CN101497815A - Isomerization method for light hydrocarbon - Google Patents
Isomerization method for light hydrocarbon Download PDFInfo
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- CN101497815A CN101497815A CNA2008100572645A CN200810057264A CN101497815A CN 101497815 A CN101497815 A CN 101497815A CN A2008100572645 A CNA2008100572645 A CN A2008100572645A CN 200810057264 A CN200810057264 A CN 200810057264A CN 101497815 A CN101497815 A CN 101497815A
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Abstract
The invention relates to a light hydrocarbon isomerization method. Isomerization reaction is performed for light hydrocarbon raw material in an isomerization reactor at the front part, gas-liquid separation is performed for the outlet stream of the reactor at the front part, the obtained liquid phase stream is separated in an isohexane removing tower, the overhead stream mainly comprising C5 cut fraction and dimethyl C6 alkane is mixed with the bottom stream mainly comprising C7 and cut fractions more than C7 so as to be used as isomate to enter into a gasoline stabilizer, the side stream mainly comprising C6 n-alkane and monomethyl C6 alkane is led into an isomerization reactor at the rear part; after the reaction stream of the isomerization reactor at the rear part is separated, the liquid phase stream all returns and is mixed with the liquid phase stream of a gas-liquid separator of the isomerization reactor at the front part so as to be used as the feeding of the isohexane removing tower. The method has higher n-alkane isomerization ratio and greatly improves the octane number of the light hydrocarbons raw material because the C6 n-alkane basically realizes the full isomerization.
Description
Technical field
The present invention relates to a kind of isomerization method for light hydrocarbon, more particularly, is that a kind of straight-chain paraffin that carbonatoms is less generates branched isoparaffin to improve the method for light hydrocarbon feedstocks octane value by hysomer.
Background technology
In the time processing and secondary processing process of crude oil, can produce with C5, C6 is the main light ends fractionation of forming, and this light ends fractionation can be used as the raw material of blending component, cracking of ethylene raw material or the lighter hydrocarbons producing hydrogen from steam conversion of gasoline.Owing to do not contain alkene and aromatic hydrocarbons in the described lighter hydrocarbons, be a kind of gasoline blending component preferably therefore, but the octane value of described lighter hydrocarbons is lower, and its blending ratio in gasoline is restricted.The light hydrocarbon isomerization technology is exactly that the normal paraffin in the lighter hydrocarbons is converted into isoparaffin, improves the octane value of lighter hydrocarbons, to increase the blending ratio of lighter hydrocarbons in the gasoline, helps the production of clean gasoline.
Because the light hydrocarbon isomerization reaction is controlled by thermodynamic(al)equilibrium, under specific temperature of reaction and pressure condition, the transformation efficiency of normal paraffin is certain in the raw material.Therefore, improve the transformation efficiency of normal paraffin, need to change the residing condition of isomerization reaction, one of method of employing is suitably to reduce temperature of reaction, but under the specific catalyst condition, the reduction of temperature of reaction is subjected to the restriction of speed of response; Two of the method that adopts is that the normal paraffin in the isomerization reaction product is separated with isoparaffin, and partly or entirely the inlet of normal paraffin Returning reactor carries out further isomerization reaction.
