CN104447164A - Method for preparing propylene by performing oxidative dehydrogenation on propane - Google Patents

Method for preparing propylene by performing oxidative dehydrogenation on propane Download PDF

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CN104447164A
CN104447164A CN201410834215.3A CN201410834215A CN104447164A CN 104447164 A CN104447164 A CN 104447164A CN 201410834215 A CN201410834215 A CN 201410834215A CN 104447164 A CN104447164 A CN 104447164A
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propane
propylene
oxidative dehydrogenation
reaction
metal oxide
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CN104447164B (en
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康金灿
解泉华
张庆红
郁风驰
王野
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Xiamen University
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Xiamen University
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

The invention discloses a method for preparing propylene by performing oxidative dehydrogenation on propane, and relates to a method for preparing propylene. The method comprises the steps of: heating a catalyst to the temperature of 400 to 700 DEG C, keeping the temperature for 10 to 120 minutes, introducing mixed reaction gas to pass through a catalyst bed layer, and reacting to obtain the product of propylene. The mixed reaction gas propane, oxygen, hydrogen halide gas and inert gas. A small amount of hydrogen halide is introduced into the reaction system to effectively activate the propane, the selectivity of the propylene is more than 80 percent, a once through yield of the propylene is close to 50 percent, and performance of the propylene is much better than the performance of the traditional propylene which is obtained by directly dehydrogenizing and performing oxidative dehydrogenation on the propane; a reaction process is gentle, advanced oxidation for oxidative dehydrogenation of propane to prepare the propylene is greatly suppressed at the presence of halogen hydride, the selectivity of the propylene is greatly improved, and a problem of low selectivity of the propylene at high conversion rate of the propane is solved; and the hydrogen halide is recoverable and reused, energy consumption is low, the employed catalyst is a non-noble metal catalyst, and the components is remained stable during the reaction.

Description

A kind of method preparing propylene from oxidative dehydrogenation of propane
Technical field
The present invention relates to the preparation method of propylene, especially relate to a kind of method preparing propylene from oxidative dehydrogenation of propane.
Background technology
Propylene is the very important basic petrochemical raw material being only second to ethene, mainly for the production of important Chemicals such as polypropylene, vinylformic acid and lipid thereof, vinyl cyanide, propylene oxide, epoxy chloropropane, Virahol, phenol, acetone, butanols and octanols.Present stage, the production of propylene derives from steam cracking and petroleum naphtha fluid catalystic cracking (FCC) process of the hydrocarbon producing ethene mainly as by product.In recent years, what increase fast by acryloyl derivative consumption pulls, and propylene demand continues to rise, and the propylene imbalance between supply and demand of China becomes increasingly conspicuous.
The new technology of some production propylene obtains increasing application in recent years, as propane direct dehydrogenation (PDH), methanol-to-olefins (MTO) and preparing propylene from methanol (MTP), has become the important channel of propylene enhancing.So far, existing PDH, MTO and MTP device that overlaps of China is gone into operation more.But these new technologies also exist some problems, the process as PDH is subject to the control of thermodynamic(al)equilibrium, severe reaction conditions (high temperature, 1000K), not higher than 30%, and there is the problems such as catalyst deactivation in once through yield, regeneration need be repeated, considerably increase the cost of this process.MTO and MTP is novel coal chemical technology, the multistep process of experience producing synthesis gas from coal, synthesising gas systeming carbinol and methanol-to-olefins, overall cost of ownership is high, and catalyzer also exists the problem of inactivation, and what is more important often consumes and CO with high water from the process of coal 2emission problem; If with outsourcing methyl alcohol for raw material, then economy and competitive power will significantly decline.
