CN104151121A - Method for coupling MTO (Methanol to Olefins) process with naphtha cracking front-end depropanization process - Google Patents
Method for coupling MTO (Methanol to Olefins) process with naphtha cracking front-end depropanization process Download PDFInfo
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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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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Abstract
The invention relates to a method for coupling an MTO (Methanol to Olefins) process with a naphtha cracking front-end depropanization process, and mainly aims to solve the problems of unreasonable flow design, high investment and low raw material product efficiency in the conventional coupling technology. By adopting the method for coupling the MTO process with the naphtha cracking front-end depropanization process, MTO product gas enters a pre-cutting tower after being compressed and dried, material flow containing components having less than 2 carbon atoms and a part of components having 3 carbon atoms enters a debutanizer in a naphtha cracking front-end depropanization process flow, material flow containing the remaining components including 3 carbon atoms enters a debutanizer in an MTO separating flow, and hydrocarbon material flow containing components having over 4 carbon atoms enters a debutanizer in the naphtha cracking front-end depropanization process. By adopting the technical scheme, the problems are well solved. The method can be applied to the production of light olefins.
Description
Technical field
The present invention relates to a kind of method of MTO technique and the coupling of naphtha cracking predepropanization technique.
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.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 predepropanization technique 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 predepropanization technique, MTO gas product is compressed, after dry, enter precut tower, MTO gas product is divided into three parts, a part is for comprising below C2 and the logistics of part C3 component, a part is the logistics of remainder C3 component, another part is the above component logistics of C4, comprise that the following and part C3 component logistics of C2 enters the depropanizing tower in the technical process of naphtha cracking predepropanization, the logistics of remainder C3 component enters the propylene rectification tower in MTO separation process, propylene rectification tower top obtains propylene product, propylene rectification tower still obtains propane, the above component logistics of C4 enters the debutanizing tower in the technical process of naphtha cracking predepropanization, wherein, rely on the technical process of naphtha cracking predepropanization 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 depropanizing tower charging in the technical process of described naphtha cracking predepropanization by reducing naphtha feed amount, propylene flow is constant.
In technique scheme, preferably, the operational condition of described precut column overhead: temperature is-30 DEG C～15 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 predepropanization technique.
In technique scheme, preferably, the propane that described MTO technique separating unit separates, ethane and the propane that predepropanization technique separates return to pyrolyzer.
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 precut tower, propylene rectification tower, and without the propylene refrigeration unit of building highly energy-consuming, deethanizing column, demethanizing tower, depropanizing tower, ethylene rectification tower, process design is reasonable, 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.80～1,200,000 tons/year of ethylene units can lack lapidation cerebrol 85.86～128.88 ten thousand ton/year, ten thousand tons/year of propylene enhancing 6.75～20.2; Product and raw material price difference can be saved approximately 25～3,900,000,000 yuans/year.Compared with building a set of complete MTO device, can save approximately 4～800,000,000 yuans of investments simultaneously, obtain good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
The technical process of naphtha cracking predepropanization is described: naphtha cracking raw material enters pyrolyzer generation steam heat scission reaction and generates the materials such as ethene, 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 depropanizing tower, depropanizing tower tower top component enters demethanizing tower, tower top obtains methane hydrogen, tower bottoms enters deethanizing column, tower top is isolated C2 light constituent material, and tower reactor is isolated C3 component materials; C2 light constituent material send ethylene rectification tower, and tower top is isolated polymer grade ethylene product, and tower reactor is isolated ethane material; C3 component is sent propylene rectification tower, and tower top is isolated polymerization-grade propylene product, and tower reactor is isolated propane material; Depropanizing tower reactor material 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 to generate ethene, the low-carbon alkenes such as propylene also become MTO gas product after the pre-treatment such as chilling, MTO gas product send washing/soda-wash tower after the supercharging of product air compressor, the gas product material of tower top send precut tower after compressor supercharging, MTO gas product is divided into three parts, a part is for comprising below C2 and the logistics of part C3 component, a part is the logistics of remainder C3 component, another part is the above component logistics of C4, comprise that the following and part C3 component logistics of C2 enters the depropanizing tower in the technical process of naphtha cracking predepropanization, the logistics of remainder C3 component enters the propylene rectification tower in MTO separation process, propylene rectification tower top obtains propylene product, propylene rectification tower still obtains propane, the above component logistics of C4 enters the debutanizing tower in the technical process of naphtha cracking predepropanization.
