CN100564331C - Utilize refinery C four to produce the combination process of alkene - Google Patents
Utilize refinery C four to produce the combination process of alkene Download PDFInfo
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- CN100564331C CN100564331C CNB2006101655190A CN200610165519A CN100564331C CN 100564331 C CN100564331 C CN 100564331C CN B2006101655190 A CNB2006101655190 A CN B2006101655190A CN 200610165519 A CN200610165519 A CN 200610165519A CN 100564331 C CN100564331 C CN 100564331C
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Abstract
Of the present inventionly utilize refinery C four to produce alkene to belong to the technical field of producing alkene, in order to solve the technical problem that to utilize refinery C four at present fully, the present invention proposes refinery C four and at first carries out pre-separation and remove wherein propane, propylene and Trimethylmethane, be sent to the olefins by catalytic cracking system then, the splitting gas mixture that produces enters cooling system and cools, enter the compression section compression again, catalytically cracked gas after the compression enters the absorption tower, reach more heavy constituent as absorption agent with carbon five, methane, the second-class light constituent of carbon is from the cat head extraction, the logistics of tower still separates through separation system, obtains carbon three components respectively, carbon four components, carbon five and more heavy constituent.Combination process of the present invention has can make full use of refinery C four, hydrogen recycle is few, energy consumption is low, propene yield is high, simple to operate and invest advantages such as low.
Description
Technical field
The present invention relates to a kind of method of producing alkene, specifically, relate to a kind of olefins by catalytic cracking, oil of adopting and absorb and to produce and the novel process of separating alkene with the method for extracting rectifying.
Background technology
Along with the raising of crude oil in China working ability, carbon four hydrocarbon that the catalytic cracking unit of refinery is a large amount of with by-product.By excessive, cheap carbon four hydrocarbon transform to produce ethene, propylene be oiling in conjunction with, efficiently utilize the important channel of carbon four resources, can bring remarkable economic efficiency to petroleum chemical enterprise.Round the comprehensive utilization of refinery C four, each major company and research unit have carried out a large amount of research both at home and abroad, have obtained certain progress, but realize industrial application seldom.
The OCT process using high temperature tungsten-based catalyst of ABB Lummus Global company carries out C 4 olefin and ethene producing propylene with dismutation.Butylene (butylene also can be obtained by ethylene dimerization) from steam cracking device and catalytic cracking unit generates propylene with ethene disproportionation in fixed bed or moving-burden bed reactor, and unreacted butylene and ethylene recycle are used.The iso-butylene that contains in the raw material does not influence the performance of catalyzer.The per pass conversion of butylene is greater than 60% in the reaction, and total conversion rate is about 92%, and propylene quality selectivity is near 100%.OCT technology and preparing ethylene by steam cracking process integration use the P/E value is brought up to more than 0.95, and can be according to the price change flexible product structure of market ethene, propylene, butylene.At present, all adopt the mode with the OCT process integration to produce propylene on the ethylene unit of Lyonden company, BASF AG and Fina company etc.
ATOFINA company and Uop Inc. have developed jointly a kind of novel process-ATOFINA-UOP technology that propylene and ethene are produced in light olefin (C4～C8 hydrocarbon) cracking that is used for.ATOFINA-UOP technology can use C4～C8 hydrocarbon from steam cracking, catalytic cracking and MTO device by-product as raw material.This technological process is used the ZSM-5 molecular sieve catalyst, under 500～600 ℃, the reaction conditions of 1～5MPa (cutting off), higher space velocity, catalytic cracking reaction takes place in the contact of fixed-bed reactor catalyst neutralisation in raw material, propylene total mass yield is about 60% in the reaction, ethene total mass yield is about 15%, and the value of propylene/ethylene is 4.Decaying catalyst is regenerated in reactor.Do not need to add water vapour in the ATOFINA-UOP technological process, the raw material air speed is higher.The ATOFINA-UOP technological process mode of production is flexible, both can unite to form new technological process with steam cracking device, thus can be according to the demand flexible propylene in market and the ratio of ethene; Can also unite use with catalytic cracking unit, to reduce the light olefin content in the pressure gasoline, propylene enhancing; In addition,, can reduce the content of carbon four and carbon pentaene hydrocarbon in the product, improve the yield of propylene and ethene if ATOFINA-UOP technology and MTO device are united use.