Oxidative dehydrogenation of propane (ODH) is as a kind of new way of propylene processed, can overcome thermodynamic(al)equilibrium be limited in more gentle temperature of reaction under (<800K) obtain high transformation efficiency, and catalyzer does not need frequent regeneration, therefore enjoy the extensive concern of investigator.In recent years, relevant oxidative dehydrogenation of propane research is comparatively deep.The high performance catalyst reported comprises vanadium base, molybdenum base, chromium base and nickel-base catalyst etc.If the conversion of propane of V/MgO catalyzer 500 DEG C time is 22.5%, Propylene Selectivity is 59.8% (J.Catal.1987,105,483); With MCF be carrier loaded V catalyzer on, 550 DEG C time, conversion of propane is 40.8%, and Propylene Selectivity is 68.5%, and propene yield reaches about 28% (J.Catal.2006,239,125); The catalyzer 3%Cs with optimum performance reported 2o/2CeO 2/ CeF 3, its conversion of propane 500 DEG C time is 53.4%, and Propylene Selectivity is 67.5%, and yield reaches 36% (Catal.Today.1999,51,161).Nickel-base catalyst is the oxidative dehydrogenation of propane catalyzer (see Chinese patent CN1557546A, CN101543781A, CN101219389A, CN102294251A) that a class has better low-temperature catalytic activity, as CN1557546A discloses a kind of nano-composite catalyst containing Ce, Ni, when temperature of reaction is 300 DEG C, conversion of propane is 52%, and Propylene Selectivity is 31.7%; CN 101219389A discloses a kind of heteropolyacid alkali (soil) metal-salt composite catalyst containing NiO, and propene yield reaches 20%.
Although the research of preparing propene by oxidative dehydrogenation of propane has obtained certain achievement, generate COx because deep oxidation easily occurs in this reaction, propene yield is not substantially higher than 30%.Under high alkane conversion, obtain high olefin selectivity still have challenge.If further develop novel method or the new way of propane propylene, improve conversion of propane and Propylene Selectivity, this process will have more economy and competitive power.
Summary of the invention
The present invention aims to provide a kind of method preparing propylene from oxidative dehydrogenation of propane with highly selective and high yield.
Described a kind of chemical equation preparing the method for propylene from oxidative dehydrogenation of propane is:
A kind of described method preparing propylene from oxidative dehydrogenation of propane, concrete steps are as follows:
Catalyzer is heated to 400 ~ 700 DEG C, and keeps 10 ~ 120min, then pass into reaction mixture gas body, obtain product propylene through catalyst bed reaction, described reaction mixture gas body comprises propane, oxygen, hydrogen halide and rare gas element.
Described heating can by catalyzer in the mixed gas of air or oxygen and nitrogen from room temperature with not higher than 20 DEG C of min -1temperature rise rate heating, be preferably heated to 500 ~ 600 DEG C with the temperature rise rate not higher than 5 ~ 10 DEG C of min, and keep 10 ~ 60min.
The chemical constitution of described catalyzer can be at least one in rare earth oxide, VB family metal oxide, group vib metal oxide, group VIII metal oxide compound, IB family metal oxide, VA family metal oxide etc.
Described rare earth oxide can be selected from La 2o 3, CeO 2, Pr 2o 3, Nd 2o 3, Sm 2o 3, Eu 2o 3, Dy 2o 3, Er 2o 3deng at least one; Described VB family metal oxide can be selected from V 2o 5, Nb 2o 5, Ta 2o 5deng at least one; Described group vib metal oxide can be selected from Cr 2o 3, MoO 3, WO 3deng at least one; Described group VIII metal oxide compound can be selected from Fe 3o 4, Co 3o 4, Ni 2o 3deng at least one; Described IB family metal oxide can be CuO etc.; Described VA family metal oxide can be selected from Bi 2o 3, Sb 2o 3deng at least one.
The composition of described reaction mixture gas body by volume per-cent can be propane 1.5% ~ 20%, oxygen 1.5% ~ 40%, hydrogen halide 1.5% ~ 10%, and surplus is rare gas element.
Described hydrogen halide can be selected from least one in HCl, HBr, HI etc.
Described rare gas element can adopt nitrogen etc.
The air speed of described reaction mixture gas body is 1800 ~ 30000h -1, temperature of reaction is 300 ~ 600 DEG C.
The method preparing propylene from oxidative dehydrogenation of propane provided by the present invention, can be used for fixed bed reaction process, also can be used for fluidized-bed reaction process.
