CN106348996B - A kind of propane or dehydrogenation producing propylene technique and its device rich in propane lower carbon number hydrocarbons - Google Patents

Abstract

The invention discloses a kind of propane or rich in the dehydrogenation producing propylene technique and its device of propane lower carbon number hydrocarbons, including riser reaction system and catalyst cyclic regeneration system, heat carrier recirculation system, propane is in riser after uplink reaction a period of time, temperature declines in riser, and dehydrogenation reaction speed reduces；High temperature little particle heat carrier enters the low temperature position in riser at this time, improves the temperature of oil gas and catalyst, continues dehydrogenation reaction；Heat carrier is so riser concurrent heating 2-6 times, makes dehydrogenation reaction close to equilibrium conversion；Enter Second reactivator through the heat carrier that cyclone separator separates, is contacted with the high-temperature flue gas of dry combustion gas and retrieve high-temperature heat carrier and be recycled to each portion of riser；The bulky grain microspherical catalyst entered from riser top is separated by gravitational settling to riser lower part, and promotion is transported to the first regenerator, under the conditions ofs low temperature, hypoxemia etc. by catalyst regeneration after, recycled back riser upper entrance realizes catalyst circulation.

Description

A kind of propane or dehydrogenation producing propylene technique and its device rich in propane lower carbon number hydrocarbons

Technical field:

The present invention relates to a kind of dehydrogenating technology of low-carbon alkanes, relate more specifically to a kind of propane or rich in propane lower carbon number hydrocarbons Dehydrogenation producing propylene technique and its device.

Background technique:

Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technique has the features such as high income, hydrogen obtained by dehydrogenation is high value added product, is The main method of current production propylene.There are many method of Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane disclosed in the prior art, such as CN100460371C discloses a kind of device of preparing propylene by dehydrogenating propane under hydrogen plasma, due to its needs wait from Under conditions of son, laboratory test state can only be rested at present, it is difficult to carry out plant-scale implementation.USP4418237, USP4435607, USP4788371, USP4886928, CN1179930C etc. disclose a kind of by removing hydrogen in reaction process The method of dehydrogenating of hydrocarbon raw material.CN1268589C then discloses a kind of improved fixed bed low-carbon hydrocarbon dehydrogenation method, passes through circulation Portion of product gas enters reaction zone and improves conversion ratio and improve catalyst life.The caltalyst of preparing propylene by dehydrogenating propane Owner will have oxidative dehydrogenation type catalyst, chromium-based catalysts and platinum group catalyst etc..It is existing to change in terms of catalyst Into dehydrogenating low-carbon alkane technology it is very much, using Cr/Al catalyst prepared by infusion process as disclosed in GB2177317A, It is de- by the heterogeneously catalyzed partial of improved noble metal catalyst fixed bed hydrocarbon disclosed in CN101384525, CN101460433 Hydrogen methods, and the acidity of catalyst adjust and burn generated in method of dehydrogenating disclosed in CN1220659C Hydrogen but burns up valuable hydrogen and will affect economy so as to improve the space-time yield of dehydrogenation reaction.

A kind of typical fixed bed dehydrogenating propane method HOUDRYCATOFIN method is disclosed by USP2419997, is used The dehydrogenating propane technique of fixed bed reactors is wherein generally operated in parallel using multiple reactors in conversion zone, a part reaction Device production, while a part of reactor regenerates, the regeneration period of catalyst is generally several hours.Dehydrogenating propane reaction is molecule The increased endothermic reaction, therefore high temperature and low pressure are conducive to the progress of reaction.CN101252989A is changed on this basis Into the inert material such as alpha-oxidation aluminium ball for adding 30~50% in catalyst bed is used for accumulation of heat to improve the conversion of bed Efficiency.

CN1037765C then disclose by stainless steel reactor formed stannide protective layer improve process unit and Reaction conversion temperature can be improved in method, to improve transformation efficiency.

