CN101367701B - Method for converting oxygen-containing compound into propylene with moving bed technique - Google Patents
Method for converting oxygen-containing compound into propylene with moving bed technique Download PDFInfo
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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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method of transforming oxygenated chemicals into propylene with the technology of moving bed. The steps comprises: the oxygenated chemicals contacts catalyst in a first reaction area and a first material flow is generated; the first material flow is separated and the propylene product, the components of C5+ and other components are obtained; partial C5+ components go through a second reaction area, which makes the catalyst deposit carbon ahead of time; the proportion of carbon deposit amount on surface and the carbon deposit amount in a hole is at least 10; a second material flow is obtained and then is combined with the first material flow; the catalyst with deposited carbon goes into the first reaction area and contacts the oxygenated chemicals and then goes into a regenerator after reaction; after being regenerated, the catalyst is distributed to the first reaction area and the second reaction area. In the method of the invention, partial C5+ components go into the second reaction alone and contact the catalyst for the reaction. The catalyst with the high proportion of the carbon deposit amount on surface and the carbon deposit amount in a hole is obtained. The selectivity of the catalyst for the propylene in the first reaction area is improved and consequently, the yield of the propylene is improved.
Description
Technical field
The present invention relates to a kind of method for preparing propylene, relate in particular to a kind of moving bed technique that uses the method for oxygenate as propylene.
Background technology
Light olefin (comprising ethene, propylene, butylene) is an important chemical material, mainly obtains through petroleum cracking.Continuous rising along with oil price; Its production cost also increases sharply, industrial production to the demand of light olefin then still in constantly increasing, propylene especially; According to the raising the output ability of present production rate and existing full scale plant, expectation will keep the state that supply falls short of demand for a long time.
Oxygenatedchemicalss such as methyl alcohol optionally are converted into propylene, be that the non-oil resource that petrochemical industry is pursued is produced one of operational path of propylene, and methyl alcohol can adopt coal or Sweet natural gas to make through sophisticated production technique always.The technology of methanol-to-olefins mainly contains at present: the oxygenatedchemicals system olefin process (OTO) of the methanol-to-olefins technology (MTO) of UOP/Hydro company, the preparing propylene from methanol technology (MTP) of Lurgi company and ExxonMobil company.
The MTO process using has better optionally SAPO series non-zeolitic molecular sieve, especially SAPO-34 molecular sieve to light olefin, and adopts circulating fluid bed reactor.This technology yield of light olefin can reach more than 90%, but not high to the selectivity of propylene.
Patented claim WO2001092190 (being the MTP technology of Lurgi company) discloses optionally methanol-to-olefins technology of a kind of high propylene; The catalyzer that this technology is used is a kind of shape-selective catalyst bigger with respect to the SAPO-34 molecular sieve bore diameter-modified ZSM-5 zeolite catalyzer; Reaction has very high propylene selectivity to the modified ZSM-5 zeolite catalyzer to methanol conversion; And the speed of this catalyst carbon deposition inactivation is lower, and above-mentioned technology can adopt the simple fixed-bed reactor of form.
Three placed in-line fixed-bed reactor of above-mentioned process using, and through increasing the methyl alcohol pre-reactor, progressively adding the thermostability that mode such as reaction raw materials keeps single main reactor.In order further to improve propene yield, the part by product is C especially
4 +Component is recycled to main reactor and continues to be converted into propylene.This technology has proposed dual-function catalyst and heavy olefin recycle, but is limited to fixed-bed reactor, complicated operation.
Chinese patent 98806533.9 discloses the method that sieve catalyst that a kind of usefulness contains the requirement carbonaceous sediment makes conversion of oxygenates to olefins; This method through the regenerated catalyst total reaction volume an only part and said regeneration section is mixed with regenerated catalyzer total reaction volume not, the carbonaceous sediment of maintenance requirement on the catalyzer total reaction volume.
Carbonaceous sediment can cover the low optionally acid active sites of molecular sieve outer surface; Thereby reduce the selectivity of by product, improve propene yield, this is known in those skilled in the art; But carbonaceous sediment is too much; Can reduce activity of such catalysts, reduce speed of response, and the catalyzer of carbon deposition quantity ratio can address the above problem in high surface area carbon amount/hole.