CN1493659 has proposed a kind of catalysis conversion method that utilizes C-4-fraction volume increase small-numerator olefin, be that the hydrocarbon gas that will be rich in C-4-fraction injects fluidized-bed or riser reactor, contact with the catalyzer that contains the five-ring supersiliceous zeolite, reaction, temperature of reaction are that 500～750 ℃, catalyzer and the weight ratio that is rich in the C-4-fraction hydrocarbon gas are 1～180: 1, the bed weight hourly space velocity is 0.1～20h
-1Or the reaction times be 0.1～10 second, making coke deposited on catalyst charcoal amount is 0.1～1.0 heavy %; Contact with gasoline fraction and/or heavy oil fraction with the reacted band Pd/carbon catalyst of the hydrocarbon gas that is rich in C-4-fraction again and be 1～100 in the weight ratio of 500～700 ℃, catalyzer and gasoline fraction or heavy oil fraction: 1, the reaction times is that 0.1～5 second or bed weight hourly space velocity are 0.1～30h
-1, water vapor and gasoline fraction or heavy oil fraction weight ratio be to react under 0.0～0.25: 1 the condition; Reaction product isolated and reclaimable catalyst; Reclaimable catalyst Returning reactor after stripping, regeneration recycles.
Above-mentioned study portion has solved the problem of utilizing of carbon four resources, but does not make full use of various alkane and alkene in carbon four hydrocarbon, and great majority are to be propylene with the conversion of olefines in carbon four hydrocarbon, and the alkane in carbon four hydrocarbon can't be utilized effectively.
For making full use of alkene and the alkane in the mixed c 4, often need alkene and alkane are separated.But because the each component boiling point is approaching in the carbon four, it is very little that relative volatility differs, thereby industrial very difficult method with conventional distillation separates each component, and need the method for employing special extract rectification, as extracting rectifying.The butylene extraction process that at present industrial many employings are made extraction agent with acetonitrile (ACN), N-Methyl pyrrolidone (NMP), dimethyl formamide method (DMF) separates butylene and butane.
Summary of the invention
The present invention is in order to solve the not high problem of refinery C four utilization ratios, and proposing a kind of is raw material with refinery C four, adopts olefins by catalytic cracking, oil to absorb and produces, separates the technical process that obtains ethene, propylene and carbon four with the method for extracting rectifying.
Concrete technical scheme is as follows:
The combination process that utilizes refinery C four to produce alkene that the present invention proposes may further comprise the steps:
(1) pre-separation: refinery C four enters the pre-separation tower, and from removed overhead propane, propylene and Trimethylmethane wherein, the logistics of tower still is sent to the olefins by catalytic cracking system;
(2) olefins by catalytic cracking: the mixed c 4 material that comes from pre-separation tower still enters the catalytic cracking reaction device,
Reaction generates the catalytic pyrolysis gas mixture that contains propylene and ethene;
(3) cooling: the catalytic pyrolysis gas mixture enters cooling system and cools, and recovery heat, described cooling system adopts earlier through oil scrubber through the water wash column cooling again or adopts the waste heat boiler heat exchange to produce middle pressure steam and reclaim heat, enters the compression section after making the catalytic pyrolysis gas mixture reduce to 30～80 ℃;
(4) compression: cooled catalytically cracked gas enters the compression section, and the compressed catalytic pyrolysis atmospheric pressure that makes reaches 1.4～1.8MPa (cutting off), and interchanger and surge tank are set in the compression section, with cooling catalytically cracked gas and the liquid phase of separating the compression generation;
(5) absorb: the catalytically cracked gas after the compression enters the absorption tower, reaches more heavy constituent as absorption agent with carbon five; The light constituent that contains methane, carbon two contains carbon three components, carbon four components, carbon five and the more logistics of heavy constituent from the cat head extraction from the extraction of tower still;
(6) separate: enter separation system from the next logistics of absorption tower still and separate, obtain carbon three components, carbon four components, carbon five and more heavy constituent respectively.
