CN100434407C - Method for preparing propylene by dehydrogenating propane - Google Patents
Method for preparing propylene by dehydrogenating propane Download PDFInfo
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- CN100434407C CN100434407C CNB2006100013308A CN200610001330A CN100434407C CN 100434407 C CN100434407 C CN 100434407C CN B2006100013308 A CNB2006100013308 A CN B2006100013308A CN 200610001330 A CN200610001330 A CN 200610001330A CN 100434407 C CN100434407 C CN 100434407C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
This invention discloses a method for producing propylene by propane dehydrogenation. The method comprises contacting propane with catalyst for dehydrogenation. The catalyst comprises an orderly structured carrier with parallel pores, and a coating layer containing matrix and active metal components for dehydrogenation. The thickness of the coating layer is distributed gradient along the axis of the carrier, with a thicker end of 60-400 mums, and a thinner end of 1-60 mums. The pore cross-sectional area of the thicker end is not smaller than 10% that of the carrier. The method has high propane conversion rate and high propylene yield.
Description
Technical field
The invention relates to a kind of method of propane catalytic dehydrogenation system propylene.
Background technology
Propylene is important basic chemical raw materials, is widely used in to produce polypropylene (PP), isopropyl benzene, oxo-alcohols, vinyl cyanide, propylene oxide, vinylformic acid and other Chemicals.Along with modern chemical industry to the propylene growth of requirement, promoted the development of various production of propylene technology.The approach that obtains propylene at present mainly contains steam heat cracking, heavy crude catalytic pyrolysis and catalytic pyrolysis, propane catalytic dehydrogenation and the olefin metathesis reactions in fluidized-bed of petroleum naphtha in the blank pipe reactor.Wherein the preparing propylene by dehydrogenating propane technology comes into one's own in recent years gradually, has become tertiary propylene source, estimate by the propone output of dehydrogenating propane production and in propone output shared ratio will further improve.
Developed multiple dehydrogenating propane technology up to now.For example: the Oliflex technology of Uop Inc. is carried out the dehydrogenating propane reaction with continuous moving-burden bed reactor, and catalyst system therefor is the Pt/Al of Sn, K modification
2O
3Catalyzer; The Catofin technology of ABB Lummus is carried out dehydrogenation reaction with fixed-bed reactor under the condition that vacuumizes, catalyst system therefor is the Cr of alkali metals modified
2O
3/ Al
2O
3Catalyzer; The PDH process using fixed-bed tube reactor of the Star technology of Phillips company and Linde company reacts, Star process using Pt/ZnAlO
2Catalyzer, PHD process using Cr
2O
3/ Al
2O
3Catalyzer; The FBD technology of Snamprogetti yarsintaz is to carry out dehydrogenation reaction with fluidized-bed reactor, adopts the Cr of additive modification
2O
3/ Al
2O
3Catalyzer.
Adopt the dehydrogenating propane technology of fixed-bed reactor, generally comprise preheating section, conversion zone, the segregation section of product and the stages such as exquisite section of product of raw material, wherein at conversion zone, a plurality of reactor parallel operations, the production of part reactor, simultaneously a part of reactor regeneration.For example, Catofiin technology: earlier fresh propane and propane recirculation material are heated to 650 ℃, enter reactor then, react under the absolute pressure of 0.05MPa, reacted material compresses after overcooling, and the material after the compression is through flash separation, lighter hydrocarbons in the gaseous product act as a fuel, its heavy constituent are advanced the product separation tower with product liquid, obtain propylene from the cat head of product separation tower, and bottoms is then as the recirculation material.Filling chromium Al catalysts in the reactor, after reaction for some time, stop propane feed, switching steam purges reactor, feed warm air then catalyzer is regenerated, mend fuel gas simultaneously and come additional heat, after regeneration finishes, reactor is evacuated to vacuum state again, prepares the next operational cycle.In order to realize operate continuously, reactive system is made up of the reactor of a plurality of parallel connections, wherein a part of reactor is produced, part reactor carries out preheating/regeneration, some reactor vacuumizes, steaming out, again the pressurization etc. the operation [Chen Jianjiu etc., preparing propylene by dehydrogenating propane Technology, " Speciality Petrochemicals progress ", 2000,1 (12): 23].
