CN1285707C - Naphtha optimized utilization method - Google Patents
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- CN1285707C CN1285707C CN 200510027614 CN200510027614A CN1285707C CN 1285707 C CN1285707 C CN 1285707C CN 200510027614 CN200510027614 CN 200510027614 CN 200510027614 A CN200510027614 A CN 200510027614A CN 1285707 C CN1285707 C CN 1285707C
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Abstract
The present invention discloses a method for optimizing the utilization of naphtha. By an adsorptive separation process, the naphtha is divided into a desorbing oil product rich in normal hydrocarbons and an absorbing excess oil product rich in non-normal hydrocarbons, wherein the desorbing oil is used as a high-grade steam cracking raw material or is cut into narrow fractions by rectification to prepare a reagent and a high-grade solvent oil product; the absorbing excess oil is used as a high-grade catalytic reforming raw material or a component for proportioning clean high-octane gasoline. According to the situations of the quantity of naphtha resources and market demands, the adsorptive separation technology of the naphtha is coupled with a subsequent processing technology to realize the reasonable allocation of resources. Compared with similar methods, the method of the present invention has the advantages of convenient process, low energy consumption, strong adaptability, etc.
Description
Technical field
The optimized Separation that the present invention relates to a kind of petroleum naphtha is utilized method, is specifically related to a kind of molecular sieve adsorption that adopts and separates that the reorganization of normal paraffin and isoparaffin utilizes method in the petroleum naphtha.
Background technology
Petroleum naphtha is meant in the crude oil and begins distilled temperature (being initial boiling point) to the lighting end 200 ℃ (or 180 ℃) from air distillation that its hydrocarbon composition carbon number distribution is at C
4～C
10Between.Mainly consist of normal paraffin, isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons, wherein the content of normal paraffin is 20%-50%, and non-positive structure hydrocarbon content is 50%-80%.By the ADSORPTION IN A FIXED BED sepn process, obtain two kinds of products: inhale excess oil and desorption oil.Desorption oil is the oil product that is rich in normal paraffin, C
4～C
10The content of positive structure hydrocarbon is 80%-100%, and the content of non-positive structure hydrocarbon (comprising isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons) is 0%-20%.Inhaling excess oil is the oil product that is rich in non-positive structure hydrocarbon, and the content of non-positive structure hydrocarbon (comprising isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons) is 90%-100%, and positive structure hydrocarbon content is 0%-10%.
Traditional refining of petroleum flow process is taked the cut management Strategy, promptly according to the distillation characteristics of material the mixture in the crude oil is cut into the product of different boiling ranges, gives corresponding use according to the character of product then.Resource often can not obtain reasonable use the most under this management mode.Such as, the purposes of petroleum naphtha in petroleum refining industry mainly contains three kinds at present: (1) produces stop bracket gasoline or aromatic hydrocarbon product as the raw material of catalytic reforming; (2) as the cracking of ethylene raw material; (3) be used for the allotment of vehicle fuel gasoline, but can run into the underproof problem of vapour pressure, contain a large amount of normal paraffins in the petroleum naphtha simultaneously, octane value is very low.
Consider from building resource-conserving and ecological environment-friendly type social requirement how to optimize that to utilize naphtha resource be to be worth the further problem of research.
Because crude oil in China lays particular stress on, the yield of petroleum naphtha is lower, and the problem that exists cracking of ethylene and catalytic reforming to contend over raw materials for a long time is in order to satisfy the raw material supply of ethylene industry, the reformer under-capacity operation of many refineries as far as possible.In order to improve the utilising efficiency of petroleum naphtha, alleviate this contradiction, the molecule management mode more and more demonstrates its superiority.The molecule management is that the separating mixture component is made the best use of everything to reach according to the specific requirement of different purposes to products molecule.For petroleum naphtha, thinking according to the molecule management, isolate wherein normal paraffin as high-quality cracking of ethylene raw material or cut into close-cut fraction and produce the solvent oil product, non-positive structure part (mainly being isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons) is as high-quality catalytic reforming raw material or stop bracket gasoline blend component.