The carbon distribution of outside surface is with respect to the oxidized removal in revivifier more easily of the carbon distribution in the hole; Therefore the catalyzer through carbon deposition quantity ratio in the high area carbon amount/hole of partial regeneration acquisition is infeasible in actually operating; Above-mentioned patent has been introduced a kind of method of holomorphosis part catalyzer; And it is mixed with the not regenerated catalyst of remainder, make mixed catalyst on TV, keep carbon deposition quantity ratio in high area carbon amount/hole.But for individual body catalyst, it can only be catalyzer holomorphosis or that do not regenerate, does not possess carbon deposition quantity ratio in high area carbon amount/hole.
One Chinese patent application CN1803738A discloses a kind of method of using moving bed technique and independently heavy alkene change step oxygen-containing organic compound to be converted into propylene; This method at first feeds first reaction zone and the first dual-function catalyst contact reacts with oxygenatedchemicals and thinner; Generate first burst of logistics; First burst of logistics obtains a plurality of components through separation; Wherein first be rich in that C4+ alkene feeds second reaction zone and the second dual-function catalyst contact reacts in the C4+ alkene part; Obtain second burst of logistics, second logistics is merged to first burst of logistics, after regeneration, send first reaction zone and second reaction zone back to respectively at first dual-function catalyst of first reaction zone and second dual-function catalyst of second reaction zone.
The main flow process of this patented process still is similar to the MTP technology of Lurgi, through by product is recycled to main reactor, through the effect of dual-function catalyst; Increase the yield of propylene; But this patent is also just carried out simple parts regeneration to catalyzer, can't obtain the catalyzer of carbon deposition quantity ratio in high surface area carbon amount/hole, and is therefore bad to the selectivity of propylene; Cause the propylene yield not high, by product is more.
Summary of the invention
The invention provides a kind of moving bed technique that uses with the method for oxygenate as propylene, the yield of this method propylene is high, and by product is few.
A kind of moving bed technique that uses may further comprise the steps the method for oxygenate as propylene:
(a) blended oxygenatedchemicals and thinner are fed first reaction zone continuously and contact with sieve catalyst, reaction generates first burst of logistics, and described first reaction zone comprises 2～10 placed in-line moving-burden bed reactors;
Oxygenatedchemicals is oxygen-containing organic compounds such as various alcohol, ether, ketone, and particular methanol and dme most preferably are dme.
Thinner can reduce the dividing potential drop of raw material; Improve the selectivity of low-carbon alkene; The general rare gas element that adopts can be water vapour, nitrogen, methane etc., and water vapour can also suppress the carbon distribution of catalyzer effectively as thinner; And have the good thermal carrier effect, so preferably water steam of the present invention is as thinner.
The ratio of thinner will be confirmed according to the response characteristic of catalyzer, is generally 10%～40% molar content (with respect to oxygenatedchemicals).
Sieve catalyst can be at least a in micro porous molecular sieve and the mesopore molecular sieve, preferably all belongs at least a in zeolite molecular sieve and the ELAPO molecular sieve of micro porous molecular sieve, most preferably is at least a in ZSM-5 molecular sieve and the SAPO-34 molecular sieve.
The oxygenate that prior art adopts is that the temperature of reaction of low-carbon alkene is generally 350～550 ℃, and lower temperature more helps the generation of propylene, and the present invention chooses 350～450 ℃ and is optimal reaction temperature.When reaction raw materials is flowed through reactor reaction; Temperature continues to increase; Too high temperature can cause reactant exit catalyst carbon deposition excessive velocities; Reactor drum is imported and exported the selectivity that wide temperature distribution can reduce propylene simultaneously, so the import and export temperature difference of reaction raw materials should be controlled in 80 ℃ 60 ℃ of Nei Gengjia.In sum, the inlet temperature of parallel feeding generally is controlled between 350～390 ℃ in first reaction zone.
The products distribution of the residence time to oxygenatedchemicals system propylene has remarkable influence, and the residence time is short, and raw material contacts insufficient with catalyzer, and reaction conversion ratio is low, and the residence time is oversize, causes by products such as methane in the product, aromatic hydrocarbons and carbon distribution to increase easily.With the parameter of weight hourly space velocity (WHSV) as the residence time, WHSV refers to the ratio of the quality and the catalyst in reactor quality of reaction raw materials in the per hour charging, and WHSV numerical value is big more represents the residence time short more, and state of the art is generally chosen 0.1～1000hr
-1, the preferred 1～20hr of the present invention
-1
(b) first burst of logistics separated, obtain product propylene, C
5 +Mixture behind component and the remaining reaction;
Mixture comprises C behind the remaining reaction
1Component, C
2Component, propane, the aqueous distillate that contains micro oxygen containing compound and C
4Component.
