CN103087758A - Naphtha industrial cracking furnace value maximization model construction method - Google Patents
Naphtha industrial cracking furnace value maximization model construction method Download PDFInfo
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Abstract
The invention relates to a naphtha industrial cracking furnace value maximization model construction method. In petrochemical enterprises adopting industrial cracking furnaces as leading production devices, based on naphtha steam cracking experiment data, a naphtha cracking furnace cracking product yield prediction model is established, and naphtha industrial cracking furnace n-pentane yield data is acquired and is adopted to correct and check the established prediction model, such that a calculation result of the prediction model and an actual operation result of the industrial cracking furnace are the same; and based on the corrected and checked model, a naphtha cracking furnace cracking product value maximization model is established, and is adopted to optimize operation of the naphtha cracking furnace, such that the total value of petrochemical products produced by the industrial naphtha cracking furnace is maximized.
Description
Technical field
The present invention relates to the optimization method of pyrolyzer operation in petrochemical production device, more specifically, relate to a kind of construction process of petroleum naphtha industrial pyrolysis furnace value maximization model.
Background technology
Petrochemical industry is mainstay of the national economy industry, and petrochemicals (abbreviation petroleum chemicals) widespread use national economy every field has important to promoting national economic development.The most of intermediates of petrochemical complex and petroleum chemicals are all take low-carbon alkene and aromatic hydrocarbons as basic material.The raw materials used hydrocarbon of low-carbon alkene and aromatic hydrocarbons accounts for petrochemical iy produced and always consumes 3/4ths of raw material hydrocarbon.Low-carbon alkene mainly is made of ethene, propylene, divinyl, and aromatic hydrocarbons mainly is made of benzene,toluene,xylene.In petrochemical industry, except producing aromatic hydrocarbons by reforming and by Propylene recovery, butylene, divinyl in the catalytic cracking by product, mainly producing various alkene and aromatic hydrocarbons by ethylene unit.Ethylene unit is made of pyrolyzer and tripping device, and pyrolyzer is the leading production equipment of ethylene unit.
Ethene is most important basic organic chemical raw material, and present ethene more than 98% is produced in the steam cracking mode by pyrolyzer.Ethene is mainly for the production of petroleum chemicals such as high-pressure polyethylene, low pressure polyethylene, linear low density polyethylene, polyvinyl chloride, oxyethane, ethylene glycol, ethanol, vinylbenzene, acetaldehyde, acetic acid, alpha-olefin, polyvinyl alcohol, ethylene-propylene rubber(EPR).
The petroleum chemicals such as propylene is fine mainly for the production of polypropylene, propylene, phenol, acetone, butanols, octanol, Virahol, vinylformic acid and lipid thereof, propylene oxide, epoxy chloropropane, polypropylene fibre.At present, the propylene more than 50～70% is produced with steam cracking by pyrolyzer.
Divinyl is mainly used in generating the petroleum chemicals such as cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, chloroprene rubber, polyhutadiene, SBS, ABS resin.At the petrochemical industry initial stage, divinyl is mainly by butylene or butane dehydrogenation production.At present, the divinyl more than 90% is produced in the steam cracking mode by pyrolyzer.
Iso-butylene is mainly used in isoprene-isobutylene rubber, polyisoprene rubber, methyl methacrylate, polyisobutene, the trimethyl carbinol and auxiliary agent production etc. as the petrochemical complex basic material.In recent years, due to as methyl tertiary-butyl ether (MTBE) high speed development, the iso-butylene demand is surged.Iso-butylene is produced iso-butylene by butane isomerization and dehydrogenation on a small quantity except from refinery and ethylene unit.
Butylene is mainly for the production of petroleum chemicals such as divinyl, cis-butenedioic anhydride, sec-butyl alcohol, heptene, polybutene.Along with the development of linear low density polyethylene, the 1-butylene consumption is increasing, becomes the butylene main application, and remaining butylene is mainly for the production of stop bracket gasoline additive and civil liquefied gas.
Aromatic hydrocarbons as the petrochemical complex basic material mainly comprises benzene,toluene,xylene.
Benzene is mainly for the production of vinylbenzene, hexanaphthene (further producing polyamide fibre), phenol.In addition, benzene also can be used for the production of the products such as aniline, alkylbenzene, cis-butenedioic anhydride and medicine and agricultural chemicals.
Toluene is mainly for the production of benzene, dimethylbenzene.In addition, also consume the toluene of a great deal of in the productions such as solvent, coating, agricultural chemicals, explosive, cresols, tolylene diisocyanate (TDI).
Dimethylbenzene comprises p-Xylol, o-Xylol, m-xylene.As petrochemical materials, the p-Xylol consumption is maximum, mainly for the production of terephthalic acid (PTA) and bis--terephthalate (DMT), further produce thus polyester (PET), on a small quantity for the production of butylene terephthalate (PBT).M-xylene and o-Xylol are mainly used in isomerization and produce p-Xylol, and wherein o-Xylol also can be used for producing the production of phthalic anhydride, coating, solvent, pesticide intermediate.
Ethylene unit is when producing ethene, and by-product propylene, butylene, divinyl, aromatic hydrocarbons (benzene,toluene,xylene) become the main source of petrochemical industry basic material.Ethylene unit is except producing ethene, and 70% propylene, 90% divinyl, 30% aromatic hydrocarbons are all from the by-product of ethylene unit.In " triolefin " (ethene, propylene, divinyl) and " triphen " (benzene,toluene,xylene) total amount, approximately 65% from ethylene producing device.
Go back by-product a large amount of other alkene and aromatic hydrocarbons when producing ethene due to steam cracking process, correspondingly, ethylene production is inevitable to be linked together with multiple intermediates and petroleum chemicals production.Therefore, petrochemical industry is always centered by ethylene production, with the leading production equipment of pyrolyzer, the associated enterprises of supporting multiple product processing.The scale of ethylene production, cost, production stability, quality product all will play dominating role to whole associated enterprises.Ethylene unit becomes core production equipment related to the overall situation in petrochemical complex.Pyrolyzer is the faucet device in petrochemical complex, and the operation of pyrolyzer directly will affect the production operation of other petrochemical units.