In preparing ethylene by steam cracking technology, expense of raw materials accounts for 60%～80% of ethylene production total cost.As cracking stock, the yield of ethene of cracking technology is the highest with normal paraffin.Present good linear dependence between the BMCI of yield of ethene and cracking stock (Bureau of Mines Correlation Index, the correlation index) value.The BMCI value of hydro carbons is more little, and the expression fatty is strong more, and then the yield of ethene is high more.The BMCI value of normal paraffin approaches zero, therefore is best cracking of ethylene raw material.
Simultaneously, removed the oil product arene underwater content height of normal paraffin, the catalytic reforming raw material of doing preferably.The normal paraffin dehydrocyclization becomes the speed of reaction of aromatic hydrocarbons very slow, and transformation efficiency is low.Can add the carrying out of fast response though improve temperature of reaction, but can aggravate catalyst junction carbon, the production cycle is shortened, also higher to the requirement of operation and equipment.The severity that the minimizing of normal paraffin content will significantly help improving aromatics yield and reduce reaction conditions in the reformer feed.
The added value of solvent oil is far above fuel gasoline, but the refining bottleneck that often becomes the production of restriction solvent oil of solvent oil.Solvent oil the most defective phenomenon of normal appearance be that aromaticity content exceeds standard, boiling range is wide and flash-point defective etc., treating process tends to make the solvent oil yield to descend, production cost rises.The desorption oil of fractionation by adsorption is rich in normal paraffin, aromatic free, and the relative volatility between each component is big, is easy to be separated by the means of rectifying, produces reagent products such as high-quality solvent oil product or polymerization-grade normal hexane, the high-purity normal hexane of pharmaceutical grade, normal heptane.
The octane value of gasoline and its hydrocarbon composition are in close relations.Aromatic hydrocarbon and isoparaffin octane value are the highest, can reach more than 100, and alkene and naphthenic hydrocarbon take second place, and normal paraffin is minimum, are zero as normal heptane, and octane is a negative value.Normal paraffin content height in the petroleum naphtha, octane value is lower, usually about 60.After normal paraffin in the gasoline removed, the octane value of inhaling excess oil had raising by a relatively large margin, can be used as the stop bracket gasoline blend component.
Separating the most economical and effective means of normal paraffin from petroleum naphtha is to utilize the shape absorption principle of selecting of 5A molecular sieve to carry out fractionation by adsorption.The mean pore size in 5A microporous molecular sieve road is 5.1 , and the diameter of normal paraffin molecule is about 4.9 , can enter in the microporous molecular sieve road, but not the molecular diameter of positive structure hydrocarbon is greater than this, then can not be adsorbed.Because the aperture homogeneous of molecular sieve pore passage, separation efficiency is very high.
English Patent 2119398 openly comes selective adsorption to separate positive isomeric hydrocarbon and sulphur compound with the 5A molecular sieve, and what emphasize is that certain specific structure of molecular sieve is used for adsorbing positive structure hydrocarbon and repels non-positive structure hydrocarbon, and has emphasized the centrifugation to sulfide.The disclosed molecular sieve crystal that is to use in this patent is of a size of 1500 dusts to 0.5 micron, is not suitable for large-scale industrial application.
H.J.Bieser is at United States Patent (USP) 4006197, and S.Kulprathipanja discloses employing continuous simulation moving-bed (SMB) adsorption separating method respectively at United States Patent (USP) 4455444 and has been used for the normal paraffin recovery.D.B.Broughton also discloses use in United States Patent (USP) 3291726 simulation moving-bed, separates normal paraffin from petroleum derived fraction.Yet the molecular sieve simulated mobile bed separation process is the liquid phase separation that adopts, and liquid phase separation desorption efficient is low, back-mixing needs to increase preceding fractionation and aftercut device easily, and not only technology is loaded down with trivial details, process cost height, and simulation moving-bed and rotary valve equipment complexity, facility investment is big.