C
1Component, C
2Component and propane are collected as by product; C
4Component circulates again and feeds first reaction zone, can increase the propylene yield.
(c) with portion C
5 +Component feeds second reaction zone and contacts with sieve catalyst, and reaction generates second burst of logistics, incorporates second burst of logistics into first burst of logistics and is circulated to step (b), and described second reaction zone comprises 1～5 moving-burden bed reactor;
C
5 +Component continues catalyzed reaction and generates lower carbon number hydrocarbons such as propylene in second reaction zone, temperature of reaction is controlled at 450～550 ℃, preferred 470～500 ℃; For reducing the generation of micro-molecular gas such as methane, reactor pressure is 1～10bar, and WHSV is 1～1000hr
-1, preferred 1～30hr
-1
(d) sieve catalyst and the C in the step (c)
5 +Preparatory carbon distribution after the component contact reacts makes that the ratio of carbon deposition quantity is at least 10 in the area carbon amount/hole of sieve catalyst;
Catalyzer of the present invention is a kind of shape-selective catalyst with small-bore; It allows the small molecules turnover catalyzer duct in specific effective molecular diameter scope; The velocity of diffusion of molecule in the duct of different effective molecular diameters is different; The big more velocity of diffusion of effective diameter is slow more, so small molecules such as propylene can pass in and out the catalyzer duct apace, and the big diffusion motion of component in the duct of effective diameter is restricted.Relatively, the outside surface of catalyzer does not then have this shape effect of selecting, and all components all can freely spread absorption at outside surface.
Aromatic hydrocarbons is acknowledged as the presoma of carbon distribution reaction, and aromatic hydrocarbons can generate carbon distribution by further dehydrogenation polymerization on acidic site, thereby covers acidic site, makes catalyst deactivation.
The present invention is with portion C
5 +Component rather than oxygenatedchemicals pass through second reaction zone, so mainly are the C that diffuses into from the outside in the catalyzer duct
5 +Component and since the duct select the shape restriction, heavy constituent concentration such as the aromatic hydrocarbons the duct in obviously descend with respect to outside surface, owing to there is not the existence of oxygenatedchemicals, can't generate a large amount of heavy constituent such as aromatic hydrocarbons in the duct, while C
2, C
4Small molecules such as alkene have got into first reaction zone circulation after separating, further reduced the generation of heavy constituent such as aromatic hydrocarbons in the duct.
Pass through aforesaid method; Carbon distribution preferentially generates at the outside surface of catalyzer; Through the residence time of controlling reactor inner catalyst, the control level of response of reactant on catalyzer, the carbon deposition quantity ratio in area carbon amount/hole of can obtaining is greater than 10 preparatory carbon deposition catalyst.
(e) the preparatory carbon deposition catalyst in the step (d) is fed first reaction zone, carry out contact reacts with oxygenatedchemicals and thinner;
(f) when sieve catalyst in first reaction zone is lower than 95% to the transformation efficiency of oxygenatedchemicals, feed revivifier, regeneration back at least a portion feeds second reaction zone.
Described sieve catalyst is to containing the oxygenatedchemicals total amount that oxygen bonded thing transformation efficiency=(the unreacted oxygenatedchemicals amount of oxygenatedchemicals total amount-unit time that the unit time feeds)/unit time feeds.
Because it is lower from the effusive catalyst activity of second reaction zone; Therefore a part of regenerated catalyst is fed first reaction zone, improve speed of response, the regenerated catalyst that feeds first reaction zone accounts for 0%～50% of regenerated catalyst total amount; All the other all feed second reaction zone; Because in the middle of conversion process, catalyzer is loss to some extent, can replenish at second reaction zone.
The inventive method obtains C through separating first burst of logistics that first reaction zone comes out
5 +Component is separately with C
5 +Component feeds second reaction zone and catalyzer contact reacts, obtains the catalyzer of carbon deposition quantity ratio in high surface area carbon amount/hole, can improve the selectivity of the first reaction zone inner catalyst to propylene, thereby improves the yield of propylene.