The temperature of reaction of hydrocarbon vapours cracking higher (780-870 ℃), reaction process are strong endothermic processes, and the production run of pyrolyzer consumes a large amount of fuel.Therefore ethylene industry is the high energy consumption industry, and Energy consumption of cracking furnace accounts for 70% left and right of ethylene unit energy consumption.Therefore, optimizing the pyrolyzer production operation, reduce production costs, improve the economic benefit of manufacturing enterprise, is the difficult problem that petroleum chemical enterprise pays close attention to for many years always.
Pyrolyzer patent business has very important effect in pyrolyzer technical development process, merge the whole world through constantly recombinating at present and form six large pyrolyzer patent business, i.e. LUMMUS, S﹠amp; M, KBR, TECKNIP, LINDE, SINOPEC.Pyrolyzer patent business is based on steam cracking reaction mechanism or steam cracking experimental data, adopt the methods such as derivation or mathematical regression to set up the industrial pyrolysis furnace simulation software, be used for prediction yield of cracked product and the cycle of operation etc., as the PYPS of LUMMUS, the SPYRO of TECHNIP etc.Although the numerous pyrolyzer of pyrolyzer patent business Design ﹠ reform, but the operation optimization for pyrolyzer, only there are at present ASPEN and TECHNIP to propose the prioritization scheme of diene (ethene+propylene) yield, utilize the SPYRO software of TECHNIP and tripping device simulation technique and the Advanced Control Techniques thereof of APSEN, optimize the pyrolyzer production operation, mainly the mode of the yield by improving diene attempts to improve the economic benefit of manufacturing enterprise.
In split product, diene (ethene and propylene) weight yield is 38～60%.Except ethene and propylene, also have other split products, take out remaining cut, aromatic hydrocarbons (benzene,toluene,xylene), pyrolysis gasoline, Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO etc. as hydrogen, divinyl, carbon four, all have certain economic worth or higher economic value added, can produce rubber, aromatic hydrocarbons production polyester, chemical fibre etc. as divinyl.The market value of petroleum chemicals is subjected to oil price and the demand-supply relation and fluctuates, the huge market demand and the petroleum chemicals price of supply is high, and market demand is little and to supply large petroleum chemicals price lower.Therefore, in pyrolyzer production operation process, its petroleum chemicals price of split product that yield is high may not be high, and its petroleum chemicals price of split product that yield is low may not be low.Therefore, the pyrolyzer operation optimization only considers that ethene and propene yield can not effectively improve the income of petrochemical complex manufacturing enterprise.
In addition, the Organic Chemicals such as triolefin triphen that domestic ethylene is produced are are seldom bought and sold on market, the overwhelming majority is by the corresponding petroleum chemicals of middle and lower reaches production equipment production, produce polyolefin resin as ethene and propylene by the manufacture of polyolefins device, divinyl is produced rubber by poly-unit, and aromatic hydrocarbons is produced polyester and chemical fibre etc. by devices such as extraction plant, polyester.Therefore, the petroleum chemicals market value of domestic petroleum chemical enterprise middle and lower reaches device production determines the income of manufacturing enterprise.The production operation of pyrolyzer not only will be considered diene, also will consider the total value of all petroleum chemicals that pyrolyzer is produced.Only make the petroleum chemicals total value of petrochemical production device production reach maximum, could effectively improve like this is the income of petrochemical enterprise.
Summary of the invention
Attempt to realize improving the economic benefit of ethylene unit in prior art by improving the diene yield, but ignored economic worth or the economic value added of other petroleum chemicals, the actual income that can not effectively improve petrochemical enterprise.In order to overcome the defective of traditional pyrolyzer operation optimization method, the method that adopts raising diene yield to increase economic efficiency from prior art is different, the present invention builds petroleum naphtha industrial pyrolysis furnace split product value maximization model, be used for optimizing petroleum naphtha industrial crack furnace operating, make the petroleum chemicals total value of naphtha cracking stove production reach maximum, thereby effectively improve the income of petrochemical enterprise.
The present invention relates to the method for petroleum naphtha industrial pyrolysis furnace split product value maximization model construction, in the petrochemical enterprise with the leading production equipment of industrial pyrolysis furnace, set up naphtha cracking stove split product predictive model based on the naphtha steam cracking experimental data, then utilize the Skellysolve A yield data of petroleum naphtha industrial pyrolysis furnace actual motion to check predictive model, make predictive model calculated value and industrial pyrolysis furnace actual operating data basically identical; Based on the predictive model of checking, set up petroleum naphtha industrial pyrolysis furnace split product value maximization model, and be used for the optimization of naphtha cracking furnace operating, make the petroleum chemicals total value of naphtha cracking stove production reach maximum.
Concrete technical scheme is as follows:
The present invention relates to the construction process of petroleum naphtha industrial pyrolysis furnace split product value maximization model, in the petrochemical enterprise with the leading production equipment of industrial pyrolysis furnace, adopt Mathematical Modeling Methods to set up naphtha cracking stove split product predictive model based on the naphtha steam cracking experimental data, then the Skellysolve A yield data that gathers petroleum naphtha industrial pyrolysis furnace actual motion is checked predictive model, makes the calculated value of predictive model and industrial pyrolysis furnace actual operating data basically identical; Based on the predictive model of checking, set up petroleum naphtha industrial pyrolysis furnace split product value maximization model, and be used for the optimization of naphtha cracking furnace operating, make the petroleum chemicals total value of naphtha cracking stove production reach maximum, thereby effectively improve the income of petrochemical enterprise.
The construction process of described a kind of petroleum naphtha industrial pyrolysis furnace value maximization model comprises the following steps:
(1) set up predictive model: based on the naphtha steam cracking experimental data, utilize Mathematical Modeling Methods to set up petroleum naphtha industrial pyrolysis furnace yield of cracked product predictive model, can calculate yield of cracked product according to petroleum naphtha physical property, industrial pyrolysis furnace operational condition.