T.D. the ethylene production that passes through steam cracking of normal structure hydrocarbon has been described at Chinese patent CN 1476474A in welfare and S.W. Sohne, and the feedstream that adds whole device in this method is fractionated into the second stage that comprises other raw materials that generates C5 stream and feeding adsorption separation device and flows.C5 stream is used as desorbing agent in fractionation by adsorption, and this logistics has a large portion and enters residual oil absorber, influences product purity.Mention the product that will be rich in positive structure hydrocarbon in this patent and be used as the cracking of ethylene raw material, the product that will be rich in non-positive structure hydrocarbon is as catalytic reforming raw material.This is a kind of improvement that naphtha resource is utilized.Yet above-mentioned patent is disclosed all is by the method recovery suction excess oil of rectifying and the desorbing agent in the desorption oil, the energy consumption of rectifying even surpass adsorption process itself, cause economy to reduce, thereby seriously descend by the effect of simulated moving bed adsorption separating technology raising oil product utilising efficiency.
The optimization that Chinese patent CN 1621497A discloses a kind of petroleum naphtha utilizes method, this technology adopts the method for extracting and separating, petroleum naphtha is separated into raffinates oil and extract oil out, the extraction oil that is obtained is as the reformer raw material, raffinate oil as the ethylene cracker raw material, because the selective problems of extraction process, it is difficult to reach the clear level of cutting apart of molecule management, in the time of will raffinating oil as the cracking of ethylene raw material, owing to raffinate oil is the mixture of normal paraffin and isoparaffin, and yield of ethene is starkly lower than the raw material based on normal paraffin.
Summary of the invention
The technical issues that need to address of the present invention are that the optimization that discloses a kind of petroleum naphtha utilizes method, to overcome the defective that prior art exists, with the suitable oil of petroleum naphtha then alkene, suitable Fang Zefang of oil, suitable alkene then,, realize improving the utilising efficiency of naphtha resource by the molecule management.
Method of the present invention comprises the steps:
(1) the petroleum naphtha heating is vaporized post-heating to 180-450 ℃, feeding is filled with the ADSORPTION IN A FIXED BED knockout tower of 5A molecular sieve, normal paraffin in the petroleum naphtha is attracted in the microchannel of bed molecular sieve, suction excess oil after the adsorption treatment flows out the ADSORPTION IN A FIXED BED knockout tower, be cooled to 0～150 ℃, inhale excess oil and be condensed, liquefaction, the suction excess oil of non-positive structure hydrocarbon is rich in acquisition, and non-positive structure hydrocarbon weight content is 90～100% in the suction excess oil;
Gaseous state naphtha feed air speed is 20-1000h
-1, adsorption time is 5-100min;
Term " air speed " is defined as: fluid advances the volumetric flow rate of reactor and the ratio of reactor volume;
Term " adsorption time " is defined as: in an absorption/desorption circulation, and the time of when petroleum naphtha begins to be fed to the bed adsorption penetration, being experienced;
In order to improve the utilising efficiency of molecular sieve in the bed, the ADSORPTION IN A FIXED BED knockout tower is a right cylinder, and the aspect ratio that is filled with the fixed bed of 5A molecular sieve is 2～20: 1, preferred aspect ratio 3～15: 1;
The desorbing agent feeding ADSORPTION IN A FIXED BED knockout tower that with temperature is 180-450 ℃ then carries out desorption, the desorbing agent that carries normal paraffin flows out the ADSORPTION IN A FIXED BED knockout tower, be cooled to 0～150 ℃, normal paraffin is condensed, liquefy, and separate voluntarily, obtain to be rich in the desorption oil of positive structure hydrocarbon with desorbing agent, the weight content of positive structure hydrocarbon is 80～100% in the desorption oil, and desorbing agent recycles;
Desorbing agent charging air speed is 5-600h
-1, desorption time is 5-100min;
Said desorbing agent is selected from nitrogen, hydrogen, ammonia steam, water vapor, carbonic acid gas, methane gas, Sweet natural gas or refinery gas, and the desorbing agent weight consumption is the 0.5%-80% of petroleum naphtha;
Described petroleum naphtha is virgin naphtha, hydrocracking petroleum naphtha or hydrocracking petroleum naphtha.
