CN104193570A - MTO process and naphtha cracking sequence separating process coupling method - Google Patents
MTO process and naphtha cracking sequence separating process coupling method Download PDFInfo
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- CN104193570A CN104193570A CN201410401066.1A CN201410401066A CN104193570A CN 104193570 A CN104193570 A CN 104193570A CN 201410401066 A CN201410401066 A CN 201410401066A CN 104193570 A CN104193570 A CN 104193570A
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention relates to an MTO process and naphtha cracking sequence separating process coupling method which is mainly used for solving the problems of unreasonable process design, relatively high investment and relatively low raw material product benefit in the traditional coupling technology. The problems are better solved through the technical scheme that the MTO process and naphtha cracking sequence separating process coupling method comprises the steps of compressing and drying MTO product gas, and then, enabling the compressed and dried MTO product gas to enter a crude separating tower; enabling a material flow which comprises components lower than C2 and parts of C3 components and is located at the top of the crude separating tower to enter a cold box provided in a naphtha cracking sequence separating process; enabling a material flow which comprises the rest C3 components and components higher than C4 and is located in the crude separating tower to enter a depropanizer provided in an MTO separating process; and enabling a material flow located in the depropanizer to enter a debutanizer provided in a process for preparing ethylene through naphtha steam cracking. The MTO process and naphtha cracking sequence separating process coupling method can be used for production of low-carbon olefin.
Description
Technical field
The present invention relates to a kind of method of MTO technique and the coupling of naphtha cracking order separating technology.
Background technology
Low-carbon alkene, i.e. ethene and propylene, is two kinds of important basic chemical industry raw materials, ethene, propylene are mainly to produce by petroleum path at present, ethene as processed in naphtha steam cracking, propylene technology.US 20070083071 has announced the processing method of a kind of hydrocarbon catalytic pyrolysis production ethene, propylene, hydrocarbon feed is converted into the product that comprises low-carbon alkene in catalytic cracker, then product stream is separated into C2～C3 alkane, C2～C3 alkene, three kinds of logistics of C4+ hydrocarbon by series of process, C2～C3 alkane is returned to tube cracking furnace and carry out thermo-cracking, C4+ hydrocarbon returns to catalytic cracker and carries out catalytic pyrolysis, finally obtains ethene, the propylene product of higher yields.
But due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people start to greatly develop technology, especially methanol-to-olefins (MTO) technique of alternative materials conversion ethene processed, propylene, can, by coal or natural gas via preparing low-carbon olefin by using methanol, reduce the dependency degree to petroleum resources.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene in US6166282, are announced, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, rise to after the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all greatly reduce.
In ethylene unit, the light hydrocarbon mixture that hydrocarbon pyrolysis apparatus produces, generally separates by cryogenic method.Low temperature separation process flow process is divided into again order separation process, front-end deethanization separation process and predepropanization separation process according to the difference of first rectifying tower weight key ingredient.Wherein, order separation process is pressed splitting gas composition and is separated with the order of molecular weight, and then carry out the separation of hydrocarbons of same carbonatoms, adopt back end hydrogenation to remove the method for alkynes, because of technology maturation, various raw materials are had to more intense adaptability, smooth running is reliable, good product quality is widely adopted in full scale plant.In addition, cracking reactor effluent also contains higher alkane and the aromatic hydrocarbons family of certain marketable value conventionally, can carry out industrial application.CN101539364 discloses a kind of pyrolysis gas compression system of featuring light dydrocarbon sequential separation procedure and has improved one's methods, by interchanger being set at cracking gas compressor end outlet, light hydrocarbon feedstocks is cooled to 10-20 DEG C step by step, and gas-liquid separation device is set, isolated gaseous phase materials is delivered to gas phase moisture eliminator, after dry, deliver to downstream cryogenic system, an isolated liquid phase material part is returned to suction surge tank or the condensate stripper of cracking gas compressor upper level, residual solution phase materials is delivered to liquid phase moisture eliminator, send after drying cryogenic system, avoid light constituent material that lime set produces in the time of flash distillation and stripping in the intersegmental circulation of cracking gas compressor, reduce the load of cracking gas compressor, realize the energy-saving and production-increase transformation of ethylene unit.Although it is energy-conservation that cracker has through transformation, the high enterprise of current existing cracker raw material petroleum naphtha price, cracking cost is higher, and competitive variation needs to consider the economic benefit that ethylene unit moves.
