CN101070260A - Zeolite catalyzing and separating method for increasing yield of preparing olefin by methyl alcohol dewatering - Google Patents
Zeolite catalyzing and separating method for increasing yield of preparing olefin by methyl alcohol dewatering Download PDFInfo
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- CN101070260A CN101070260A CNA2007100423294A CN200710042329A CN101070260A CN 101070260 A CN101070260 A CN 101070260A CN A2007100423294 A CNA2007100423294 A CN A2007100423294A CN 200710042329 A CN200710042329 A CN 200710042329A CN 101070260 A CN101070260 A CN 101070260A
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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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Abstract
Present invention belong to chemical engineering technique region, concrete relates to a means of methanol dehydration to make alkene. Four thermal-insulating catalytic reaction beds are housed different functional selecting form ZSM - 5 zeolite molecular sieve catalyzer; the four thermal-insulating catalytic reaction beds and adsorbent bed of hydrophobic silicon zeolite adsorbent compose the device, and methanol carries out dehydration to make propylene as main offspring alkene. The methanol carries out dehydration to generate methyl ether, dimethyl ether and methanol carry out dehydration to gain propylene, byproduct C4 hydrocarbon carries out spallation to gain alkene, and light gasoline carries out spallation to gain alkene. The reactions carry out under optimizing condition, apparently advance alkene productive rate, depress carbon knoting of main reaction thermal-insulating fixed bedtype reactors catalyzer, advance stability of catalytic activity, prolong regeneration period and longevity of catalyzer, save consumption of catalyzer. The ounce methanol and dimethyl ether that not converted in the large amount offspring water will be absorpted and reclaimed by hydrophobic silicon zeolite, at the same time organic pollution is cleared and the discharge water reach environmental requirements.
Description
Technical field
The invention belongs to chemical technology field, be specifically related to a kind of method of preparing olefin by methyl alcohol dewatering.
Technical background
Ethene and propylene are the important chemical basic materials, and annual requirement is huge, mainly are taken from refining of petroleum at present.In recent years, international oil price is always in the high position more than 50 dollars/barrel.The petroleum resources of China are limited, and present required oil relies on import more than 40%.Therefore, be that the methyl alcohol of raw material production is catalytically conveted to ethene and propylene technology has important strategic meaning and application prospect with the coal.Methanol conversion is that ethene is main technology (MTO) and is entering the eve of extensive industrialization at present based on the technology (MTP) of propylene.MTO technology is catalyzer with the SAPO-34 molecular sieve, is reactor with the fluidized-bed.MTP is a catalyzer with the ZSM-5 zeolite, is reactor with insulation fix bed.Germany Lu Qi company has multinomial MTP patent (EP448000, WO192190, WO2006136433, DE1020050159232 etc.), and has finished the continuous operation test of demonstration project.The Catalytic processes of the said firm part is made up of two unit insulation fix bed reactors, and prime is catalyzer with the aluminum oxide, and methyl alcohol is converted into product based on dme and water, and unconverted methanol mixture steam at 250～300 ℃ by this catalyzer.Then enter the second unit insulation fix bed reactor that the ZSM-5 zeolite is housed, under 450～500 ℃, react, be converted into the hydrocarbon mixture product.The total content of ethene and propylene is 40～60% in this hydrocarbon mixture product, butylene＞10%, and all the other are C1-C7 alkane and higher olefins and a small amount of aromatic hydrocarbons.For improving target principal product propylene overall yield, C2, C3 hydrocarbon (comprising ethene) after separating, C4 hydrocarbon (comprising butylene), and the above hydro carbons (petroleum naphtha) of C5 returns in the second unitary ZSM-5 catalytic bed again, together transforms with dme, methyl alcohol and the water vapour of first reaction member.This conversion reaction is very complicated, comprises that dme and methanol dehydration are alkene, and butylene is cracked into alkene and other hydrocarbon, and the petroleum naphtha cracking produces alkene and other hydrocarbon, and ethene and butylene transposition are converted into propylene etc.Through the reaction of this complexity, the propylene/ethylene of system ratio can reach 10～20, and diene overall yield (the C-H total amount of compound that should transform with the total quantity of methyl alcohol that drops into of system calculates) reaches 67.7% (ature of coal technology, 2005,3, p45-47) or 73.2% (Coal Chemical Industry, 2005,1172, p6-7).Because of the ZSM-5 zeolite catalyst in its main insulation fix bed reactor seriously tie carbon, cause successive reaction need after 400～700 hours with air and nitrogen the mixed gas in-situ regeneration (chemistry world 2003,12, p674-677).