(2) desorption oil enters the ethene steam cracking device as the cracking of ethylene raw material, and cracking generates ethene, the third rare and divinyl.Operational condition is as follows: the heater outlet temperature of ethene steam cracking is 700-940 ℃, the residence time is 0.15-0.9 second, dilution steam generation is 0.2-1.0 with desorption oil quality ratio, yield of ethene is 39～50%, improve the 9-17 percentage point than prior art, for identical ethylene production capacity, the expense that can economize in raw materials 20%-30%, and have advantages such as ethylene concentration improves in the cracked gas, follow-up alkene separating energy consumption reduces and the coking situation of boiler tube is obviously improved, cycle of operation prolongation simultaneously;
Or desorption oil enters rectifier unit, cut into close-cut fraction and then can produce the high-quality solvent oil product (6# solvent oil, NY-190 solvent oil) or the reagent (analytical pure normal hexane, normal heptane and octane) of the multiple trade mark, can meet or exceed the quality index of similar products at home and abroad.
(3) inhale excess oil and enter catalytic reforming unit as catalytic reforming raw material, obtain aromatic hydrocarbon product, operational condition is as follows: temperature of reaction is 350-550 ℃, and reaction pressure is 0.2-3.5Mpa, hydrogen and the mol ratio 1-8 that inhales excess oil; Aromatics yield is 65～85%, improves 12-25 percentage point than corresponding petroleum naphtha;
Or inhale the blend component of excess oil as the high-octane rating clean gasoline, octane value improves 20 more than the unit than corresponding petroleum naphtha.
The pyrolyzer of said ethene steam cracking can adopt prior art, as SH type and CBL type pyrolyzer.Because with the desorption oil that is rich in normal paraffin is the ethane cracking furnace charging, yield of ethene and triolefin total recovery have significantly raising than existing ethylene raw petroleum naphtha.
Said catalytic reforming reactor can adopt prior art, as S.R device and CCR device.Because to be rich in the high suction excess oil of non-positive structure hydrocarbon arene underwater content is catalytic reforming raw material, aromatics yield is significantly increased than existing reformer feed petroleum naphtha.
Further, in traditional fractionation by adsorption flow process, sorbent material in the fixed bed single or in parallel often can not be fully used, in order to improve the utilising efficiency of molecular sieve in the bed, method of the present invention can be provided with a plurality of ADSORPTION IN A FIXED BED knockout towers, a plurality of ADSORPTION IN A FIXED BED knockout towers are in parallel or/and be connected in series by pipeline, with the parallel connection that realizes adsorption separation process or/and serial operation preferably is provided with 2～4 ADSORPTION IN A FIXED BED knockout towers; Simultaneously because for a certain adsorption tower, the desorption oil concentration descends with the prolongation of desorption time in the desorption gas, replace serial operation by multitower, can partly replace fresh desorbing agent that another adsorption tower is carried out desorption with the desorption gas of low desorption oil concentration, thereby can reduce the consumption of 30% fresh desorbing agent on the whole.
The present invention is owing to adopt 5A molecular sieve ADSORPTION IN A FIXED BED to separate, and adopt petroleum naphtha with gaseous state by bed and noncondensable gas as desorbing agent, have not only than other patented technologies that technical process is short, easy and simple to handle, energy consumption is low, adaptability is strong; And device is simple, and the equipment one-time investment can reduce by 50% with first-class advantage.Especially adopt noncondensable gas to make desorbing agent, and desorption is after condensation phase-splitting voluntarily, desorption oil cooling lime setization, desorption gas is a gas still, thereby realizes separating in gas-liquid separator, and promptly desorption oil separates with desorbing agent simply, can realize separating voluntarily, desorbing agent can cycling and reutilization; This external cause adopts the desorbing gas agent, inhale and do not contain desorbing agent when excess oil leaves adsorption bed, need not to inhale separating of excess oil and desorbing agent, the inventive method can reduce the about 20-30% of separation costs, and desorbing agent convenient sources of the present invention, cheap, do not need special processing treatment, also reduced the desorption cost.
The inventive method, adsorption process and desorption process can change rapidly and hocket.Technology of the present invention can also realize the reasonable resources configuration with separating technology and subsequent machining technology coupling.
The present invention is directed to the singularity of this system, can alternately switch by absorption, middle oil cutting and three processes of desorption and carry out, also can alternately switch by absorption and two processes of desorption.