Dehydrogenating propane reaction is the thermo-negative reaction that molecule increases, and therefore, high temperature and low pressure help the carrying out that react.At present, the outstanding problem that adopts the dehydrogenating propane technology existence of fixed-bed reactor is that the catalyzer heap is than big, the space that bed can supply reactant or product to pass through is little and resistance is big, the reaction pressure drop is bigger, reaction velocity is lower, mass-and heat-transfer causes the even product of reaction bed temperature skewness that side reaction further takes place slowly easily, make the reaction preference variation, and carrying out along with reaction, because the change of catalyzer physical strength changes the beds structure, normally carrying out of influence reaction, shortened the work-ing life of catalyzer, the physical strength to catalyzer has proposed high requirement like this.
Ordered structure catalyst (monolithic catalyst) is to make catalyzer cellular or dipping or coated catalysts component on honeycomb support.The catalyticreactor that loads this catalyzer is called novel fixed-bed reactor, compares with common fixed-bed reactor, has reaction pressure and reduces the characteristics that mass-and heat-transfer is effective and reaction efficiency is high.US6623707 discloses a kind of ordered structure catalyst reactor and has been used for ethyl benzene dehydrogenation preparation of styrene, to organize ordered structure catalyst in this invention is seated in the reaction chamber more, be divided into two or more conversion zones, each intersegmental heating unit that is provided with is to provide reaction needed heat.This reactor can reduce the bed pressure drop of ethylbenzene dehydrogenation reaction, improves the effect of ethylbenzene dehydrogenation.This method can be used for preparing propylene by dehydrogenating propane, but that the problem that exists is the selectivity of conversion of propane and propylene is low.
Summary of the invention
The present invention is directed to the preparing propylene by dehydrogenating propane method that adopts ordered structure catalyst, conversion of propane and the low shortcoming of propylene selectivity provide a kind of new optionally preparing propylene by dehydrogenating propane method of higher conversion of propane and propylene that has.
Method provided by the invention is included under the reaction conditions of dehydrogenating propane, propane feed is contacted with catalyzer, it is characterized in that, described catalyzer contains ordered structure carrier with parallel duct and the coating that contains matrix, dehydrogenation activity metal component that is coated on this carrier, coating distributes along the axial gradient of ordered structure carrier, thick coating end thickness is the 60-400 micron, and thin end thickness is the 1-60 micron, and the sectional area of thick coating stomidium be not less than carrier hole sectional area 10%.
Compare with existing method, the conversion of propane and the propylene selectivity that the invention provides method obviously improve.For example: utilizing method provided by the invention, is that 0.12MPa, gas space velocity are 15000h at 620 ℃, reaction absolute pressure
-1Condition under, adopting thick coating end thickness is 130 microns, the gradient ordered structure catalyst that thin end thickness is 40 microns, react that the transformation efficiency of propane is 42.4 weight % after 1 hour, selectivity is 90.7 weight %: and under the same reaction conditions, adopt coating even, and thickness is 89 microns ordered structure catalyst, its conversion of propane only is 38.1 weight %, and the propylene selectivity only is 61.5 weight %.
Embodiment
According to method provided by the present invention, the hole density of wherein said ordered structure carrier preferred cross-sections is that the sectional area in 31-140 hole/square centimeter, single hole is the honeycomb substrate of 0.6-4.0 square millimeter.Described honeycomb substrate can be made by non-metallic material or metallic substance.For example: the non-metallic material honeycomb substrate can be to be prepared from by in trichroite, mullite, diamond, corundum, zircon corundum, quartz, nepheline, the feldspar one or more.The metallic substance carrier is that one or more elements that add in common stainless steel or Stainless Steel Alloy in aluminium, silicon, nickel, chromium, manganese, titanium, yttrium and the zirconium constitute.The shape of the regular carrier hole of described honeycomb can be square (or wing square, promptly the centre bit of four edges is equipped with the inside wing of vertical edges in square hole, its length be the square length of side 1/5～2/5), equilateral triangle, regular hexagon, circle and corrugated etc.They can be commercially available commodity or adopt any existing method preparation.