Gas chemicals company, the U.S. has industrialized Catofin dehydrogenating propane technique and complexes, Graig R G, Delaney TJ, DuffaloJ M.Catalytic Dehydrogenation Performance of Catofin Process Petrocheical Review.Houston.Dewitt.1990, EP192059, GB2162082, it is insulation fix bed Reactor soaks the chromium of 18~20wt% for activated aluminum bead using Cr2O3/Al2O3 catalyst.At tiny structure (49Kpa), newly Fresh propane operates at a temperature of being preheated to 550~750 DEG C (preferably 620~670 DEG C) after mixing with recycled propane.Temperature of reactor and Pressure can all influence the yield of propylene, and propane conversion per pass is 55~60mol%, and density of propylene is 52% or so.This work The several reactors of skill are in parallel, including a reaction, reactor switching, catalyst regeneration cycle, and the catalyst in reactor steams When vapour regeneration, coking on catalyst are burnt, the energy discharged can be used as the heat that dehydrogenation reaction is absorbed, and be recycled It carries out forming continuous production process.Entire technique propene yield is 83%.

The STAR technique of Philips Petroleum Co., U.S. exploitation is also a kind of fixed-bed intermittent regeneration technology and process unit, Dunn RO, et al.The Phillips Steam Active Re2forming (STAR) ProcessC3, C1 and C₅ Paraffin for the Dehydrogenation.Petrochemical Review.HoustonDewitt, 1992, USP4167532, USP4902849, USP4926005, USP4996387, USP5389342, naphtha (≤C5) dehydrogenating technology are adopted With isothermal operation, one group of heterogeneous fixed bed reactor is entered after vapoury raw material preheating, there are many roots to be catalyzed for each reactor Agent filling pipe.Reactor operation is circulation, goes to carry out catalyst regeneration after can be switched such as each reactor, keeps certain embodiments It is carried out continuously.Steam is mainly used for diluting, and keeps gross pressure in reactor constant, reduces the partial pressure of hydrocarbon and hydrogen, and reaction can be made flat Weighing apparatus is intended to increase the conversion ratio of C5.Switch after reactor online production 7 hours, decaying catalyst was through combustive regeneration 1 hour After can activate completely.It is reported that 1 to 2 years catalyst entire lives.The technique propylene is 80% to propane recovering rate.What side reaction generated CO2 must be removed from reactant in separation.

The POH fixed-bed intermittent regenerative response technique and process unit of German Linde Co are also anti-using fixed bed tubular type Answer device, Peter Elsle.Ullman ' s Encyclopedia of Industrial Chemistry.Vol A22 Barbara Elvers HansJugen 2,1993.211~222, key problem in technology are that reaction temperature is low, reactor is non-etc. Warm heat-insulating is operated under conditions of close to isothermal reaction, with reduce the thermal cracking of propane with it is coking.It is to urge with chromium oxide Agent has 9 hours relatively long circulating periods, and the difference with other techniques is that raw material propane does not need hydrogen or Steam dilution.Cause This with 91% more highly selective, product available polymerization-grade propylene after separation.Process avoids Catofin techniques The problems such as negative-pressure operation and Oleflex technique are diluted with H2, it is at low cost, pollution less, power consumption it is low and investment it is less make its with Similar technique, which is compared, has stronger competitiveness, is carrying out industrialization design.

Currently, outstanding problem existing for dehydrogenating propane technique using fixed bed reactors is catalyst heap than big, bed The space passed through for reactant or product is small and resistance is big, and reaction pressure drop is larger, and reaction velocity is lower, and mass-and heat-transfer is easy slowly It causes reaction bed temperature to be unevenly distributed uniform product further occurrence side reaction, so that reaction selectivity is deteriorated, and with anti- The progress answered influences being normally carried out for reaction since the change of catalytic mechanical intensity makes catalyst bed structure change.

Uop Inc., the U.S. exploitation Oleflex technique use moving bed continuous regenerative reaction process device, be by Pacol technological development, Pujado, P.R, Vora, B.V.Hydrocarbon Process, 1990,69 (3): 65, USP3584060, USP3878131, USP4438238, USP4595673, USP4716143, USP4786265, USP4827072, Nineteen ninety realizes industrialized production.Both preparing propylene by dehydrogenating propane techniques of Oleflex and Catofin are substantially the same, and institute is different Only dehydrogenation and catalyst regeneration part, Oleflex technique use Pt/Al2O3 moving-bed of catalyst reactor, be one absolutely Hot continuous processing, reaction institute's calorific requirement is by the heated rear offer again of the temperature difference between reacting each step.The technique carries out under micro-positive pressure Operation, using palladium as catalyst, the selectivity to propylene is 89~91%.Dehydrogenation can be recycled through regeneration, that is, inactivate Catalyst separates in a regenerator, burns, and removes the coking of catalyst surface, and regenerated catalyst sends dehydrogenation reactor back to.It will Gained propylene passes through continuous dethanizer, depropanizing tower, can get polymerization-grade propylene.The advantages of Oleflex technique is that operation connects Continuous, load uniformly, space-time yield it is constant, the catalytic activity in reactor cross section is constant, and catalyst regeneration carries out under isothermal.It should Technique propene yield is 86.4%, hydrogen yield 3.5%.