Compared with the technology of existing propane propylene, haloid acid is introduced on method innovation ground provided by the present invention, and facilitate the activation of propane, the beneficial effect produced embodies in the following areas:
(1) be greatly suppressed in the coexist deep oxidation reaction of lower preparing propene by oxidative dehydrogenation of propane of hydrogen halide, Propylene Selectivity significantly promotes, and solves the difficult problem that Propylene Selectivity under high conversion of propane is lower.
(2) under the reaction conditions optimized, Propylene Selectivity is higher than 80%, and propylene once through yield can reach 50%, far above the catalytic performance of oxydehydrogenation and direct dehydrogenation.
(3) above-mentioned beneficial effect can be obtained when hydrogen halide consumption is lower, and hydrogen halide is recyclable and recycle.
(4) this process reaction mild condition (temperature is lower than 600 DEG C), compared to the reaction of propane direct dehydrogenation, energy consumption significantly reduces.
(5) catalyzer adopted is non-precious metal catalyst, cheap, and keeps stable at reaction process composition.
To sum up, use the novel method from preparing propene by oxidative dehydrogenation of propane provided by the present invention, Propylene Selectivity and yield are far above the performance of prior art, and catalyzer is with low cost, and the gentle and hydrogen halide of process can be recycled, and has good prospects for commercial application.
Embodiment
Further describe the method preparing propylene from oxidative dehydrogenation of propane provided by the present invention below.
Embodiment 1
Get 1.0g30 ~ 60 object commodity La 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 200ml min at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 200ml min -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 30ml min -1, 10ml min -1, 40mlmin -1, temperature of reaction is 500 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 1.
Table 1 La 2o 3catalytic performance (T=500 DEG C, HCl) (%) of catalyzer
Conversion of propane 45.2
Propylene Selectivity 75.1
Propenyl chloride selectivity 7.4
Vinylchlorid selectivity 3.1
Carbon monoxide selective 6.1
Carbon dioxide selectivity 8.3
Embodiment 2
Get 1.0g30 ~ 60 object commodity Eu2O3 catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 100mlmin at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 450 DEG C and keep 60min, then with 200mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogen bromide, nitrogen, and flow velocity is respectively 15ml min -1, 30ml min -1, 8ml min -1, 47ml min -1, temperature of reaction is 550 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 2.
Table 2 Eu 2o 3catalytic performance (T=550 DEG C, HBr) (%) of catalyzer
Conversion of propane 55.9
Propylene Selectivity 81.3
Bromopropylene selectivity 6.0
Bromine ethylene selectivity 2.2
Carbon monoxide selective 5.0
Carbon dioxide selectivity 5.5
Embodiment 3
Get 1.0g30 ~ 60 object commodity CeO respectively 2, Pr 2o 3, Nd 2o 3, Sm 2o 3, Dy 2o 3, Er 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 100ml min at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 450 DEG C and keep 60min, then with 200ml min -1nitrogen purging 60min.Catalyzed reaction is carried out respectively in atmospheric fixed bed reactor, and reaction conditions is with embodiment 1.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 3.
Catalytic performance (T=500 DEG C, HCl) (%) of each catalyzer of table 3
Catalyzer CeO 2 Pr 2O 3 Nd 2O 3 Sm 2O 3 Dy 2O 3 Er 2O 3
Conversion of propane 53.5 66.6 38.9 71.0 49.7 35.6
Propylene Selectivity 78.1 72.4 82.2 65.3 73.2 70.1
Propenyl chloride selectivity 7.3 8.0 4.4 5.1 7.2 6.3
Vinylchlorid selectivity 3.1 4.3 1.5 3.2 2.1 1.9
Carbon monoxide selective 6.2 6.2 7.3 14.5 10.8 12.8
Carbon dioxide selectivity 5.3 9.1 4.6 11.9 6.7 8.9
Embodiment 4
Get 1.0g30 ~ 60 object commodity V respectively 2o 5and Nb 2o 5catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 200ml min at flow velocity -1air atmosphere under, with 15 DEG C of min -1temperature rise rate from room temperature, be heated to 480 DEG C and keep 30min, then with 100ml min -1nitrogen purging 30min.Catalyzed reaction is carried out respectively in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogen iodide, nitrogen, and flow velocity is respectively 15ml min -1, 20ml min -1, 10mlmin -1, 55ml min -1, temperature of reaction is 490 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 4.