Ordered structure catalyst of the present invention is that the coating ingredients that will contain matrix and dehydrogenation activity metal component is coated on the ordered structure carrier surface and is prepared from.The coated weight of coating ingredients is that benchmark is 0.5～25 weight % with the weight of ordered structure carrier, is preferably 2～20 weight %.Wherein said gradient ordered structure catalyst is meant coating ingredients axial (direction of gas communication) Gradient distribution along the ordered structure carrier on the surface of ordered structure carrier, promptly the end coating at the ordered structure carrier is thicker, and it is thinner in the other end coating of ordered structure carrier, thick end coat-thickness is the 60-400 micron, thin end coat-thickness is 1～60 micron, and the sectional area of thick coating stomidium be not less than carrier hole sectional area 10%, preferred thick end coat-thickness is the 70-350 micron, thin end coat-thickness is 5～50 microns, and the sectional area of thick coating stomidium be not less than carrier hole sectional area 30%.The axial gradient of the thickness of catalyzer distributed does not have particular requirement, is preferably 0.1～20 micron/centimetre.
The matrix of catalyst coat of the present invention is selected from one or more in aluminum oxide, silicon-dioxide, zirconium dioxide, titanium dioxide, magnesium oxide, the zinc oxide, can also can pass through commercially available by the various method preparations of knowing.Preferred aluminum oxide wherein further preferably has the aluminum oxide of γ, δ, θ or α phase structure, further preferred gama-alumina.
Metal component with dehydrogenation activity of the present invention is selected from one or more of VIB, VIIB or group VIII metal, for example be selected among Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, the Pt one or more, be preferably Pt or Cr, with matrix weight is benchmark, is 0.1～15 weight % in its content of metal.When active ingredient was precious metal, preferred metal content was 0.1～5 weight %; When active ingredient when being non-noble metal, preferred metal content is 3～14 weight %.
Coating of the present invention also contains adjuvant component, and adjuvant component is selected from one or more of basic metal, alkaline-earth metal, III A, IVA, IIB family metal, is benchmark with matrix weight, is no more than 5 weight % in its content of metal oxide.Preferred auxiliary agent is that potassium is or/and tin.
The preparation method of coating ingredients of the present invention comprises that any one method of knowing for preparing propane dehydrogenation catalyst of employing prepares.For example, the soluble salt wiring solution-forming of active ingredient can be used for flooding matrix, drying and roasting obtains required coating ingredients then; If contain auxiliary agent in the coating ingredients, then can flood auxiliary agent more earlier with after the matrix impregnation metal active constituent, also can flood auxiliary agent earlier, and then the dipping active metal component, the final drying roasting obtains the catalyst coat component.Can through drying and roasting, carry out the dipping of other component again after component of dipping yet, obtain the propane dehydrogenation catalyst coating ingredients through drying and roasting more at last, the sequencing to each component dipping in steeping process does not require.
The coating method of coating ingredients of the present invention can carry out with reference to the method described in the CN 1199733C, applies the mode of sweeping with wind the back and purges the back that finishes by control and place for some time and form the coating of Gradient distribution.
Preferred manufacturing procedure of gradient ordered structure catalyst of the present invention may further comprise the steps:
(1) preparation of coating ingredients slurry: the coatings prepared component is mixed with deionized water, regulate pH=1～7 with nitric acid or hydrochloric acid, it is that 20～45 weight %, particle diameter are 1～20 micron coating ingredients slurry that wet ball grinding obtains solid content; (2) preparation of surfactant soln: the tensio-active agent of 1 weight part is dissolved in 9～99 parts by weight of deionized water, add nitric acid or salt acid for adjusting pH value then and be 0.5～6.0 or add ammoniacal liquor to regulate the pH value be 7.5～9.5, obtain surfactant soln, wherein tensio-active agent can be selected from one or more in polyoxyethylene glycol, glycerol, carboxymethyl cellulose, polyvinyl alcohol or the polyacrylic acid; (3) clean of carrier: water carries out clean to the carrier with ordered structure, and drying is removed moisture then; (4) modification of coating ingredients slurry: (2) gained solution is mixed with (1) gained coating ingredients slurry, and the add-on of surfactant soln is 0.1～10 weight % of active ingredient butt weight; (5) modification of carrier: will handle the carrier impregnation obtain in (2) gained solution through (3), the time of dipping is 0.5～2 hour, dry 1～5 hour then; (6) coating of coating ingredients slurry: the slurry of (4) or (2) is coated on the carrier, carries out folk prescription to purging with pressurized air then, catalyzer is placed 5-30 minute then, the mode of placement is the direction that the carrier duct direction of catalyzer is parallel to gravity; The amount that applies makes that the thickness of the thickest end active component coating of catalyzer is 60～400 microns, and the thickness of the thinnest end active component coating is 1～60 micron, and thick end coat-thickness is preferably the 70-350 micron, and thin end coat-thickness is preferably 5～50 microns.Described carrier can be the carrier with ordered structure without any processing, also can be the carrier of handling through (3) or (5).Wherein, the pressure of described air can be 0.1～2MPa according to the thickness of required coating, is preferably 0.1～1MPa, and purge time can be 1-10 minute, is preferably 1-4 minute.