Description of drawings
The reaction unit structural representation that Fig. 1 adopts for the inventive method.
Embodiment
As shown in Figure 1; A kind of is the device of propylene with oxygenate; Comprise first reaction zone, second reaction zone and revivifier, first reaction zone comprises 3 placed in-line moving-burden bed reactors, and 3 moving-burden bed reactors reduce along raw material flow direction volume one by one; Be provided with interchanger between two adjacent moving-burden bed reactors, second reaction zone is made up of an independent moving-burden bed reactor.
Revivifier is communicated with through pipeline with each moving-burden bed reactor of first reaction zone and second reaction zone, the sieve catalyst continuous flow that in first reaction zone, second reaction zone and revivifier, circulates.Raw material oxygenatedchemicals and the thinner of vaporization is divided in 3 strands of 3 moving-burden bed reactors that get into first reaction zones and sieve catalyst carries out contact reacts; Carry out heat exchange with interchanger earlier after wherein preceding two moving-burden bed reactor raw material reactions are accomplished, and then get into next moving-burden bed reactor.
The material that comes out from last moving-burden bed reactor is first burst of logistics, and first burst of logistics is steam condition, wherein contains various components such as product propylene, and the product propylene can obtain through traditional separation method, and separation method of the present invention adopts following form:
At first first burst of logistics is compressed into and reaches 400～500 pounds/inch
2The pressure of (table) is removed the oxide compound of carbonic acid gas and so on after the drying;
Then above-mentioned dried first strand of material delivered to deethanizing column, depropanizing tower and debutanizing tower successively, can collect C from the deethanizing column top
1, C
2Component, C
2Component comprises ethane and a spot of ethene; Can collect propylene and propane from the depropanizing tower top, propylene can obtain polymerization-grade propylene with propane after separating; Can collect various C from the debutanizing tower top
4Component, C
4Component is capable of circulation to first reaction zone, to obtain more propylene; That come out from the debutanizing tower bottom is various C
5 +Component and the aqueous distillate that contains oxygenatedchemicals on a small quantity, aqueous distillate can be used as thinner and lead to back first reaction zone again.
Portion C
5 +Component feeds second reaction zone and the sieve catalyst contact reacts obtains second burst of logistics, because C of the present invention
5 +The major function of component is to let the preparatory carbon distribution of sieve catalyst, so can not will all C
5 +Component feeds second reaction zone, remaining C
5 +Component is as gasoline component.Second burst of logistics merges to first burst of logistics immediately after second reaction zone comes out, separate then.
Sieve catalyst and C in second reaction zone
5 +Preparatory carbon distribution after the component contact reacts; In advance carbon deposition catalyst in area carbon amount/hole carbon deposition quantity more than or equal to 10 o'clock; Get into first reaction zone; With raw material and the further carbon distribution of thinner contact reacts, when sieve catalyst in first reaction zone was lower than 95% to the transformation efficiency of oxygenatedchemicals, the sieve catalyst in first reaction zone flowed into revivifier regeneration.
To use oxygen level in the revivifier be 4% regeneration air stream with carbon deposition catalyst burns to carbon content and is lower than 0.05%, causes the permanent inactivation of catalyzer for avoiding high temperature, and regeneration temperature remains 550～650 ℃.Be assigned to again in the middle of each moving-burden bed reactor of first reaction zone and second reaction zone after the sieve catalyst regeneration.
Embodiment 1
It is propylene with oxygenate that present embodiment adopts above-mentioned reaction unit, and the sieve catalyst that is wherein adopted prepares through following method:
Be that the part by weight of pressing 1:1 in 80 the HZSM-5 zeolite (through acidifying ZSM-5 zeolite molecular sieve) adds matrix toward silica alumina ratio, be prepared into the spherical catalyst of the about 1.5mm of diameter through rolling ball method.
