CN109382122A - A kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin - Google Patents
A kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin Download PDFInfo
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- CN109382122A CN109382122A CN201710683476.3A CN201710683476A CN109382122A CN 109382122 A CN109382122 A CN 109382122A CN 201710683476 A CN201710683476 A CN 201710683476A CN 109382122 A CN109382122 A CN 109382122A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/24—Chlorinating
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the alkali- or alkaline earth metals or beryllium
- C07C2523/04—Alkali metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/135—Compounds comprising a halogen and titanum, zirconium, hafnium, germanium, tin or lead
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to the preparation fields of dehydrogenation, disclose a kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin.This method comprises: dipping introduces active component in alumina support, catalyst precarsor is obtained after drying, then in 600-700 DEG C of progress high temperature oxychlorination processing, then it restores, repeat high temperature oxychlorination processing and reduction step 1-10 times later, catalyst for dehydrogenation of low-carbon paraffin is obtained, the catalyst for dehydrogenation of low-carbon paraffin includes alumina support and the content counted on the basis of carrier is the platinum group metal of 0.1~1 mass %, the IVA race metal of 0.1~1 mass %, the alkali metal of 0.5~2 mass % and the chlorine of 0.5~1.5 mass %.The dehydrogenation activity and selectivity with higher prepared by this method, and stability is high.
Description
Technical field
The present invention relates to the preparation fields of dehydrogenation, and in particular, to a kind of work of catalyst for dehydrogenation of low-carbon paraffin
Change restoring method.
Background technique
With the increase of crude oil in China processing capacity, a large amount of ethane of the technical process such as catalytic cracking of oil plant meeting by-product,
The low-carbon alkanes such as propane, iso-butane.These resources how are efficiently used, the low-carbon alkene of high added value is translated into, to mentioning
The economic benefit of high oil plant is of great significance.
Propylene is a kind of important basic organic chemical industry raw material, is widely used in producing polypropylene, acetone, acrylonitrile, ring
A variety of chemical products such as Ethylene Oxide, acrylic acid；Isobutene is the primary raw material for producing methyl tertiary butyl ether(MTBE) (MTBE)；Butylene is main
For being alkylated, coinciding, isomerization and dimerization processes synthesize useful gasoline component and synthesis MTBE and ETBE gasoline additive
Equal fuel areas, and it is widely used in field of chemicals.Therefore, manufacturing olefin by low-carbon alkane dehydrogenation is one raw using low-carbon alkanes
Produce the viable process route of corresponding alkene.
Support type platinum based catalyst is important one kind in catalyst for dehydrogenation of low-carbon paraffin, usually using aluminium oxide as carrier,
It is modified by adding other components, to improve the activity and selectivity of catalyst.Since dehydrogenating low-carbon alkane reaction is heated
Mechanical balance limitation, reaction will carry out under the harsh conditions of high temperature and low pressure.Excessively high reaction temperature can aggravate cracking reaction
And deep dehydrogenation, accelerate the coke deposit rate of catalyst, makes catalyst inactivation.Therefore exploitation high activity, highly selective and high stable
Property dehydrogenation become the technology key.
In order to improve the anti-carbon deposition ability of catalyst, extends the service life of catalyst, other than the selection of carrier, use
Suitable method for activating and reducing is also to improve one of preferable measure of catalyst activity stability.
CN102380426A discloses dehydrogenation first through vapor dechlorination, the hydrogen sulfide in gaseous mixture used in activation
Molar ratio with hydrogen is 1:(2~30), and diluent gas is added.
CN102463148A is disclosed after dehydrogenation is impregnated with Containing Sulfur agent solution and is carried out heat in the presence of water vapor
Processing carries out dehydrogenation reaction after finally carrying out reduction treatment using the hydrogen containing ammonia.
CN102909094A discloses dehydrogenation after vapor dechlorination, is restored with hydrogen at 240~350 DEG C, so
After be warming up to dehydrogenation reaction thermotonus.
CN102909095A discloses point that dehydrogenation carries out high temperature and low temperature procedure heating using low-concentration hydrogen
Section restoring method, does not vulcanize.