Table 4 V 2o 5and Nb 2o 5catalytic performance (T=490 DEG C, HI) (%) of catalyzer
Catalyzer V 2O 5 Nb 2O 5
Conversion of propane 62.8 58.6
Propylene Selectivity 78.6 77.0
Iodopropylene selectivity 5.1 7.3
Iodoethylene selectivity 1.2 2.0
Carbon monoxide selective 6.2 7.1
Carbon dioxide selectivity 8.9 6.6
Embodiment 5
Get 1.0g30 ~ 60 object commodity Ta 2o 5catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 480 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 45ml min -1, 10ml min -1, 70ml min -1, temperature of reaction is 500 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 5.
Table 5 Ta 2o 5catalytic performance (T=500 DEG C, HCl) (%) of catalyzer
Conversion of propane 42.6
Propylene Selectivity 70.5
Propenyl chloride selectivity 5.1
Vinylchlorid selectivity 1.6
Carbon monoxide selective 15.6
Carbon dioxide selectivity 7.2
Embodiment 6
Get 1.0g30 ~ 60 object commodity MoO 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 100mlmin at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 450 DEG C and keep 60min, then with 200mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 15ml min -1, 30ml min -1, 5ml min -1, 50ml min -1, temperature of reaction is 510 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 6.
Table 6 MoO 3catalytic performance (T=510 DEG C, HCl) (%) of catalyzer
Conversion of propane 65.9
Propylene Selectivity 73.3
Propenyl chloride selectivity 6.1
Vinylchlorid selectivity 1.1
Carbon monoxide selective 10.0
Carbon dioxide selectivity 9.5
Embodiment 7
Get 1.0g30 ~ 60 object commodity Cr 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 100mlmin at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 100mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 15ml min -1, 25ml min -1, 8ml min -1, 52ml min -1, temperature of reaction is 520 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 7.
Table 7 Cr 2o 3catalytic performance (T=520 DEG C, HCl) (%) of catalyzer
Conversion of propane 60.1
Propylene Selectivity 69.9
Propenyl chloride selectivity 6.8
Vinylchlorid selectivity 2.1
Carbon monoxide selective 10.5
Carbon dioxide selectivity 10.7
Embodiment 8
Get 1.0g30 ~ 60 object commodity WO 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 100mlmin at flow velocity -1air atmosphere under, with 10 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 100mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogen bromide, nitrogen, and flow velocity is respectively 15ml min -1, 25ml min -1, 5ml min -1, 55ml min -1, temperature of reaction is 500 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 8.
Table 8 WO 3catalytic performance (T=500 DEG C, HBr) (%) of catalyzer
Conversion of propane 48.6
Propylene Selectivity 65.8
Bromopropylene selectivity 8.9
Bromine ethylene selectivity 3.2
Carbon monoxide selective 15.1
Carbon dioxide selectivity 7.0
Embodiment 9
Get 1.0g30 ~ 60 object commodity Fe 3o 4catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogen iodide, nitrogen, and flow velocity is respectively 40ml min -1, 60ml min -1, 20ml min -1, 100ml min -1, temperature of reaction is 500 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 9.
Table 9 Fe 3o 4catalytic performance (T=500 DEG C, HI) (%) of catalyzer
Conversion of propane 35.6
Propylene Selectivity 78.9
Iodopropylene selectivity 8.0
Iodoethylene selectivity 2.5
Carbon monoxide selective 6.6
Carbon dioxide selectivity 4.0
Embodiment 10
Get 1.0g30 ~ 60 object commodity Co 3o 4catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 30ml min -1, 10ml min -1, 60ml min -1, temperature of reaction is 520 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 10.
