CN101172923A - Combination technique for producing olefin hydrocarbon with mixed C_4 - Google Patents
Combination technique for producing olefin hydrocarbon with mixed C_4 Download PDFInfo
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Abstract
The invention discloses a compounding technology of preparing olefin with compound C4, which solves the problems that the C4 resource is unable to be fully utilized and the schizolysis separation cryogenic system has relatively much recycle hydrogen. The invention is characterized in that the compounding technology takes schizolyzied C4 or refined C4 as raw material; combines an ethylene device; combines technologies such as olefin catalyses and schizolysis, hydrogenation and steam thermal schizolysis to respectively process C4olefin and alkane; the C4 single olefin which comprises no dialkene and alkyne is transformed into low carbon olefin which mainly comprises propylene through the olefin catalyses and the schizolysis; and the alkane is transformed into low carbon olefin which mainly comprises ethylene through steam thermal schizolysis so as to maximally produce the ethylene and the propylene. The invention has the advantages that the compounding technology fully utilizes the C4 resource, thereby obtaining maximal economic benefit; the expensive schizolysis raw materials, for example naphtha, are replaced with the cheap refined C4, thereby decreasing the production cost, avoiding the interference of organic sulfur, decreaseing the load of the cold area and reducing the energy consumption.
Description
Technical field
The present invention relates to a kind of method of producing ethene, propylene with mixed c 4, specifically, relating to a kind of is raw material with cracking c_4 or refinery C four, adopts combination techniques such as olefins by catalytic cracking, hydrogenation, steam heat cracking, separation, produces the method for ethene, propylene.
Background technology
Raising along with China's ethylene production and crude capacity, the C4 hydrocarbon that steam cracking device and catalytic cracking unit are a large amount of with by-product, in addition China " smooth implementation of West-east Gas plan, a large amount of liquefied gas (main ingredient is the C4 hydro carbons) also are badly in need of the new chemical utilization approach of searching.By excessive, cheap C4 hydrocarbon transform that to produce ethene, propylene be oiling in conjunction with, efficiently utilize the important channel of C4 resource, can bring remarkable economic efficiency to petroleum chemical enterprise.
Conventional ethylene unit is a cracking stock with petroleum naphtha or lighter hydrocarbons generally, obtains splitting gas through the steam heat cracking, enters chilling compression separation system then, obtains cracking c_4 at the debutylize cat head.Comprise components such as Trimethylmethane, normal butane, iso-butylene, butene-1, butene-2, divinyl, ethylacetylene, vinylacetylene in the cracking c_4.Cracking c_4 can return pyrolyzer after hydrogenation is saturated, as the raw material of cracking of ethylene, also can be used as the mixed c 4 product, further processing.Cracking c_4 can be by alkane and the monoolefine that obtains behind divinyl extracting or selection hydrogenation and removing diolefine and the alkynes, after etherificate (generating MTBE) removes iso-butylene wherein, isolate butene-1 as product by refining again, and remaining butene-2, normal butane can not get good utilization as byproduct.The cracking c_4 of each ethylene unit utilizes situation to have nothing in common with each other at present, but all exists the not high problem of utilization ratio.
On the other hand, refinery C four also contains components such as a large amount of Trimethylmethanes, butene-1, butene-2 after etherificate is removed iso-butylene.This carbon four should not if carry out hydrotreatment, then make the very fast inactivation of hydrogenation catalyst because of containing more organosulfur in the refinery C four, so effective utilization of refinery C four exist problem always directly as cracking stock.