CN102909011A discloses dehydrogenation during the preparation process through vapor dechlorination, is contained using preceding direct use
The mixed gas of hydrogen and hydrogen sulfide is activated and is vulcanized, and hydrogen sulfide therein generates reactor, vulcanization from hydrogen sulfide
Hydrogen, hydrogen molar ratio be 1:(2~30).
CN102909012A is disclosed dehydrogenation and is gone back in advance using the preceding gaseous mixture temperature programming through nitrogen and hydrogen
Original, then constant temperature reduction, be then passivated with the mixed gas of hydrogen, hydrogen sulfide and nitrogen, hydrogen sulfide, hydrogen and nitrogen
Molar ratio is 1:9:(0~30).
CN103041807A carries out steam dechlorination after disclosing alumina support dipping platinum family dehydrogenation activity metal component
Processing, while catalyst is restored using the reducibility gas of hydrogen, then vulcanized, sulfiding gas is Containing Sulfur
The mixed gas of hydrogen and diluent gas, molar ratio are 1:(0.5~20).
In the method for activating and reducing of the above dehydrogenation, it usually needs handled by steam dechlorination, to reduce catalysis
Chlorinity in agent, and it is dense when being vulcanized with hydrogen sulfide.
Summary of the invention
The object of the present invention is to provide a kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin, are prepared by this method
Dehydrogenation activity and selectivity with higher, and stability is high.
To achieve the goals above, the present invention provides a kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin, should
Method includes: the dipping introducing active component in alumina support, catalyst precarsor is obtained after dry, then in 600-700 DEG C
High temperature oxychlorination processing is carried out, then restores, repeats high temperature oxychlorination processing and reduction step 1-10 times later, obtain low
Carbon alkane dehydrogenation, the catalyst for dehydrogenation of low-carbon paraffin includes alumina support and the content counted on the basis of carrier is
The platinum group metal of 0.1~1 mass %, the IVA race metal of 0.1~1 mass %, 0.5~2 mass % alkali metal and 0.5~1.5
The chlorine of quality %.
It according to the method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin of the present invention, does not need to be vulcanized, reduce
The usage amount of sulfur-bearing noxious material, reduces harmfulness, simplifies treatment process；And in the height for keeping dehydrogenation active component
While dispersed, the activity stability of catalyst can be improved.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin of the present invention includes: to impregnate to draw in alumina support
Enter active component, obtains catalyst precarsor after dry, then in 600-700 DEG C of progress high temperature oxychlorination processing, then restore, it
After repeat high temperature oxychlorination processing and reduction step 1-10 times, obtain catalyst for dehydrogenation of low-carbon paraffin, the low-carbon alkanes
Dehydrogenation includes alumina support and the content counted on the basis of carrier is the platinum group metal of 0.1~1 mass %, 0.1~1
The chlorine of the IVA race metal of quality %, the alkali metal of 0.5~2 mass % and 0.5~1.5 mass %.Activating and reducing side of the invention
It does not need to carry out steam dechlorination in method, and catalyst preparation process does not need to be vulcanized, and reduces sulfur-bearing noxious material
Usage amount, reduce harmfulness.
In method of the present invention, under preferable case, the chlorinity after activating and reducing in gained catalyst is with carrier
On the basis of be calculated as 0.8~1.5 mass %, specifically, such as can be 0.8 mass %, 0.85 mass %, 0.9 mass %, 0.95
Quality %, 0.97 mass %, 1 mass %, 1.05 mass %, 1.1 mass %, 1.2 mass %, 1.26 mass %, 1.3 matter
The arbitrary value between range that amount %, 1.4 mass % or 1.5 mass % and any two numerical value are constituted, more preferably
0.95-1.3 mass %.