Table 10 Co 3o 4catalytic performance (T=520 DEG C, HCl) (%) of catalyzer
Conversion of propane 56.8
Propylene Selectivity 73.5
Propenyl chloride selectivity 5.1
Vinylchlorid selectivity 3.2
Carbon monoxide selective 8.3
Carbon dioxide selectivity 9.9
Embodiment 11
Get 1.0g30 ~ 60 object commodity Ni 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 500 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 35ml min -1, 10ml min -1, 65ml min -1, temperature of reaction is 520 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 11.
Table 11 Ni 2o 3catalytic performance (T=520 DEG C, HCl) (%) of catalyzer
Conversion of propane 46.5
Propylene Selectivity 62.8
Propenyl chloride selectivity 6.6
Vinylchlorid selectivity 4.4
Carbon monoxide selective 15.2
Carbon dioxide selectivity 11.0
Embodiment 12
Get 1.0g30 ~ 60 object commodity CuO catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 480 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogen bromide, nitrogen, and flow velocity is respectively 20ml min -1, 35ml min -1, 10ml min -1, 75ml min -1, temperature of reaction is 520 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 12.
Catalytic performance (T=520 DEG C, HBr) (%) of table 12 CuO catalyzer
Conversion of propane 63.1
Propylene Selectivity 75.4
Bromopropylene selectivity 5.9
Bromine ethylene selectivity 2.2
Carbon monoxide selective 10.2
Carbon dioxide selectivity 6.3
Embodiment 13
Get 1.0g30 ~ 60 object commodity Sb 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm), is 150mlmin at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 480 DEG C and keep 60min, then with 150mlmin -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 35ml min -1, 15ml min -1, 80ml min -1, temperature of reaction is 540 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 13.
Table 13 Sb 2o 3catalytic performance (T=540 DEG C, HCl) (%) of catalyzer
Conversion of propane 53.9
Propylene Selectivity 68.8
Propenyl chloride selectivity 5.1
Vinylchlorid selectivity 1.2
Carbon monoxide selective 10.9
Carbon dioxide selectivity 14.0
Embodiment 14
Get 0.5g30 ~ 60 object commodity Bi 2o 3with 0.5g30 ~ 60 object commodity Sb 2o 3catalyzer, loading in crystal reaction tube (internal diameter 10mm) after mixing, is 150ml min at flow velocity -1air atmosphere under, with 5 DEG C of min -1temperature rise rate from room temperature, be heated to 480 DEG C and keep 60min, then with 150ml min -1nitrogen purging 60min.Catalyzed reaction is carried out in atmospheric fixed bed reactor, and reaction conditions is: reactant gases propane, oxygen, hydrogenchloride, nitrogen, and flow velocity is respectively 20ml min -1, 35ml min -1, 15ml min -1, 80ml min -1, temperature of reaction is 450 DEG C, normal pressure.Reaction product adopts gas chromatograph to carry out on-line analysis.Concrete reactivity worth is listed in table 14.
Table 14 Bi 2o 3+ Sb 2o 3catalytic performance (T=450 DEG C, HCl) (%) of catalyzer
Conversion of propane 42.8
Propylene Selectivity 70.1
Propenyl chloride selectivity 6.2
Vinylchlorid selectivity 2.4
Carbon monoxide selective 12.0
Carbon dioxide selectivity 9.3
The present invention uses propane for raw material, under hydrogen halide exists, solid catalyst is directly prepared by propane and air or oxygen generation oxidative dehydrogenation the method for propylene.The chemical constitution of solid catalyst be rare earth oxide, VB family metal oxide, group vib metal oxide, group VIII metal oxide compound, IB family metal oxide, VA family metal oxide one or more.The unstripped gas of oxidative dehydrogenation of propane reaction, by propane, oxygen, hydrogenchloride, also can be mixed into rare gas element.Wherein preferably reaction gas consists of: propane volume content is 1.5 ~ 20%, and oxygen volume content is 1.5 ~ 40%, and the volume content of hydrogen halide is 1.5 ~ 10%, and remaining is nitrogen.Preferably reaction conditions is: with air speed for 1800 ~ 30000h -1mixed gas obtain product through catalyst bed reaction, temperature of reaction is 300 ~ 600 DEG C.Use the present invention, in reaction system, introduce a small amount of hydrogen halide effectively can activate propane, Propylene Selectivity is higher than 80%, propylene once through yield is close to 50%, far above the performance of existing propane direct dehydrogenation and oxidative dehydrogenation of propane, and reaction process is gentle, catalyzer is cheap, has a good application prospect.