The disadvantage of Oleflex technique is the concurrent heating mode between multistage reactor.It needs institute in upper level reactor There is substance (including reaction raw materials and product) to draw reactor, returns to next order reaction after heating up into heating furnace supplementary heating The reaction was continued for device, this makes the residence time of reaction raw materials and product at high temperature considerably beyond the original required reaction of dehydrogenation Time, the side reactions such as cracking, condensation, the coking of such reaction raw materials and product at high temperature are all significantly increased, and reduce reaction and produce While product Propylene Selectivity, separating energy consumption is significantly increased.

It is de- to C2~C5 light chain alkane that CN1082018 discloses a kind of noble metal catalyst that can be used for fluidized-bed reactor The manufacturing technology of hydrogen catalyst, but full mixed bed is difficult to ensure the conversion ratio of propane.

CN2009102048269 is asked using the cyclic regeneration that riser Circulating Fluidized Bed Process then can solve catalyst Topic.But highly endothermic dehydrogenating propane is reacted, how the heat supply in riser, guarantee that reaction temperature problem does not solve, and And high temperature regeneration is used, thermally equilibrated simultaneously in realization, propane dehydrogenation catalyst is easy to inactivate.

CN100453161 discloses a kind of method that is harmonious that greatly different particles multistage mixes, exchanges heat, reacts, is classified.Its base Present principles be it is different using of different sizes, the heap density of particle, fluidized state is different and realize size under certain gas velocity The separation of grain.The patent is using multistage gas-solid fluidized bed series connection, and large and small particle is respectively from the large and small of the gas-solid fluidized bed body of level-one Article inlet pipe enters fluidized bed body, enters fluidizing gas in fluidized bed body by gas distribution grid from entering tracheae, with particle Interact it is bottom-up form the dense bed and dilute-phase leanphase fluidized bed that are thoroughly mixed, control the superficial gas velocity of air-flow, make little particle from small Particle outlet pipe, which is less easily entrained by, leaves fluidized bed body, and bulky grain is then discharged from bulky grain outlet, realizes intergranular classification. But the heat-carrying function of large and small particle is not developed, and large and small particle shares a regenerator, it is living to be unfavorable for catalyst The protection of property.

Summary of the invention:

The first aspect of the present invention purpose is to provide a kind of high conversion rate, the propane that low energy consumption or rich in propane lower carbon number hydrocarbons Dehydrogenation producing propylene device produces high value added product fine propylene and hydrogen.

The technical solution adopted by the present invention is as follows:

A kind of propane or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, including riser reaction system, catalyst follow Ring regenerative system, heat carrier recirculation system, in which:

Riser reaction system includes riser reactor, and the lower part of riser reactor is material inlet, and riser is anti- The top for answering device is catalyst inlet, and riser reactor is set gradually from lower to upper as several conversion zones, in each conversion zone It is correspondingly arranged on the heat carrier delivery pipe that concurrent heating is carried out to reaction；Reacting-settler is set to the top of riser reactor, instead It answers and is equipped with oil gas cyclone separator in settler；

Catalyst cyclic regeneration system includes the first regenerator for catalyst regeneration, and first regenerator one end is to be generated Catalyst input terminal strips inclined tube, reclaimable catalyst delivery pipe by reclaimable catalyst and is connected with the lower part of riser reactor, The first regenerator other end is regenerated catalyst output end, passes through the top phase of regenerated catalyst inclined tube and riser reactor Even；

Heat carrier recirculation system includes that regenerated Second reactivator is carried out for heat carrier, one end of Second reactivator be to Heat carrier input terminal receives the heat carrier to be generated that oil gas cyclone separator is isolated by heat carrier inclined tube to be generated, and second again The other end of raw device is regeneration heat carrier output end, by each conversion zone phase for regenerating heat carrier inclined tube and riser reactor Even, for exporting regenerated high-temperature heat carrier to each conversion zone of riser reactor.