For how reducing petroleum naphtha consumption, adopt methyl alcohol to substitute petroleum naphtha and produce low-carbon alkene, and MTO technique and preparing ethylene by steam cracking technique are effectively coupled, become one of direction of research.CN103755510A relates to a kind of alcohol hydrocarbon refining technology altogether of utilizing and produces the technique of propylene, is ethylene unit or oil refining apparatus are refined to shared disengaging zone, reaction zone altogether with alcohol hydrocarbon, realizes the technique of integrated production.CN 102408294 discloses the comprehensive of methanol to olefins reaction system and hydrocarbon pyrolysis system, having described a kind of comprehensive MTO synthesizes and hydrocarbon pyrolysis system, wherein make MTO system and its supplementary cracking of olefins reactor and the combination of hydrocarbon pyrolysis reactor, by supplement cracking of olefins reactor combination treatment oxygenate alkene MTO processed reactor effluent compared with the lighter fraction of the effluent of last running and hydrocarbon pyrolysis system, can be successfully by comprehensive to MTO system and hydrocarbon pyrolysis system, and the output of larger Olefin conversion light olefin is increased, promote the flexible production of alkene and other petroleum chemicals.
All there is the problem that flow scheme design is unreasonable, investment is large, process cost is higher in existing coupling technique.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that in existing coupling technique, flow scheme design is unreasonable, investment is large, raw produce benefit is lower, and a kind of method of new MTO technique and the coupling of naphtha cracking order separating technology is provided.The method, for the production of low-carbon alkene, has advantages of that flow scheme design is reasonable, investment is less, better results for raw produce.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of MTO technique and the coupling of naphtha cracking order separating technology, MTO gas product is compressed, after dry, enter roughing out tower, comprise that C2 roughing out column overhead logistics following and part C3 component enters the ice chest in naphtha cracking order separation process scheme, the roughing out tower reactor logistics that comprises remainder C3 and the above component of C4 enters the depropanizing tower in MTO separation process, depropanizing tower overhead stream enters the propylene rectification tower in MTO separation process, propylene rectification tower top obtains propylene product, propylene rectification tower still obtains propane, the logistics of depropanizing tower reactor enters the debutanizing tower in naphtha cracking order separation process scheme, wherein, rely on naphtha cracking order separation process scheme to obtain methane hydrogen, ethene, ethane, part propane, part propylene, the above hydrocarbon product of hybrid C 4 and C5, from MTO technique separation process, obtain remainder propane, remainder propylene product, keep the ethene in the deethanizing column charging in described naphtha cracking order separation process scheme by reducing naphtha feed amount, propylene flow is constant.
In technique scheme, preferably, the operational condition of described roughing out tower: temperature is-20 DEG C～10 DEG C, and pressure is 0.6～3.0MPaG.
In technique scheme, preferably, ethene and propylene mass ratio 0.8～1.5:1 in described MTO gas product.
In technique scheme, preferably, propylene and ethene mass ratio 0.47～0.53:1 in the splitting gas of described naphtha cracking order separating technology.
In technique scheme, preferably, described MTO technique separating unit institute chilling requirement is provided by freezing water station.
In technique scheme, preferably, described in comprise that C2 roughing out column overhead logistics following and part C3 component enters the deethanizing column in naphtha cracking order separation process scheme after supercharging.