Round the comprehensive utilization of cracking c_4 and 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 Meta-4 technology of Inst Francais Du Petrole's exploitation is used catalyst based C4 alkene and the ethene producing propylene with dismutation of carrying out of Re.The Meta-4 process unit can with steam cracking device or the coupling of MTBE device.This technology can adopt from the thick C 4 fraction of steam cracking and from the C4 alkene of MTBE device as raw material.Thick C 4 fraction from steam cracking at first will pass through hydrogenation, isomery pre-treatment, should remove iso-butylene from the C4 alkene of MTBE device before participating in reaction and make and be rich in 2-butylene in the raw material.This technological process both can be used fixed-bed reactor, also can use moving-burden bed reactor.Catalyst reaction and reprocessing cycle operation.Catalyst regeneration adopts the method for similar continuous reforming process, and decaying catalyst is sent into revivifier at 500～600 ℃ of coke burning regenerations.Reaction product is isolated ethene in first knockout tower, isolate propylene and C4 alkene and C5 hydrocarbon in second knockout tower, and C4 alkene recycles, and C5 hydrocarbon (RON is 97) can directly enter gasoline pool.The 2-butylene per pass conversion is about 63% in the reaction, and total conversion rate is about 90%, and propylene quality selectivity is greater than 98%, and propylene and ethene mass ratio (P/E value) are 0.73.
The olefin dismutation reaction technology of BASF AG is used Re
2O
7/ Al
2O
3Catalyzer, wherein the load quality mark of rhenium oxide is preferably 8%～12%, and rhenium oxide loads on the shell of carrier, and shell is thick in 1.5mm.The particle diameter of rhenium oxide is less than 1nm, and its specific surface area is more than or equal to 0.4m
2/ g.Do not need activation before this catalyst reaction.In this technology, from the thick C 4 fraction outside the battery limit (BL) through selective hydrogenation, isomery, refining after, divinyl, alkynes, 1-butylene in the raw material are converted into 2-butylene, and remove impurity such as sulfide in the raw material, oxide compound.Raw material contacts with catalyzer in fixed-bed reactor, is higher than under the condition of C4 alkene vapour pressure at 20～90 ℃, pressure, and 1-butylene and 2-butylene disproportionation generate propylene and 2-amylene, and by product is ethene and 2-hexene.In distillation tower, isolate low boiler cut ethene and propylene, mid-boiling point cut butylene and high boiling fraction amylene and hexene respectively.The butylene Returning reactor recycles.Disproportionation reaction further takes place and generates propylene and 1-butylene in high boiling fraction and ethene.Decaying catalyst adopts and burns in 550 ℃ of air earlier, and the mode that cools in rare gas element is then regenerated.The C4 olefin conversion is about 80% in the reaction, propylene total mass selectivity about 90%.This technology does not need or only need add small amount of ethylene.
Catalyst based C4 alkene and the ethene producing propylene with dismutation of carrying out of the OCT process using high temperature W of ABB Lummus Global company.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.
Superflex technology is by ARCO chemical company (present Lyondell company) research and development, KBR company issue license by the C4/C5 olefin catalytic cracking to produce propylene, the technology of the ethene of coproduction simultaneously.Superflex process using fluidized-bed reactor is a catalyzer with a kind of new zeolite molecular sieve, and its reaction conditions (500～700 ℃, 0.1～0.2MPa, WHSV=2.5h
-1) and existing catalytic cracking process conditional likelihood.The key problem in technology of this technology is considered to adopt the new zeolite molecular sieve catalyst.In Superflex technology, can use C4/C5 cut or the cut that alkene is rich in catalytic cracking, the petroleum naphtha of coker etc. of steam cracking by-product to carry out catalytic cracking for producing propylene using as raw material.Reaction raw materials answers selective hydrogenation to remove alkynes and diolefine before using.Adopting Superflex technology, is raw material with the C 4 fraction of deviating from alkynes and diolefine, under suitable reaction conditions, can obtain the result of propylene mass yield 40%, ethene mass yield 20%.