Preferably, the olefins by catalytic cracking technology described in the step (2) is raw material with the carbon four that step (1) obtains, and mixes with water vapor, and the mass ratio of water vapor and carbon four is 0.3～0.8.Mixed material contacts with catalyzer in fixed-bed reactor, at 400～600 ℃ of temperature of reaction, pressure 0.1～0.5MPa (cutting off) and mass space velocity 1～10h
-1Condition under react, generate the mixture contain propylene and ethene.The selectivity of purpose product propylene reaches 40%, and productivity of propylene reaches 25～35%.Wherein used catalyzer is that silica alumina ratio is preferably 50～300 ZSM type molecular sieve, and wherein molecular sieve carries out modification with heteropolyacid, and heteropolyacid content is preferably 5 weight %～20 weight % in the catalyzer.ZSM type molecular sieve preferably adopts the ZSM-5 molecular sieve, and the commerce of more preferably using economic technology trade center, Garden of Ten-Thousand Trees, Beijing to sell is called the molecular sieve of ZRP series, and this molecular sieve is the ZSM-5 molecular sieve of modification.Molecular sieve silica alumina ratio more preferably 180～300.What heteropolyacid was selected the combination of heteroatoms (P, Si, Fe, Co etc.) and polyatom (Mo, W, V, Nb, Ta etc.) for use in the catalyzer contains the oxygen polyacid, and preferred tungsten is heteropolyacid, more preferably phospho-wolframic acid, and content is preferably 8.0 weight %～15.0 weight %.
Surge tank preferably is provided with bypass channel described in the step (4), and water and oil phase are separated.The water of telling is sent the battery limit (BL) as process water.
Preferably, in step (5), the cat head working pressure on described absorption tower is 1.0～1.6MPa (cutting off), and tower top temperature is 35～45 ℃, and tower still temperature is 40～60 ℃, and the mass ratio of absorption agent and catalytically cracked gas is 1.0～2.5.Carbon two components that obtain contain a large amount of ethene and a spot of methane, ethane, can be sent to ethylene unit.
Preferably, between step (5) and step (6), soda-wash tower can be set as required, to remove the sulphur in the catalytically cracked gas.Moisture eliminator can be set as required, to remove the moisture in the system.
Can separate by debutylize unit, depropanizing unit, butylene extracting unit, propylene refining unit as required from the material that obtains at absorption Tata still, these separating units can be accepted or rejected and arrange in pairs or groups as required, obtain carbon three components, carbon four components, carbon five and more heavy constituent.
Preferably, in step (6), described carbon three components contain a large amount of propylene, preferably as the charging of propylene refining tower, obtain polymerization-grade propylene through separation.Described carbon four components contain butane and butylene, the preferred method of extracting rectifying that adopts is separated alkane with alkene, the mixture that adopts one or more kinds in acetonitrile (ACN), N-Methyl pyrrolidone (NMP), dimethyl formamide (DMF), N-N-formyl morpholine N-(NFM), the morpholine equal solvent is as extraction agent, more preferably acetonitrile is as extraction agent, butane is sent to the pyrolyzer of ethylene unit as the thermo-cracking raw material, and C 4 olefin loops back the catalytic cracking reaction device as the catalytic pyrolysis raw material.Preferred described carbon five and more the part of heavy constituent return the absorption tower as absorption agent, surplus is sent the battery limit (BL) as product.
Owing to the present invention is directed to the problem that the refining plant C 4 that exists in the existing full scale plant does not also make full use of, many prior aries are optimized combination, proposition is fit to make full use of the combination process of refining plant C 4, therefore, employed isolation technique and catalyzer etc. can adopt prior art among the present invention, enforcement of the present invention is not subjected to that disclosed or undocumented technical essential limits among the present invention, those skilled in the art can be according to circumstances selected suitably, but the present invention anything but these prior aries simply enumerate combination, but solved the problem that present industrial production exists really, have quite significant industrial value.