(2) gather the Skellysolve A yield data: under the constant condition of petroleum naphtha physical property, inlet amount, quantity of steam, in industrial pyrolysis furnace coil outlet temperature (COT) normal operation range, gather the Skellysolve A yield data of petroleum naphtha industrial pyrolysis furnace actual motion by adjusting COT.
(3) check: utilize the Skellysolve A yield data of the petroleum naphtha industrial pyrolysis furnace that is obtained by step (2) to check the predictive model that is obtained by step (1), make the data of the calculated value of predictive model of check and industrial pyrolysis furnace actual motion basically identical.
(4) set up naphtha cracking stove split product value maximization model: set up cracked product of cracking furnace value maximization model according to the predictive model that step (3) obtains, can utilize split product price, petroleum naphtha physical property, naphtha cracking stove service data to calculate the pyrolyzer operational condition of split product (petroleum chemicals) total value maximum.
Preferably, the production equipment of described petrochemical enterprise mainly comprises pyrolyzer, tripping device, polyolefin device etc. with the leading production equipment of pyrolyzer.According to the design of petrochemical enterprise, also may comprise aromatic extraction unit, styrene device, glycol unit, rubber device, ethylene oxide device, propylene oxide unit, polyester device, chemical fibre device etc.
Preferably, described petroleum naphtha physical property comprises density, grace formula distillation boiling range (ASTM), group composition (PONA), hydrogen richness or carbon content or ratio of carbon-hydrogen, carboloy residue, molecular weight, correlation index (BMCI), refractive index etc., perhaps detailed component and the content thereof of described petroleum naphtha.The petroleum naphtha component reaches hundreds of at least, therefore utilizes comparatively difficulty of its detailed component and content thereof, usually selects density, grace formula distillation boiling range (ASTM), group composition (PONA) etc. as physical parameter.
Preferably, described split product mainly comprises hydrogen, carbon monoxide, carbonic acid gas, methane, ethane, ethene, acetylene, propane, propylene, propine, propadiene, butane, butylene, divinyl, benzene,toluene,xylene, ethylbenzene, vinylbenzene, pyrolysis gasoline (aromatic free), Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO etc.Although the formation of petroleum naphtha differs greatly, and their split product component is basic identical, only the yield of split product component distributes different.
Preferably, described petroleum chemicals refer to the product of petrochemical enterprise public offering on market, as polyethylene, polypropylene, styrene-butadiene rubber(SBR), polyester etc.In addition, Organic Chemicals or other products public offering on market that petrochemical enterprise is produced can be considered petroleum chemicals, as hydrogen, LPG, ethene, propylene, divinyl, benzene,toluene,xylene, vinylbenzene etc.The kind of the petroleum chemicals of petrochemical enterprise production depends on design and the production and sales plan of production equipment.If ethene all for the production of polyethylene and in market with the polyethylene product public offering, ethene can not be considered as petroleum chemicals; If at the market public offering, ethene can be considered petroleum chemicals to part ethene with industrial chemicals, other petroleum chemicals by that analogy.
In the petrochemical enterprise production equipment, petroleum naphtha from oil refining apparatus is heated to the splitting gas that low-carbon alkene and aromatic hydrocarbons are rich in the production of high temperature generating steam scission reaction in pyrolyzer, splitting gas is split product, mainly comprises hydrogen, carbon monoxide, carbonic acid gas, methane, ethane, ethene, acetylene, propane, propylene, propine, propadiene, butane, butylene, divinyl, benzene,toluene,xylene, ethylbenzene, vinylbenzene, pyrolysis gasoline (aromatic free), Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO etc.
Splitting gas is through the separation of tripping device and purify formation Organic Chemicals and other raw materials, as hydrogen, fuel gas, ethene, propylene, C-4-fraction (comprising butane, butylene, divinyl), pyrolysis gasoline (containing aromatic hydrocarbons), Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO etc.In tripping device, although the technical process that different patent business provides order is different, as order separation process, the front-end deethanization flow process of LINDE, the S﹠amp of LUMMUS; The predepropanization process of W, but final all separate and purify according to the carbon number of hydrocarbon.Tripping device comprises the devices such as oil scrubber, water wash column, compressor, ice chest, demethanizing tower, deethanizing column, ethylene rectification tower, depropanizing tower, propylene rectification tower, debutanizing tower, carbon two carbon three hydrogenation units.Splitting gas part component forms raw material through the separating-purifying of tripping device, as hydrogen, ethene, propylene, C-4-fraction (comprising butane, butylene, divinyl), pyrolysis gasoline (containing aromatic hydrocarbons); The part component is consumed or recycle, processes forming fuel gas by methanation device as carbon monoxide, and methane generates fuel gas by demethanizing tower, and fuel gas is consumed as the fuel of pyrolyzer; Carbonic acid gas is absorbed by soda-wash tower; Acetylene, propine and propadiene generate ethene and ethane, propylene and propane through hydrogenator; Ethane, propane form cycle ethane, recycled propane through ethylene rectification tower, propylene rectification tower after purifying, and cycle ethane and recycled propane are returned to pyrolyzer as petroleum naphtha; Pyrolysis gas oil PGO and Pyrolysis fuel oil PFO form oil fuel through oil scrubber.
Ethene is produced polyvinyl resin and the rubber of the various trades mark by polyethylene device, as high-pressure polyethylene, low pressure polyethylene, linear low density polyethylene, polyvinyl chloride, polyvinyl alcohol, ethylene-propylene rubber(EPR) etc.Ethene is also for the production of organic products, as oxyethane, ethylene glycol, ethanol, vinylbenzene, acetaldehyde, acetic acid, alpha-olefin etc.
Propylene is produced the polypropylene of the various trades mark by polypropylene plant.In addition, propylene is used for producing multiple organic products, the petroleum chemicals such as fine in propylene, phenol, acetone, butanols, octanol, Virahol, vinylformic acid and lipid thereof, propylene oxide, epoxy chloropropane, polypropylene fibre.