The thickness of floating coat of the present invention obtains by the method in scanning electron microscope scanning catalyzer end face or cross section.
Propane feed of the present invention can contain diluent gas, and carrier gas can be hydrogen or water vapor, and the volume ratio of carrier gas and propane is no more than 3 in the charging.
Dehydrogenating propane of the present invention reaction can be to carry out under 500～700 ℃ isothermal or the adiabatic condition in temperature, and the reaction absolute pressure is 0.01～0.4MPa, and reaction velocity is 1500～20000h
-1
According to the method described in the present invention, after preferably propane feed being heated to temperature of reaction, enter reactor, earlier with the thick end in contact of catalyst coat of the present invention, then along the mobile limit reaction of the porthole edge of gradient ordered structure catalyst, outflow reactor then.
The product of reaction separates and the refining propylene that obtains through overcooling, pressurization, and the unreacted propane that separation obtains turns back to opening for feed and reacts again.
Method provided by the present invention is particularly suitable for dehydrogenating propane and produces propylene, and described propane can be pure propane flammable gas, also can be splitting gas that is derived from catalytic cracking, hydroeracking unit or the oil field gas that is rich in propane.
Further specify the present invention below by example.
Example 1
This example illustrates the preparation of gradient ordered structure catalyst of the present invention.
Get 437.7 and restrain pseudo-boehmites (alumina content is 33%, and Qilu Petrochemical company catalyst plant is produced) adding deionized water, 50 ℃ are stirred the aging uniform sizing material that alumina content is 18 heavy % that gets after 30 minutes.Regulate pH=2.0 with dilute hydrochloric acid, stirred 40 minutes, obtain alumina gel at 50 ℃; Above-mentioned gel 650 ℃ of roastings 6 hours, obtains gama-alumina again in 130 ℃ of oven dry 4 hours.
Get the good alumina supporter hybrid infusion of a certain amount of Platinic chloride wiring solution-forming and roasting, the amount of Platinic chloride makes dipping back Pt content be equivalent to 0.55% of alumina weight, vibrations are 2 hours under action of ultrasonic waves, make dipping evenly, again it was dried 2 hours at 80 ℃, then 120 ℃ of oven dry 4 hours, again 550 ℃ of roastings 2 hours, and roasting 1 hour under the condition of 550 ℃ of water flowing steam, obtain the coating ingredients of catalyzer.
Get above-mentioned coating ingredients 100g, add deionized water and the surfactant soln that contains POLYPROPYLENE GLYCOL 5 weight % that accounts for this component 3 weight %, levigate with ball mill, the slurries of preparation solid content 30 weight %.Apply hole density 62 hole/square centimeters with above-mentioned slurries, the sectional area in hole is 1.6 square millimeters,
The square hole cordierite honeycomb carrier (Shanghai Corning Incorporated product) of millimeter 30 seconds, the temperature of control catalyst component slurry is 40～50 ℃, and be that the pressurized air of 0.2MPa axially carries out folk prescription to purging 3～4 minutes along carrier with pressure, then with the vertical placement of catalyzer 30 minutes, in 120 ℃ of dryings 4 hours, promptly obtained the gradient ordered structure catalyst in 4 hours 550 ℃ of roastings at last again.Coat-thickness through measuring prepared catalyzer is: thick end is 122 microns, and thin end thickness is 38 microns, and the coated weight of coating is 11.5 weight %.