The present invention adopts olefins by catalytic cracking, oil to absorb and extracting rectifying combination process system alkene technology has the following advantages:
(1) made full use of refinery C four resources, adopting olefins by catalytic cracking is ethene, propylene with the conversion of olefines in carbon four hydrocarbon, adopts oil-absorption process to separate catalytically cracked gas and obtains carbon two components, carbon three components and carbon four components; Carbon two components are sent to ethylene unit, and carbon three components can further be separated and obtained polymerization-grade propylene, and carbon four components are separable to obtain that butylene returns cat-cracker, butane is sent to ethylene plant's pyrolyzer as charging, and each component all is fully used;
(2) refinery C four of available cheapness substitutes comparatively expensive thermo-cracking raw materials such as petroleum naphtha, thereby reduces production costs; Because refinery C four adopts olefins by catalytic cracking, is not subjected to the influence of organosulfur in the refinery C four substantially, therefore avoided the interference of organosulfur;
(3) olefins by catalytic cracking can be ethene, propylene with most conversion of olefines, reduced the circulation of the hydrogen that steam heat cracking behind whole hydrogenation of olefins is brought, the methane content of olefins by catalytic cracking generation simultaneously is significantly less than the methane content that the steam heat cracking is produced, thereby reduced the load of cold-zone, reduced energy consumption;
(4) adopt extraction rectifying method separating butane and butylene, isolated butylene recycle, improved the productive rate of purpose product propylene, isolated butane can be used as product and is sent to ethylene unit, reached the purpose that makes full use of carbon four each components, and this technology has, and product purity height, thermal load are little, simple to operate, the characteristics of less investment;
(5) olefins by catalytic cracking can obtain higher propene yield;
(6) reach more heavy constituent with refinery C five and remove carbon two and methane, absorb the cat head service temperature about 40 ℃, can cool off simple to operate, less investment with recirculated water as absorption agent.
Description of drawings
Fig. 1 is the synoptic diagram that utilizes refinery C four to produce the combination process of alkene of the present invention.
Fig. 2 is the schematic flow sheet of the solution of the present invention 1.
Fig. 3 is the schematic flow sheet of the solution of the present invention 2.
Nomenclature:
1 refinery C four; 2 carbon, two components; 3 carbon five and more heavy constituent; 4 carbon, three components; 5 carbon, four components; 6 butylene; 7 butane; 8 propylene; 9 propane; 10 catalytic cracking reaction devices; 11 oil scrubbers; 12 water wash columns; 13 compressors; 14 absorption towers; 15 debutanizing towers; 16 depropanizing towers; 17 butylene extraction plants; 18 propylene refining towers; 19 separating tanks; 20 separate out tower.
Embodiment
Produce the combination process of alkene below with reference to accompanying drawing 1～3 further employing catalytic pyrolysis of the present invention, oil absorption and the extraction rectifying method explained, but the present invention is not limited to these schemes.
Fig. 1 is the principle process synoptic diagram of combination process of the present invention, can make amendment, increase other technology on this principle flow chart.With reference to Fig. 1, novel process of the present invention adopts olefins by catalytic cracking, oil to absorb and extraction rectifying method, and refinery C four is made full use of.Refinery C four is isolated wherein propane, propylene and Trimethylmethane through the pre-separation tower, enter the olefins by catalytic cracking reactor after being preheating to certain temperature then, the catalytically cracked gas that produces enters the cooling system cooling, enter the compression section then, catalytically cracked gas after the compression enters the absorption tower, adopt oil-absorption process to isolate carbon one, carbon two components from cat head, be dissolved with carbon three, carbon four, carbon five and more the tower still logistics of heavy constituent enter the debutylize unit and the depropanizing unit of back, separate obtaining mixing carbon three, mixed c 4 and carbon quintet branch.Part carbon five reaches more heavy constituent and loops back the absorption tower as absorption agent, another part extraction.As required, separate the charging that carbon three components that obtain can be used as the propylene refining tower, separate obtaining polymerization-grade propylene.As required, carbon four components can be used as the charging of butylene extraction plant, adopt the method separation of extracting rectifying to obtain butane and butylene, and butylene loops back the recycle of catalytic cracking reaction device, and butane can be used as the charging of ethylene plant's pyrocrack furnace.