The Propylur technology of Lurgi company (issued license by Linder company then be called FBCC technology) is the static catalytic cracking process that a kind of hybrid C 4 alkene (butylene, amylene, hexene etc.) that will remove divinyl, iso-butylene changes into propylene.This technological process has effectively improved the P/E value in the steam cracking, can be used as the substitute technology of butylene disproportionation production technique.Use in the reaction from the C4 of steam cracking and C5 alkene as raw material, the diolefine massfraction is controlled at below 1.5% in the raw material, and alkane, naphthenic hydrocarbon, cycloolefin and aromatic hydrocarbons etc. influence the performance of catalyzer hardly in the raw material.Propylur (FBCC) process using ZSM-5 molecular sieve (silica alumina ratio is 10～200) is a catalyzer, at 500 ℃, 0.1～0.2MPa, air speed 1～3h
-1, water vapour and hydrocarbon mass ratio be that the total conversion rate that carries out light olefin in the reaction response under 0.5～3 the condition is about 83%, propylene one way mass yield is 40%～45%, ethene one way mass yield is 10%.If unreacted butylene recycles the mass yield that can make propylene and ethene and brings up to 60% and 15% respectively.Catalyst regeneration cycle 1000h, about 15 months of life-span.Add water vapour in the reaction, increased facility investment and running cost to a certain extent.Do not need continuous regeneration set in the reaction process, decaying catalyst can be in reactor in containing the N2 atmosphere of little air coke burning regeneration.This technology has been finished the pilot scale of 9000h, now just at the construction technique demonstration unit.
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, 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 P/E value 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 C4 and C5 alkene in the product, improve the yield of propylene and ethene if ATOFINA-UOP technology and MTO device are united use.
CN1355158 has proposed a kind of method of utilizing the sulfur-bearing mixed c 4 production high-purity butylene-1 of catalytic cracking by-product, when its objective is from the hybrid C 4 cut separating butane-1, distillation removes the sulfocompound among the C4, promptly remove most of iso-butylene by etherification reaction, utilize fractionation to make butene-1 with light, heavy carbon four components are separated, make sulfide content in the butene-1 product be lower than sulfide content in the raw material simultaneously, and utilize selective hydrogenation reaction to make to the selected monoolefine that is hydrogenated to of small part divinyl, can also make to the small part butene-2 by isomerization reaction in case of necessity to be turned to butene-1 by isomery.
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, react with the catalyzer that contains the five-ring supersiliceous zeolite, temperature of reaction is 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 0.1～20 hour
-1Or the reaction times be 0.1～10 second, making coke deposited on catalyst charcoal amount is 0.1 weight %～1.0 weight %; 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 0.1～30 hour
-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.
CN1624082 provides a kind of processing method of effective C4 hydro carbons catalyzed conversion, with the pre lift zone of the pre lift zone of catalytic gasoline upgrading auxiliary reactor or heavy oil fluid catalytic cracking as C4 hydro carbons catalytic conversion reactor, or before catalytic gasoline upgrading auxiliary reactor, set up a C4 hydro carbons catalytic conversion reactor separately, after the C4 hydro carbons enters C4 hydro carbons catalytic conversion reactor from the bottom, with from the high temperature catalyst of revivifier temperature of reaction be contact under the certain condition, mixing and catalytic conversion reaction, generate a part of aromatic hydrocarbons and second, propylene; Reaction product and catalyzer enter catalytic gasoline upgrading auxiliary reactor or heavy oil cracking master riser reactor, this method can be in volume increase aromatic hydrocarbons, second/propylene, by reducing the loss that catalyst temperature helps reducing catalytic gasoline upgrading process, or reduce dry gas yied by reducing the heavy oil catalytic cracking process reaction times.
Solved the problem of utilizing of carbon four resources above-mentioned study portion, but do not made full use of various alkane and alkene in carbon four hydrocarbon, 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.And the hydrogen recycle amount was big during cracking separated, and the cold-zone load is big, and energy consumption is higher.