The present invention carries out fractionation by adsorption with petroleum naphtha, and adopts different processing treatment schemes to inhaling excess oil with desorption oil.This technology with class methods relatively, have advantages such as simple flow, energy consumption is low, adaptability is strong.The desorbing agent convenient sources does not need special processing treatment, and desorption oil separates by the condensation phase-splitting voluntarily with desorbing agent, the desorbing agent recycle.Inhale in the excess oil and do not contain desorbing agent, need not to inhale separating of excess oil and desorbing agent.
Comparatively speaking, the liquid phase separation that original molecular sieve simulated mobile bed separation process adopts, easy back-mixing, fractionation and aftercut device before needing to increase, the energy consumption height, technology is loaded down with trivial details, and simulation moving-bed and rotary valve equipment complexity, and facility investment is big.
By above-mentioned disclosed technical scheme as seen, method of the present invention can significantly improve the utilising efficiency of petroleum naphtha, and provide high quality raw material for downstream complete processing (cracking of ethylene and catalytic reforming), blend component or high-quality solvent wet goods cleaning chemistry product that simultaneously can coproduction high-octane rating clean gasoline.According to naphtha resource quantity and market requirement situation, can realize the reasonable resources configuration neatly with petroleum naphtha adsorptive separation technology and subsequent machining technology coupling.
Description of drawings
Fig. 1 is the schema of method of the present invention.
Embodiment
Referring to Fig. 1, method of the present invention comprises the steps:
The gaseous state petroleum naphtha is fed the first ADSORPTION IN A FIXED BED knockout tower 1 that is filled with 5A molecular sieve 2, normal paraffin in the petroleum naphtha is attracted in the microchannel of bed molecular sieve, suction excess oil after the adsorption treatment flows out ADSORPTION IN A FIXED BED knockout tower 1, cooling is inhaled excess oil and is condensed, liquefaction, the suction excess oil of non-positive structure hydrocarbon is rich in acquisition, send into catalytic reforming unit 3, obtain reformate, as benzene, toluene and dimethylbenzene;
By switching valve 6, the gaseous state petroleum naphtha is fed the second ADSORPTION IN A FIXED BED knockout tower 5 that is filled with 5A molecular sieve 2 then;
Simultaneously, desorbing agent is fed ADSORPTION IN A FIXED BED knockout tower 1 carry out desorption, the desorbing agent that carries normal paraffin flows out ADSORPTION IN A FIXED BED knockout tower 1, cooling, and normal paraffin is condensed, liquefaction, the desorption oil of positive structure hydrocarbon is rich in acquisition, sends into to enter ethene steam cracking device 4, obtains the cracking product, as ethene, the third rare and divinyl, desorbing agent recycles;
The working method of the second ADSORPTION IN A FIXED BED knockout tower 2 is identical with the first ADSORPTION IN A FIXED BED knockout tower 1.
The boiling range that contains mass concentration and be 26.50% normal paraffin is 50-180 ℃ of virgin naphtha vaporization and is heated to 200 ℃ that the feed rate of petroleum naphtha is 6kg/ hour; By temperature is 200 ℃ fixed bed molecular sieve bed, filling 20kg5A molecular sieve in the bed, and bed height is 100cm, aspect ratio is 6: 1, and adsorption process was carried out 30 minutes, obtains 2.11kg after the condensation and inhales excess oil, yield is 70.4%, and normal paraffin content is 0.30% in the suction excess oil.
After adsorption process finishes, with nitrogen purging bed desorption, nitrogen temperature is 400 ℃, consumption is 1% of a petroleum naphtha treatment capacity, and desorption time is 1 minute, the desorption air-flow that comes out from bed, by condenser and gas-liquid separator, obtain the middle oil of 0.13kg, yield is 4.3%, and normal paraffin concentration is 40.1% in the middle oil.
After middle oily cutting process finishes, with nitrogen purging bed desorption, nitrogen temperature is 400 ℃, consumption is 29% of a petroleum naphtha treatment capacity, and desorption time is 29 minutes, the desorption air-flow that comes out from bed, by condenser and gas-liquid separator, obtain 0.74kg desorption oil, yield is 24.7%, and normal paraffin content is 99.5% in the desorption oil.Nitrogen circulation is used.