Summary of the invention
The objective of the invention is to propose a kind of olefins yield height, the catalyst regeneration cycle is long, the method for the preparing olefin by methyl alcohol dewatering of discharge water compliance with environmental protection requirements.
The preparing olefin by methyl alcohol dewatering method that the present invention proposes comprises zeolite catalysis and separates.This method adopts four insulation fix bed reactors to constitute the MTP catalytic reaction system: methanol dehydration is second insulation fix bed reactor (MTP-main reaction) R2 of the first insulation fix bed reactor R1, dme and the methanol dewatered propylene of dme (MTD), the 3rd insulation fix bed reactor R3 of by product C4 hydrocarbon pyrolysis system alkene and the 4th insulation fix bed reactor R4 of petroleum naphtha cracking system alkene.Each reactor uses the ZSM-5 zeolite catalyst that is suitable for this reaction separately, and under to this reaction optimized reaction conditions, move, can obviously improve the olefins yield of whole production technology, reduce in the main insulation fix bed reactor knot carbon of ZSM-5 zeolite [molecular sieve among the R2, to improve the stability of catalytic activity, prolong the regeneration period and the life-span of catalyzer.Simultaneously, but the also usage quantity of save catalyst of the raising of catalyzed reaction efficient.Contain in a large amount of product waters a spot of unconverted methyl alcohol and dme in adsorption bed by hydrophobic silicon zeolite adsorbent absorption, recovery and reuse, can eliminate the organic pollutant in the discharge water, make it reach the environmental requirement of discharging.
The concrete steps of the inventive method are as follows:
(1) at first industrial crude first alcohol and water Hybrid Heating is become steam, feed the first adiabatic stationary fixed-bed reactor R1, methyl alcohol partly is converted into the mixing steam of dme and water; Be equipped with in the reactor and select shape ZSM-5 zeolite [molecular sieve, 180～220 ℃ of temperature of reaction, mass space velocity 2.0～6.0h
-1
(2) mixing steam that obtains of step (1) feeds the second insulation fix bed reactor R2 after heating, carry out catalyzed reaction, be converted into propylene and ethylene content and account for the mixture steam of the moisture vapor of total hydrocarbons product more than 50%, this reactor uses selects shape ZSM-5 zeolite [molecular sieve, 460～520 ℃ of temperature of reaction, mass space velocity 1-2h
-1
(3) the product mixing steam that obtains of step (2) is delivered to by pipeline among the first condenser L1 of separating unit and is cooled to 10-30 ℃, and the product that cools down in this condenser exists with gas phase, water and oil phase three-phase; The bottom of condenser is the water that contains a small amount of unconverted methyl alcohol and dme, the oil phase of the liquid petroleum naphtha that the upper strata of water is made up of the C5-C7 hydrocarbon mixture, and the top of condenser L1 is the C1-C4 hydrocarbon mixture of gas phase.This C1-C4 hydrocarbon mixture is sent into the second condenser L2 with pipeline, under-5～-10 ℃, the C4 hydrocarbon is liquefied, separate with gaseous state C1-C3 hydrocarbon mixture, after pipeline was sent into the moisture eliminator K1 that the 3A molecular sieve is housed and removed less water, input cryogenic separator F1 separated the target product propylene respectively with ethene and by product C1-C3 mixed alkanes the latter again.