Several delivery pipes are arranged according to the reaction number of segment of riser reactor design in the regeneration heat carrier inclined tube.

The second aspect of the present invention is to provide a kind of propane or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, feature It is, comprising the following steps:

(1) catalytic dehydrogenation:

Raw material after preheated is introduced into the first conversion zone of riser reactor bottom, in reaction temperature 530 DEG C~680 DEG C, under the conditions of pressure 0.03MPa~0.4MPa, contacted with the downflowing catalyst entered from riser top and carry out dehydrogenation reaction； Propane is in riser reactor after uplink reaction a period of time, and temperature declines in riser reactor, dehydrogenation reaction speed drop It is low；Enter the low temperature position in riser reactor from the high-temperature heat carrier that Second reactivator comes out at this time, improves oil gas and urge The temperature of agent, lower temperature oil gas continue with the second conversion zone for entering riser reactor after high-temperature heat carrier mixing concurrent heating Dehydrogenation reaction so repeats, until the close balance of dehydrogenation reaction；

(2) heat carrier recycles:

The heat carrier isolated through oil gas cyclone separator enters Second reactivator, the second regeneration along heat carrier inclined tube to be generated Obtaining high-temperature flue gas by burning in device is heat carrier heat supply to be generated, becomes high-temperature heat carrier, high-temperature heat carrier passes through regenerated heat Each conversion zone that carrier inclined tube enters riser reactor is recycled；

(3) catalyst circulation:

Into riser reactor top catalyst under gravity, be deposited to the lower part of riser reactor Out, under the action of lift gas, it is delivered to the first regenerator through reclaimable catalyst stripping inclined tube, reclaimable catalyst delivery pipe, Under the conditions ofs low temperature, hypoxemia etc. by catalyst regeneration after, the top through regenerated catalyst inclined tube recycled back riser reactor Entrance realizes catalyst circulation.

The present invention carries out concurrent heating to riser reactor using high-temperature heat carrier, makes dehydrogenation reaction close to equilibrium conversion； Hereafter oil gas leaves riser reactor together with heat carrier, isolates oil gas product through oil gas cyclone separator, oil gas is pressed It is conventional to enter cooling, aerostatic press compression section, knockout tower is finally entered, tower top separates fine propylene as product and goes out device, tower bottom Alkane product Returning reacting system is further reacted.

In riser reactor, raw material at 550 DEG C~630 DEG C of reaction temperature, pressure 0.03MPa~0.15Mpa, with Various dehydrogenations carry out dehydrogenation conversion reaction, and conversion per pass is 10~90%.

Riser reactor is divided into several segments, and in each section, propane carries out dehydrogenation reaction, object after contacting with catalyst Material temperature degree reduces, the decline of dehydrogenation speed, introduces high-temperature heat carrier at each section of rear portion, after high-temperature heat carrier is contacted with material, Make material and catalyst temperature back to 530 DEG C~680 DEG C, carry out dehydrogenation reaction quickly again, repeatedly, until oil gas with Heat carrier leaves riser reactor together, into cyclone separator, separates product oil gas into cooling, compression section, under sedimentation The heat carrier come is recycled to Second reactivator, and acquisition heat is contacted with the high-temperature flue gas of burning becomes high-temperature heat carrier again.

By the air velocity in control riser reactor, control at 0.9 times of catalyst carrying velocity hereinafter, heat carries The 2 times or more of body carrying velocity, to realize the separation of catalyst and heat carrier in riser.

The heat carrier is the stable and inert inorganic compound in 500-750 DEG C, and heat carrier is partial size in 10-100 μ The microsphere particle of m, apparent bulk density < 1.0g/ml, since the grain diameter of heat carrier is smaller, carrying velocity is smaller, easily and oil gas Together, it forms piston flow and enters cyclone separator separation.Preferably, the grain diameter of the heat carrier is 30-80 μm, apparent heap Density < 0.9g/ml.