The selected developmental level with isomerization catalyst of isomerization reaction temperature is closely-related, improve selectivity of catalyst as much as possible under the prerequisite that guarantees catalyst activity.One of isomerization method for light hydrocarbon commonly used is to carry out hydroisomerization reaction more than 250 ℃ with the difunctional isomerization catalyst of zeolite type, described zeolite type dual-function catalyst mainly is meant with the crystalline silicate to be carrier, aluminum oxide and other refractory oxide are binding agent, supported V III family metal, it mainly is the catalyzer of platinum or palladium preparation, used carrier mainly contains X type zeolite, y-type zeolite and mordenite at present, because mordenite has good high-temperature stability, therefore be that the isomerization catalyst of preparing carriers has obtained development rapidly with the mordenite.But because the zeolite type dual-function catalyst is to lean on the acidity of carrier to promote the normal alkane isomerization reaction, activity of such catalysts is lower, needs higher temperature of reaction.USP4,789,655 introduce chlorine by the gas phase oxi-chlorination in the mordenite catalyst that carries platinum, and making cl content is the catalyzer of 0.5～10 heavy %.USP3,932,554 adopt fluorine-containing halon to contact with the mordenite catalyst that carries platinum or palladium, make the modified catalyst that fluorine content is at least 0.86 heavy %.Owing in carrier, introduced chlorine and fluorine element, improved activity of such catalysts, isomerization reaction can be carried out under lower temperature condition, help improving the transformation efficiency of normal paraffin, but in the use of catalyzer, chlorine or fluorine can run off gradually along with the carrying out of reaction, cause catalyst activity reduction, and device is corroded.In recent years, the β zeolite is applied in the carrier of catalyst for isomerizing light hydrocarbon, and as USP5,095,169 to disclose a kind of be the isomerization catalyst of preparing carriers with activatory β zeolite, and this catalyzer has had raising to a certain degree aspect selectivity.
It is that adjustment by processing method realizes that normal paraffin returns partly or entirely that the isomerization reaction system transforms once more.The characteristics of the isomerization process of normal paraffin cyclical patterns are: isomerization reaction product is separated isoparaffin wherein by suitable separation means with normal paraffin, then, again part or all of normal paraffin is delivered to the inlet of reactor, realize the circulation of normal paraffin in reactive system, improve the transformation efficiency of normal paraffin.As USP4,831, the light hydrocarbon isomerization technology of mentioning in 209, C5, the C6 paraffinic feedstock is through isomerization reactor, behind gas-liquid separator and the preflash tower, enter and take off the isohexane tower, the positive structure C6 alkane of separating draws the inlet that is back to reactor, but this method is owing to enter reactor once more after returning material and raw material mixing, be implemented in the circulation in the reactive system, the isoparaffin that contains in the raw material can suppress the isomerization reaction of normal paraffin, to further improve the transformation efficiency of normal paraffin, have only the flow that returns material by increase, thereby cause the increase of plant energy consumption.USP5,233,120 and USP5, in the light hydrocarbon isomerization technology of mentioning in 602,291, isomerization reaction product has been carried out the selective adsorption separation, the normal paraffin that obtains is back to the inlet of reactor, normal paraffin almost can be converted into isoparaffin fully, and the increase rate of the octane value of light hydrocarbon feedstocks is bigger, but the facility investment of whole technological process and process cost are all higher.
ZL03102218.9 has proposed a kind of isomerization method for light hydrocarbon, its principal feature is: two portions before and after the isomerization reaction system is divided into, the isomerization reaction product of anterior reactive system is after gas-liquid separation, again after taking off the separation of isoparaffin tower, to serve as that the main tower base stream of forming is introduced the rear portion reactive system with the C6 normal paraffin, the isomerization reaction product of rear portion reactive system is after gas-liquid separation, a part is returned and as the charging of taking off the isoparaffin tower, another part mixes the back and goes the gasoline stable system as isomerization product with the overhead stream that takes off the isoparaffin tower.The deficiency of this method is, the part of the liquid phase stream of the gas-liquid separator of rear portion isomerization reaction system is drawn as isomerization product, because isomerization reaction is controlled by thermodynamic(al)equilibrium, draw in the logistics and must contain a certain amount of normal paraffin, the octane value that improves isomerization reaction product there is negative impact, and can't solves the accumulation problem of heavy constituent in reactive system if do not establish this burst logistics.Therefore, in fact the isomerization method for light hydrocarbon of ZL03102218.9 proposition has only realized that the part circulation of normal paraffin transforms, and is not easy to obtain having more high-octane isomerization product.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of on the basis of existing technology normal paraffin in the raw material is converted into isoparaffin with higher transformation efficiency, thereby improves the isomerization method for light hydrocarbon of raw material octane value greatly.
