymerization in strong acid and strong acid, make catalyst quick carbon distribution inactivation and produce a large amount of C
1and C
2gas.
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, Pt and Zn is carried on carrier surface by complexing total immersion method by the present invention, and catalyst prepared by the inventive method has higher alkane conversion, olefine selective and good stability in dehydrogenating low-carbon alkane reaction.
The preparation method of catalyst for dehydrogenation of low-carbon paraffin of the present invention, comprises following content:
(1) ZSM-5 molecular sieve, aluminium oxide, sesbania powder and dilute nitric acid solution are mixed, after making beating, kneading, extrusion, dry, roasting obtains the alumina support of doping ZSM-5 molecular sieve; Wherein the relative crystallinity of ZSM-5 molecular sieve is 40% ~ 80%, preferably 50% ~ 70%;
(2) with the carrier obtained containing the precursor solution impregnation steps (1) of Sn, then drying, roasting, obtain containing Sn carrier;
(3) 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;
(4) with the impregnation fluid step (2) that step (3) obtains obtain containing Sn carrier, then drying, roasting, obtain catalyst for dehydrogenation of low-carbon paraffin.
In the inventive method, the mass ratio of the molecular sieve described in step (1), aluminium oxide, sesbania powder and dilute nitric acid solution is 100:100 ~ 400:3 ~ 20:5 ~ 80, preferred 100:150 ~ 330:10 ~ 15:20 ~ 50; The silica of ZSM-5 molecular sieve and the mol ratio (hereinafter referred to as silica alumina ratio) of aluminium oxide are 50 ~ 300, preferably 80 ~ 200; The mass concentration of dust technology is 3% ~ 15%, preferably 5% ~ 10%; Described aluminium oxide is γ-Al
2o
3.
In the inventive method, the baking temperature described in step (1) is 60 DEG C ~ 150 DEG C, and be preferably 80 DEG C ~ 120 DEG C, drying time is 8h ~ 24h, preferred 10h ~ 20h, and preferably dry in the shade 10h ~ 48h before the drying naturally; Sintering temperature is 400 DEG C ~ 800 DEG C, is preferably 500 DEG C ~ 700 DEG C, roasting time 2h ~ 24h, is preferably 4h ~ 8h.
In the inventive method, described in step (2) can be cationic tin salt containing Sn predecessor, as one or more in nitric acid tin, butter of tin, tin acetate etc., also can be stannic acid metalloid salt, as sodium stannate, potassium stannate etc. one or more, preferred butter of tin.
In the inventive method, the ZnCl described in step (3)
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%; Zn in maceration extract
2+with NH
4 +mol ratio be 1:4 ~ 1:5; Zn in maceration extract
2+mass concentration be 0.0005g/ml ~ 0.03g/ml, preferred 0.001g/ml ~ 0.02g/ml.
In the inventive method, described in step (3) 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, the maceration extract described in step (4) and the volume ratio of carrier are 1:1 ~ 3:1.
In the inventive method, step (2) and the dipping described in (4), drying and method of roasting are method well known to those skilled in the art; Actual conditions is: described dip time is 1h ~ 36h, preferred 2h ~ 16h; Baking temperature is 60 DEG C ~ 150 DEG C, and be preferably 80 DEG C ~ 120 DEG C, drying time is 1h ~ 24h, preferred 4h ~ 8h; Sintering temperature is 400 DEG C ~ 800 DEG C, is preferably 500 DEG C ~ 700 DEG C, roasting time 2h ~ 24h, is preferably 4h ~ 8h.
Catalyst for dehydrogenation of low-carbon paraffin of the present invention, this catalyst with the aluminium oxide of the ZSM-5 molecular sieve that adulterates for carrier, Pt is active component, Sn and Zn is co catalysis component, and in vehicle weight, ZSM-5 molecular sieve is 20% ~ 50%, preferably 30% ~ 40%, Sn is 0.1% ~ 5%, Pt be 0.1% ~ 2%, Zn is 0.5% ~ 4%.(active component and auxiliary agent are with elemental metal), wherein the relative crystallinity of ZSM-5 molecular sieve is 40% ~ 80%, preferably 50% ~ 70%, the silica of ZSM-5 molecular sieve and the mol ratio (hereinafter referred to as silica alumina ratio) of aluminium oxide are 50 ~ 300, preferably 80 ~ 200.
The test of the relative crystallinity described in the present invention adopts the XD-3A type X-ray diffractometer of Japanese Shimadzu Corporation to test.