The temperature in of each moving-burden bed reactor is about 350 ℃ in first reaction zone, and temperature out is 410 ± 4 ℃, and temperature of reaction is 350～410 ℃, and pressure is 0.45 ± 0.01bar, and WHSV is 2.6hr
-1, oxygen-containing compound material adopts methyl alcohol, gets into respectively in 3 moving-burden bed reactors in first reaction zone with the weight ratio of 2:1.5:1, and the raw material that the moving-burden bed reactor that wherein volume is big more adds is many more, and thinner is a water, accounts for 20% of weight oxygenate.The temperature of reaction of the moving-burden bed reactor of second reaction zone is 500～550 ℃, and temperature head is less than 50 ℃ in the beds, and pressure is 3bar, and WHSV is 30hr
-1
Under above-mentioned reaction conditions, the preparatory carbon deposition catalyst carbon deposition quantity that comes out from second reaction zone is less than 0.9%, and the carbon deposition quantity ratio can reach more than 30 in area carbon amount/hole.This preparatory carbon deposition catalyst is admitted to the first reaction zone catalyzed reaction and further carbon distribution, and the decaying catalyst carbon deposition quantity that comes out from first reaction zone is not less than 95% less than 3% to conversion of methanol.
Sieve catalyst is admitted to revivifier regeneration after first reaction zone comes out; Catalyzer after the regeneration turns back to first, second reaction zone respectively; The regenerated catalyst mass ratio that wherein gets into second reaction zone is 80%; The regenerated catalyst that gets into first reaction zone gets into each moving-burden bed reactor with the ratio of 3:2:1 respectively, and the catalyzer that the moving-burden bed reactor that wherein volume is more little distributes is few more.
Table 1 has been listed the material balance under the above-mentioned condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.From table, can know that the methanol feeding amount is 208333kg/hr, the propylene amount that is generated is 69534kg/hr, and methanol conversion is greater than 99%.
Table 1 material balance
| Material | The material flow rate |
| Methyl alcohol | 208333kg/hr |
| Propylene | 66534kg/hr |
| LPG(Liquefied?Petroleum?Gas) | 7850kg/hr |
| Gasoline | 14210kg/hr |
| Water (comprising micro oxygen containing compound) | 117365kg/hr |
| Fuel gas # | 1857kg/hr |
| Coke etc. * | 517kg/hr |
# comprises small amount of ethylene
*Comprise the loss in the material circulation
Each product is converted into the butt percentage composition that dewaters later, as shown in table 2.
Table 2 products distribution
| Product | The butt percentage |
| Propylene | 73.14％ |
| LPG | 8.63％ |
| Gasoline | 15.62％ |
| Fuel gas | 2.04％ |
| Coke | 0.57％ |
From table 2, can know; The propylene selectivity obviously improves; Adopting fixed-bed reactor propylene selectivity under same catalyst and operational condition is 65%～68%, and therefore optimization method of the present invention can improve 5% or higher than bed technology propylene selectivity.Adopt traditional moving-burden bed reactor technology; Promptly do not adopt second reaction zone and preparatory carbon deposition catalyst; CN1989086A is said like patent; The propylene selectivity is about 71.2% under same catalyst and operational condition, and therefore optimization method of the present invention can improve 1% or higher than traditional moving bed reaction technology propylene selectivity.
Embodiment 2
Adopt the spherical catalyst identical with embodiment 1, on the basis that embodiment 1 installs, change the first reaction zone moving-burden bed reactor into 5, the moving-burden bed reactor of second reaction zone changes 3 into.Wherein the temperature in of each reactor drum is about 390 ℃ in first reaction zone, and temperature out is 450 ± 4 ℃, and temperature of reaction is 390～450 ℃, and pressure is 3 ± 0.01bar, and WHSV is 20hr
-1Oxygen-containing compound material adopts methyl alcohol; Mass ratio with 3:2.5:2:1.5:1 gets into 5 moving-burden bed reactors in first reaction zone respectively; Placed in-line moving-burden bed reactor increases along the mobile direction volume of catalyzer one by one, and the raw material oxygenatedchemicals that the moving-burden bed reactor that volume is big more feeds is many more.Thinner is a water, is 20% with respect to the mass ratio of oxygenatedchemicals.The temperature of reaction of second each moving-burden bed reactor of reaction zone is 450～500 ℃, and the beds temperature difference is less than 50 ℃, and pressure is 0.1bar, and WHSV is 1hr
-1
Under above-mentioned reaction conditions, the preparatory carbon deposition catalyst carbon deposition quantity that comes out from second reaction zone is less than 1.3%, and the carbon deposition quantity ratio can reach 20 in area carbon amount/hole.This preparatory carbon deposition catalyst is admitted to the first reaction zone catalyzed reaction and further carbon distribution, and the decaying catalyst carbon deposition quantity that comes out from first reaction zone is not less than 95% less than 3% to conversion of methanol.