Summary of the invention
The present invention proposes a kind of combination technique that the mixed c 4 resource is produced ethene, propylene that makes full use of in order to solve the problem that existing carbon four resources are not fully effectively utilized.The present invention is a raw material with cracking c_4 or refinery C four, in conjunction with ethylene unit, carbon four monoolefines that adopt olefins by catalytic cracking will not contain diolefine and alkynes are converted into the low-carbon alkene based on propylene, and the alkane that adopts the steam heat cracking will not contain or contain less alkene is converted into the low-carbon alkene based on ethene.By the combination of technology such as olefins by catalytic cracking, hydrogenation, steam heat cracking, separation, respectively the alkene in the mixed c 4, alkane are handled, producing ethene, propylene to greatest extent, thereby make full use of carbon four resources, obtain maximum economic benefits.
Concrete technical scheme is as follows.
A kind of combination technique for producing olefin hydrocarbon with mixed C _ 4, comprise the steam heat cracking technique, the ethylene quenching isolation technique, catalytic pyrolysis technology and carbon four full hydrogen addition technologies, the hot cracked stove of described petroleum naphtha or petroleum naphtha and lighter hydrocarbons is cracked into splitting gas, splitting gas separates through the ethylene quenching separation system, isolate cracking c_4 through debutanizing tower again, cracking c_4 is through taking off separated into two parts material behind diolefin and the alkynes, part material turns back to pyrolyzer as cracking stock through full hydrogenation, another part material is converted into C 4 olefin through the olefins by catalytic cracking technology and comprises propylene, ethene is in interior component, send into the ethylene unit quencher then, after the splitting gas mixing that pyrolyzer comes, enter described ethylene quenching separation system.
Described combination technique can also comprise refinery C four pre-separation technology, and described refinery C four pre-separation technology are meant that refinery C four isolates Trimethylmethane through the pre-separation systems, leftover materials and carry out olefins by catalytic cracking together from the material of cracking c_4.
Described cracking c_4 takes off diolefin and the alkynes technology can adopt selection hydrogen addition technology or extraction and separation technology.Concrete which kind of technology that adopts can be determined according to the concrete of each factory, under the situation of market demand divinyl, if factory condition possesses, preferably adopts extraction and separation technology.Do not have carbon four extracting and separating devices at divinyl market collapse or factory, can consider the preferential selection hydrogen addition technology that adopts.
The material that preferred cracking c_4 removes after diolefin and the alkynes carries out etherificate, removes iso-butylene wherein, and leftover materials carry out olefins by catalytic cracking again.Iso-butylene is good industrial chemicals, has certain economic benefits, and therefore the iso-butylene of isolating wherein by the etherificate technology is the feasible scheme of a kind of economical and effective.The etherificate technology also is a kind of technology of comparative maturity at present.
C 4 materials after the preferred etherificate carries out the refining separation of butene-1, and isolated butene-1 is as product, and isolated carbon three and Trimethylmethane return pyrolyzer as cracking material, and isolated butene-2 carries out olefins by catalytic cracking.
There is no particular limitation at all cracking c_4 materials cracking c_4 to be gone the part of full hydrogenation, can determine according to concrete production, considers that from more satisfactory angle cracking c_4 goes the shared ratio of the part of full hydrogenation to be preferably 10 weight %～90 weight %.
Combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention relies on ethylene unit, is made up of processes such as refinery C four pre-separations, olefins by catalytic cracking, carbon four full hydrogenation, steam heat cracking, separation, and the principle schematic block diagram of its technical process as shown in Figure 1.Each technology that is adopted in the combination technique for producing olefin hydrocarbon with mixed C _ 4 that the present invention proposes is existing known technology, and employed catalyzer is existing disclosed catalyzer.