In order to realize that catalyst is not taken out of in riser by high speed oil gas, catalyst granules is higher using heap density, grain The biggish particle of diameter, catalyst granules control is at 200-2000 μm, apparent bulk density 0.8-1.8g/ml, preferred catalyst Grain control is at 400-1500 μm, apparent bulk density 1.0-1.5g/ml.

Propane from the above mentioned is rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process, the raw material propane or is rich in third The lower carbon number hydrocarbons of alkane, including propane, casing-head gas, condensate, liquefied petroleum gas, refinery gas and natural gas moisture, preferably propane And liquefied petroleum gas.

Propane from the above mentioned or the Second reactivator rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process unit are system heat The afterburning medium of amount includes dry gas, liquefied gas, light diesel fuel and fuel oil.

Beneficial effects of the present invention are as follows:

1, the present invention uses riser reaction system and catalyst cyclic regeneration system, heat carrier recirculation system, catalyst Using bulky grain microspherical catalyst, catalyst granules is controlled at 200-2000 μm, and apparent bulk density answers 0.8-1.8g/ml, catalysis Due to higher using heap density, the biggish particle of partial size may be implemented catalyst and not taken out of by high speed oil gas in riser for agent, Complete the regeneration and circulation of catalyst；Heat carrier selects high temperature little particle heat carrier, and heat carrier partial size is at 10-100 μm, apparent heap Density answers < 1.0g/ml, and since the partial size of heat carrier particle is smaller, carrying velocity is smaller, easily together with oil gas, forms piston flow It is separated into cyclone separator.

In this way, bulky grain microspherical catalyst cooperates catalyst cyclic regeneration system, the circulation and regeneration of catalyst are realized, High temperature little particle heat carrier cooperates heat carrier recirculation system, realizes lasting concurrent heating to riser reaction system, realize efficiently, Environmentally friendly, energy-efficient dehydrogenation producing propylene technique.

2, it since Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technique is a strong endothermic reaction process, is provided using fixed bed reactors Heat is more difficult, and the technological reaction regeneration period is short, switching is frequent, reaction, regeneration interruption switching, and safety is poor, heat utilization efficiency It is low.And the moving bed reaction system in prior art, multi-floating bodies are needed, preheating furnace is reacted before each kettle, make oil gas at high temperature Residence time is significantly increased, and the side reactions such as cracking, condensation, the coking of reaction raw materials and product at high temperature are all significantly increased, drop Low reaction product Propylene Selectivity；In addition the pre- heat utilization efficiency of preheating furnace is low, energy consumption is high, and operating cost and labor intensity are high.Although It is also successive reaction and regeneration, but invests and take up an area larger.Catalyst unit price is higher and reduction with catalyst activity, needs not Disconnected to change operating condition to maintain desired conversion ratio, product distribution is unstable.The high-temperature position heat utilization rate for burning generation is low, temperature Degree constantly decline, affects conversion ratio.Matched high-cost noble metal catalyst also will affect the economy of process unit Property.

Compared with the prior art, propane provided by the present invention or rich in propane lower carbon number hydrocarbons dehydrogenation producing propylene process unit and The advantages of method, is embodied in, due to promoting tube reaction-catalyst cyclic regeneration system-heat carrier recirculation system using fluidized bed. Catalyst carries out dehydrogenation (concurrent heating) reaction in recirculating fluidized bed riser reactor, is conducive to the progress of mass transfer and heat transfer, makes Reaction can be carried out continuously, and the high-temperature residence time of oil gas is short, and the conversion ratio and selectivity of reaction are higher.Heat carrier can continuously be de- Hydrogen reaction provides heat, and low energy consumption.The independent loops system of catalyst, can be effectively controlled the regeneration condition of catalyst, ensure that Catalyst activity.Smooth operation stable product quality can make present invention process device carry out continuous-stable long period at full capacity Safety in production, and invest and land occupation it is smaller.

Below by embodiment and the present invention is further elucidated with reference to the figures, but not thereby limiting the invention.