Explain the various embodiments of combination process of the present invention below respectively with reference to Fig. 2～3.
Scheme 1: as shown in Figure 2, this technology is raw material with refinery C 41, enter the pre-separation tower, from removed overhead propane, propylene and Trimethylmethane wherein, the logistics of tower still enters catalytic cracking reaction device 10 after preheating, generates the catalytically cracked gas that contains components such as ethene, propylene through catalytic cracking reaction, catalytically cracked gas is through cooling, compression, separate through oil-absorption process, obtain carbon two components 2, carbon three components 4 and carbon four components 5, carbon four components 5 are isolated wherein alkene recycle through extracting.Cooling system wherein adopts earlier lowers the temperature through water wash column 12 through oil scrubber 11 again, and the method that this cooling system also can adopt waste heat boiler to produce middle pressure steam reclaims heat.Cooled catalytically cracked gas enters compression section 13, enters separating tank 19 after 2 sections compressions, and isolated liquid phase enters separates out tower 20, and isolated gas phase enters absorption tower 14.Reach more heavy constituent as absorption agent with carbon five in the absorption tower, absorb carbon three, carbon four components in the catalytically cracked gas, the light constituent 2 that mainly contains methane and ethene, ethane is from the cat head extraction.Separate out tower still logistics carbon three, carbon four, carbon five and more heavy constituent, enter debutanizing tower 15, tower still logistics 3 is carbon five and more heavy constituent, and a part is returned absorption tower 14 recycles, part extraction, overhead stream be carbon four and more light constituent be admitted to depropanizing tower 16.Depropanizing tower still extraction carbon four components 5 are sent to butylene extraction plant 17, and isolated butylene 6 is sent to 10 recycles of catalytic cracking reaction device, and butane 7 is sent to the pyrocrack furnace of ethylene plant and makes raw material.This butylene extraction plant adopts acetonitrile as extraction agent, takes one-section abstraction technology separation of alkane and alkene.Depropanizing tower 16 top extraction carbon three components 4 are sent the battery limit (BL) as product.
Scheme 2: as shown in Figure 3, this scheme and scheme 1 adopt refinery C 41 raw materials in the same manner, employing enters separation system after with the identical pre-separation of scheme 1, catalytic cracking reaction, cooling, compression, absorption, carbon three, carbon four, carbon five reach more heavy constituent and enter debutanizing tower 15, carbon five reaches more heavy constituent from the extraction of tower still, a part is returned absorption tower 14 recycles, a part of extraction, carbon four and more light constituent send into depropanizing tower 16 from the cat head extraction.Depropanizing tower still extraction carbon four components 5 can be used as product.Depropanizing cat head extraction carbon three components 4 are sent to propylene refining tower 18, obtain polymerization-grade propylene 8 from propylene refining tower 18 cats head, and the propane 9 that the tower still obtains can be used as the raw material of ethylene plant's pyrocrack furnace.
Further explain combination process of the present invention in the mode of embodiment below.