Full hydrogenation technique in the combination technique of the present invention is selected appendix master active ingredient for use and is helped the aluminum oxide of active ingredient as catalyzer, wherein main active ingredient is selected from one or both of Pt, Pd, content is 0.01 weight %～1.0 weight %, help active ingredient to be selected from least a among Cu, Ag, Au, Pb, Ni, Co, the Mn, content is 0.001 weight %～1.0 weight %; Help active ingredient to be preferably Ag or Pb.Total olefin content in the full hydrogenation after product is less than 5%.Concrete reaction process condition is as follows: the reaction temperature in is generally 20～150 ℃, is preferably 20～60 ℃; Reaction pressure is generally 1.0～5.0MPa; The mol ratio of hydrogen and alkene is generally 0.8～3.0, is preferably 0.8～1.5; Volume liquid air speed is generally 1～30h
-1, be preferably 15～25h
-1The recycle feed volume ratio is 0～25, is preferably 0～15.
Olefins by catalytic cracking technology in the combination technique of the present invention is raw material with carbon four hydrocarbon mixtures that do not contain diolefine and alkynes, mixing the back with water vapor and contact in the fixed-bed reactor catalyst neutralisation, is that 400～600 ℃, pressure are that 0.1～0.5Mpa and liquid phase volume air speed are 1～10h in temperature of reaction
-1Condition under react, generate the mixture contain propylene and ethene, after refrigerated separation, obtain propylene and ethene.The selectivity of purpose product propylene has reached 40%, and productivity of propylene reaches 35%.Wherein used catalyzer is that silica alumina ratio is 50～300 ZSM type molecular sieve, and wherein molecular sieve carries out modification with heteropolyacid, and heteropolyacid content is 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.The molecular sieve silica alumina ratio is 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 %.
Combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention has following characteristics:
(1) various carbon four resources have been made full use of, adopting olefins by catalytic cracking is propylene, ethene with the conversion of olefines in carbon four hydrocarbon, adopt full hydrogenation and steam heat cracking that the alkane in carbon four hydrocarbon is converted into ethene, propylene, each takes what he needs like this, complement each other, various carbon four hydrocarbon can both effectively be transformed, thereby obtain maximum economic benefits;
(2) refinery C four of available cheapness substitutes comparatively expensive cracking stocks such as petroleum naphtha, thereby reduces production costs; Because refinery C four does not adopt full hydrogenation, replace olefins by catalytic cracking, and 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) refinery C four removes earlier olefins by catalytic cracking again after pre-separation removes Trimethylmethane, can improve the yield of olefins by catalytic cracking process propylene, ethene on the one hand, can avoid Trimethylmethane devaporation thermo-cracking on the other hand and produce a large amount of methane, cause the rising of energy consumption, material consumption;
(4) olefins by catalytic cracking can be propylene, ethene with most conversion of olefines, reduced circulation with the hydrogen that cracking brought behind whole hydrogenation of olefins, 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;
(5) olefins by catalytic cracking can obtain higher propene yield, and its propylene/ethylene ratio is far longer than steam heat cracked propylene/ethylene ratio.Adopt ethene amount that combination technique of the present invention produces usually smaller or equal to the steam heat cracking, also can adjust and make ethylene yield greater than the steam heat cracking, the propylene amount is then more than or equal to the steam heat cracking.Therefore can regulate the product structure of ethene, propylene by combination technique, to meet the need of market better;
(6) combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention relies on ethylene unit, does not change existing procedure, only increases equipment component, less investment, and instant effect, benefit is obvious.
Description of drawings
Fig. 1 is the principle process synoptic diagram of combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention.
Fig. 2 is the schematic flow sheet that combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention adopts carbon four extraction and separation technologies.
Fig. 3 is the schematic flow sheet that combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention adopts carbon four extraction and separation technologies and refinery C four process pre-separation technology.
Fig. 4 is that combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention adopts carbon four to select the schematic flow sheet of hydrogen addition technology and refinery C four process pre-separation technology.
Fig. 5 is that combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention adopts carbon four to select hydrogen addition technology, etherificate technology and refinery C four schematic flow sheet through the pre-separation technology.