Example 2
This example illustrates the preparation of gradient ordered structure catalyst of the present invention.
Prepare gama-alumina as example 1 described method.
Get the good alumina supporter hybrid infusion of a certain amount of Platinic chloride wiring solution-forming and roasting, the amount of Platinic chloride makes dipping back Pt content be equivalent to 0.50% of alumina weight, vibrations are 2 hours under action of ultrasonic waves, make dipping evenly, again it was dried 2 hours at 80 ℃, then in 120 ℃ of oven dry 4 hours, roasting 4 hours in 500 ℃ air again.Use SnCl then
2The solution impregnation said components that is made into makes that SnO content is equivalent to 0.55% of alumina weight in the catalyzer, in 120 ℃ of dryings after 4 hours again 500 ℃ of roastings 4 hours, obtain containing the coating ingredients of 0.55%SnO, 0.50%Pt.This coating ingredients is flooded with potassium nitrate solution, make that the content of potassium oxide is equivalent to 1.3% of alumina weight in the final coating ingredients.120 ℃ of dryings are after 4 hours, again 550 ℃ of roastings 1 hour, and roasting 1 hour under the condition of 550 ℃ of water flowing steam, obtain the coating ingredients of catalyzer.
Get above-mentioned coating ingredients 100g, add deionized water and the surfactant soln that contains POLYPROPYLENE GLYCOL 5 weight % that accounts for this component 3 weight %, levigate with ball mill, the slurries of preparation solid content 35 weight %.Apply hole density 62 hole/square centimeters with above-mentioned slurries, the sectional area in hole is 1.6 square millimeters,
The square hole cordierite honeycomb carrier (Shanghai Corning Incorporated product) of millimeter 30 seconds, the temperature of control catalyst component slurry is 40～50 ℃, and be that the pressurized air of 0.2MPa axially carries out folk prescription to purging 3～4 minutes along carrier with pressure, then with the vertical placement of catalyzer 30 minutes, in 120 ℃ of dryings 4 hours, promptly obtained the gradient ordered structure catalyst in 4 hours 550 ℃ of roastings at last again.Thick end thickness through measuring this gradient ordered structure catalyst is 130 microns, and thin end thickness is 40 microns, and the coated weight of coating is 12.8 weight %.
Example 3
This example illustrates the preparation of gradient ordered structure catalyst of the present invention.
Method as example 2 prepares the gradient ordered structure catalyst, and different is, the coatings prepared component is a benchmark with the weight of matrix, and each components contents is: Pt 0.7%, and SnO 0.45%, K
2O 1.1%, and used ordered structure carrier is 31 hole/square centimeters, and the sectional area in hole is 3.2 square millimeters,
The square hole cordierite honeycomb carrier (Shanghai Corning Incorporated product) of millimeter, the purging pressure after the carrier coated catalysts active ingredient is 0.15MPa, purge time is 2～3 minutes.The coat-thickness of prepared catalyzer: thick end is 148 microns, and thin end is 50 microns, and the coated weight of coating is 10.3 weight %.
Example 4
This example illustrates the preparation of gradient ordered structure catalyst of the present invention.
Method as example 2 prepares the gradient ordered structure catalyst, and different is, the coatings prepared component is a benchmark with the weight of matrix, and each components contents is: Pt 0.50%, and SnO 0.70%, K
2O1.2%, the solid content of prepared slurries are 25 weight %, and used ordered structure carrier hole density is 93 hole/square centimeters, and the sectional area in hole is 1.1 square millimeters,
The square hole cordierite honeycomb carrier (Shanghai Corning Incorporated product) of millimeter, the purging pressure after the carrier coated catalysts active ingredient is 0.45MPa, purge time is 3～4 minutes.The coat-thickness of prepared catalyzer is: thick end is 70 microns, and thin end is 5 microns, and the coated weight of coating is 7.1 weight %.
Comparative Examples 1
The preparation method of the uniform ordered structure catalyst of this Comparative Examples explanation coating.
Method as example 1 prepares coating ingredients, and different is, the weight with matrix in the coatings prepared component is benchmark, and the content of Pt is 0.6 weight %.