Catalyst for dehydrogenation of low-carbon paraffin of the present invention is applied to low-carbon alkanes (as propane, iso-butane etc.) dehydrogenation reaction, and general condition is: 500 ~ 650 DEG C, normal pressure or low pressure reaction, and volume space velocity is 200 ~ 5000h
-1.
Catalyst of the present invention processes through following before carrying out dehydrogenation reaction:
Hydro-thermal dechlorination: condition is: in fixed bed hydro-thermal dechlorination reaction device, at 500 ~ 550 DEG C with the gaseous mixture (wherein nitrogen volumn concentration is 5% ~ 50%) of pure water vapor or steam and nitrogen by beds 1 ~ 8h.Gas volume air speed is 0.5 ~ 5h
-1, pressure is 0.1 ~ 0.5MPa.
The activation of catalyst, condition is: with high-purity hydrogen by beds, at 450 ~ 550 DEG C of constant temperature 0.5 ~ 8h.The volume space velocity of hydrogen is 100 ~ 4000h
-1, pressure is 0.1 ~ 0.5MPa.
The passivation of catalyst, condition is: pass through beds, mass space velocity 200 ~ 2000h with the mixed gas of hydrogen sulfide and nitrogen
-1, the volume ratio of hydrogen sulfide and nitrogen is 1:2 ~ 1:10, temperature 450 ~ 550 DEG C, passivation time 0.5 ~ 5h, and pressure is 0.1 ~ 0.5MPa.
ZSM-5 molecular sieve as catalyst or catalyst carrier, the pore passage structure special with it and the acidity of modulation can be widely used in petrochemical industry.This type of application, all based on complete crystallization or the ZSM-5 close to complete crystallization (relative crystallinity is greater than 90%), realizes catalytic process by meticulous modulation pore structure and acidity.Because the aperture of ZSM-5 molecular sieve is about 0.54 ~ 0.56nm, and Pt particle diameter is about 1.4 ~ 2.0nm.The present invention is in the process of preparation maceration extract, and first Zn forms complex with the amino molecule in solution and chlorion, then adds under the condition of heating water bath containing Pt compound, and it is the complex group that the diameter of part is larger that Pt and Zn is formed jointly with ammonia.So when using conventional infusion process to be carried on ZSM-5 molecular sieve by this complex, this complex group cannot enter inside, ZSM-5 molecular sieve duct, but is adsorbed on the outer surface of ZSM-5 crystal grain.But the acid site overwhelming majority of ZSM-5 molecular sieve is distributed in inside, duct, the acid amount of outer surface only accounts for about 3% ~ 5% of total acid content.
Though the ZSM-5 molecular sieve of half crystallization state does not possess closed, complete, regular pore passage structure, also ensure that a large amount of B acid sites is exposed to outside simultaneously.Pt and Zn formation is that the macromolecule complex group of part just can be adsorbed near a large amount of B acid sites without the need to entering duct with ammonia, forms the cluster of Pt and Zn close to each other after roasting.The cluster of Pt and Zn close to each other in dehydrogenation reaction produces collaborative dehydrogenation, and can pass through C with adjacent B acid site
+mechanism carry out or the transfer of hydride to realize certain embodiments.This catalyst not only has excellent alkane conversion and olefine selective.Doping use molecular sieve can avoid alkane high temperature and a large amount of in strong acid and strong acid center existence under there is the generation of the side reaction such as cracking, polymerization, suppress carbon distribution, the one way service cycle of extending catalyst catalyst, improve the stability of catalyst.
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
The preparation of carrier: choosing relative crystallinity is 50%, silica alumina ratio is the ZSM-5 molecular sieve 200g of 100, and the dilute nitric acid solution being 10% with 350g aluminium oxide, 25g sesbania powder and 50g mass concentration mixes, kneading extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 12h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 6h.Fragment into length after cooling be 2 ~ 5mm and measure this carrier of 50ml, dip loading co catalysis component S n, select butter of tin to be presoma, obtain containing Sn carrier through super-dry, roasting.Be placed in Rotary Evaporators, vacuumize 30min.
Preparation maceration extract: by appropriate ZnCl
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 appropriate CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.Suck in Rotary Evaporators by maceration extract again, 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.
comparative example 3
The preparation of carrier: choosing relative crystallinity is 50%, silica alumina ratio be 100 ZSM-5 molecular sieve 200g mix with 30g aluminium oxide, 5g sesbania powder, add the dilute nitric acid solution that 15g mass concentration is 10%, kneading extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 12h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 6h.Fragmenting into length after cooling is 2 ~ 5mm.