Desorption oil is as the cracking of ethylene raw material, and cracking condition is: the residence time is 0.40s, and the dilution steam generation ratio is 0.6, and the cracking temperature out is 840 ℃.Compare with feed naphtha, gas recovery ratio brings up to 94.8% by 85.8%, and yield of ethene brings up to 43.2% from 31.4%, and ethene, propylene and divinyl triolefin total recovery bring up to 64.5% from 52.1%.
Desorption oil is through precise rectification tower rectifying, and producing normal hexane reagent quality concentration is 99.7%, and producing normal heptane reagent quality concentration is 99.5%, and producing octane reagent quality concentration is 99.8%.
The operational condition of catalytic reforming unit is that the temperature of reaction of catalytic reforming is 450 ℃, and reaction pressure is 1.5Mpa, hydrogen/oil mol ratio 2.The aromatics yield of suction excess oil is compared from 55.4% with corresponding raw material petroleum naphtha and is elevated to 70.5%.
The octane value of inhaling excess oil is compared with the raw material petroleum naphtha from 65 and is brought up to 86, has improved 21 units.
The boiling range that contains mass concentration and be 26.50% normal paraffin is 60-180 ℃ of virgin naphtha vaporization and is heated to 200 ℃ that the feed rate of petroleum naphtha is 6kg/ hour; By temperature is 200 ℃ fixed bed molecular sieve bed, filling 20kg5A molecular sieve in the bed, and bed height is 100cm, aspect ratio is 6: 1, and adsorption process was carried out 30 minutes, obtains 2.10kg after the condensation and inhales excess oil, yield is 70.3%, and normal paraffin content is 0.30% in the suction excess oil.
After adsorption process finishes, with nitrogen purging bed desorption, nitrogen temperature is 400 ℃, consumption is 10% of a petroleum naphtha treatment capacity, and desorption time is 30 minutes, the desorption air-flow that comes out from bed, by condenser and gas-liquid separator, obtain desorption oil 0.87kg, yield is 29.1%, and normal paraffin content is 90.4% in the desorption oil.Nitrogen circulation is used.
Desorption oil is as the cracking of ethylene raw material, and cracking condition is: the residence time is 0.30s, and the dilution steam generation ratio is 0.5, and the cracking temperature out is 800 ℃.Compare with feed naphtha, gas recovery ratio brings up to 92.9% by 85.8%, and yield of ethene brings up to 42.7% from 31.4%, and ethene, propylene and divinyl triolefin total recovery bring up to 64.6% from 52.0%.
The operational condition of catalytic reforming unit is that the temperature of reaction of catalytic reforming is 500 ℃, and reaction pressure is 2.5Mpa, hydrogen/oil mol ratio 5.The aromatics yield of suction excess oil is compared from 55.7% with petroleum naphtha and is elevated to 71.3%.
The octane value of inhaling excess oil is compared with the raw material petroleum naphtha from 65 and is brought up to 86, has improved 21 units.
Embodiment 3
The boiling range that contains mass concentration and be 39.43% normal paraffin is 50-200 ℃ of virgin naphtha vaporization and is heated to 400 ℃ that the feed rate of petroleum naphtha is 10kg hour; By temperature is 400 ℃ fixed bed molecular sieve bed, filling 30kg5A molecular sieve in the bed, and bed height is 200cm, aspect ratio is 15: 1, and adsorption process was carried out 30 minutes, obtains 2.86kg after the condensation and inhales excess oil, yield is 57.2%, and normal paraffin content is 1.2% in the suction excess oil.
After adsorption process finishes, with nitrogen purging bed desorption, nitrogen temperature is 350 ℃, consumption is 10% of a petroleum naphtha treatment capacity, and desorption time is 40 minutes, the desorption air-flow that comes out from bed, by condenser and gas-liquid separator, obtain desorption oil 2.12kg, yield is 42.3%, and normal paraffin content is 91.6% in the desorption oil.Nitrogen circulation is used.