Get above-mentioned coating ingredients 100g, add deionized water and the surfactant soln that contains POLYPROPYLENE GLYCOL 5 weight % that accounts for this component 3 weight %, levigate with ball mill, the slurries of preparation solid content 30 weight %.The temperature of control slurries is 50～60 ℃, applies hole density 62 hole/square centimeters with above-mentioned slurries, and the sectional area in hole is 1.6 square millimeters,
The square hole cordierite honeycomb carrier (Shanghai Corning Incorporated product) 30 seconds of millimeter is that the pressurized air of 0.3MPa respectively purged the above-mentioned regular carrier that has applied catalyst component 2～3 minutes vertically from two ends with pressure then.After 4 hours, promptly obtained ordered structure catalyst in 4 hours 120 ℃ of dryings in 550 ℃ of roastings.Coating amount through measuring catalyzer is: 13.5wt%, coat-thickness evenly are 89 microns.
Example 5
This example illustrates the effect of method dehydrogenating propane reaction provided by the invention.
Example 1 prepared gradient ordered structure catalyst is placed
In the millimeter quartz tube reactor, with the homo(io)thermism of this reactor of electric furnace heating control.After 1 hour, feed propane at 500 ℃ of logical hydrogen reducings, reaction conditions: temperature is 620 ℃, and absolute pressure is 0.12MPa, and gas space velocity is 15000h
-1Calculate the transformation efficiency of propane and the selectivity of propylene, the results are shown in table 1.
Example 6
This example illustrates the effect of method dehydrogenating propane reaction provided by the invention.
Example 2 prepared gradient ordered structure catalysts are placed
In the millimeter quartz tube reactor, with the homo(io)thermism of this reactor of electric furnace heating control.After 1 hour, feed the mixed air (volume ratio of propane and hydrogen is 1: 1) of propane and hydrogen at 500 ℃ of logical hydrogen reducings, reaction conditions: temperature is 620 ℃, and absolute pressure is 0.12MPa, and gas space velocity is 15000h
-1Calculate the transformation efficiency of propane and the selectivity of propylene, the results are shown in table 1.
Example 7
This example illustrates the effect of method dehydrogenating propane reaction provided by the invention.
Example 3 prepared gradient ordered structure catalysts are placed
In the millimeter quartz tube reactor, with the homo(io)thermism of this reactor of electric furnace heating control.After 1 hour, feed the mixed air (volume ratio of propane and hydrogen is 1: 1) of propane and hydrogen at 500 ℃ of logical hydrogen reducings, reaction conditions: temperature is 620 ℃, and absolute pressure is 0.12MPa, and gas space velocity is 15000h
-1Calculate the transformation efficiency of propane and the selectivity of propylene, the results are shown in table 1.
Example 8
This example illustrates the effect of method dehydrogenating propane reaction provided by the invention.
Example 4 prepared gradient ordered structure catalysts are placed
In the millimeter quartz tube reactor, with the homo(io)thermism of this reactor of electric furnace heating control.After 1 hour, feed the mixed air (volume ratio of propane and hydrogen is 1: 1) of propane and hydrogen at 500 ℃ of logical hydrogen reducings, reaction conditions: temperature is 620 ℃, and absolute pressure is 0.12MPa, and gas space velocity is 15000h
-1Calculate the transformation efficiency of propane and the selectivity of propylene, the results are shown in table 1.
Comparative Examples 2
The uniform ordered structure catalyst of this Comparative Examples explanation coating is used for the effect of dehydrogenating propane reaction.
The catalyzer of Comparative Examples 1 preparation is placed
In the quartz tube reactor, with the homo(io)thermism of this reactor of electric furnace heating control.After 1 hour, feed propane at 500 ℃ of logical hydrogen reducings, reaction conditions: temperature is 620 ℃, and absolute pressure is 0.12MPa, and gas space velocity is 15000h
-1Calculate the transformation efficiency of propane and the selectivity of propylene, the results are shown in table 1.
The composition of propane and product obtains with gas chromatographic analysis in example and the Comparative Examples.