Fig. 6 is that combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention adopts carbon four to select hydrogen addition technology, etherificate technology, butene-1 purification techniques and refinery C four schematic flow sheet through the pre-separation technology.
Embodiment
Further explain combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention below with reference to Fig. 1～6, but be not limited to this.
Fig. 1 is the principle process synoptic diagram of combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention.Can on this principle process schema, make amendment, increase other technology.With reference to Fig. 1, combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention, comprise the steam heat cracking technique, the ethylene quenching isolation technique, catalytic pyrolysis technology and carbon four full hydrogen addition technologies, the hot cracked stove of described petroleum naphtha or petroleum naphtha and lighter hydrocarbons is cracked into splitting gas, splitting gas separates through the ethylene quenching separation system, isolate cracking c_4 through debutanizing tower again, cracking c_4 is through taking off separated into two parts material behind diolefin and the alkynes, part material turns back to pyrolyzer as cracking stock through full hydrogenation, another part material is converted into C 4 olefin through the olefins by catalytic cracking technology and comprises propylene, ethene is in interior component, send into the ethylene unit quencher then, after the splitting gas mixing that pyrolyzer comes, enter described ethylene quenching separation system.
Described combination technique can also comprise refinery C four pre-separation technology, and refinery C four is isolated Trimethylmethane through the pre-separation systems, leftover materials and carry out olefins by catalytic cracking together from the material of cracking c_4.
Explain the various embodiments of combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention respectively below with reference to Fig. 2～6.
As shown in Figure 2, certain ethylene plant is raw material with the petroleum naphtha, through cracking, chilling, compression, separation, obtains cracking c_4 at the debutylize cat head.Cracking c_4 obtains carbon-4 after the divinyl extracting, the not further again processing and utilization of carbon-4 is only taken out as product.Now adopt combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention that existing procedure is improved.A carbon-4 part is removed full hydrogenation, and the material behind the hydrogenation goes pyrolyzer as the charging of steam heat cracked, and another part removes olefins by catalytic cracking, and the product after the conversion returns the ethylene unit quencher.After the improvement, propylene, ethene increase, and carbon-4 is utilized effectively.
As shown in Figure 3, certain ethylene plant is raw material with the petroleum naphtha, through cracking, chilling, compression, separation, obtains cracking c_4 at the debutylize cat head.Cracking c_4 obtains carbon-4 after the divinyl extracting, the not further again processing and utilization of carbon-4 is only taken out as product.Now adopt combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention that existing procedure is improved.A carbon-4 part is removed full hydrogenation, and the material behind the hydrogenation goes pyrolyzer as the charging of steam heat cracked, and another part removes olefins by catalytic cracking.In addition by introducing one refinery C four outside the battery limit (BL), remove Trimethylmethane with the pre-separation technology after, enter olefins by catalytic cracking with carbon-4, the product after the conversion returns the ethylene unit quencher.After the improvement, guaranteeing under the constant condition of compressor gas phase load, 1 ton of alternative approximately 1 ton of petroleum naphtha of refinery C four, propone output increases, and ethylene yield slightly reduces, and total propylene, ethylene yield increase, and the methane content of generation reduces, and the cold-zone load descends.
As shown in Figure 4, certain ethylene plant is raw material with the petroleum naphtha, through cracking, chilling, compression, separation, obtains cracking c_4 at the debutylize cat head.Cracking c_4 removes diolefine and alkynes through selective hydrogenation of butadiene.Adopt combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention that existing procedure is improved.Cracking c_4 part behind the selection hydrogenation is removed full hydrogenation, and the material behind the hydrogenation goes pyrolyzer as the charging of steam heat cracked, and another part removes olefins by catalytic cracking.By introducing one refinery C four outside the battery limit (BL), after pre-separation removes Trimethylmethane, enter olefins by catalytic cracking with cracking c_4 in addition, the product after the conversion returns the ethylene unit quencher.Improve the back and guaranteeing under the constant condition of compressor gas phase load, 1 ton of alternative approximately 1 ton of petroleum naphtha of refinery C four, propone output increases, and ethylene yield slightly reduces, and total propylene, ethylene yield increase, and the methane content of generation reduces, and the cold-zone load descends.