Claims (10)

1. prepare a method for propylene from oxidative dehydrogenation of propane, it is characterized in that its concrete steps are as follows:
Catalyzer is heated to 400 ~ 700 DEG C, and keeps 10 ~ 120min, then pass into reaction mixture gas body, obtain product propylene through catalyst bed reaction, described reaction mixture gas body comprises propane, oxygen, hydrogen halide and rare gas element.
2. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, it is characterized in that described heating be by catalyzer in the mixed gas of air or oxygen and nitrogen from room temperature with not higher than 20 DEG C of min -1temperature rise rate heating.
3. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, is characterized in that described heating is that catalyzer is heated to 500 ~ 600 DEG C, and keeps 10 ~ 60min.
4. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 2, is characterized in that described heating is heated from room temperature with the temperature rise rate not higher than 5 ~ 10 DEG C of min in the mixed gas of air or oxygen and nitrogen by catalyzer.
5. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, is characterized in that the chemical constitution of described catalyzer is at least one in rare earth oxide, VB family metal oxide, group vib metal oxide, group VIII metal oxide compound, IB family metal oxide, VA family metal oxide.
6. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 5, is characterized in that described rare earth oxide is selected from La 2o 3, CeO 2, Pr 2o 3, Nd 2o 3, Sm 2o 3, Eu 2o 3, Dy 2o 3, Er 2o 3in at least one; Described VB family metal oxide can be selected from V 2o 5, Nb 2o 5, Ta 2o 5in at least one; Described group vib metal oxide can be selected from Cr 2o 3, MoO 3, WO 3in at least one; Described group VIII metal oxide compound can be selected from Fe 3o 4, Co 3o 4, Ni 2o 3in at least one; Described IB family metal oxide can be CuO; Described VA family metal oxide can be selected from Bi 2o 3, Sb 2o 3in at least one.
7. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, the composition that it is characterized in that described reaction mixture gas body by volume per-cent is propane 1.5% ~ 20%, oxygen 1.5% ~ 40%, hydrogen halide 1.5% ~ 10%, surplus is rare gas element.
8. a kind of method preparing propylene from oxidative dehydrogenation of propane as described in claim 1 or 7, is characterized in that described hydrogen halide is selected from least one in HCl, HBr, HI.
9. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, is characterized in that described rare gas element adopts nitrogen.
10. a kind of method preparing propylene from oxidative dehydrogenation of propane as claimed in claim 1, is characterized in that the air speed of described reaction mixture gas body is 1800 ~ 30000h -1, temperature of reaction is 300 ~ 600 DEG C.
CN201410834215.3A 2014-12-29 2014-12-29 A kind of method preparing propylene from oxidative dehydrogenation of propane Active CN104447164B (en)

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CN107812533A (en) * 2017-11-14 2018-03-20 江苏师范大学 A kind of preparation method of propane dehydrogenation catalyst
CN111250084A (en) * 2018-11-30 2020-06-09 中国石油化工股份有限公司 Non-noble metal propane dehydrogenation catalyst with modified spherical bagel mesoporous material silica gel composite material as carrier and preparation method and application thereof

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CN107537556A (en) * 2016-06-29 2018-01-05 中国石油化工股份有限公司 Dehydrogenation of isobutane catalyst and its method in the presence of carbon dioxide mild oxidizing agent
CN107537556B (en) * 2016-06-29 2020-09-04 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst in presence of carbon dioxide mild oxidant and method thereof
CN107812533A (en) * 2017-11-14 2018-03-20 江苏师范大学 A kind of preparation method of propane dehydrogenation catalyst
CN111250084A (en) * 2018-11-30 2020-06-09 中国石油化工股份有限公司 Non-noble metal propane dehydrogenation catalyst with modified spherical bagel mesoporous material silica gel composite material as carrier and preparation method and application thereof

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