The present invention relies on ethylene unit existing installation, with the integrated technique propylene enhancing product of methyl alcohol Substitute For Partial petroleum naphtha, ensure that naphtha steam cracking ethylene process flow process processed and equipment are constant, MTO technical process only need to be built roughing out tower, propylene rectification tower, depropanizing tower, chilled water system, and without the propylene refrigeration unit of building highly energy-consuming, deethanizing column, demethanizing tower, ethylene rectification tower, process design is reasonable, 100～1,200,000 tons/year of ethylene units can lack lapidation cerebrol 86.13～129.30 ten thousand ton/year, ten thousand tons/year of propylene enhancing 6.35～19.93, raw produce benefit approximately reaches 24.8～39.0 hundred million yuans/year, do not increase at ethene aggregated capacity, under the condition that equipment is not transformed, just can solve currently available products part-structure problem, ensure ethene production capacity, propylene enhancing, and reduction energy consumption, greatly reduce investment and production cost, obtain good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
Naphtha cracking order separation process scheme is described: naphtha cracking raw material enters pyrolyzer generation steam heat scission reaction and generates ethene, the materials such as propylene, the Pintsch process gas material of pyrolyzer outlet is through quench zone quenching, splitting gas material after splitting gas material compressed district supercharging after chilling enters demethanizing tower after ice chest, the components such as demethanizer column overhead methane and hydrogen are returned to ice chest, methane and hydrogen-rich gas flow out from ice chest, demethanizing tower tower reactor liquid enters deethanizing column, tower top is isolated C2 light constituent material, tower reactor is isolated C3 and the above heavy constituent material of C3, C2 light constituent material send ethylene rectification tower, and tower top is isolated polymer grade ethylene product, and tower reactor is isolated ethane material, deethanizing tower reactor material send depropanizing tower, and tower top is isolated C3 material, and tower reactor is isolated C4 and the above heavy constituent material of C4, C3 material send propylene rectification tower, and tower top is isolated polymerization-grade propylene product, and tower reactor is isolated propane material, the above heavy constituent material of C4 and C4 send debutanizing tower, and tower top is isolated hybrid C 4 material, and tower reactor is isolated C5 and the above heavy constituent material of C5.
The main flow process of MTO device is described: methanol feedstock send MTO reaction member generation catalyzed reaction generate the low-carbon alkenes such as ethene, propylene and after the pre-treatment such as chilling, become MTO gas product, MTO gas product send washing/soda-wash tower after the supercharging of product air compressor, the gas product material of tower top send roughing out tower after compressor supercharging, tower top is isolated containing part C3 and the following light constituent material of C2, send the ice chest of naphtha cracking order separation process scheme after compressor supercharging; Roughing out tower reactor is isolated the depropanizing tower that send MTO device containing part C3 and the above heavy constituent material of C4, and tower top is isolated C3 material, and tower reactor is isolated C4 and the above heavy constituent material of C4; C3 material send propylene rectification tower, and tower top is isolated polymerization-grade propylene product, and tower reactor is isolated propane material; The above heavy constituent material of C4 and C4 send the debutanizing tower of naphtha cracking order separation process scheme.
[comparative example 1]
On naphtha steam cracking as above ethylene unit processed, employing order separation process scheme, in splitting gas, the mass ratio of propylene and ethene is 0.51, polymer grade ethylene purity >=99.95mol%, ethene production capacity is 120.00 ten thousand tons/year; Polymerization-grade propylene purity >=99.6mol%, propylene production capacity is 61.20 ten thousand tons/year.