Desorption oil is as the cracking of ethylene raw material, and cracking condition is: the residence time is 0.80s, and the dilution steam generation ratio is 0.3, and the cracking temperature out is 900 ℃.Compare with feed naphtha, gas recovery ratio brings up to 94.9% by 86.3%, and yield of ethene brings up to 43.8% from 32.5%, and ethene, propylene and divinyl triolefin total recovery bring up to 64.5% from 54.5%.
The operational condition of catalytic reforming unit is that the temperature of reaction of catalytic reforming is 380 ℃, and reaction pressure is 3.0Mpa, hydrogen/oil mol ratio 5.The aromatics yield of suction excess oil is compared from 47.4% with petroleum naphtha and is elevated to 66.8%.
The octane value of inhaling excess oil is compared with the raw material petroleum naphtha from 61 and is brought up to 85, has improved 24 units.
The boiling range that contains mass concentration and be 35.63% normal paraffin is 50-200 ℃ of virgin naphtha vaporization and is heated to 310 ℃ that the feed rate of petroleum naphtha is 15kg/ hour; By temperature is 310 ℃ fixed bed molecular sieve bed, filling 40kg5A molecular sieve in the bed, and bed height is 100cm, aspect ratio is 5: 1, and adsorption process was carried out 20 minutes, charging 5kg, obtain 3.06kg after the condensation and inhale excess oil, yield is 61.2%, and normal paraffin content is 0.8% in the suction excess oil.
After adsorption process finishes, with nitrogen purging bed desorption, nitrogen temperature is 310 ℃, consumption is 40% of a petroleum naphtha treatment capacity, is 30 minutes between desorption time, the desorption air-flow that comes out from bed, by condenser and gas-liquid separator, obtain desorption oil 1.91kg, yield is 38.2%, and normal paraffin content is 92.0% in the desorption oil.Nitrogen circulation is used.
Desorption oil is as the cracking of ethylene raw material, and cracking condition is: the residence time is 0.80s, and the dilution steam generation ratio is 0.6, and the cracking temperature out is 900 ℃.Obtain ethene 0.81kg, ethene, propylene and divinyl triolefin total amount 1.26kg.
To inhale excess oil and advance catalytic reforming unit, operational condition is that the temperature of reaction of catalytic reforming is 450 ℃, and reaction pressure is 2.5Mpa, hydrogen/oil mol ratio 2.Obtain aromatic hydrocarbon product 2.02kg.
Comparative Examples 1
According to traditional work flow, it is that the boiling range of 35.63% normal paraffin is a 50-200 ℃ of virgin naphtha that 5kg is contained mass concentration, is divided into two portions of 1.90kg and 3.10kg, respectively as cracking of ethylene raw material and catalytic reforming raw material.
1.90kg contain mass concentration and be the boiling range of 35.63% normal paraffin and be 50-200 ℃ of virgin naphtha as the cracking of ethylene raw material, cracking condition is: the residence time is 0.80s, the dilution steam generation ratio is 0.6, and the cracking temperature out is 900 ℃.Obtain ethene 0.63g, ethene, propylene and divinyl triolefin total amount 1.04kg.
3.10kg containing mass concentration and be the boiling range of 35.63% normal paraffin is that 50-200 ℃ of virgin naphtha advances catalytic reforming unit, operational condition is that the temperature of reaction of catalytic reforming is 450 ℃, and reaction pressure is 2.0Mpa, hydrogen/oil mol ratio 2.Obtain aromatic hydrocarbon product 1.55kg.
By embodiment 4 and Comparative Examples 1 as can be known, to contain mass concentration be that the boiling range of 35.63% normal paraffin is that 50-200 ℃ of virgin naphtha directly sees Table 1 as the product production of cracking of ethylene and catalytic reforming raw material and application this patent integrated optimization technology to 5kg.