Detailed description of the invention:

Fig. 1 is system structure diagram of the invention；

Figure label: 01, riser reactor, 02, reacting-settler, 03, regenerated catalyst inclined tube, 04, catalysis to be generated Agent inclined tube, 05, reclaimable catalyst delivery pipe, the 06, first regenerator, 07, heat carrier inclined tube to be generated, 08, Second reactivator, 09, Regeneration heat carrier inclined tube, 10, oil gas cyclone separator, 11, flue gas cyclone separator, 12, flue gas cyclone separator, 13, raw material, 14, the first conversion zone, the 15, second conversion zone, 16, third conversion zone, the 17, the 4th conversion zone, 18, exhanst gas outlet, 19, oil gas goes out Mouthful, 20, stripping vapour, 21, air, 22, promotion gas, 23, fuel gas.

Specific embodiment:

Embodiment 1:

As shown in Figure 1, a kind of propane of the invention or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, including riser Reaction system, catalyst cyclic regeneration system, heat carrier recirculation system, in which:

Riser reaction system includes riser reactor 01, and the lower part of riser reactor 01 is material inlet, is promoted The top of pipe reactor 01 is catalyst inlet, and riser reactor 01 is set gradually from lower to upper as several conversion zones, every A conversion zone is correspondingly arranged on the heat carrier delivery pipe that concurrent heating is carried out to reaction；Reacting-settler 02 is set to riser reactor 01 top, reacting-settler 02 is interior to be equipped with oil gas cyclone separator 10；

Catalyst cyclic regeneration system includes the first regenerator 06 for catalyst regeneration, and 06 one end of the first regenerator is Reclaimable catalyst input terminal strips inclined tube 04, reclaimable catalyst delivery pipe 05 and riser reactor 01 by reclaimable catalyst Lower part be connected, 06 other end of the first regenerator be regenerated catalyst output end, pass through regenerated catalyst inclined tube 03 and riser The top of reactor 01 is connected；

Heat carrier recirculation system includes carrying out regenerated Second reactivator 08, one end of Second reactivator 08 for heat carrier For heat carrier input terminal to be generated, carried by what heat carrier inclined tube 07 to be generated reception oil gas cyclone separator 10 was isolated to heat Body, the other end of Second reactivator 08 are regeneration heat carrier output end, pass through regeneration heat carrier inclined tube 09 and riser reactor 01 each conversion zone is connected, for exporting regenerated high-temperature heat carrier to each conversion zone of riser reactor 01, regenerated heat Carrier inclined tube 09 can according to the reaction number of segment of riser reactor 01, be arranged several delivery pipes, as Fig. 1 embodiment in, The reaction number of segment of riser reactor 01 is set as four sections, then is provided with 3 delivery pipes (9-1,9-2,9-3).

Flue gas cyclone separator 11, flue gas cyclonic separation are respectively arranged in the first regenerator 06, Second reactivator 08 Device 12.

As shown in Figure 1, a kind of propane of the invention or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, including following step It is rapid:

(1) catalytic dehydrogenation:

Raw material 13 after preheated is introduced into the first conversion zone 14 of 01 bottom of riser reactor, and from riser top The downflowing catalyst contact of entrance carries out dehydrogenation reaction；Propane after uplink reaction a period of time, mentions in riser reactor 01 Temperature declines in riser reactors 01, and dehydrogenation reaction speed reduces；At this time from the first delivery pipe 9-1 convey high-temperature heat carrier into Enter in riser reactor 01 low temperature position (i.e. the end of the first conversion zone, the present embodiment use four concurrent heatings, be located at promoted 1/4 position of pipe reactor), improve oil gas and catalyst temperature, lower temperature oil gas with after high-temperature heat carrier mixing concurrent heating Into riser reactor 01 the second conversion zone 15 continue dehydrogenation reaction, the second conversion zone 15 after the reaction was completed, lower temperature Oil gas with after the high-temperature heat carrier mixing concurrent heating of the second delivery pipe 9-2, into riser reactor 01 third conversion zone 16 after Continuous dehydrogenation reaction, after the reaction was completed, lower temperature oil gas mixes third conversion zone 16 with the high-temperature heat carrier of third delivery pipe 9-3 After concurrent heating, the 4th conversion zone 17 into riser reactor 01 continues dehydrogenation reaction, at this point, the close balance of dehydrogenation reaction.