As shown in Figure 5, certain ethylene plant is raw material with the petroleum naphtha, through cracking, chilling, compression, separation, obtains cracking c_4 at the debutylize cat head.Cracking c_4 removes iso-butylene through etherificate again after selective hydrogenation of butadiene removes diolefine and alkynes.Adopt combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention that existing procedure is improved.Cracking c_4 part behind the selection hydrogenation is removed full hydrogenation, and the material behind the hydrogenation goes pyrolyzer as the charging of steam heat cracked, and another part removes olefins by catalytic cracking.By introducing one refinery C four outside the battery limit (BL), after pre-separation removes Trimethylmethane, enter olefins by catalytic cracking with cracking c_4 in addition, the product after the conversion returns the ethylene unit quencher.Improve the back and guaranteeing under the constant condition of compressor gas phase load, 1 ton of alternative approximately 1 ton of petroleum naphtha of refinery C four, propone output increases, and ethylene yield slightly reduces, and total propylene, ethylene yield increase, and the methane content of generation reduces, and the cold-zone load descends.
As shown in Figure 6, certain ethylene plant is raw material with the petroleum naphtha, through cracking, chilling, compression, separation, obtains cracking c_4 at the debutylize cat head.Cracking c_4 removes iso-butylene through etherificate again after selective hydrogenation of butadiene removes diolefine and alkynes, enter the butene-1 refined unit then, separate to obtain the butene-1 product, and byproduct C3 and Trimethylmethane, butene-2 is taken out.Adopt combination technique for producing olefin hydrocarbon with mixed C _ 4 of the present invention that existing procedure is improved.The butene-2 part that the butene-1 refined unit obtains is removed full hydrogenation, and the material behind the hydrogenation goes pyrolyzer as the charging of steam heat cracked, and another part removes olefins by catalytic cracking.By introducing one refinery C four outside the battery limit (BL), after pre-separation removes Trimethylmethane, enter olefins by catalytic cracking with butene-2 in addition, the product after the conversion returns the ethylene unit quencher.Improve the back and guaranteeing under the constant condition of compressor gas phase load, 1 ton of alternative approximately 1 ton of petroleum naphtha of refinery C four, propone output increases, and ethylene yield slightly reduces, and the methane content of generation reduces, and the cold-zone load descends.
Further explain the present invention in the mode of embodiment below.
Embodiment 1
4 pairs of flow processs describe with reference to the accompanying drawings.