C-4-fraction forms divinyl by butadiene extraction unit and carbon four is taken out remaining cut, and divinyl can be used for producing various rubber by rubber device, as cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, chloroprene rubber, polyhutadiene, SBS, ABS resin etc.; Carbon four is taken out remaining cut can produce MTBE or LPG by ether-based device.If do not build butadiene extraction unit in petrochemical enterprise, C-4-fraction is produced LPG through hydrotreatment usually, or C-4-fraction is sold the petrochemical enterprise that other have butadiene extraction unit.
Pyrolysis gasoline (containing aromatic hydrocarbons) is by gasoline hydrogenation device and aromatic extraction unit production C5 fraction, benzene,toluene,xylene, the above cut of carbon nine, the product such as raffinate oil, and C5 fraction can be produced the resins such as cyclopentadiene, isoprene through further separation, purification, polymerization.Benzene can be used for producing the production of vinylbenzene, hexanaphthene (further producing polyamide fibre), phenol, aniline, alkylbenzene, cis-butenedioic anhydride and the products such as medicine and agricultural chemicals; Toluene is produced benzene or produces dimethylbenzene and benzene by transalkylation unit by taking off the alkyl device, also can be used for producing solvent, coating, agricultural chemicals, explosive, cresols, tolylene diisocyanate (TDI).Dimethylbenzene by the device such as isomerization for the production of the production of p-Xylol, terephthalic acid (PTA) and bis--terephthalate (DMT), polyester (PET), chemical fibre, butylene terephthalate (PBT), phthalic anhydride, coating, solvent, pesticide intermediate etc.; The above cut of carbon nine is generally used for the raw material of compressor washing oil or toluene disproportionation; Can be used as petroleum naphtha more than taking out, also can be used for producing sherwood oil or be used as gasoline sales.If do not build the devices such as pyrolysis gasoline hydrogenation and Aromatics Extractive Project in petrochemical enterprise, pyrolysis gasoline (containing aromatic hydrocarbons) external disclosure is usually sold.
Pyrolysis gas oil PGO and Pyrolysis fuel oil PFO can be produced oil fuel or be used as the raw material of producing the products such as naphthalene.
The Organic Chemicals that domestic ethylene is produced is seldom sold on market, usually is transported to the middle and lower reaches device and produces the petroleum chemicals such as resin, rubber.Therefore, the kind quantity of petroleum chemicals depends on design and the production program arrangement of petrochemical enterprise production equipment usually, and the income of the petrochemical enterprise overwhelming majority is from the sale of the petroleum chemicals of middle and lower reaches device production.Therefore, the difference of the production equipment of petrochemical enterprise middle and lower reaches design, the petroleum chemicals of production exist certain difference.
Preferably, described split product price depends on whether the split product component can form petroleum chemicals and the selling price thereof of market sale through petrochemical production device.Petroleum naphtha generating steam scission reaction in pyrolyzer is produced splitting gas (split product), and itself does not have price split product, has certain value but split product is formed on through petrochemical production device the petroleum chemicals of selling on market.Therefore, fail to be formed on the split product component of the petroleum chemicals of selling on market through petrochemical production device, its price is set to zero, as methane, carbon monoxide, carbonic acid gas, ethane, propane etc.; Be formed on the cracking component of the petroleum chemicals of selling on market through petrochemical production device, its price is the market value of these petroleum chemicals.This shows, be the petroleum chemicals prices by the split product price, makes its split product price reach maximum by optimizing the pyrolyzer operation, maximum even the petroleum chemicals total price of pyrolyzer production reaches.
In split product, the height of split product component price depends on the market value of the petroleum chemicals that it is produced by petrochemical unit.For acetylene, propine and propadiene, they generate ethene and ethane, propylene and propane through hydrogenation, its price is the transformation efficiency of ethene and propylene price and hydrogenation catalyst and product optionally, lacking the hydrogenation catalyst transformation efficiency and optionally under condition, its price can be considered the price of ethene and propylene; Form a kind of split product component of petroleum chemicals through petrochemical production device, the petroleum chemicals price that its price forms for this component is as hydrogen, Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO; Form the split product component of multiple petroleum chemicals through petrochemical production device, its price can be calculated in the following manner:
P wherein
iThe price of expression split product component, x
jThe market value of expression petroleum chemicals, w
jRepresent that this split product component is for the production of the shared part by weight of these petroleum chemicals.After establishing the split product price, in fact the split product price is exactly the petroleum chemicals price.
Optimize for the production operation of naphtha cracking stove, key is naphtha cracking stove split product value maximization model.Naphtha cracking stove split product value maximization model is used for optimizing the production operation of pyrolyzer, makes the split product total value of naphtha cracking stove production reach maximum.By naphtha cracking stove split product value maximization model, the operation optimization of naphtha cracking stove is associated with the petroleum chemicals market value.
The construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model of the present invention, set up industrial pyrolysis furnace split product predictive model based on the naphtha steam cracking experimental data, utilize the Skellysolve A yield of petroleum naphtha industrial pyrolysis furnace actual motion to check predictive model, then utilize the check model to set up petroleum naphtha industrial pyrolysis furnace split product value maximization model, use it for the optimization of naphtha cracking furnace operating, make the market value summation of the petroleum chemicals of petroleum naphtha industrial pyrolysis furnace production reach maximum, thereby improve the income of petrochemical complex manufacturing enterprise.
Preferably, described petroleum naphtha industrial pyrolysis furnace split product value maximization model is take naphtha cracking stove yield of cracked product predictive model as the basis, physical property, pyrolyzer service data, split product price according to petroleum naphtha, in pyrolyzer operational condition restriction range, adopt the Mathematics Optimization Method search or calculate the maximum corresponding operational condition of split product total value.
More preferably, described industrial pyrolysis furnace service data is naphtha feed amount, dilution steam generation amount or thinning ratio, across section temperature (XOT), and the operational condition of optimization is coil outlet temperature (COT).The COT operation span of control of naphtha cracking stove is controlled at 810-845 ℃ usually, in the optimizing process of naphtha cracking stove split product value maximization, within COT necessarily is controlled at normal operating restraint, if the COT that optimizes surpasses the upper limit of normal running or rolls off the production line, can select the upper limit or the operation of rolling off the production line when optimizing and revising COT.