With reference to the accompanying drawings 2, the refinery C 41 that with the flow is 17500kg/h is a raw material, and it is mainly formed (mass percent) and is: propane 7.3%, iso-butylene 14.0%, 1-butylene 14.0%, suitable-2-butylene 16.3%, anti--2-butylene 20.2%, normal butane 17.0%, Trimethylmethane 0.5～10.0%, surplus are propylene.Refinery C four advances the pre-separation tower, the plate number of pre-separation tower is 130, operational condition is: tower top pressure 0.9MPa (cutting off), 39.4 ℃ of tower top temperatures, 73.7 ℃ of tower still temperature and reflux ratio 26.6, from cat head extraction light constituent, wherein Trimethylmethane content (quality) is 51%.Enter in the olefins by catalytic cracking reactor 10 after the logistics of tower still is preheating to 500 ℃ and react, the amount 9850kg/h of water vapour, 7 tons of the loadings of catalyzer, catalyzer adopts the catalyzer of the trade mark BOC-1 of Beijing Chemical Research Institute, and reaction conditions is: 500 ℃ of temperature, pressure 0.2MPa (cutting off), mass space velocity 2.5h
-1Reaction conditions under, catalytic cracking reaction takes place in fixed-bed reactor catalyst neutralisation contact in carbon four raw materials, propylene total mass yield is about 30% in the reaction, ethene total mass yield is about 15%.The catalytically cracked gas that reaction generates enters oil scrubber, the oil wash stage number is 5, and as refrigerant, consumption is 5000kg/h with an oil in the refinery, operational condition is 199.4 ℃ of 137.3 ℃ of tower top temperatures, pressure 0.15MPa (cutting off), tower still temperature, and cat head catalytically cracked gas temperature is 137.3 ℃.Catalytically cracked gas is gone into water wash column through oil scrubber is laggard, operational condition is: 40 ℃ of tower top temperatures, pressure 0.12MPa (cutting off), the catalytically cracked gas temperature is reduced to 40 ℃, enter compression section 13 then, the pressure of catalytically cracked gas reaches 1.6MPa (cutting off) after 2 grades of compressions, heat exchange, splitting gas at first enters knockout drum 19, and isolated gas phase is gone to absorption tower 14, and isolated liquid phase removes to separate out tower 20.The stage number on absorption tower is 20, reach the logistics 3 of more heavy constituent as absorption agent with main carbon containing five, solvent ratio (mass ratio of absorption agent and splitting gas) is 10, cat head extraction carbon two components 2, flow is 1532.5kg/h, wherein contains the ethene of 70% (quality), this burst logistics can be sent to ethylene unit, knockout drum 19 is sent in absorption tower still logistics, and isolated gas phase is returned the absorption tower, and liquid phase is sent into and separated out tower 20.The operational condition of separating out tower is: 87 ℃ of 20 of column plates, 39 ℃ of tower top temperatures, tower top pressure 1.5MPa (cutting off), tower still temperature.Separated out from absorption agent in these part carbon two components that are dissolved in the absorption agent, the logistics of tower still be dissolved with carbon three and more the absorption agent of heavy constituent be admitted to debutanizing tower 15.The stage number 50 of debutanizing tower 15,38 ℃ of tower top temperatures, tower top pressure 0.9MPa (cutting off), 139 ℃ of tower still temperature, reflux ratio 1.5.The logistics of debutanizing tower still be carbon five and more heavy constituent 3,74% return absorption tower 14 recycles, 26% extraction, carbon four and more light constituent be sent to depropanizing tower 16 from the cat head extraction.The stage number of depropanizing tower is 40,51 ℃ of tower top temperatures, tower top pressure 2.0MPa (cutting off), 111 ℃ of tower still temperature, reflux ratio 2.Depropanizing tower still extraction carbon four components are sent to butylene extraction plant 17 separates, and extraction plant adopts acetonitrile to make solvent, and the operational condition of extractive distillation column is: solvent ratio 10,46 ℃ of tower top temperatures, tower top pressure 0.45MPa (cutting off), reflux ratio 20.Isolated alkene 6 loops back process furnace to be continued to utilize, separate that to obtain flow be that the butane 7 of 3480kg/h is sent the battery limit (BL) as product, wherein mainly forming (quality) is that Trimethylmethane 8.8%, normal butane 90.3%, surplus are carbon five, and this logistics can be used as the charging of ethene pyrocrack furnace.
With reference to the accompanying drawings 3, employing is with the identical raw material of embodiment 1, behind pre-separation tower 1, alkene cracking reactor 10, oil scrubber 11, water wash column 12, compressed element 13, enter knockout drum 19, isolated gas phase is gone to absorption tower 14, isolated liquid phase removes to separate out tower 20, separates out the logistics of tower still and is sent to debutanizing tower 15; The logistics of debutylize cat head is sent to depropanizing tower 16, and tower still stream portions loops back the absorption tower, the part extraction, and its ratio is 2.8: 1; More than each unitary operational condition with embodiment 1.The stage number of depropanizing tower is 40,51 ℃ of tower top temperatures, tower top pressure 2.0MPa (cutting off), reflux ratio 2.Carbon four components of depropanizing tower still extraction are sent the battery limit (BL) as product, and carbon three components of cat head extraction are sent to propylene refining tower 18.The stage number of propylene refining tower is 170,44 ℃ of tower top temperatures, tower top pressure 1.8MPa (cutting off), 63 ℃ of tower still temperature, reflux ratio 17.6.Cat head extraction purity is greater than 99.6% propylene product 5812kg/h, and tower still extraction propane is sent the battery limit (BL).