The present embodiment, to 01 4 progress concurrent heatings of riser reactor, makes dehydrogenation reaction close to balance using high-temperature heat carrier Conversion ratio；Hereafter oil gas leaves riser reactor 01 together with heat carrier, isolates oil gas product through cyclone separator 10, Oil gas routinely enters the processes such as cooling, aerostatic press compression, finally enters knockout tower, and tower top separates fine propylene and goes out to fill as product It sets, tower bottom alkane product Returning reacting system is further reacted.

(2) heat carrier recycles:

The heat carrier isolated through oil gas cyclone separator 10 enters Second reactivator 08 along heat carrier inclined tube 07 to be generated, the Natural gas burns under high temperature and excess oxygen in two regenerators 08 obtains high-temperature flue gas as heat carrier heat supply, becomes high warm and carries Body, high-temperature heat carrier are recycled by each conversion zone that regeneration heat carrier inclined tube 09 enters riser reactor 01.Second again Raw device 08 must be passed through natural gas/combustion oil continuously to improve regeneration temperature and maintain the heat balance of reaction-regeneration system.

(3) catalyst circulation:

Into 01 top of riser reactor catalyst under gravity, be deposited under riser reactor 01 Part goes out, and under the action of lift gas, is delivered to first through reclaimable catalyst stripping inclined tube 04, reclaimable catalyst delivery pipe 05 Regenerator 06, under the conditions ofs low temperature, hypoxemia etc. by catalyst regeneration after, it is anti-through 03 recycled back riser of regenerated catalyst inclined tube The upper entrance of device 01 is answered, realizes catalyst circulation.

Catalyst, heat carrier and the technological parameter selection of embodiment 1 are as shown in table 1.

Embodiment 2:

With embodiment 1, difference is process equipment, and catalyst, heat carrier, technological parameter are as shown in table 2.

Effect detection:

It by the technique and device of the embodiment of the present invention 1,2, is compared with the prior art, comparative example selection The technique of USP9051230, catalyst are prepared according to USP4827072 and GB2162082, and reaction result is shown in Table 1.

Table 1, the control of dehydrogenating propane reaction result

As can be seen from Table 1: the present invention compared with prior art: the selectivity of propylene improves, and total propene yield rises, tool There is better economic benefit.

Claims (11)

1. a kind of propane or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, which comprises the following steps:

(1) catalytic dehydrogenation:

Raw material after preheated is introduced into the first conversion zone of riser reactor bottom, 530 DEG C~680 DEG C of reaction temperature, Under the conditions of pressure 0.03MPa~0.4MPa, is contacted with the downflowing catalyst entered from riser top and carry out dehydrogenation reaction；Propane In riser reactor after uplink reaction a period of time, temperature declines in riser reactor, and dehydrogenation reaction speed reduces；This When from the high-temperature heat carrier that Second reactivator comes out enter the low temperature position in riser reactor, improve oil gas and catalyst Temperature, lower temperature oil gas are anti-with the second conversion zone continuation dehydrogenation for entering riser reactor after high-temperature heat carrier mixing concurrent heating It answers, so repeats, until the close balance of dehydrogenation reaction；

(2) heat carrier recycles:

The heat carrier isolated through oil gas cyclone separator enters Second reactivator along heat carrier inclined tube to be generated, in Second reactivator Obtaining high-temperature flue gas by burning is heat carrier heat supply to be generated, becomes high-temperature heat carrier, and high-temperature heat carrier passes through regeneration heat carrier Each conversion zone that inclined tube enters riser reactor is recycled；

(3) catalyst circulation:

Into riser reactor top catalyst under gravity, the lower part for being deposited to riser reactor separates, Under the action of lift gas, it is delivered to the first regenerator through reclaimable catalyst stripping inclined tube, reclaimable catalyst delivery pipe, low By after catalyst regeneration under the conditions of temperature, hypoxemia etc., the upper entrance through regenerated catalyst inclined tube recycled back riser reactor, Realize catalyst circulation.