Sieve catalyst is admitted to revivifier regeneration after first reaction zone comes out; Catalyzer after the regeneration turns back to first, second reaction zone respectively; The regenerated catalyst mass ratio that wherein gets into second reaction zone is 70%; The regenerated catalyst that gets into first reaction zone gets into 1 to 5 moving-burden bed reactor with the ratio of 5:4:3:2:1 respectively, and wherein, the catalyzer that the moving-burden bed reactor that volume is more little distributes is few more.
Table 3 has been listed the material balance under the above-mentioned condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.From table, can know that the methanol feeding amount is 208333kg/hr, the propylene amount that is generated is 65734kg/hr, and methanol conversion is greater than 99%.
Table 3 material balance
| Material | The material flow rate |
| Methyl alcohol | 208333kg/hr |
| Propylene | 65743kg/hr |
| LPG | 8258kg/hr |
| Gasoline | 14310kg/hr |
| Water (comprising micro oxygen containing compound) | 117297kg/hr |
| Fuel gas # | 2051kg/hr |
| Coke etc. * | 674kg/hr |
# comprises small amount of ethylene
*Comprise the loss in the material circulation
Each product is converted into the butt percentage composition that dewaters later, as shown in table 4.
Table 4 products distribution
| Product | The butt percentage |
| Propylene | 72.22％ |
| LPG | 9.07％ |
| Gasoline | 15.72％ |
| Fuel gas | 2.25％ |
| Coke | 0.74％ |
Can know that from table 4 the propylene selectivity descends than embodiment 1 slightly, still improve 5% or more, throw away than traditional moving bed process and improve 1% or more but compare fixed bed reaction technology.LPG, fuel gas and coke content all slightly improve in addition, explain that oxygenatedchemicals trends towards being converted into small molecules product and coke when more moving-burden bed reactor is connected.
Embodiment 3
Present embodiment under the situation that does not change other conditions, is all sent regenerated catalyst into second reaction zone with reference to embodiment 1, and the preparatory carbon deposition catalyst carbon deposition quantity that comes out from second reaction zone is less than 0.9%, and the carbon deposition quantity ratio is greater than 30 in area carbon amount/hole.
Under these conditions, methanol conversion is less than 99% in first reaction zone, and this is because catalyst carbon deposition causes active the reduction, owing to do not have replenishing of live catalyst, methanol conversion scarce capacity under the same conditions.Therefore improve methanol conversion through increasing the residence time.Under the situation that does not change other conditions, the WHSV of each moving-burden bed reactor in first reaction zone is adjusted into 1hr
-1, reaction pressure is adjusted into 0.1bar, and temperature of reaction is 350～400 ℃, and methanol conversion is greater than 99%.
Table 5 has been listed the material balance under this condition, and this material balance is based on experimental data and is enlarged into the annual treatment capacity acquisition of 1,000,000 tons of methyl alcohol through computer simulation.From table, can know that the methanol feeding amount is 208333kg/hr, the propylene amount that is generated is 69534kg/hr, and methanol conversion is greater than 99%.
Table 5 material balance
| Material | The material flow rate |
| Methyl alcohol | 208333kg/hr |
| Propylene | 66477kg/hr |
| LPG | 7849kg/hr |
| Gasoline | 14119kg/hr |
| Water (comprising micro oxygen containing compound) | 117592kg/hr |
| Fuel gas # | 1879kg/hr |
| Coke etc. * | 417kg/hr |
# comprises small amount of ethylene
*Comprise the loss in the material circulation
Each product is converted into the butt percentage composition that dewaters later, as shown in table 6.
Table 6 products distribution
| Product | The butt percentage |
| Propylene | 73.26％ |
| LPG | 8.65％ |
| Gasoline | 15.56％ |
| Fuel gas | 2.07％ |
| Coke | 0.46％ |
Can know that from table 6 each products distribution is similar with embodiment 1, propylene increases slightly, and the coke amount then descends slightly, but amplitude is all less.Yet increase conversion of methanol owing to improved the residence time, therefore for identical methanol treatment amount, certainly will will increase reactor volume, and then equipment cost increases thereupon also.