Employing enters knockout drum 19 with the identical raw material of embodiment 2 behind pre-separation tower 1, alkene cracking reactor 10, oil scrubber 11, water wash column 12, compressed element 13, through the absorption tower 14, separate out tower 20, debutanizing tower 15; Debutylize Tata still stream portions loops back the absorption tower, the part extraction, and its ratio is 2.8: 1; The logistics of debutylize cat head is sent to depropanizing tower 16, and depropanizing cat head extraction carbon three component 6790kg/h send the battery limit (BL) as product; Depropanizing tower still extraction carbon four component 8780kg/h send the battery limit (BL) as product.More than each unitary operational condition with embodiment 2.
Claims (10)
1. a combination process that utilizes refinery C four to produce alkene is characterized in that, described combination process may further comprise the steps:
(1) pre-separation: refinery C four enters the pre-separation tower, and from removed overhead propane, propylene and Trimethylmethane wherein, the logistics of tower still is sent to the olefins by catalytic cracking system;
(2) olefins by catalytic cracking: enter the catalytic cracking reaction device after the next mixed c 4 material preheating of pre-separation Tata still, reaction generates the catalytic pyrolysis gas mixture that contains propylene and ethene;
(3) cooling: the catalytic pyrolysis gas mixture enters cooling system and cools, and recovery heat, described cooling system adopts earlier through oil scrubber through the water wash column cooling again or adopts the waste heat boiler heat exchange to produce middle pressure steam and reclaim heat, enters the compression section after making the catalytic pyrolysis gas mixture reduce to 30～80 ℃;
(4) compression: cooled catalytically cracked gas enters the compression section, and the compressed catalytic pyrolysis atmospheric pressure that makes reaches absolute pressure 1.4～1.8MPa, and interchanger and surge tank are set in the compression section, with cooling catalytically cracked gas and the liquid phase of separating the compression generation;
(5) absorb: the catalytically cracked gas after the compression enters the absorption tower, and with carbon five and more heavy constituent are as absorption agent, the light constituent that contains methane, carbon two contains carbon three components, carbon four components, carbon five and the more logistics of heavy constituent from the cat head extraction from the extraction of tower still;
(6) separate: enter separation system from the next logistics of absorption Tata still and separate, obtain carbon three components, carbon four components, carbon five and more heavy constituent respectively.
2. combination process as claimed in claim 1, it is characterized in that, olefins by catalytic cracking technology described in the step (2) is raw material with the carbon four that step (1) obtains, after water vapor mixes, in fixed-bed reactor, contact, at 400～600 ℃ of temperature of reaction, absolute pressure 0.1～0.5MPa and liquid phase volume air speed 1～10h with catalyzer
-1Condition under react, generate the mixture contain propylene and ethene.
3. combination process as claimed in claim 2, it is characterized in that in the fixed bed of olefins by catalytic cracking, described catalyzer is that silica alumina ratio is 50～300 ZSM type molecular sieve, described molecular sieve carries out modification with heteropolyacid, contains the heteropolyacid of 5 weight %～20 weight % in the described catalyzer.
4. combination process as claimed in claim 1 is characterized in that, surge tank is provided with bypass channel described in the step (4), and water and oil phase are separated.
5. combination process as claimed in claim 1 is characterized in that, in step (5), the cat head working pressure on described absorption tower is absolute pressure 1.0～1.6MPa, tower top temperature is 35～45 ℃, and tower still temperature is 40～60 ℃, and the mass ratio of absorption agent and catalytically cracked gas is 1.0～2.5.
6. combination process as claimed in claim 1 is characterized in that, between step (5) and step (6), soda-wash tower is set, to remove the sulphur in the catalytically cracked gas.