The selectivity method of calculation of the transformation efficiency of propane and propylene are as follows in the table 1:
Amount * 100% of the propane in the transformation efficiency of propane=(amount of propane in the amount-product of the propane in the charging)/charging
The yield of propylene=(amount of propylene * 44/42 in the product)/(amount of propane in the amount-product of the propane in the charging) * 100%
Table 1
By table 1 as seen, utilize the preparing propylene by dehydrogenating propane of method provided by the invention, conversion of propane reduces very little with the reaction times, the propylene selectivity slightly rises, and utilizes existing method preparing propylene by dehydrogenating propane, and conversion of propane sharply descended with the reaction times, catalyst deactivation is fast, and the propylene selectivity is low.
Claims (15)
1. the method for a preparing propylene by dehydrogenating propane, be included under the reaction conditions of dehydrogenating propane, propane feed is contacted with catalyzer, it is characterized in that, described catalyzer contains ordered structure carrier with parallel duct and the matrix that contains that is coated on this carrier, the coating of dehydrogenation activity metal component, coat-thickness distributes along the axial gradient of ordered structure carrier, wherein, thick coating end thickness is the 60-400 micron, thin end thickness is the 1-60 micron, the variation of described coat-thickness along the axial gradient in carrier duct be the 0.1-20 micron/centimetre, and the sectional area of thick coating stomidium be not less than carrier hole sectional area 10%.
2. in accordance with the method for claim 1, it is characterized in that described ordered structure carrier is that hole, cross section density is that the sectional area in 31-140 hole/square centimeter, single hole is the honeycomb substrate of 0.6-4.0 square millimeter.
3. in accordance with the method for claim 1, it is characterized in that, is benchmark with the weight of ordered structure carrier, and the content of described catalyst coat is 0.5～25 weight %.
4. in accordance with the method for claim 3, it is characterized in that, is benchmark with the weight of ordered structure carrier, and the content of described catalyst coat is 2～20 weight %.
5. in accordance with the method for claim 1, it is characterized in that described thick coating end thickness is the 70-350 micron, thin end thickness is the 5-50 micron, the sectional area of thick stomidium be not less than carrier hole sectional area 30%.
6. in accordance with the method for claim 1, it is characterized in that described matrix is selected from one or more in aluminum oxide, silicon-dioxide, zirconium dioxide, titanium dioxide, magnesium oxide, the zinc oxide.
7. in accordance with the method for claim 6, it is characterized in that described aluminum oxide is a gama-alumina.
8. in accordance with the method for claim 1, it is characterized in that described dehydrogenation activity metal component is selected from one or more of VIB, VIIB family or group VIII metal.
9. in accordance with the method for claim 8, it is characterized in that described group VIII metal component is a platinum, is benchmark in metal and with the weight of matrix, and its content is 0.1～5.0 weight %.
10. in accordance with the method for claim 8, it is characterized in that described vib metal component is a chromium, is benchmark in metal and with the weight of matrix, and its content is 3～14 weight %.
11. in accordance with the method for claim 1, it is characterized in that, also contain one or more adjuvant components that are selected from basic metal, alkaline-earth metal, IIIA, IVA, IIB family metal in the described coating, in metal oxide and with the weight of matrix is benchmark, and the content of described adjuvant component is no more than 5 weight %.
12. in accordance with the method for claim 11, it is characterized in that described adjuvant component is potassium and/or tin.
13. according to each described method of claim 1～12, it is characterized in that described dehydrogenation reaction conditions comprises: temperature is 500～700 ℃, absolute pressure is 0.01～0.4MPa, and air speed is 1500～20000h
-1
14. according to each described method of claim 1～12, it is characterized in that, also contain in the described propane feed and be selected from H
2Or the carrier gas of water vapor, the volume ratio of described carrier gas and propane is no more than 3.
15., it is characterized in that to be propane enter from an end of the thick coating of catalyzer the mode that described propane feed contacts with catalyzer, discharges from the end that coating is thin according to each described method of claim 1～12.
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| CN100464849C (en) * | 2007-07-26 | 2009-03-04 | 南京大学 | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene |
| CN101927196B (en) * | 2009-06-26 | 2012-03-07 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof |
| CN102040445B (en) * | 2009-10-14 | 2013-10-23 | 卓润生 | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon |
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