Method provided by the invention comprises: isomerization reaction forwardly takes place in the isomerization reactor earlier in light hydrocarbon feedstocks, the outlet logistics of anterior reactor is after gas-liquid separation, the gained liquid phase stream separates in taking off the isohexane tower, serve as the main overhead stream of forming and serve as the main tower base stream mixing of forming with C 5 fraction and dimethyl C6 alkane with C7 and above cut, go the gasoline stable system as isomerization product, with C6 normal paraffin and monomethyl C6 alkane serves as that the side-stream of the main tower of forming is introduced in the rear portion isomerization reactor, the reactant flow of rear portion isomerization reactor is after gas-liquid separation, the gained liquid phase stream all returns and mixes with the liquid phase stream of the gas-liquid separator of anterior isomerization reaction system, common as the charging of taking off the isohexane tower, said light hydrocarbon feedstocks is one or more in C4～C7 hydro carbons.
Said light hydrocarbon feedstocks is preferably one or more in C5～C6 hydro carbons.This raw material comes from normal pressure tops, hydrogenation unit light naphthar, reformer light naphthar etc. based on various alkane.
The temperature of reaction of anterior isomerization reactor is 100～400 ℃, is preferably 230～300 ℃; Reaction pressure is 0.5～5.0MPa, is preferably 1.0～3.0MPa; Raw material feed weight air speed is 0.2～10.0h
-1, be preferably 0.5～3.0h
-1Hydrogen/oil mol ratio is 0.05～5.0, is preferably 0.1～3.0.
The temperature of reaction of rear portion isomerization reactor is 100～380 ℃, is preferably 230～290 ℃; Reaction pressure is 0.5～5.0MPa, is preferably 1.0～3.0MPa; Raw material feed weight air speed is 0.2～10.0h
-1, be preferably 0.5～3.0h
-1Hydrogen/oil mol ratio is 0.05～5.0, is preferably 0.1～3.0.
The temperature of reaction of anterior isomerization reactor can be identical with the temperature of reaction of rear portion isomerization reactor, also can be different; The temperature of reaction of preferred rear portion reactor is hanged down 5～20 ℃ than the temperature of reaction of anterior reactor.
Among the present invention, the outlet logistics of front and rear isomerization reactor can a shared gas-liquid separator or respectively each with a gas-liquid separator; The gas phase of the gas-liquid separator of front and rear isomerization reaction system can a shared recycle compressor or a recycle compressor is set respectively.
Isomerization method for light hydrocarbon provided by the invention has following advantage:
1. two portions before and after the isomerization reaction system being divided into, differential responses characteristics according to C 5 fraction and C6 cut, forwardly adopt different reaction conditionss with the rear portion reactive system, when guaranteeing the normal alkane isomerization rate, make isomerization product have higher liquid yield, the coke deposit rate of catalyzer can also suitably reduce.
2. after anterior isomerization reaction product and rear portion isomerization reaction product being passed through gas-liquid separation respectively, it is common as the charging of taking off the isohexane tower that liquid phase material mixes the back, the C6 normal paraffin has been realized complete isomerization substantially in reactive system, compared with prior art, the octane value of isomerization reaction product has had raising by a relatively large margin.
3.C7 do not enter the rear portion reactor cycles with the above component of C7, reduced catalyst carbon deposit speed, increased the running period of device.
4. the present invention is applicable to that also with idle plant modification be the light hydrocarbon isomerization device except that being applicable to new device.Being particularly useful for idle catalytic reforming unit is that the basis transform isomerization unit as, and the rate that reuses of device is very high, does not need to increase newly equipment substantially.
5. anterior isomerization reaction system and rear portion isomerization reaction system can shared gas-liquid separators, can also a shared recycle compressor, and this all helps the energy consumption of saving facility investment and reducing device.