The process of load auxiliary agent and active component is with embodiment 1.In 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 B3.
comparative example 4
The preparation of carrier: choosing relative crystallinity is 100%, silica alumina ratio be 100 ZSM-5 molecular sieve 200g mix with 350g aluminium oxide, 25g sesbania powder, add the dilute nitric acid solution that 50g mass concentration is 10%, kneading extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 12h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 6h.Fragmenting into length after cooling is 2 ~ 5mm.
The process of load auxiliary agent and active component is with embodiment 1.In 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 B4.
comparative example 5
The preparation of carrier: choosing relative crystallinity is 100%, silica alumina ratio be 100 ZSM-5 molecular sieve 200g mix with 30g aluminium oxide, 5g sesbania powder, add the dilute nitric acid solution that 15g mass concentration is 10%, pinch extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 12h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 6h.Fragmenting into length after cooling is 2 ~ 5mm.
The process of load auxiliary agent and active component is with embodiment 1.In 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 B5.
embodiment 2
The preparation of carrier: choosing relative crystallinity is 70%, silica alumina ratio is the ZSM-5 molecular sieve 200g of 100, and the dilute nitric acid solution being 10% with 400g aluminium oxide, 25g sesbania powder and 50g mass concentration mixes, kneading extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 10h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 7h.Fragment into length after cooling be 2 ~ 5mm and measure this carrier of 50ml, dip loading co catalysis component S n, select butter of tin to be presoma, obtain containing Sn carrier through super-dry, roasting.Be placed in Rotary Evaporators, vacuumize 30min.
Preparation maceration extract: by appropriate ZnCl
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 appropriate CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.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 carrier: choosing relative crystallinity is 60%, silica alumina ratio is the ZSM-5 molecular sieve 200g of 150, and the dilute nitric acid solution being 10% with 350g aluminium oxide, 25g sesbania powder and 50g mass concentration mixes, kneading extruded moulding.Carrier after shaping dries in the shade through 24h, then is placed in 110 DEG C of dry 10h of baking oven, then is placed in Muffle furnace 600 DEG C of roasting 7h.Fragment into length after cooling be 2 ~ 5mm and measure this carrier of 50ml, dip loading co catalysis component S n, select butter of tin to be presoma, obtain containing Sn carrier through super-dry, roasting.Be placed in Rotary Evaporators, vacuumize 60min.
Preparation maceration extract: by appropriate ZnCl
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 appropriate CDCP is added in above-mentioned solution, stirs and heating water bath to 60 DEG C.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 3h
-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.
By testing above and can finding out: Pt, Zn are carried on the carrier of half crystallization ZSM-5 molecular sieve and aluminium oxide mixing by complexing total immersion can obtain higher alkane conversion, olefine selective and stability.The Pt system dehydrogenation that B1 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.Acidity due to alumina support is more weak and be L acid site, and step load Pt and Zn is difficult to guarantee two kinds of atoms and forms contiguous cluster at carrier surface because catalyst alkane conversion and olefine selective lower.The ethanolic solution of the mixing containing cerium or zinc and tin and carrier are carried out incipient impregnation by B2, by dry, roasting, by above-mentioned product dip loading active component Pt, and acid more weak carrier is used to make dehydrogenation equally, dehydrogenation activity and selective not good.B3 and B5 uses half crystallization ZSM-5 molecular sieve to make carrier, and small amounts aluminium makes binding agent, and carrier acid amount is comparatively large, though initial conversion is high, less stable, a large amount of acid sites also causes accessory substance to increase, selective poor.B4 doping uses the ZSM-5 molecular sieve of complete crystallization, and make Pt-Zn cluster be difficult to enter molecular sieve pore passage, a large amount of B acid site cannot give full play to synergy in dehydrogenation reaction, and catalyst activity is lower.
Claims (10)
1. the preparation method of a catalyst for dehydrogenation of low-carbon paraffin, it is characterized in that comprising following content: ZSM-5 molecular sieve, aluminium oxide, sesbania powder and dilute nitric acid solution mix by (1), after making beating, kneading, extrusion, dry, roasting obtains the alumina support of doping ZSM-5 molecular sieve; Wherein the relative crystallinity of ZSM-5 molecular sieve is 40% ~ 80%; (2) with the carrier obtained containing the precursor solution impregnation steps (1) of Sn, then drying, roasting, obtain containing Sn carrier; (3) 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, fully stir, make maceration extract; (4) with the impregnation fluid step (2) that step (3) obtains obtain containing Sn carrier, then drying, roasting, obtain catalyst for dehydrogenation of low-carbon paraffin.