The splitting gas temperature that is produced by the petroleum naphtha thermo-cracking is 820 ℃, pressure 0.15MPa, enters quenching system and is cooled to 40 ℃, sloughs heavy constituent wherein, enters the compression separation system again, obtains heavy constituent such as ethene, propylene, hybrid C 4 and C5 respectively.The hybrid C 4 component that obtains by separation system, 40 ℃ of temperature, pressure 0.3MPa, main form and mass percentage content is: 1,3-butadiene 50%, Trimethylmethane 0.5%, normal butane 2.3%, anti--2-butylene 7.3%, suitable-2-butylene 5.1%, iso-butylene 22.8%, 1-butylene 10%.The cracking hybrid C 4 enters the selective hydrogenation reaction device, removes wherein diolefine and alkynes.This reactor is fixed-bed reactor, and catalyzer is for adding the 8th family's metal catalyst of rare earth element, for example disclosed alkynes and diolefin hydrogenate catalyzer among the patent CN99112545.2.Reaction conditions is 40 ℃ of temperature, pressure 1.0MPa, liquid air speed 20h
-1Select hydrogenation products to be divided into two strands, one enters the olefins by catalytic cracking reactor after refining plant C 4 that pre-separation removes Trimethylmethane mixes with passing through, and second strand enters full hydrogenator, and the allocation proportion of two bursts of logistics is 40%: 60%.In full hydrogenator, alkene and hydrogen reaction generate alkane, and product returns pyrocrack furnace as cracking stock and carries out recycle.By the hybrid C 4 that the refinery comes, it is mainly formed and mass percentage content is: Trimethylmethane 45.5%, normal butane 8.0%, anti--2-butylene 14.5%, suitable-2-butylene 11.4%, 1-butylene 19.5%, iso-butylene 0.6%.Refining plant C 4 enters the pre-separation system, removes Trimethylmethane wherein, selects the product of hydrogenation to mix again with from c4 cleavage, enters the olefins by catalytic cracking reactor together.The catalyzer of olefins by catalytic cracking is selected disclosed catalyzer among the CN02131461.6 for use, adopts the disclosed method for preparing ethene and propylene in this patent, at reaction conditions: (at pressure and the 5h of 500 ℃ temperature, 0.25MPa
-1The condition of weight hourly space velocity under react, catalytic cracking reaction takes place in the contact of fixed-bed reactor catalyst neutralisation in raw material, propylene total mass yield is about 35% in the reaction, ethene total mass yield is about 15%.Reaction product enters the quenching system of cracking ethylene, cools off with the splitting gas from the ethene pyrocrack furnace, enters the compression separation system again and obtains ethene, propylene.
Claims (6)
1. combination technique for producing olefin hydrocarbon with mixed C _ 4, described combination technique comprises the steam heat cracking technique, the ethylene quenching isolation technique, catalytic pyrolysis technology and carbon four full hydrogen addition technologies, it is characterized in that, the hot cracked stove of described petroleum naphtha or petroleum naphtha and lighter hydrocarbons is cracked into splitting gas, splitting gas separates through the ethylene quenching separation system, isolate cracking c_4 through debutanizing tower again, cracking c_4 is through taking off separated into two parts material behind diolefin and the alkynes, part material turns back to pyrolyzer as cracking stock through full hydrogenation, another part material is converted into C 4 olefin through the olefins by catalytic cracking technology and comprises propylene, ethene is in interior component, send into the ethylene unit quencher then, after the splitting gas mixing that pyrolyzer comes, enter described ethylene quenching separation system.
2. combination technique for producing olefin hydrocarbon with mixed C _ 4 as claimed in claim 1, it is characterized in that, described combination technique also comprises refinery C four pre-separation technology, described refinery C four pre-separation technology are meant that refinery C four isolates Trimethylmethane through the pre-separation systems, leftover materials and carry out olefins by catalytic cracking together from the material of cracking c_4.
3. combination technique for producing olefin hydrocarbon with mixed C _ 4 as claimed in claim 1 is characterized in that, described cracking c_4 takes off diolefin and the alkynes technology is selection hydrogen addition technology or extraction and separation technology.
4. combination technique for producing olefin hydrocarbon with mixed C _ 4 as claimed in claim 1 is characterized in that, the material that cracking c_4 removes after diolefin and the alkynes carries out etherificate, removes iso-butylene wherein, and leftover materials carry out olefins by catalytic cracking again.
5. combination technique for producing olefin hydrocarbon with mixed C _ 4 as claimed in claim 4, it is characterized in that, C 4 materials after the etherificate carries out the refining separation of butene-1, isolated butene-1 is as product, isolated carbon three and Trimethylmethane return pyrolyzer as cracking material, and isolated butene-2 carries out olefins by catalytic cracking.
6. combination technique for producing olefin hydrocarbon with mixed C _ 4 as claimed in claim 1 is characterized in that, it is 10 weight %～90 weight % in the shared ratio of all cracking c_4 materials that cracking c_4 goes the part of full hydrogenation.
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