In method of the present invention, the process of the high temperature oxychlorination processing can make dehydrogenation active component (such as platinum
Race's metal component) it is well dispersed on carrier.The temperature of the high temperature oxychlorination processing is 600-700 DEG C, specifically, such as
For 600 DEG C, 610 DEG C, 620 DEG C, 630 DEG C, 640 DEG C, 650 DEG C, 660 DEG C, 670 DEG C, 680 DEG C, 690 DEG C, 700 DEG C and it can appoint
The arbitrary value between range that meaning two values are constituted.Preferably, the temperature of the high temperature oxychlorination processing is 600-680
℃.The time of the high temperature oxychlorination processing can be 1-10 hours.
In method of the present invention, the high temperature oxychlorination processing carries out in the gas containing chlorine and oxygen, the gas
Water (such as water vapour) can also be contained in body.The gas is selected from air or nitrogen, and chlorine contained in gas is preferred from chlorine
Or chlorine-containing compound, the chlorine-containing compound in hydrogen chloride, chloroform, tetrachloro-ethylene, dichloroethylene and carbon tetrachloride extremely
Few one kind.When the chlorine contained in the gas comes from chlorine, oxychlorination treatment process does not contain water.The chlorine contained in the gas comes from
When above-mentioned chlorine-containing compound, when the high temperature oxychlorination processing carries out in the gas containing water, chlorine-containing gas compound and oxygen,
The molar ratio of chlorine element in water and chlorine-containing gas compound is 1~40:1, specifically, such as can for 1:1,5:1,10:1,
The arbitrary proportion between range that 15:1,20:1,25:1,30:1,35:1,40:1 and any two ratio are constituted, preferably
For 5~30:1.When high temperature oxychlorination processing carries out in the gas containing chlorine and oxygen, chlorinity can be in the gas
It specifically, such as can be 0.1 volume %, 0.5 volume %, 0.6 volume %, 0.8 volume %, 1 body for 0.1~2 volume %
Product %, 1.2 volume %, 1.4 volume %, 1.5 volume %, 1.6 volume %, 1.8 volume %, 2 volume % and any two contain
Measure any content between constituted range.
In method of the present invention, the condition of the reduction may include: that temperature is 500~650 DEG C, preferably
550~580 DEG C；Time is 1~10 hour, preferably 1~4 hour.
In method of the present invention, the process of the reduction preferably uses the mixed of hydrogen or hydrogen and inert gas
Close gas.In the gaseous mixture of the hydrogen and inert gas, the volume fraction of inert gas can be 0~70%, for example,
10%, the arbitrary value between 20%, 30%, 40%, 50%, 60% or 70% and the range that is constituted of any two numerical value.
The inert gas can be nitrogen, helium, neon, argon gas etc..
In method of the present invention, the carrier in catalyst for dehydrogenation of low-carbon paraffin is alumina support.The oxidation
Alumina supporter is preferably θ-aluminium oxide.It is further preferred that the alumina support has 50~130m2The specific surface area of/g, 0.5
The total pore volume of~1mL/g.
In the catalyst for dehydrogenation of low-carbon paraffin, using platinum group metal as dehydrogenation active component, also containing IVA race metal and
Alkali metal.
In the preferred case, the platinum group metal is platinum.
In the preferred case, IVA race metal is tin.IVA race metal preferably introduces in carrier forming process.
In the preferred case, the alkali metal is potassium.
In method of the present invention, the catalyst precarsor can be using conventional method preparation.In a kind of implementation
In mode, preparation process may include: that the alumina support of the metal of race containing IVA is introduced platinum group metal component by dipping, do
Dry, roasting, dipping introduce alkali metal.Wherein, dry temperature can be 60~150 DEG C, and drying time can be small for 1~20
When.The temperature of roasting can be 400~600 DEG C, and calcining time can be 1~10 hour.It is excellent after dipping introduces alkali metal
It is selected at 60~150 DEG C 1~20 hour dry.
In the present invention, it is preferably chloroplatinic acid that the dipping, which introduces platinum group metal compounds used in platinum group metal component,
The alumina support of the metal containing IVA is preferably stanniferous alumina support, and dipping introduces alkali metal compound used in alkali metal
Preferably at least one of potassium hydroxide, potassium chloride and potassium nitrate.