More preferably, described petroleum naphtha physical property comprises density, grace formula distillation boiling range (ASTM), group composition (PONA), hydrogen richness or carbon content or ratio of carbon-hydrogen, carboloy residue, molecular weight, correlation index (BMCI), refractive index etc., perhaps detailed component and the content thereof of described petroleum naphtha.The petroleum naphtha component reaches hundreds of at least, therefore utilizes comparatively difficulty of its detailed component and content thereof, usually selects density, grace formula distillation boiling range (ASTM), group composition (PONA) etc. as physical parameter.
More preferably, the Mathematics Optimization Method in described naphtha cracking stove split product Maximum Value model comprises searching method.
More preferably, the yield of cracked product that naphtha cracking stove yield of cracked product predictive model is used for analog calculation naphtha cracking stove distributes, and can calculate according to petroleum naphtha physical property and pyrolyzer operational condition the yield of split product.Based on the naphtha steam cracking reaction mechanism, pyrolyzer patent business releases commercial naphtha cracking stove simulation software, but the yield of cracked product of analog calculation pyrolyzer, as the SPYRO software of TECHNIP, the PYPS software of LUMMUS etc.Based on the naphtha steam cracking testing data, can set up the yield of cracked product of cracking furnace predictive model by Mathematical Modeling Methods.The naphtha steam cracking experiment can be implemented on small testing device or simulating-estimating device or industrial pyrolysis furnace, for the industrial pyrolysis furnace type of furnace and operational condition scope, steam cracking reaction process and the experimental data of simulation petroleum naphtha, experimental data comprises petroleum naphtha physical property, operational condition, yield of cracked product.The Sinopec Beijing Chemical Research Institute has set up the steam cracking evaluation experimental device, the yield of cracked product of industrial pyrolysis furnace that can the various petroleum naphthas of Simulation evaluation.
Still more preferably, described Mathematical Modeling Methods comprises the methods such as SVMs (SVM), artificial neural network, Multiple Non Linear Regression, genetic algorithm.The naphtha steam cracking experimental data is divided into two portions, and a part is used for training pattern, and a part is used for the precision of prediction of testing model.By adjusting the kernel function in Mathematical Modeling Methods, the model miscalculation of foundation is reached in 10% at least, be preferably in 5%.Predictive model input variable petroleum naphtha physical property, the operational condition set up, output variable is the yield of split product, that is:
y
i＝X(F，S，XOT，COT，P)
Y wherein
i-expression split product component yield
The F-inlet amount
The S-thinning ratio
XOT-is across the section temperature
The COT-coil outlet temperature
P-petroleum naphtha physical property
Therefore the transformation efficiency of Skellysolve A transformation efficiency ordinary representation naphtha steam cracking reaction can utilize the yield of Skellysolve A to proofread and correct the predictive model of petroleum naphtha industrial pyrolysis furnace.The demarcation of Skellysolve A yield need to be done a thief hole in the quenching boiler outlet, and thief hole is connected with water cooler.When opening thief hole, splitting gas is cooled to 0～40 ℃ and forms gas-liquid two-phase, utilize gas-chromatography and liquid chromatography to analyze respectively the content of Skellysolve A in gaseous stream and liquid phase stream, and the weight of metering gaseous stream and liquid phase stream, then can calculate the yield of petroleum naphtha industrial pyrolysis furnace Skellysolve A by material balance.Yield adopts weight content to represent usually, also can adopt molar content.Chinese patent CN1456895A is described in detail off-line sampling unit and method.
Preferably, described Skellysolve A yield data is under the constant condition of petroleum naphtha physical property, inlet amount, quantity of steam, in industrial pyrolysis furnace coil outlet temperature (COT) normal operation range, the Skellysolve A yield data during by at least three its actual motions of COT temperature acquisition of adjustment industrial pyrolysis furnace.
More preferably, preferred five COT temperature.
In the industrial pyrolysis furnace operational process, the thermopair of measuring COT usually inserts or is bundled in the waste heat boiler entrance, and has an isolation section between waste heat boiler entrance and crack furnance radiation section furnace tube outlet.Thermopair itself has certain measuring accuracy and thermopair exists systematic error in measuring process in addition, usually causes the industrial pyrolysis furnace COT that shows and the true temperature that radiant coil exports to exist certain temperature difference.
preferably, described petroleum naphtha industrial pyrolysis furnace split product predictive model check method is based on the actual motion Skellysolve A yield data that collects the petroleum naphtha industrial pyrolysis furnace, Skellysolve A yield under the operational condition of the predictive model calculating industrial pyrolysis furnace collection Skellysolve A yield that utilization is set up, calculate the Skellysolve A yield data of a plurality of COT and compare with the actual motion value, find out the temperature difference between predictive model and actual indication COT, then the temperature difference is put into predictive model, make the data of the calculated value of predictive model of check and industrial pyrolysis furnace actual motion basically identical.
More preferably, described data are basically identical be calculated value and actual motion value deviation in 10%, and the numerical value change rule is consistent.
Preferably, petroleum naphtha industrial pyrolysis furnace split product value maximization model is take the cracked product of cracking furnace predictive model as the basis, adopt Mathematics Optimization Method, under the constant condition of naphtha feed amount, water-oil ratio, XOT, petroleum naphtha physical property, split product price, in the COT of industrial pyrolysis furnace normal operation range, calculate COT corresponding to split product total value maximum value, that is:
V
max＝max(V(m))
Wherein, F-inlet amount
The S-thinning ratio
XOT-is across the section temperature
COT (m)-coil outlet temperature
P-petroleum naphtha physical property
PR
j-split product component price
V (m)-split product total value
V
max-split product total value maximum value.
More preferably, described Mathematics Optimization Method comprises the average search method.