(4) the C4 hydrocarbon that step (3) is obtained is sent into behind heating and gasifying among the 3rd insulation fix bed reactor R3 by pipeline, is cracked into the mixing hydrocarbon vapor that contains 48% above ethene and propylene; This reactor uses selects shape ZSM-5 zeolite [molecular sieve, 450～550 ℃ of temperature of reaction, mass space velocity 10～20h
-1
(5) petroleum naphtha that step (3) is obtained is sent into the 4th insulation fix bed reactor R4 by pipeline behind heating and gasifying, and catalytic pyrolysis is to contain ethene and the mixing hydrocarbon vapor of propylene more than 41%; Catalyzer in this reactor is to select shape ZSM-5 zeolite [molecular sieve, 550～650 ℃ of temperature of reaction, mass space velocity 1～4h
-1
(6) hydrocarbon vapor that is rich in ethene and propylene of step (4) and step (5) acquisition is sent into the first condenser L1, carry out the lock out operation of step (3);
(7) water that contains a small amount of unconverted methyl alcohol and dme that the bottom of the first condenser L1 of step (3) is discharged, send into the adsorption bed S1 that hydrophobic silicon zeolite adsorbent is housed and handle the back discharging, be adsorbed the methyl alcohol and the dme of agent absorption, be delivered to the second insulation fix bed reactor R2, be used further to be catalytically conveted to alkene as reaction raw materials with the steam that is rich in methyl alcohol and dme that produces behind the superheated vapour desorption.
Description of drawings
Fig. 1 is MTP assembly catalyze reaction process conceptual design figure.
Fig. 2 is MTP product separation process conceptual design figure.
Number in the figure: the insulation fix bed insulation fix bed reactor of the MTD of R1-preparing dimethyl ether from methanol, MTP master's insulation fix bed reactor of R2-methyl alcohol and dme system propylene, the R3-C4 hydrocarbon pyrolysis is converted into the insulation fix bed reactor of alkene, the R4-C5-C7 hydrocarbon transforms insulation fix bed reactor, S1-fractionation by adsorption device, L1, L2-condenser, the K1-moisture eliminator, the F1-cryogenic separator.
Embodiment
1. assembly catalyze part
In assembly catalyze technology, raw material composition, reaction type and treatment capacity that each insulation fix bed reactor entered are all inequality, can adopt and select shape ZSM-5 zeolite [molecular sieve, and this react (see Table 1) under the only reaction conditions operation.For example, it is the catalyzed reaction of dme that insulation fix bed reactor R1 is used for methanol conversion, 180～220 ℃ of its temperature of reaction, be reflected under the higher air speed and move, MTP production technique for 1,800,000 tons of methyl alcohol of year treatment capacity, suitable R1 reaction to select shape ZSM-5 zeolite [molecular sieve loading capacity be 56 tons, its transformation efficiency can be controlled in the lower scope of 40%-60%, the selectivity of product dme can keep 100%, this makes the MTP reaction conversion ratio of the second follow-up insulation fix bed reactor R2, propylene selectivity and total olefin selectivity obtain regulation and control, and help reducing the knot carbon of ZSM-5 catalyzer in this insulation fix bed reactor to improve the stability of catalytic activity, prolong the regeneration period and the life-span of catalyzer.Reactor R1 is a kind of reactor of single hop heat-insulating, and is simple in structure, and throughput is big.Be equipped with among the adiabatic fixed reactor R2 and select shape ZSM-5 zeolite [molecular sieve, the dme that is suitable for reactor R1 is exported, the mixing steam of first alcohol and water are converted into the hydro carbons based on propylene, 460～520 ℃ of its temperature of reaction, air speed 1～2h