In a preferred embodiment, the preparation of the catalyst precarsor: carrier is preferably θ-aluminium oxide, is more preferably contained
θ-aluminium oxide of Sn, auxiliary agent Sn are introduced in carrier forming process, are uniformly distributed Sn component in the carrier, content is carrier quality
0.1~1%；Alumina support containing Sn introduces platinum group metal component, preferably platinum by dipping method, and content is carrier matter
The 0.1~1% of amount adds suitable competitive adsorbate in maceration extract and controls immersion condition so that platinum is uniformly dispersed in carrier
On, then roasted 1~10 hour within drying 1~20 hour, 400~600 DEG C through 60~150 DEG C；Impregnate alkaline components again later,
Preferably potassium, content is the 0.5~2% of carrier quality, then 1~20 hour dry through 60~150 DEG C, then presses side of the invention
Method carries out activating and reducing.
In a preferred embodiment, the detailed process and condition of method for activating and reducing of the present invention are as follows:
(1) by the dehydrogenation containing Pt, Sn, K after drying in the gas containing chlorine and oxygen at 600~700 DEG C into
Row high temperature oxychlorination is handled 1~10 hour；
(2) it by oxychlorination treated catalyst in 500~650 DEG C, is carried out with the also Primordial Qi of hydrogen and inert gas
Reduction 1~10 hour；
(3) by after reduction catalyst repeat step (1) and (2) high temperature oxychlorination processing and reduction process 1-10 times,
Obtain final catalyst for dehydrogenation of low-carbon paraffin.
In method of the present invention, the low-carbon alkanes can be the alkane of C3~C5, preferably propane and/or fourth
Alkane.
Below by example, present invention be described in more detail, but the present invention is not limited thereto.
Embodiment 1
Take spherical θ-alumina support (German Sasol company production) containing Sn, specific surface area 112m2/ g, total hole body
Product is 0.72mL/g, and Sn content is the 0.3% of carrier quality, is impregnated 4 hours with the maceration extract containing chloroplatinic acid and hydrochloric acid in 25 DEG C,
The chlorine (both with respect to butt alumina support, similarly hereinafter) of platinum, 1.5 mass % in maceration extract containing 0.3 mass %, liquid/solid ratio are
1.8mL/g.Solid is dried 12 hours in 120 DEG C after dipping, 500 DEG C of roasting 4h.Solid potassium hydroxide after roasting is molten
Liquid impregnates 4 hours, the 0.9 mass % (relative to alumina support) containing potassium in solution in 25 DEG C, and liquid/solid ratio is 1.4mL/g.Dipping
Solid is 12 hours dry in 120 DEG C afterwards, obtains catalyst for dehydrogenation of low-carbon paraffin precursor, wherein count on the basis of carrier, platinum contains
Amount is 0.3 mass %, and the content of tin is 0.3 mass %, and the content of chlorine is 0.6 mass %, and the content of potassium is 0.9 mass %.
Oxychlorination and reducing condition: under air conditions, with the rate of 5 DEG C/min from room temperature to 600 DEG C, then lead to
Enter the gaseous mixture of vapor and tetrachloro-ethylene, the molar ratio of vapor and tetrachloro-ethylene is 20:1, volume space velocity 1000h-1,
Oxychlorination is carried out to above-mentioned catalyst precarsor at a temperature of this and handles 2h.After nitrogen purges, it is passed through the gaseous mixture of hydrogen and nitrogen,
The volume fraction of nitrogen is 50%, and constant temperature reductase 12 h at this temperature, repeats above-mentioned oxychlorination processing in same temperature later
With reduction process 2 times, catalyst A is made, the platinum content in catalyst is 0.3 mass %, Theil indices are 0.3 mass %, potassium contains
Amount is 0.9 mass %, chlorinity is 1.12 mass %.