[comparative example 1]
Naphtha cracking device adopts predepropanization technical process, and ethylene production capacity is 800,000 tons/year, and in splitting gas, the third rare and mass ratio ethene is 1:2, and concrete data are in table 1.
[embodiment 1]
Adopt the coupling process of MTO technique of the present invention and the technical process of naphtha cracking predepropanization, keep 800,000 tons/year of the ethylene product amounts of whole coupling flow process constant, the operational condition of precut column overhead is: temperature is 8 DEG C, and pressure is 2.6MPaG.MTO reaction scale is 1,800,000 tons/year, and raw material is methyl alcohol, and in splitting gas, the third rare and mass ratio ethene is 1:2, and in MTO gas product, ethene is 0.9:1 with the third rare mass ratio, and specifically data are in table 1.
[comparative example 2]
According to the condition described in comparative example 1, ethylene production capacity is 1,000,000 tons/year, and concrete data are in table 1.
[embodiment 2]
According to the condition described in embodiment 1, keep 1,000,000 tons/year of the ethylene product amounts of whole coupling flow process constant, the operational condition of precut column overhead is: temperature is 0 DEG C, pressure is 2.0MPaG.MTO reaction scale is 1,800,000 tons/year, and raw material is methyl alcohol, and in splitting gas, the third rare and mass ratio ethene is 1:2, and in MTO gas product, ethene is 1:1 with the third rare mass ratio, and specifically data are in table 1.
[comparative example 3]
According to the condition described in comparative example 1, ethylene production capacity is 1,200,000 tons/year, and concrete data are in table 1.
[embodiment 3]
According to the condition described in embodiment 1, keep 1,200,000 tons/year of the ethylene product amounts of whole coupling flow process constant, the operational condition of precut column overhead is: temperature is-2 DEG C, pressure is 1.8MPaG.MTO reaction scale is 1,800,000 tons/year, and raw material is methyl alcohol, and in splitting gas, the third rare and mass ratio ethene is 1:2, and in MTO gas product, ethene is 1.2:1 with the third rare mass ratio, and specifically data are in table 1.
[embodiment 4]
According to the condition described in embodiment 1, keep 1,200,000 tons/year of the ethylene product amounts of whole coupling flow process constant, the operational condition of precut column overhead is: temperature is 13 DEG C, pressure is 3.0MPaG.MTO reaction scale is 1,800,000 tons/year, and raw material is methyl alcohol, and in splitting gas, the third rare and mass ratio ethene is 1:2, and in MTO gas product, ethene is 0.8:1 with the third rare mass ratio, and specifically data are in table 1.
[embodiment 5]
According to the condition described in embodiment 1, keep 1,200,000 tons/year of the ethylene product amounts of whole coupling flow process constant, the operational condition of precut column overhead is: temperature is-30 DEG C, pressure is 0.6MPaG.MTO reaction scale is 1,800,000 tons/year, and raw material is methyl alcohol, and in splitting gas, the third rare and mass ratio ethene is 1:2, and in MTO gas product, ethene is 1.5:1 with the third rare mass ratio, and specifically data are in table 1.
Table 1
Contrast by above embodiment and comparative example can be found out, the present invention is leveraging fully on the ethylene unit existing installation of predepropanization process, and keep under prerequisite that ethene aggregated capacity is constant, adopt after the integrated technique of methyl alcohol Substitute For Partial petroleum naphtha propylene enhancing, 80～1,200,000 tons/year of ethylene units can lack lapidation cerebrol 85.86～128.88 ten thousand ton/year, ten thousand tons/year of propylene enhancing 6.75～20.2; Product and raw material price difference can be saved approximately 25～3,900,000,000 yuans/year.Compared with building a set of complete MTO device, can save approximately 4～800,000,000 yuans of investments simultaneously.
Claims (5)
1. the method for a MTO technique and the coupling of naphtha cracking predepropanization technique, MTO gas product is compressed, after dry, enter precut tower, MTO gas product is divided into three parts, a part is for comprising below C2 and the logistics of part C3 component, a part is the logistics of remainder C3 component, another part is the above component logistics of C4, comprise that the following and part C3 component logistics of C2 enters the depropanizing tower in the technical process of naphtha cracking predepropanization, the logistics of remainder C3 component enters the propylene rectification tower in MTO separation process, propylene rectification tower top obtains propylene product, propylene rectification tower still obtains propane, the above component logistics of C4 enters the debutanizing tower in the technical process of naphtha cracking predepropanization, wherein, rely on the technical process of naphtha cracking predepropanization 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 depropanizing tower charging in the technical process of described naphtha cracking predepropanization by reducing naphtha feed amount, propylene flow is constant.