-1, transformation efficiency can be more than 98%.Selecting shape ZSM-5 zeolite [molecular sieve loading capacity is 149 tons, is loaded in the multiple-step adiabatic formula reactor, is convenient to reaction heat is disperseed, and avoids the bed temperature runaway.Obviously, along with the raising of (propylene+ethene) productive rate among the reactor R2, the C4 hydrocarbon in its product and the productive rate of petroleum naphtha descend thereupon, and therefore the treatment capacity of the third and fourth insulation fix bed reactor R3 and R4 and the load of catalyzer also reduce.To C4 hydrocarbon pyrolysis reaction, the shape ZSM-5 zeolite [molecular sieve of selecting of use is fit to high-speed (10-20h
-1) under, higher temperature of reaction interval (450～550 ℃) operation, only 3 tons of required loading capacitys.This catalyzer is loaded in the single hop adiabatic reactor.The 4th insulation fix bed reactor R4 uses ZSM-5 zeolite [molecular sieve, 550～650 ℃ of temperature of reaction, air speed 1～4h
-1, be loaded in 22 tons of catalyst levelss in the single hop adiabatic reactor.Analyze the variation of experimental data according to reaction product such as the transformation efficiency of the used commercial catalysts of each insulation fix bed reactor and selectivity, by 230 tons of catalyzer of total loading capacity, year handle 1,800,000 tons of thick methyl alcohol scales of primary industries and calculate and to obtain the relation (seeing Table 2) that each insulation fix bed reactor efficient of the present invention (ultimate production of ethene+propylene) and system overall yield change.
Table 1
| Insulation fix bed reactor | Reaction type | Catalyzer *Loading capacity **(ton) | Temperature of reaction (℃) | Mass space velocity h-1 | Transformation efficiency (%) | Second+propylene selectivity (%) |
| ?R1 | ?MTD | ?56 | ?180～220 | ?2.0～6.0 | ?40～60 | 100 (dme) |
| ?R2 | ?MTP | ?149 | ?460～520 | ?1～2 | ?95～100 | ?45～65 |
| ?R3 | The C4 cracking | ?3 | ?450～550 | ?10～20 | ?70～75 | ?40～55 |
| ?R4 | The petroleum naphtha cracking | ?22 | ?550～650 | ?1～4 | ?65～75 | ?35～55 |
| Add up to | ?230 | ?98～100 | ?75～81 |
*The modification molecule that the multiple rising sun molecular sieve company limited in Shanghai produces is selected shape ZSM～5 zeolite molecular sieve commercial catalystss;
*Calculate with the industrial scale of handling 1,800,000 tons of methyl alcohol year.
Table 2.
| Insulation fix bed reactor | ||||||||
| Yield % | Output * (Ten thousand tons) | Yield % | Output *(ten thousand tons) | Yield % | Output *(ten thousand tons) | Yield % | Output *(ten thousand tons) | |
| ?R2 | ?53.2 | ?40.77 | ?56.5 | ?44.09 | ?60 | ?46.82 | ?64 | ?49.94 |
| ?R3 | ?48.0 | ?8.52 | ?51 | ?8.38 | ?54 | ?8.34 | ?54 | ?7.8 |
| ?R4 | ?41.0 | ?6.05 | ?44 | ?6.01 | ?47 | ?6.04 | ?47 | ?5.66 |
| Total system | ?74.6 | ?57.21 | ?75.0 | ?58.47 | ?78.4 | ?61.2 | ?81.2 | ?63.4 |
*(ethene+propylene) annual production.
The data of table 2 show that as not using third and fourth insulation fix bed reactor R3 and the R4, ethene and propylene total recovery only are 53%-64%.And can be increased to 74%～81% with the total recovery of R3 and R4 combination; Obviously, the optimization of the performance of R2 catalyzer and catalytic reaction condition is main to the contribution that improves total recovery.Because what the second insulation fix bed reactor R2 will transform only is the mixing steam of dme, first alcohol and water, reaction type is comparatively simple, and the knot carbon of catalyzer can obviously reduce.Experiment confirms, the second kind of molecule that loads among the R2 select shape ZSM-5 zeolite [molecular sieve, under the reaction conditions shown in the table 1, operation just needed regeneration in 1100 hours, and regeneration condition is gentle simple, the activity and the selectivity of the rear catalyst of regenerating can be recovered fully.Show good industrial using character.