Embodiment 2
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 10 DEG C/min from room temperature to 620 DEG C, then
It is passed through the gaseous mixture of vapor and hydrogen chloride, the molar ratio of vapor and hydrogen chloride is 15:1, volume space velocity 1000h-1, herein
At a temperature of to above-mentioned catalyst precarsor carry out oxychlorination handle 4h.After nitrogen purges, it is passed through pure hydrogen, and permanent at this temperature
Warm reductase 12 h, later in the above-mentioned oxychlorination processing of same temperature repetition and reduction process 5 times, obtained catalyst B, catalyst
Platinum content is 0.3 mass %, Theil indices are 0.3 mass %, potassium content is 0.9 mass %, chlorinity is 1.05 mass %.
Embodiment 3
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 10 DEG C/min from room temperature to 650 DEG C, then
It is passed through the gaseous mixture of chlorine and nitrogen, wherein the volumetric concentration of chlorine is 1%, volume space velocity 1000h-1, right at this temperature
Above-mentioned catalyst precarsor carries out oxychlorination and handles 6h.After nitrogen purges, it is passed through pure hydrogen, and constant temperature restores at this temperature
2h repeats above-mentioned oxychlorination processing and reduction process 8 times in same temperature later, and catalyst C, the platinum content in catalyst is made
For 0.3 mass %, Theil indices be 0.3 mass %, potassium content is 0.9 mass %, chlorinity is 1.23 mass %.
Embodiment 4
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 10 DEG C/min from room temperature to 680 DEG C, then
It is passed through the gaseous mixture of chlorine and nitrogen, wherein the volumetric concentration of chlorine is 1%, volume space velocity 1000h-1, right at this temperature
Above-mentioned catalyst precarsor carries out oxychlorination and handles 2h.After nitrogen purges, it is passed through pure hydrogen, and constant temperature restores at this temperature
1h repeats above-mentioned oxychlorination processing and reduction process 3 times in same temperature later, and catalyst D, the platinum content in catalyst is made
For 0.3 mass %, Theil indices be 0.3 mass %, potassium content is 0.9 mass %, chlorinity is 1.18 mass %.
Comparative example 1
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 10 DEG C/min from room temperature to 500 DEG C, then
It is passed through the gaseous mixture of vapor and hydrogen chloride, the molar ratio of vapor and hydrogen chloride is 15:1, volume space velocity 1000h-1, herein
At a temperature of to above-mentioned catalyst precarsor carry out oxychlorination handle 4h.After nitrogen purges, it is passed through pure hydrogen, and permanent at this temperature
Catalyst E is made in warm reductase 12 h, and the platinum content in catalyst is 0.3 mass %, Theil indices are 0.3 mass %, potassium content is
0.9 mass %, chlorinity are 1.05 mass %.
Comparative example 2
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 5 DEG C/min from room temperature to 500 DEG C, then lead to
Enter the gaseous mixture of vapor and air, the volume ratio of vapor and air is 1:30, volume space velocity 1000h-1, at this temperature
Above-mentioned catalyst precarsor is carried out to wash chlorine 4h.Then 550 DEG C are warming up to the rate of 5 DEG C/min in hydrogen, and in this temperature
Catalyst F is made in lower constant temperature reductase 12 h, and the platinum content in catalyst is 0.3 mass %, Theil indices are 0.3 mass %, potassium content
It is 0.15 mass % for 0.9 mass %, chlorinity.
Comparative example 3
Catalyst for dehydrogenation of low-carbon paraffin precursor is prepared by the identical method of example 1.
Oxychlorination and reducing condition: under air conditions, with the rate of 5 DEG C/min from room temperature to 600 DEG C, then lead to
Enter the gaseous mixture of vapor and tetrachloro-ethylene, the molar ratio of vapor and tetrachloro-ethylene is 20:1, volume space velocity 1000h-1,
Oxychlorination is carried out to above-mentioned catalyst precarsor at a temperature of this and handles 2h.After nitrogen purges, it is passed through the gaseous mixture of hydrogen and nitrogen,
The volume fraction of nitrogen is 50%, and constant temperature reductase 12 h at this temperature, and catalyst G is made, and the platinum content in catalyst is 0.3
Quality %, Theil indices are 0.3 mass %, potassium content is 0.9 mass %, chlorinity is 1.1 mass %.