[embodiment 1]
Naphtha steam cracking ethylene unit employing order processed separation process scheme, ethene production capacity is 1,200,000 tons/year, in splitting gas, the mass ratio of propylene and ethene is 0.51, and the methyl alcohol treatment scale of newly-increased MTO device is 1,800,000 tons/year, and in MTO gas product, the mass ratio of ethene and propylene is 1.5.MTO device product gas is after roughing out tower separates and compresses, and 50% C3 and all more light constituents are sent to five sections of compression outlets of cracker, enters the ice chest of cracker together with splitting gas; MTO device product gas is after depropanizing tower separates, and the debutanizing tower that enters ethylene unit together with the depropanizing tower reactor liquid of tower bottoms and naphtha steam cracking ethylene unit processed carries out separation.Adopt coupling process of the present invention, the operational condition of roughing out tower: temperature is-10 DEG C, pressure is 1.5MPaG.Polymer grade ethylene purity >=the 99.95mol% obtaining, polymerization-grade propylene purity >=99.6mol%, concrete data are in table 1.Compared with comparative example 1,129.30 ten thousand tons/year of few lapidation cerebrols, 6.35 ten thousand tons/year of propylene enhancings.
[comparative example 2]
According to condition and step described in comparative example 1, just change ethylene unit scale, ethene production capacity is 110.00 ten thousand tons/year, propylene production capacity is 56.10 ten thousand tons/year.
[embodiment 2]
According to condition and step described in embodiment 1, naphtha steam cracking ethylene unit ethene processed production capacity is 1,100,000 tons/year, and concrete data are in table 1.Compared with comparative example 2,129.30 ten thousand tons/year of few lapidation cerebrols, 6.35 ten thousand tons/year of propylene enhancings.
[comparative example 3]
According to condition and step described in comparative example 1, just change ethylene unit scale, ethene production capacity is 100.00 ten thousand tons/year, propylene production capacity is 51.00 ten thousand tons/year.
[embodiment 3]
According to condition and step described in comparative example 1, naphtha steam cracking ethylene unit ethene processed production capacity is 1,000,000 tons/year, and in newly-increased MTO device product gas, the mass ratio of ethene and propylene is 0.8.Adopt coupling process of the present invention, the operational condition of roughing out tower: temperature is-20 DEG C, pressure is 0.6MPaG.Concrete data are in table 1.Compared with comparative example 3,86.13 ten thousand tons/year of few lapidation cerebrols, 19.93 ten thousand tons/year of propylene enhancings.
[embodiment 4]
According to condition and step described in embodiment 3, just in MTO gas product, the mass ratio of ethene and propylene is 0.9.Concrete data are in table 1.Compared with comparative example 3,93.36 ten thousand tons/year of few lapidation cerebrols, 17.55 ten thousand tons/year of propylene enhancings.
[embodiment 5]
According to condition and step described in embodiment 3, just in MTO gas product, the mass ratio of ethene and propylene is 1.0.The operational condition of roughing out tower: temperature is 5 DEG C, pressure is 2.5MPaG.Concrete data are in table 1.With compared with comparative example 3,100.36 ten thousand tons/year of few lapidation cerebrols, 15.38 ten thousand tons/year of propylene enhancings.
[embodiment 6]
According to condition and step described in embodiment 3, just in MTO gas product, the mass ratio of ethene and propylene is 1.2.The operational condition of roughing out tower: temperature is 0 DEG C, pressure is 2.2MPaG.Concrete data are in table 1.Compared with comparative example 3,113.31 ten thousand tons/year of few lapidation cerebrols, 11.47 ten thousand tons/year of propylene enhancings.
[embodiment 7]
According to condition and step described in embodiment 3, just in MTO gas product, the mass ratio of ethene and propylene is 1.5.The operational condition of roughing out tower: temperature is-15 DEG C, pressure is 1.0MPaG.Concrete data are in table 1.Compared with comparative example 3,129.30 ten thousand tons/year of few lapidation cerebrols, 6.35 ten thousand tons/year of propylene enhancings.