7. combination process as claimed in claim 1 is characterized in that, between step (5) and step (6), moisture eliminator is set, to remove the moisture in the system.
8. combination process as claimed in claim 1 is characterized in that, in step (6), described carbon three components contain a large amount of propylene, and the charging as the propylene refining tower obtains polymerization-grade propylene through separation.
9. combination process as claimed in claim 1, it is characterized in that, in step (6), described carbon four components contain butane and butylene, adopt the method for extracting rectifying that alkane is separated with alkene, the mixture that adopts one or more the kind solvents in acetonitrile, N-Methyl pyrrolidone, dimethyl formamide, N-N-formyl morpholine N-and the morpholine is as extraction agent, butane is sent to the pyrolyzer of ethylene unit as the thermo-cracking raw material, and C 4 olefin loops back the catalytic cracking reaction device as the catalytic pyrolysis raw material.
10. combination process as claimed in claim 1 is characterized in that, in step (6), described carbon five and more the part of heavy constituent return the absorption tower as absorption agent, surplus is sent the battery limit (BL) as product.
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| CNB2006101655190A CN100564331C (en) | 2006-12-21 | 2006-12-21 | Utilize refinery C four to produce the combination process of alkene |
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Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101734987B (en) * | 2008-11-07 | 2012-11-21 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
| CN102285857B (en) * | 2010-06-18 | 2015-04-15 | 中国石油化工股份有限公司 | Method for increasing yields of propylene and ethylene |
| CN102285851B (en) * | 2010-06-18 | 2015-04-15 | 中国石油化工股份有限公司 | Method for increasing yields of ethylene and propylene |
| CN102285853A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yield of propylene and ethylene by using cracked C4 as raw material |
| CN102285852B (en) * | 2010-06-18 | 2015-08-19 | 中国石油化工股份有限公司 | Utilize the method for refinery C four increasing output of ethylene and propylene |
| CN102070390B (en) * | 2011-01-12 | 2016-03-16 | 王伟跃 | The method of refinery's mixed c 4 propylene |
| CN102861604B (en) * | 2011-07-07 | 2014-06-25 | 中国石油化工股份有限公司 | Olefin catalytic agent prepared by naphtha catalytic cracking and preparation method and application thereof |
| CN103159581B (en) * | 2011-12-12 | 2015-09-09 | 中国石油化工股份有限公司 | A kind of system and method for absorption extraction catalytic pyrolysis gas product polymerization-grade propylene |
| CN103772126B (en) * | 2012-10-25 | 2016-03-30 | 中国石油化工股份有限公司 | Take oil refinery dry gas as the combined method of waste ethylbenzene |
| CN103423969A (en) * | 2013-08-30 | 2013-12-04 | 北京麦科直通石化工程设计有限公司 | Method for optimizing ethylene device compression area and reducing outlet pressure of cracking furnace |
| CN104557475B (en) * | 2013-10-23 | 2017-02-15 | 中国石油化工股份有限公司 | Comprehensive utilization method of light hydrocarbon of refinery plants |
| CN105367366B (en) * | 2014-08-27 | 2017-10-27 | 中国石油化工股份有限公司 | Utilize the method for mixing the production of carbon four ethene, propylene |
| CN107879876B (en) * | 2016-09-30 | 2020-07-24 | 中国石油化工股份有限公司 | Method and device for producing ethylene and propylene from light hydrocarbon raw material |
| CN109704899B (en) * | 2017-10-26 | 2022-07-08 | 中国石油化工股份有限公司 | Method for preparing olefin from synthesis gas |
| CN111116290B (en) * | 2018-10-30 | 2023-04-07 | 中国石油化工股份有限公司 | Energy expanding method for olefin cracking device |
| CN112694383A (en) * | 2019-10-22 | 2021-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene by catalytic cracking of olefin |
| CN112694384A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for separating olefin catalytic cracking products |
| CN112707780A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene from raw materials with four or more carbon atoms |
| CN114516776A (en) * | 2020-11-19 | 2022-05-20 | 中国石油化工股份有限公司 | Method and apparatus for producing ethylene and propylene |
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