Test case
In the quartz tube reactor of micro-reactor, it is packed into 2 milliliters of catalyst and (above-described embodiment and comparative example is respectively adopted
The catalyst of preparation), using the mixed gas of hydrogen and propane as raw material, in 630 DEG C, 0.135MPa (gauge pressure), propane feed matter
Amount air speed is 11h-1, hydrogen/propane molar ratio be 0.5:1, note sulfur content (sulfur-containing compound used is H2S) relative to propane into
Material quality is reacted 40 hours under conditions of being 80ppm, every the primary progress chromatography of sampling in 1 hour.Calculate conversion of propane
And Propylene Selectivity, it the results are shown in Table 1.
Table 1
As shown in Table 1, by the dehydrogenation of method for activating and reducing of the present invention preparation relative to comparative catalyst
E, F, G, conversion of propane with higher and Propylene Selectivity, and there is preferable activity stability, Propylene Selectivity is kept
Stablize, catalyzer coke content is far below comparative catalyst, has excellent reactivity worth.
Claims (11)
1. a kind of method for activating and reducing of catalyst for dehydrogenation of low-carbon paraffin introduces this method comprises: impregnating in alumina support
Active component obtains catalyst precarsor after dry, then in 600-700 DEG C of progress high temperature oxychlorination processing, then restores, later
Repeat high temperature oxychlorination processing and reduction step 1-10 times, obtain catalyst for dehydrogenation of low-carbon paraffin, the low-carbon alkanes are de-
Hydrogen catalyst includes alumina support and the content counted on the basis of carrier is the platinum group metal of 0.1~1 mass %, 0.1~1 matter
Measure IVA race metal, the alkali metal of 0.5~2 mass % and the chlorine of 0.5~1.5 mass % of %.
2. according to the method described in claim 1, wherein, the chlorinity in gained catalyst is 0.8~1.5 mass %.
3. according to the method described in claim 1, wherein, the temperature of the high temperature oxychlorination processing is 600-680 DEG C.
4. according to the method described in claim 1, wherein, the high temperature oxychlorination processing is containing water, chlorine-containing gas compound
It is carried out in the gas of oxygen, and the molar ratio of the chlorine element in water and chlorine-containing gas compound is 1-40:1, chlorine-containing gas chemical combination
Object is at least one of hydrogen chloride, chloroform, tetrachloro-ethylene, dichloroethylene and carbon tetrachloride.
5. according to the method described in claim 4, wherein, the high temperature oxychlorination processing in the gas containing chlorine and oxygen into
It goes, chlorinity is 0.1~2.0 volume % in the gas.
6. method according to claim 1 or 2, wherein the temperature of the reduction is 550~650 DEG C, and reducing gas is hydrogen
The gaseous mixture of gas or hydrogen and inert gas, wherein in the gaseous mixture of the hydrogen and inert gas, the body of inert gas
Fraction is 0~70%.
7. method according to claim 1 or 2, wherein the alumina support is θ-aluminium oxide.
8. method according to claim 1 or 2, wherein the platinum group metal is platinum, and IVA race metal is tin, and alkali metal is
Potassium.
9. according to the method described in claim 1, wherein, the preparation method of the catalyst precarsor includes that will contain IVA race metal
Alumina support platinum group metal component, dry, roasting are introduced by dipping, dipping introduces alkali metal.
10. according to the method described in claim 9, wherein, the dipping introduces platinum group metal used in platinum group metal component
Conjunction object is chloroplatinic acid, and the alumina support of the metal containing IVA is stanniferous alumina support, and dipping introduces the gold of alkali used in alkali metal
Category compound is at least one of potassium hydroxide, potassium chloride and potassium nitrate.
11. method according to claim 1 or 2, wherein the low-carbon alkanes are C3~C5Alkane.
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| CN115703063A (en) * | 2021-08-17 | 2023-02-17 | 中国石油天然气股份有限公司 | Dehydrogenation method for hydrogenated aromatic compound |
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