Claims (9)
1. one kind is used moving bed technique with the method for oxygenate as propylene, may further comprise the steps:
(a) blended oxygenatedchemicals and thinner are fed first reaction zone continuously and contact with sieve catalyst, reaction generates first burst of logistics, and described first reaction zone comprises at least 1 moving-burden bed reactor;
(b) first burst of logistics separated, obtain product propylene, C
5 +Mixture behind component and the remaining reaction;
(c) with portion C
5 +Component feeds second reaction zone and contacts with sieve catalyst, and reaction generates second burst of logistics, incorporates second burst of logistics into first burst of logistics and is circulated to step (b), and described second reaction zone comprises at least 1 moving-burden bed reactor;
(d) sieve catalyst and the C in the step (c)
5 +Preparatory carbon distribution after the component contact reacts makes that the ratio of carbon deposition quantity is at least 10 in the area carbon amount/hole of sieve catalyst;
(e) the preparatory carbon deposition catalyst in the step (d) is fed first reaction zone, carry out contact reacts with oxygenatedchemicals and thinner;
(f) when sieve catalyst in first reaction zone is lower than 95% to the transformation efficiency of oxygenatedchemicals, feed revivifier, regeneration back at least a portion feeds second reaction zone.
2. method according to claim 1 is characterized in that: described thinner is a water vapor.
3. method according to claim 1 is characterized in that: described oxygenatedchemicals is a methyl alcohol.
4. method according to claim 1 is characterized in that: described sieve catalyst is at least a in ZSM-5 molecular sieve and the SAPO-34 molecular sieve.
5. method according to claim 1 is characterized in that: comprise mixture behind the remaining reaction in the step (b) is separated, obtain C
4Component also feeds first reaction zone with this component circulation.
6. method according to claim 1 is characterized in that: the regenerated catalyst that feeds second reaction zone in the described step (f) accounts for 50%～100% of regenerated catalyst gross weight, and all the other regenerated catalysts feed first reaction zone.
7. method according to claim 1 is characterized in that: the carbon deposition quantity of regenerated catalyst is less than 0.1% in the said step (f).
8. method according to claim 1 is characterized in that: temperature of reaction is 350～450 ℃ in described first reaction zone, and reaction pressure is 0.1～3bar, and WHSV is 1～20hr
-1
9. method according to claim 1 is characterized in that: temperature of reaction is 450～550 ℃ in described second reaction zone, and reaction pressure is 0.1～3bar, and WHSV is 1～30hr
-1
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| CN101585747B (en) * | 2009-06-25 | 2013-03-20 | 浙江大学 | Method for transforming oxygenates into propylene |
| CN102060644B (en) * | 2009-11-17 | 2013-07-10 | 中国石油化工集团公司 | Method for preparing olefin by dehydration of methanol |
| CN102060645B (en) * | 2009-11-17 | 2013-07-24 | 中国石油化工集团公司 | Process for preparing olefins by methanol dehydration |
| CN101830769B (en) * | 2010-05-12 | 2012-11-14 | 浙江大学 | Method for converting methanol into propylene |
| CN102942435B (en) * | 2012-11-06 | 2014-12-17 | 浙江大学 | Reaction technology using moving bed technique to convert methanol into propylene |
| CN107032944B (en) * | 2016-02-03 | 2019-12-17 | 中石化广州工程有限公司 | Method for converting methanol into propylene |
| CN110860306B (en) * | 2018-08-27 | 2022-08-09 | 中国石油化工股份有限公司 | Regeneration method of inactivated ZSM-5 molecular sieve |
| CN112090375B (en) * | 2020-08-27 | 2022-05-10 | 大唐国际化工技术研究院有限公司 | Catalytic reactor for preparing propylene from methanol and method for preparing propylene from methanol |
| CN111974462A (en) * | 2020-09-01 | 2020-11-24 | 大唐国际化工技术研究院有限公司 | Method for recycling waste MTP catalyst |
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| CN1803738A (en) * | 2005-01-14 | 2006-07-19 | 环球油品公司 | Conversion of oxygenate to propylene using moving bed technology and a separate heavy olefin interconversion step |
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| CN1803738A (en) * | 2005-01-14 | 2006-07-19 | 环球油品公司 | Conversion of oxygenate to propylene using moving bed technology and a separate heavy olefin interconversion step |
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