The present invention is based on the naphtha steam cracking experimental data and set up petroleum naphtha industrial pyrolysis furnace split product predictive model, utilize the Skellysolve A yield data of petroleum naphtha industrial pyrolysis furnace actual motion to check predictive model, set up naphtha cracking stove split product value maximization model and be used for optimizing the pyrolyzer operation based on the predictive model of checking, make the petroleum chemicals market total price of naphtha cracking stove production reach maximum, thereby effectively improve the income of petrochemical enterprise.
Description of drawings
Fig. 1 is that the GK-V pyrolyzer price of embodiment 1 maximizes the result of optimizing.
Embodiment
Further describe the present invention below in conjunction with embodiment.The present invention includes but be not limited to the related content of these embodiment.
Certain petrochemical enterprise has production equipment by ethylene unit, glycol unit, ethylene oxide device, polyethylene device, polypropylene plant, aromatic extraction unit, toluene dealkylation device, PTA device, terylene production equipment, polyester device (staple fibre), LPG device.Ethylene unit has 6 pyrolyzer, and tripping device adopts the order separating technology of LUMMUS, and yearly capacity reaches 360,000 tons.Pyrolyzer has 5 to be the GK-V pyrolyzer, and 1 is CBL-III type pyrolyzer (cracking stock is hydrogenation tail oil), and the pyrolyzer operational condition sees Table 1.
GK-V type pyrolyzer is by the industrial pyrolysis furnace of TECKNIP company design, adopts 32 groups of 2-1 configuration boiler tubes, and minutes four organize greatly chargings, have two traditional quenching boilers, and petroleum naphtha is petroleum naphtha or lighter hydrocarbons.
Table 1 pyrolyzer operational condition
| The type of furnace | GK-V |
| Raw material | Petroleum naphtha |
| Inlet amount (ton/hour) | 24.788 |
| Thinning ratio | 0.633 |
| XOT(℃) | 633 |
| COT(℃) | 825 |
Petroleum chemicals mainly comprise polyethylene, oxyethane, ethylene glycol, polypropylene, LPG, purified petroleum benzin, p-Xylol, pure terephthalic acid, oil fuel, polyester slice, terylene (staple fibre).According to the petroleum chemicals market value historical data that this petroleum chemical enterprise sells, selects that in two periods, the petroleum chemicals selling price is for the value maximization operation optimization of pyrolyzer, the petroleum chemicals market value sees table 2 for details.
Table 2 petroleum chemicals market value (yuan/ton)
| Price | |
| High-pressure polyethylene | 7800 |
| Low pressure polyethylene | 7600 |
| Linear polyethylene | 7700 |
| Oxyethane | 10000 |
| Ethylene glycol | 4300 |
| Polypropylene | 6750 |
| LPG | 4500 |
| Purified petroleum benzin | 3000 |
| P-Xylol | 6000 |
| The pure terephthalic acid | 4480 |
| Pyrolysis gasoline | 6800 |
| Pyrolysis gas oil PGO | 2210 |
| Oil fuel | 2210 |
| Polyester slice | 6000 |
| Terylene (short fiber) | 7200 |
According to the petrochemical production device flow process, determined that the price of split product sees table 3 for details, method is specific as follows:
(1) hydrogen is mainly for oil refining apparatus and hydrogenation unit, and not for sale in market, its price is 0;
(2) methane, carbon monoxide, carbonic acid gas, ethane, propane are consumed by production equipment or absorb, and its price is 0;
(3) ethene is for the production of high-pressure polyethylene, low pressure polyethylene, linear polyethylene, ethylene glycol, oxyethane, its part by weight is respectively 30%, 20%, 20%, 15%, 15%, the price of ethene is made of the market value of these five kinds of petroleum chemicals, that is:
Ethene price=Market of High Pressure Polyethylene price * 30%+ low pressure polyethylene market value * 20%+ linear polyethylene market value * 20%+ ethylene glycol market value * 15%+ oxyethane market value * 15%.
(4) acetylene, propine and propadiene generate ethene and ethane, propylene and propane through the hydrogenation unit of separation system, and due to selectivity of catalyst and transformation efficiency all very high (surpassing 95%), its price is substantially identical with ethene, propylene price;
(5) propylene is for the production of polypropylene, and its price is polyacrylic market value;
(6) C-4-fraction is sold as LPG in market after hydrogenation, and its price is the market value of LPG;
(7) benzene is for the production of purified petroleum benzin, and its price is the market value of purified petroleum benzin;
(8) toluene is for the production of benzene, and its price is the market value of purified petroleum benzin;
(9) dimethylbenzene is for the production of p-Xylol, pure terephthalic acid, polyester slice, terylene, and its price is made of these four kinds of petroleum chemicals market value, that is:
Dimethylbenzene price=p-Xylol market value * 40%+ essence p-Xylol market value * 30%+ polyester market value * 15%+ terylene market value * 15%;
(10) pyrolysis gasoline mixes with petroleum naphtha and returns to pyrolyzer as petroleum naphtha, and its price is 0;
(11) ethylbenzene, vinylbenzene mix with petroleum naphtha with pyrolysis gasoline as petroleum naphtha, and its price is 0;
(12) Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO are used for oil fuel public offering on market, and its price is the market value of oil fuel.
Table 3 split product price (yuan/ton)
| Price | |
| Hydrogen | 0 |
| Carbon monoxide | 0 |
| Carbonic acid gas | 0 |
| Methane | 0 |
| Ethane | 0 |
| Ethene | 7545 |
| Acetylene | 7545 |
| Propane | 0 |
| Propylene | 6750 |
| Propine | 6750 |
| Propadiene | 6750 |
| Butane | 4500 |
| Butylene | 4500 |
| Divinyl | 4500 |
| Benzene | 3000 |
| Toluene | 3000 |
| Dimethylbenzene | 5724 |
| Ethylbenzene | 0 |
| Vinylbenzene | 0 |
| Pyrolysis gasoline | 0 |
| Pyrolysis gas oil PGO | 2210 |
| Oil fuel | 2210 |
Embodiment 1
According to the GK-V type pyrolyzer type of furnace, set up GK-V type pyrolyzer steam cracking naphtha cracking product value maximization model, modeling process is as follows.