Description of drawings
Accompanying drawing is the synoptic diagram of isomerization method for light hydrocarbon provided by the present invention.
Embodiment
The present invention is so concrete enforcement:
Two portions before and after the light hydrocarbon isomerization reactive system is divided into.The raw material of anterior reactive system is one or more in C4～C7 hydro carbons, one or more in preferred C5～C6 hydro carbons; The raw material of rear portion reactive system is the side-stream of taking off the isohexane tower, and it mainly consists of C6 normal paraffin and monomethyl C6 alkane.
The light hydrocarbon isomerization raw material of anterior reactive system mixes with recycle hydrogen after the fresh feed pump supercharging, mixture passes through the feed exchanger heat exchange respectively, the heating of charging process furnace, reach the reaction temperature required after, enter anterior isomerization reactor, the isomerization reaction of normal paraffin forwardly takes place in the isomerization reactor, the reactor outlet logistics is respectively through heat exchange, after the cooling, enter gas-liquid separator, in gas-liquid separator, realize the separation of gas-liquid two-phase, wherein gas phase is main the composition with hydrogen, be delivered to recycle compressor by pipeline, after the recycle compressor supercharging, the inlet of delivering to reactor with the new hydrogen that replenishes recycles; The liquid phase of gas-liquid separator is mixed with the return logistics of rear portion reactive system, after the interchanger heat exchange, as the charging of taking off the isohexane tower.
The overhead stream that takes off the isohexane tower serves as main the composition with C 5 fraction and dimethyl C6 alkane, and tower base stream serves as main the composition with C7 and above cut, and cat head mixes the back and goes the gasoline stable system as isomerization product with tower base stream.With C6 normal paraffin and monomethyl C6 alkane serves as that the main logistics of forming is extracted out by the side line that takes off the isohexane tower, charging as rear portion isomerization reaction system, mix with recycle hydrogen, heat through process furnace, after reaching the required temperature of reaction, enter the rear portion isomerization reactor, the reactor outlet logistics enters gas-liquid separator after heat exchange, cooling, the gaseous stream of gas-liquid separator recycles after the recycle compressor supercharging, the liquid phase stream of gas-liquid separator all return and with the liquid-phase mixing of the gas-liquid separator of anterior reactive system as the charging of taking off the isohexane tower.
Anterior isomerization reaction system and rear portion isomerization reaction system can distinguish respectively with a gas-liquid separator, also can a shared gas-liquid separator.In addition, anterior reactive system and rear portion reactive system can a shared recycle compressor outside, recycle compressor separately also can be set respectively.
Isomerization reaction is thermopositive reaction, for control reaction temperature preferably, improves the selectivity of isomerization reaction, needs on the structure formation of reactor in addition special consideration.Anterior isomerization reactor and rear portion isomerization reactor, can adopt a reactor respectively, the beds of each inside reactor is divided into multistage, mend the lower medium of temperature in the space between adjacent two-stage catalytic agent bed, be generally recycle gas, in order to regulate the temperature of next beds ingress; Anterior isomerization reactor and rear portion isomerization reactor can also adopt the form of a plurality of reactors in series respectively, the number of reactors that is adopted is generally 1～3, between two adjacent reactors, replenish the lower medium of temperature, be generally recycle gas, regulate the temperature of next reactor inlet logistics effectively, help improving the transformation efficiency of normal paraffin.