Table 1
Claims (6)
1. the method for a MTO technique and the coupling of naphtha cracking order separating technology, MTO gas product is compressed, after dry, enter roughing out tower, comprise that C2 roughing out column overhead logistics following and part C3 component enters the ice chest in naphtha cracking order separation process scheme, the roughing out tower reactor logistics that comprises remainder C3 and the above component of C4 enters the depropanizing tower in MTO separation process, depropanizing tower overhead stream enters the propylene rectification tower in MTO separation process, propylene rectification tower top obtains propylene product, propylene rectification tower still obtains propane, the logistics of depropanizing tower reactor enters the debutanizing tower in naphtha cracking order separation process scheme, wherein, rely on naphtha cracking order separation process scheme to obtain methane hydrogen, ethene, ethane, part propane, part propylene, the above hydrocarbon product of hybrid C 4 and C5, from MTO technique separation process, obtain remainder propane, remainder propylene product, keep the ethene in the deethanizing column charging in described naphtha cracking order separation process scheme by reducing naphtha feed amount, propylene flow is constant.
2. the method for MTO technique and naphtha cracking order separating technology coupling according to claim 1, is characterized in that the operational condition of described roughing out tower: temperature is-20 DEG C～10 DEG C, and pressure is 0.6～3.0MPaG.
3. the method that MTO technique and naphtha cracking order separating technology are coupled according to claim 1, is characterized in that ethene and propylene mass ratio 0.8～1.5:1 in described MTO gas product.
4. the method for MTO technique and naphtha cracking order separating technology coupling according to claim 1, is characterized in that propylene and ethene mass ratio 0.47～0.53:1 in the splitting gas of described naphtha cracking order separating technology.
5. the method for MTO technique and naphtha cracking order separating technology coupling according to claim 1, is characterized in that described MTO technique separating unit institute chilling requirement is provided by freezing water station.
6. the method that MTO technique and naphtha cracking order separating technology are coupled according to claim 1, comprises described in it is characterized in that C2 roughing out column overhead logistics following and part C3 component enters the ice chest in naphtha cracking order separation process scheme after supercharging.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534946A (en) * | 2018-12-10 | 2019-03-29 | 中石化上海工程有限公司 | Naphtha and ethane cracking sequentially separate the method coupled with MTO |
| CN109651044A (en) * | 2018-12-10 | 2019-04-19 | 中石化上海工程有限公司 | The method that light hydrocarbon cracking sequence separating technology is coupled with MTO technique |
| CN110944967A (en) * | 2017-07-12 | 2020-03-31 | 林德股份公司 | Process and plant for the production of propylene combining a propane dehydrogenation and a steam cracking process, in both of which there is a preliminary separation step for partial removal of hydrogen and methane |
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| CN1847203A (en) * | 2006-05-15 | 2006-10-18 | 中国石油化工集团公司 | Separating method for converting methanol to prepare low carbon olefin gas |
| CN103964990A (en) * | 2014-03-14 | 2014-08-06 | 惠生工程（中国）有限公司 | MTO (methanol toolefin) and steam crackingto olefin mixed separation technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1660722A (en) * | 2004-12-23 | 2005-08-31 | 中国石油化工集团公司 | Method for separating catalytic splitting gas of enriching propylene and propane |
| CN1847203A (en) * | 2006-05-15 | 2006-10-18 | 中国石油化工集团公司 | Separating method for converting methanol to prepare low carbon olefin gas |
| CN103964990A (en) * | 2014-03-14 | 2014-08-06 | 惠生工程（中国）有限公司 | MTO (methanol toolefin) and steam crackingto olefin mixed separation technology |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110944967A (en) * | 2017-07-12 | 2020-03-31 | 林德股份公司 | Process and plant for the production of propylene combining a propane dehydrogenation and a steam cracking process, in both of which there is a preliminary separation step for partial removal of hydrogen and methane |
| CN109534946A (en) * | 2018-12-10 | 2019-03-29 | 中石化上海工程有限公司 | Naphtha and ethane cracking sequentially separate the method coupled with MTO |
| CN109651044A (en) * | 2018-12-10 | 2019-04-19 | 中石化上海工程有限公司 | The method that light hydrocarbon cracking sequence separating technology is coupled with MTO technique |
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