2. product separate part
From the two the third and fourth insulation fix bed reactor R2, that the hydrocarbon mixture of R3 and R4 at first enters separating unit is the first condenser L1 of heat-eliminating medium with the circulating groundwater, under temperature 10-30 ℃, water (containing a small amount of unconverted methyl alcohol and dme), C5-C7 hydrocarbon mixture (liquid petroleum naphtha phase) are separated (seeing accompanying drawing 2) with gaseous state C1-C4 hydrocarbon mixture.Gaseous state C1-C4 hydrocarbon mixture enters the second condenser L2, this condenser uses the saliferous frozen water to be heat-eliminating medium, C4 hydrocarbon with liquefaction under-5～-10 ℃ separates with gaseous state C1-C3 hydrocarbon mixture, the latter enters cryogenic separator F1 the target product propylene is separated respectively with ethene and by product C1-C3 mixed alkanes after the moisture eliminator K1 through the 3A molecular sieve is housed removes less water again.
A large amount of wastewater treatment method that the separating unit first condenser L1 of the present invention discharges are as follows: usually, the dme of second insulation fix bed reactor (R2) and the reaction conversion ratio of methyl alcohol generally can not reach 100%, usually more than 98%; Calculate with average 99.0% transformation efficiency, the engineering of 1,800,000 tons of methyl alcohol/year treatment capacity, wastewater discharge reaches more than 1,000,000 tons/year; Calculated by 8000 hour production time, per hour discharge 125 tons of waste water, wherein contain 1% i.e. 1.25 tons methyl alcohol and dme, this waste water is as treated, can not compliance with environmental protection requirements and be allowed and directly discharge.Industry hydrophobic Silicone Zeolite Molecular Sieve sorbent material (the multiple rising sun molecular sieve company limited in FX-II type-Shanghai produces) is 8～10% to the active adsorption amount of methyl alcohol and dme.An adsorption bed that loads 50 tons of hydrophobic Silicone Zeolite Molecular Sieve sorbent materials is at air speed 2.5h
-1Down, per hour can handle 125 tons of waste water its COD value is reduced to below the 10ppm, reach environmental emission standard.But this adsorption bed non-stop run 3 hours, adsorbents adsorb is near saturated.At this moment, purge sorbent material with superheated vapour, make the methyl alcohol and the dme desorption of its absorption, adsorption bed is through suitably recovering to continue to handle waste water after the cooling.From the hydrophobic Silicone Zeolite Molecular Sieve sorbent material of this adsorption bed the steam of desorption, the content of methyl alcohol and dme can reach 15～20%, is delivered to second insulation fix bed reactor R2 reaction again as reaction raw materials.Thus, the transformation efficiency of methyl alcohol of apparatus of the present invention and dme can reach 100%.For making the completely separating system non-stop run, two cover adsorption beds can be set, absorption/desorption is operation in turn.The work-ing life of hydrophobic adsorbent is more than 5 years.