The isomerization complexity of C 5 fraction in the isomerization raw material and C6 cut is different, the isomerization reaction of C 5 fraction is difficult relatively, need higher temperature of reaction, and the isomerization reaction of C6 cut is relatively easy, need lower temperature of reaction, C6 and above cut are easy to take place side reactions such as cracking under higher temperature of reaction, influence the liquid yield of isomerization product, and can accelerate the coke deposit rate of catalyzer, shorten the operational cycle of device.Therefore, anterior isomerization reactor should adopt different temperature of reaction with the rear portion isomerization reactor, the temperature of reaction that is anterior isomerization reactor is 100～400 ℃ preferred 230～300 ℃, and the temperature of reaction of rear portion isomerization reactor is 100～380 ℃ preferred 230～290 ℃; Concerning other reaction conditions, anterior and the identical condition of the general employing of rear portion isomerization reaction system, i.e. reaction pressure 0.5～5.0MPa, preferred 1.0～3.0MPa; Raw material feed weight air speed 0.2～10.0h
-1, preferred 0.5～3.0h
-1Hydrogen/oil mol ratio is 0.05～5.0, preferred 0.1～3.0.
In anterior isomerization reactor and the rear portion isomerization reactor isomerization catalyst is housed all, described isomerization catalyst is made up of VIII family metal and the carrier of 0.01～3.0 heavy %.VIII family metal in the catalyzer can be platinum, palladium, germanium, ruthenium, rhodium etc.; The carrier of catalyzer can be a mordenite, wherein contains a certain amount of halogen, also can be the complex carrier that aluminum oxide and mordenite are formed, and can also further contain the β zeolite in this complex carrier.
Below in conjunction with accompanying drawing the present invention is further detailed.
Isomerization method for light hydrocarbon flow process provided by the invention is as follows: the light hydrocarbon isomerization raw material is through pipeline 1 introducing device, after fresh feed pump 2 superchargings, enter pipeline 3, mix with recycle hydrogen from pipeline 20, enter pipeline 4, then pass through feed exchanger 5 successively, pipeline 6, charging process furnace 7, pipeline 8, reach reactor inlet temperature required after, enter anterior isomerization reactor 9, chemical reaction based on normal alkane isomerization takes place in reactor 9, reaction product is successively via pipeline 10, feed exchanger 5, pipeline 11, air-cooler 12, pipeline 13, water cooler 14 and pipeline 15 enter the separation that gas-liquid separator 16 is finished gas-liquid two-phase.
The gas phase of gas-liquid separator 16 is based on hydrogen, and this gas phase is drawn through pipeline 18, after additional new hydrogen from pipeline 21 mixes, enters recycle compressor 19, and the gas phase after the supercharging is mixed with light hydrocarbon isomerization raw material from pipeline 3 through pipeline 20.
The liquid phase of gas-liquid separator 16 is drawn through pipeline 17, after return logistics from pipeline 60 mixes, enter through pipeline 23, interchanger 24, pipeline 25 successively and take off isohexane tower 26, the effect of taking off isohexane tower 26 is that isomerization reaction product is cut into three bursts of logistics, i.e. overhead stream, tower base stream and tower side line.Overhead stream serves as main the composition with C 5 fraction and dimethyl C6 alkane, draw by cat head through pipeline 27, successively through air-cooler 28, pipeline 29, watercooler 30 and pipeline 31, enter return tank of top of the tower 32, the gas phase of return tank 32 enters the fuel gas pipe network by pipeline 33, and the liquid phase of return tank 32 is then drawn through pipeline 34, after pump 35 superchargings, a part is returned cat head through pipeline 36 as backflow, and another part is then drawn the gasoline stable system through pipeline 37.Tower base stream serves as main the composition with C7 and above cut, by extracting a back part at the bottom of the tower out at the bottom of pipeline 41, reboiler 42 and pipeline 43 return tower, provide thermal source for taking off the isohexane tower, another part material at the bottom of the tower is then drawn through pipeline 38, after pump 39 superchargings, mix and go the gasoline stable system as isomerization product via the logistics in pipeline 40 and the pipeline 37.The side line of tower serves as main the composition with C6 normal paraffin and monomethyl C6 alkane, draw by pipeline 44, after pump 45 superchargings with from the recycle hydrogen of pipeline 59, be mixed and fed into pipeline 46, after charging process furnace 47 is heated to the required temperature of reactor inlet, enter rear portion isomerization reactor 49 through pipeline 48, what mainly carry out in reactor 49 is the isomerization reaction of C6 normal paraffin, reactant flow is drawn through pipeline 50, pass through interchanger 24, pipeline 51, air-cooler 52, pipeline 53, watercooler 54 and pipeline 55 successively, enter gas-liquid separator 56.