2. in accordance with the method for claim 1, it is characterized in that: the mass ratio of the molecular sieve described in step (1), aluminium oxide, sesbania powder and dilute nitric acid solution is 100:100 ~ 400:3 ~ 20:5 ~ 80; The silica of ZSM-5 molecular sieve and the mol ratio of aluminium oxide are 50 ~ 300.
3. in accordance with the method for claim 1, it is characterized in that: the baking temperature described in step (1) is 60 DEG C ~ 150 DEG C, and drying time is 8h ~ 24h; Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h.
4. in accordance with the method for claim 1, it is characterized in that: described in step (2) containing Sn predecessor is cation pink salt or stannic acid metalloid salt, be selected from nitric acid tin, butter of tin, tin acetate, sodium stannate or potassium stannate one or more.
5. in accordance with the method for claim 1, it is characterized in that: the ZnCl described in step (3)
2the mass concentration of the aqueous solution is 1% ~ 30%; The mass concentration of ammoniacal liquor is 1% ~ 25%; Zn in maceration extract
2+with NH
4+mol ratio be 1:4 ~ 1:5; Zn in maceration extract
2+mass concentration be 0.0005g/ml ~ 0.03g/ml.
6. according to the method described in claim 1 or 4, it is characterized in that: the ZnCl described in step (3)
2the mass concentration of the aqueous solution is 5% ~ 20%; The mass concentration of ammoniacal liquor is 5% ~ 20%; Zn in maceration extract
2+mass concentration be 0.001g/ml ~ 0.02g/ml.
7. in accordance with the method for claim 1, it is characterized in that: described in step (3) is chloroplatinic acid or CDCP containing platinum compounds, and in maceration extract, the mass concentration of Pt is 0.0001g/ml ~ 0.02g/ml.
8. in accordance with the method for claim 1, it is characterized in that: the maceration extract described in step (4) and the volume ratio of carrier are 1:1 ~ 3:1.
9. in accordance with the method for claim 1, it is characterized in that: step (2) and the described dip time described in (4) are 1h ~ 36h; Baking temperature is 60 DEG C ~ 150 DEG C, and drying time is 1h ~ 24h; Sintering temperature is 400 DEG C ~ 800 DEG C, roasting time 2h ~ 24h.
10. according to catalyst for dehydrogenation of low-carbon paraffin prepared by the method described in the arbitrary claim of claim 1 ~ 9, it is characterized in that: this catalyst with the aluminium oxide of the ZSM-5 molecular sieve that adulterates for carrier, Pt is active component, Sn and Zn is co catalysis component, in vehicle weight, ZSM-5 molecular sieve is 20% ~ 50%, Sn is 0.1% ~ 5%, Pt is 0.1% ~ 2%, Zn is 0.5% ~ 4%, wherein the relative crystallinity of ZSM-5 molecular sieve is 40% ~ 80%, and the silica of ZSM-5 molecular sieve and the mol ratio of aluminium oxide are 50 ~ 300.
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| CN108435221A (en) * | 2017-02-16 | 2018-08-24 | 四川润和催化新材料股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and its preparation method and application |
| CN108786798A (en) * | 2017-05-02 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin |
| CN109092351A (en) * | 2017-06-21 | 2018-12-28 | 江苏华伦化工有限公司 | A kind of preparation method and application of the support type composite molecular screen based on microwave technology |
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| CN110813284A (en) * | 2018-08-14 | 2020-02-21 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst with silica gel as carrier and preparation method and application thereof |
| CN112007640A (en) * | 2020-09-01 | 2020-12-01 | 辽宁石油化工大学 | Preparation method of low-carbon alkane dehydrogenation catalyst |
| WO2022018081A1 (en) | 2020-07-21 | 2022-01-27 | Basf Se | A zeolite catalyst and use thereof for the dehydrogenation of alkanes |
| CN114602549A (en) * | 2022-03-28 | 2022-06-10 | 香港中文大学（深圳） | Catalyst for preparing unsaturated hydrocarbon from saturated hydrocarbon, preparation method of catalyst and method for preparing unsaturated hydrocarbon from saturated hydrocarbon |
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| WO2022018081A1 (en) | 2020-07-21 | 2022-01-27 | Basf Se | A zeolite catalyst and use thereof for the dehydrogenation of alkanes |
| CN112007640A (en) * | 2020-09-01 | 2020-12-01 | 辽宁石油化工大学 | Preparation method of low-carbon alkane dehydrogenation catalyst |
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