Claims (1)
1, a kind of zeolite catalysis and separation method that improves yield of preparing olefin by methyl alcohol dewatering, it is characterized in that adopting four insulation fix bed reactors to constitute the MTP catalytic reaction system: methanol dehydration is the second insulation fix bed reactor R2 of the first insulation fix bed reactor R1, dme and the methanol dewatered propylene of dme, the 3rd insulation fix bed reactor R3 of by product C4 hydrocarbon pyrolysis system alkene and the 4th insulation fix bed reactor R4 of petroleum naphtha cracking system alkene; Concrete steps are as follows:
(1) at first industrial crude first alcohol and water Hybrid Heating is become steam, feed the first adiabatic stationary fixed-bed reactor R1, methyl alcohol partly is converted into the mixing steam of dme and water; Be equipped with in the reactor and select shape ZSM-5 zeolite [molecular sieve, 180～220 ℃ of temperature of reaction, mass space velocity 2.0～6.0h
-1
(2) mixing steam that obtains of step (1) feeds the second insulation fix bed reactor R2 after heating, carry out catalyzed reaction, be converted into propylene and ethylene content and account for the mixture steam of the moisture vapor of total hydrocarbons product more than 50%, this reactor uses selects shape ZSM-5 zeolite [molecular sieve, 460～520 ℃ of temperature of reaction, mass space velocity 1-2h
-1
(3) the product mixing steam that obtains of step (2) is delivered to by pipeline among the first condenser L1 of separating unit and is cooled to 10-30 ℃, and the product that cools down in this condenser exists with gas phase, water and oil phase three-phase; The bottom of condenser is the water that contains a small amount of unconverted methyl alcohol and dme, the oil phase of the liquid petroleum naphtha that the upper strata of water is made up of the C5-C7 hydrocarbon mixture, and the top of condenser L1 is the C1-C4 hydrocarbon mixture of gas phase; This C1-C4 hydrocarbon mixture is sent into the second condenser L2 with pipeline, under-5～-10 ℃, the C4 hydrocarbon is liquefied, separate with gaseous state C1-C3 hydrocarbon mixture, after pipeline was sent into the moisture eliminator K1 that the 3A molecular sieve is housed and removed less water, input cryogenic separator F1 separated the target product propylene respectively with ethene and by product C1-C3 mixed alkanes the latter again;
(4) the C4 hydrocarbon that step (3) is obtained is sent into behind heating and gasifying among the 3rd insulation fix bed reactor R3 by pipeline, is cracked into the mixing hydrocarbon vapor that contains 48% above ethene and propylene; This reactor uses selects shape ZSM-5 zeolite [molecular sieve, 450～550 ℃ of temperature of reaction, mass space velocity 10～20h
-1
(5) petroleum naphtha that step (3) is obtained is sent into the 4th insulation fix bed reactor R4 by pipeline behind heating and gasifying, and catalytic pyrolysis is to contain ethene and the mixing hydrocarbon vapor of propylene more than 41%; Catalyzer in this reactor is to select shape ZSM-5 zeolite [molecular sieve, 550～650 ℃ of temperature of reaction, mass space velocity 1～4h
-1
(6) hydrocarbon vapor that is rich in ethene and propylene of step (4) and step (5) acquisition is sent into the first condenser L1, carry out the lock out operation of step (3);
(7) water that contains a small amount of unconverted methyl alcohol and dme that the bottom of the first condenser L1 of step (3) is discharged, send into the adsorption bed S1 that hydrophobic silicon zeolite adsorbent is housed and handle the back discharging, be adsorbed the methyl alcohol and the dme of agent absorption, be delivered to the second insulation fix bed reactor R2, be used further to be catalytically conveted to alkene as reaction raw materials with the steam that is rich in methyl alcohol and dme that produces behind the superheated vapour desorption.
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| CN102875290A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Reaction unit for preparing low-carbon olefins by using methanol and naphtha |
| CN103030504A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Production method of propylene |
| CN101723775B (en) * | 2008-11-04 | 2013-05-22 | 杭州林达化工技术工程有限公司 | Method and equipment for preparing hydrocarbon by methyl alcohol or/ and dimethyl ether |
| CN103242884A (en) * | 2013-05-20 | 2013-08-14 | 易高环保能源研究院有限公司 | Process for preparing high-octane high-cleanness gasoline with methanol by using multi-element catalysis method |
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| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
| CN113443955A (en) * | 2021-06-28 | 2021-09-28 | 江苏斯尔邦石化有限公司 | Method for preparing propylene by catalytic cracking of C4-C6 olefin |
| CN115259982A (en) * | 2022-08-01 | 2022-11-01 | 润和催化剂股份有限公司 | Process method and reaction system for preparing propylene by methanol conversion |
| WO2024027452A1 (en) * | 2022-08-01 | 2024-02-08 | 润和催化剂股份有限公司 | Methanol to propylene process method and reaction system |
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