Table 1
Claims (7)
1. the optimization of a petroleum naphtha utilizes method, it is characterized in that, comprises the steps:
(1) the petroleum naphtha heating is vaporized post-heating to 180-450 ℃, feed the ADSORPTION IN A FIXED BED knockout tower that is filled with the 5A molecular sieve, obtain to be rich in the suction excess oil of non-positive structure hydrocarbon; The weight content of inhaling non-positive structure hydrocarbon in the excess oil is 90～100%;
The desorbing agent feeding ADSORPTION IN A FIXED BED knockout tower that with temperature is 180-450 ℃ then carries out desorption, obtains to be rich in the desorption oil of positive structure hydrocarbon, and the weight content of positive structure hydrocarbon is 80～100% in the desorption oil;
(2) desorption oil enters the ethene steam cracking device or desorption oil enters rectifier unit, cuts into close-cut fraction and produces solvent oil;
(3) inhaling excess oil enters catalytic reforming unit or inhales the blend component of excess oil as the high-octane rating clean gasoline;
Gaseous state naphtha feed air speed is 20-1000h
-1Adsorption time is 5-100min; Desorbing agent charging air speed is 5-600h
-1Desorption time is 5-100min;
The heater outlet temperature of ethene steam cracking is 700-940 ℃, and the residence time is 0.15-0.9 second, and dilution steam generation is 0.2-1.0 with desorption oil quality ratio;
Inhale excess oil and enter catalytic reforming unit, temperature of reaction is 350-550 ℃, and reaction pressure is 0.2-3.5Mpa, hydrogen and the mol ratio 1-8 that inhales excess oil.
2. method according to claim 1 is characterized in that the ADSORPTION IN A FIXED BED knockout tower is a right cylinder, and the aspect ratio that is filled with the fixed bed of 5A molecular sieve is 2～20: 1.
3. method according to claim 1 is characterized in that, said desorbing agent is selected from nitrogen, hydrogen, ammonia steam, water vapor, carbonic acid gas, methane gas, Sweet natural gas or refinery gas, and the desorbing agent weight consumption is the 0.5%-80% of petroleum naphtha.
4. method according to claim 1 is characterized in that, a plurality of ADSORPTION IN A FIXED BED knockout towers are set, and a plurality of ADSORPTION IN A FIXED BED knockout towers are in parallel or/and be connected in series by pipeline.
5. method according to claim 4 is characterized in that, 2～4 ADSORPTION IN A FIXED BED knockout towers are set.
6. method according to claim 1 is characterized in that, described petroleum naphtha is virgin naphtha, hydrocracking petroleum naphtha or hydrocracking petroleum naphtha.
7. method according to claim 1 is characterized in that, after adsorption process finishes, carries out centre oil cutting with desorbing agent earlier.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2925065B1 (en) * | 2007-12-17 | 2012-11-30 | Inst Francais Du Petrole | NEW DIAGRAM FOR OPTIMIZING HIGH OCTANE INDEX PRODUCTION AND COPRODUCTION OF AROMATIC BASES |
| CN101759513B (en) * | 2008-12-25 | 2012-08-22 | 中国石油化工股份有限公司 | Method for utilizing naphtha |
| CN102465044B (en) * | 2010-11-15 | 2014-05-07 | 周向进 | Method for joint production of low-octane gasoline and high-octane gasoline |
| TWI544067B (en) | 2011-05-27 | 2016-08-01 | China Petrochemical Technology Co Ltd | A Method for Catalytic Recombination of Naphtha |
| CN102795958B (en) * | 2011-05-27 | 2015-03-18 | 中国石油化工股份有限公司 | Method for producing aromatic hydrocarbon and ethylene through taking naphtha as raw material |
| CN102585887A (en) * | 2012-02-29 | 2012-07-18 | 华东理工大学 | Naphtha adsorbing separation and optimized utilization method |
| CN103374395B (en) * | 2012-04-26 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of take petroleum naphtha as the method for raw material production aromatic hydrocarbons and ethene |
| CN104031680B (en) * | 2013-03-05 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method of being produced alkene and low benzene content gasoline by petroleum naphtha |
| CN104927919B (en) * | 2014-03-18 | 2017-02-15 | 中国石油化工股份有限公司 | Method for producing olefin and low-benzene-content gasoline component from naphtha |
| CN107586250B (en) * | 2016-07-08 | 2021-06-01 | 中国石化扬子石油化工有限公司 | Preparation method of high-purity n-hexane and high-purity n-heptane |
| CN112409121B (en) * | 2020-12-02 | 2023-07-11 | 恒力石化(大连)化工有限公司 | Yield increasing method and system for low-carbon olefin and aromatic hydrocarbon |
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