2. the use device of a kind of propane as described in claim 1 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, It is characterized in that: including riser reaction system, catalyst cyclic regeneration system, heat carrier recirculation system, in which:

Riser reaction system includes riser reactor, and the lower part of riser reactor is material inlet, riser reactor Top be catalyst inlet, riser reactor is set gradually from lower to upper as several conversion zones, corresponding in each conversion zone It is provided with the heat carrier delivery pipe that concurrent heating is carried out to reaction；Reacting-settler is set to the top of riser reactor, and reaction is heavy It drops and is equipped with oil gas cyclone separator in device；

Catalyst cyclic regeneration system includes the first regenerator for catalyst regeneration, and first regenerator one end is catalysis to be generated Agent input terminal strips inclined tube, reclaimable catalyst delivery pipe by reclaimable catalyst and is connected with the lower part of riser reactor, and first The regenerator other end is regenerated catalyst output end, is connected by regenerated catalyst inclined tube with the top of riser reactor；

Heat carrier recirculation system includes that regenerated Second reactivator is carried out for heat carrier, and one end of Second reactivator is to heat Carrier input terminal receives the heat carrier to be generated that oil gas cyclone separator is isolated, Second reactivator by heat carrier inclined tube to be generated The other end be regeneration heat carrier output end, be connected by regeneration heat carrier inclined tube with each conversion zone of riser reactor, use It exports in by regenerated high-temperature heat carrier to each conversion zone of riser reactor.

3. a kind of propane according to claim 1 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: Concurrent heating is carried out to riser reactor using high-temperature heat carrier, makes dehydrogenation reaction close to equilibrium conversion；Hereafter oil gas and heat carry Body leaves riser reactor together, isolates oil gas product through oil gas cyclone separator, and oil gas routinely enters cooling, gas Press compression process finally enters knockout tower, and tower top separates fine propylene as product and goes out device, and tower bottom alkane product returns to reaction System is further reacted.

4. a kind of propane according to claim 1 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: In riser reactor, raw material is at 550 DEG C~630 DEG C of reaction temperature, pressure 0.03MPa~0.15Mpa, with various dehydrogenations Catalyst carries out dehydrogenation conversion reaction, and conversion per pass is 10~90%.

5. a kind of propane according to claim 1 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: Riser reactor is divided into several segments, and in each section, propane carries out dehydrogenation reaction, temperature of charge drop after contacting with catalyst It is low, dehydrogenation speed decline, each section rear portion introduce high-temperature heat carrier, after high-temperature heat carrier is contacted with material, make material with Catalyst temperature returns to 530 DEG C~680 DEG C, carries out dehydrogenation reaction quickly again, repeatedly, until oil gas and heat carrier one It rises and leaves riser reactor, into cyclone separator, separate product oil gas into cooling, compression section, the heat to settle down carries For body circulation to Second reactivator, acquisition heat is contacted with the high-temperature flue gas of burning becomes high-temperature heat carrier again.

6. a kind of propane according to claim 1 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: Air velocity in riser reactor is controlled at 0.9 times of catalyst carrying velocity hereinafter, 2 times of heat carrier carrying velocity More than, to realize the separation of catalyst and heat carrier in riser.

7. a kind of propane according to claim 6 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: The heat carrier is the stable and inert inorganic compound in 500-750 DEG C, and heat carrier is microballoon of the partial size at 10-100 μm Particle, apparent bulk density < 1.0g/ml, since the grain diameter of heat carrier is smaller, carrying velocity is smaller, easily together with oil gas, shape Enter cyclone separator separation at piston flow.

8. a kind of propane according to claim 7 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: The grain diameter of the heat carrier is 30-80 μm, apparent bulk density < 0.9g/ml.

9. a kind of propane according to claim 6 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, it is characterised in that: In order to realize that catalyst is not taken out of in riser by high speed oil gas, catalyst granules is higher using heap density, and partial size is biggish Particle, catalyst granules are controlled at 200-2000 μm, and apparent bulk density answers 0.8-1.8g/ml.

10. a kind of propane according to claim 9 or the dehydrogenation producing propylene technique rich in propane lower carbon number hydrocarbons, feature exist In: catalyst granules is controlled at 400-1500 μm, and apparent bulk density should be 1.0-1.5g/ml.

11. a kind of propane according to claim 2 or the dehydrogenation producing propylene device rich in propane lower carbon number hydrocarbons, feature exist In: several delivery pipes are arranged according to the reaction number of segment of riser reactor in regeneration heat carrier inclined tube.