1 steam cracking experimental data
For GK-V industrial pyrolysis furnace and operational condition, gather respectively multiple petroleum naphtha in the experiment of Sinopec Beijing Chemical Research Institute's steam cracking Simulation device enforcement steam cracking, calculate the yield of cracked product of petroleum naphtha under the different operating condition by material balance and logistics compositional analysis, gather experimental data and set up GK-V pyrolyzer steam cracking reaction sample database, data-base content comprises petroleum naphtha (proportion, ASTM boiling range, group composition), operational condition (inlet amount, water-oil ratio, XOT, COT), yield of cracked product.Relevant steam experimental analysis instrument and equipment is as follows:
(1) the ANTON PEAR DE40 of company specific gravity hydrometer is measured petroleum naphtha density (20 ℃);
(2) the German tide HDA627 of company of Haier analyzes petroleum naphtha grace formula distillation boiling range (ASTM) (initial boiling point, 10%, 30%, 50%, 70%, 90%, final boiling point);
(3) U.S.'s Agilent HP6850 of company analyzes petroleum naphtha group composition (normal paraffin, isoparaffin, naphthenic hydrocarbon, aromatic hydrocarbons) and liquid-phase pyrolysis product composition and weight content thereof;
(4) U.S.'s Agilent HP7890 of company analytical pyrolysis gas forms and molar content.
2. set up GK-V type pyrolyzer steam cracking naphtha cracking product forecast model
Sample database is divided into two portions, and wherein a part is training data, and its data volume is 2/3rds of sample database amount, and remaining data is check data.Training data is inputted in SVMs (SVM), set up the yield of cracked product of cracking furnace predictive model.SVMs (SVM) kernel function adopts the RBF kernel function, mode input variable petroleum naphtha physical property (proportion, ASTM boiling range, group composition), operational condition (throwing oil mass, water-oil ratio, COT, XOT), output variable is the yield of all split products.The yield of cracked product of cracking furnace predictive model calculates the numerical value of corresponding output variable according to input variable, that is:
y
i＝X(F，S，XOT，COT，DEN，ASTM，PONA)
Y wherein
i-expression split product component yield
The F-inlet amount
The S-thinning ratio
XOT-is across the section temperature
The COT-coil outlet temperature
DEN-density
The ASTM-ASTM boiling range
The PONA-group composition
3. gather GK-V type industrial pyrolysis furnace Skellysolve A yield data
The petroleum naphtha physical property of GK-V type pyrolyzer sees Table 4.Keeping inlet amount is that 24.788 tons/hour, water-oil ratio are 0.633 constant, respectively COT is adjusted into 802 ℃, 810 ℃, 815 ℃, 831 ℃, 840 ℃, the work of taking a sample online simultaneously, the weight of metering gaseous stream and liquid phase stream, analyze molar content or the mass content of the Skellysolve A in gas phase and liquid phase stream, calculate the Skellysolve A yield data (seeing table 5 for details) of industrial pyrolysis furnace actual motion by material balance.
Table 4 petroleum naphtha physical property
The Skellysolve A yield of table 5 GK-V pyrolyzer cracking naphtha
| COT(℃) | 802 | 810 | 815 | 831 | 840 |
| Yield (wt%) | 0.68 | 0.56 | 0.53 | 0.34 | 0.23 |
4. Model Checking
Bring GK-V type industrial pyrolysis furnace service data into predictive model and carry out the Skellysolve A yield calculating of a plurality of COT temperature, obtain the COT temperature relatively more identical with industrial data, calculation result sees table 6 for details.By contrast table 5 and table 6 as can be known, calculated value and actual motion value data deviation are less than in 10%, and calculated value and actual motion value all reduce along with the rising of COT.This shows, the COT displays temperature of industrial pyrolysis furnace actual motion is than low 10 ℃ of predictive model, and therefore the COT in predictive model subtracts 10 ℃ of check predictive models.
The Skellysolve A yield that table 6 predictive model calculates
| COT(℃) | Yield (wt%) |
| 812 | 0.70 |
| 820 | 0.58 |
| 825 | 0.54 |
| 841 | 0.36 |
| 850 | 0.25 |
5. set up GK-V naphtha cracking stove split product value maximization model
Take naphtha cracking stove split product predictive model as the basis, adopt the mathematical method of average search method, under the constant condition of inlet amount, water-oil ratio, XOT, petroleum naphtha physical property (proportion, ASTM boiling range, group composition), split product price, in the COT of industrial pyrolysis furnace normal operation range, search out COT corresponding to split product total value maximum value, that is:
V
max＝max(V(m))
Wherein, F-inlet amount
The S-thinning ratio
The X-yield of cracked product
XOT-is across the section temperature
The COT-coil outlet temperature
DEN-density
The ASTM-ASTM boiling range
The PONA-group composition
P
j-split product component price
V (m)-split product total value
V
max-split product total value maximum value
6. be worth and optimize
Operation according to the GK-V naphtha cracking stove split product value maximization model optimization pyrolyzer of setting up.The physical property of GK-V pyrolyzer cracking naphtha sees Table 4, and the pyrolyzer service data sees Table 1.In split product price (seeing Table 3), petroleum naphtha physical property, service data (inlet amount, thinning ratio, XOT see Table 1) input GK-V cracked product of cracking furnace value maximization model, calculation result is seen Fig. 1.
As shown in Figure 1, under the aforesaid operations condition and under the split product price condition, the true COT of GK-V cracked product of cracking furnace value maximization is 849 ℃, the petroleum chemicals total value of producing is 100019.7 yuan/hour, and the highest true COT of petroleum naphtha normal running is 845 ℃, therefore select 845 ℃ to be the COT temperature of value optimization, and the temperature that pyrolyzer operation COT shows is 835 ℃, the petroleum chemicals total value of its production is 99974.52.The common COT service temperature of GK-V type pyrolyzer is 825 ℃, and actual real operation COT temperature is 835 ℃, and the petroleum chemicals total value of production is 99596.63 yuan/hour.Optimize by value, GK-V industrial pyrolysis furnace COT brings up to 835 ℃ by 825 ℃, and petroleum chemicals (split product) total value that pyrolyzer is produced has increased by 1103.661 yuan/hour.