2. the method for MTO technique and naphtha cracking predepropanization technique coupling according to claim 1, is characterized in that the operational condition of described precut column overhead: temperature is-30 DEG C～15 DEG C, and pressure is 0.6～3.0MPaG.
3. the method that MTO technique and naphtha cracking predepropanization technique 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 predepropanization technique 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 predepropanization technique.
5. the method for MTO technique and naphtha cracking predepropanization technique coupling according to claim 1, is characterized in that the propane that described MTO technique separating unit separates, ethane and the propane that predepropanization technique separates return to pyrolyzer.
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Cited By (10)
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| CN107056568A (en) * | 2017-05-10 | 2017-08-18 | 中石化上海工程有限公司 | The method that MTO techniques are coupled with naphtha and Deposition During Propane Pyrolysis predepropanization technique |
| CN107602323A (en) * | 2017-10-11 | 2018-01-19 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with light hydrocarbon cracking predepropanization technique |
| CN107602324A (en) * | 2017-10-11 | 2018-01-19 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with naphtha pyrolysis predepropanization technique |
| CN107673947A (en) * | 2017-10-11 | 2018-02-09 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with naphtha pyrolysis front-end deethanization technique |
| CN109438163A (en) * | 2018-11-23 | 2019-03-08 | 内蒙古中煤蒙大新能源化工有限公司 | A kind of method of tail gas recycle propane in polypropylene plant |
| CN109503309A (en) * | 2018-12-10 | 2019-03-22 | 中石化上海工程有限公司 | The method that light hydrocarbon cracking predepropanization technique is coupled with MTO technique |
| CN109651043A (en) * | 2018-12-10 | 2019-04-19 | 中石化上海工程有限公司 | The method that naphtha and ethane cracking predepropanization are coupled with MTO |
| CN110914225A (en) * | 2017-07-12 | 2020-03-24 | 林德股份公司 | Process and apparatus for the combined dehydrogenation of propane and steam cracking process wherein propane is recycled in the steam cracking process to produce propylene |
| 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 |
| CN114409492A (en) * | 2021-12-15 | 2022-04-29 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
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| CN107056568A (en) * | 2017-05-10 | 2017-08-18 | 中石化上海工程有限公司 | The method that MTO techniques are coupled with naphtha and Deposition During Propane Pyrolysis predepropanization technique |
| CN110914225A (en) * | 2017-07-12 | 2020-03-24 | 林德股份公司 | Process and apparatus for the combined dehydrogenation of propane and steam cracking process wherein propane is recycled in the steam cracking process to produce propylene |
| 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 |
| CN107602323A (en) * | 2017-10-11 | 2018-01-19 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with light hydrocarbon cracking predepropanization technique |
| CN107602324A (en) * | 2017-10-11 | 2018-01-19 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with naphtha pyrolysis predepropanization technique |
| CN107673947A (en) * | 2017-10-11 | 2018-02-09 | 中石化上海工程有限公司 | The method that dehydrogenating propane technique couples with naphtha pyrolysis front-end deethanization technique |
| CN109438163A (en) * | 2018-11-23 | 2019-03-08 | 内蒙古中煤蒙大新能源化工有限公司 | A kind of method of tail gas recycle propane in polypropylene plant |
| CN109438163B (en) * | 2018-11-23 | 2021-07-02 | 内蒙古中煤蒙大新能源化工有限公司 | Method for recovering propane from tail gas in polypropylene device |
| CN109503309A (en) * | 2018-12-10 | 2019-03-22 | 中石化上海工程有限公司 | The method that light hydrocarbon cracking predepropanization technique is coupled with MTO technique |
| CN109651043A (en) * | 2018-12-10 | 2019-04-19 | 中石化上海工程有限公司 | The method that naphtha and ethane cracking predepropanization are coupled with MTO |
| CN114409492A (en) * | 2021-12-15 | 2022-04-29 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
| CN114409492B (en) * | 2021-12-15 | 2023-12-22 | 国家能源集团宁夏煤业有限责任公司 | Device and method for preparing low-carbon olefin from methanol |
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