Claims (15)
1. the construction process of a petroleum naphtha industrial pyrolysis furnace value maximization model, it is characterized in that, in the petrochemical enterprise take industrial pyrolysis furnace as main production plant, set up petroleum naphtha industrial pyrolysis furnace value maximization model and be used for optimizing the pyrolyzer operation, make the petroleum chemicals total value of petroleum naphtha industrial pyrolysis furnace production reach maximum, described method comprises the following steps:
(1) set up predictive model: based on the naphtha steam cracking experimental data, utilize Mathematical Modeling Methods to set up petroleum naphtha industrial pyrolysis furnace yield of cracked product predictive model, can calculate yield of cracked product according to petroleum naphtha physical property, industrial pyrolysis furnace operational condition;
(2) gather the Skellysolve A yield data: under the constant condition of petroleum naphtha physical property, inlet amount, quantity of steam, at industrial pyrolysis furnace coil outlet temperature COT) in normal operation range, gather the Skellysolve A yield data of industrial pyrolysis furnace actual motion by adjusting COT;
(3) check: utilize the Skellysolve A yield data of the industrial pyrolysis furnace that is obtained by step (2) to check the predictive model that is obtained by step (1), make the data of the calculated value of predictive model of check and industrial pyrolysis furnace actual motion basically identical;
(4) set up naphtha cracking stove split product value maximization model: set up naphtha cracking stove split product value maximization model according to the predictive model that step (3) obtains, can utilize split product price, petroleum naphtha physical property, pyrolyzer service data to calculate the pyrolyzer operational condition that split product is the total value maximum of petroleum chemicals.
2. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described petrochemical enterprise is the petroleum chemicals manufacturing enterprise take pyrolyzer as main production plant, and production equipment mainly comprises pyrolyzer, separation or retrieving arrangement, polyolefin resin device.
3. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described petroleum naphtha physical property comprises density, grace formula distillation boiling range (ASTM), group composition (PONA), hydrogen richness or carbon content or ratio of carbon-hydrogen, carboloy residue, molecular weight, correlation index (BMCI) and refractive index, is perhaps that detailed composition and the content thereof of petroleum naphtha consists of.
4. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described split product mainly comprises hydrogen, carbon monoxide, carbonic acid gas, ethane, ethene, acetylene, propane, propylene, propine, propadiene, butane, butylene, divinyl, benzene,toluene,xylene, ethylbenzene, vinylbenzene, pyrolysis gasoline, Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO.
5. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described petroleum chemicals are petrochemical enterprise external disclosure product solds on market, mainly comprise ethene, propylene, divinyl, benzene,toluene,xylene, polyolefin resin, rubber, ethylene glycol, polyester, chemical fibre, oxyethane, propylene oxide, gasoline, diesel oil, oil fuel, LPG.
6. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described Skellysolve A yield data is to keep under the constant condition of petroleum naphtha physical property, inlet amount, water-oil ratio at industrial pyrolysis furnace, within pyrolyzer COT normal operation range, by adjusting temperature, at least three Skellysolve A data that the COT temperature obtains.
7. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 6, is characterized in that, described adjustment temperature is preferably five COT temperature.
8. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, the method of described model tuning is utilized the Skellysolve A yield under predictive model calculating industrial pyrolysis furnace operational condition, by the comparing calculation value and and industrial service data, adjust the COT in predictive model, make the data of Skellysolve A yield that predictive model calculates and industrial actual motion basically identical.
9. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 8, it is characterized in that, described data are basically identical be the calculated value of Skellysolve A yield and actual industrial pyrolyzer service data deviation in 10%, and the numerical value change rule is consistent.
10. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described split product price is the split product component by the market value of the production petroleum chemicals of petrochemical unit, is zero through the split product component price that petrochemical unit is consumed or petroleum chemicals are produced in absorption or recycle and failing; For acetylene, propine and propadiene, they generate ethene and ethane, propylene and propane through hydrogenation, its price is the transformation efficiency of ethene and propylene price and hydrogenation catalyst and product optionally, lacking the hydrogenation catalyst transformation efficiency and optionally under condition, its price can be considered the price of ethene and propylene; Form a kind of split product component of petroleum chemicals through petrochemical production device, the petroleum chemicals price that its price forms for this component is as hydrogen, Pyrolysis gas oil PGO, Pyrolysis fuel oil PFO; Form the split product component of multiple petroleum chemicals through petrochemical production device, its price can be calculated in the following manner:
P wherein
iThe price of expression split product component, x
jThe market value of expression petroleum chemicals, w
jRepresent that this split product component is for the production of the shared part by weight of these petroleum chemicals.
11. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 1, it is characterized in that, described naphtha cracking stove split product value maximization model is take naphtha cracking stove yield of cracked product predictive model as the basis, physical property, pyrolyzer service data, split product price according to petroleum naphtha, in pyrolyzer operational condition restriction range, adopt mathematical method to search for or calculate the operational condition of split product total value maximum.
12. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 11, it is characterized in that, described petroleum naphtha industrial pyrolysis furnace service data is by naphtha feed amount, dilution steam generation amount or thinning ratio, across section temperature (XOT) formation, and being worth the operational condition of optimizing is coil outlet temperature (COT).
13. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 11 is characterized in that described mathematical method comprises searching method.
14. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 11, it is characterized in that, described naphtha cracking stove yield of cracked product predictive model is based on the naphtha steam cracking testing data, the mathematical model that adopts Mathematical Modeling Methods to set up can be calculated yield of cracked product according to petroleum naphtha physical property and pyrolyzer operational condition.
15. the construction process of a kind of petroleum naphtha industrial pyrolysis furnace value maximization model according to claim 14, it is characterized in that, described Mathematical Modeling Methods comprises SVMs (SVM), artificial neural network, Multiple Non Linear Regression, genetic algorithm.
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