The gas phase of gas-liquid separator 56 is drawn with after the additional new hydrogen of pipeline 22 mixes through pipeline 57, delivers to recycle compressor 58, uses at rear portion reactive system internal recycle after supercharging; The liquid phase of gas-liquid separator 56 is then drawn through pipeline 60, mixes the charging that isohexane tower 26 is taken off in the back conduct with logistics in the pipeline 17.
Further specify the present invention below in conjunction with embodiment.
The used catalyzer trade mark is FI-15 in embodiment and the Comparative Examples, is produced by Fushun petrochemical corporation (complex) catalyst plant.
Present embodiment adopts technical process shown in the drawings.Describe from several aspects such as the composition of the composition of light hydrocarbon feedstocks and character, isomerization principal reaction condition and isomerization product and character below:
1. the composition of light hydrocarbon feedstocks and character
The weight of light hydrocarbon feedstocks is composed as follows:
Normal butane, heavy %2.60
Trimethylmethane, heavy %0.30
Skellysolve A, heavy %23.54
Iso-pentane, heavy %9.56
Pentamethylene, heavy %1.39
Normal hexane, heavy %32.66
Isohexane, heavy %22.13
Hexanaphthene and methylcyclopentane, heavy %4.15
Benzene, heavy %1.65
C7 and above hydro carbons, heavy %2.02
The research octane number (RON) of light hydrocarbon feedstocks is 59.4.Since at present to the OR Octane Requirements of gasoline products all than higher, generally all more than 90, if directly call in light hydrocarbon feedstocks in the gasoline products, will influence the quality of gasoline products, therefore, light hydrocarbon feedstocks is carried out isomerization handle, it is necessary improving its octane value.
2. isomerization principal reaction condition
The temperature in of anterior reactor, ℃ 250
The inlet pressure of anterior reactor, MPa 1.95
Charging is the interior weight hourly space velocity of reactor forwardly, h
-11.0
Hydrogen/oil mol ratio 2.6 in the anterior reactor
The temperature in of rear portion reactor, ℃ 245
The inlet pressure of rear portion reactor, MPa 1.85
The weight hourly space velocity of charging in the reactor of rear portion, h
-11.0
Hydrogen/oil mol ratio 2.6 in the reactor of rear portion
3. the composition of isomerization product and character
The weight of isomerization product is composed as follows:
The following alkane of C3, heavy % 2.8
Normal butane, heavy %3.3
Trimethylmethane, heavy %0.5
Skellysolve A, heavy %11.9
Iso-pentane, heavy %21.3
Pentamethylene, heavy %1.4
Normal hexane, heavy %1.9
Isohexane, heavy %50.5
Hexanaphthene and methylcyclopentane, heavy %5.5
Benzene, heavy %0.5
C7 and above hydro carbons, heavy %0.4
The research octane number (RON) of isomerization product after gasoline stabilizer removes light constituent is 83.1, its research octane number (RON) has been compared with the octane value of light hydrocarbon feedstocks very significantly and has been improved, therefore, can suitably improve the blending ratio of isomerization product in gasoline products, help cleaning oil manufacture.
Comparative Examples 1
In this Comparative Examples, adopt the technical process that proposes among the ZL03102218.9, the liquid phase of the gas-liquid separator of rear portion isomerization reaction system is all gone the gasoline stable system as isomerization product, does not establish the liquid phase stream that returns.Describe from several aspects such as the composition of the composition of light hydrocarbon feedstocks and character, isomerization principal reaction condition and isomerization product and character below:
1. the composition of light hydrocarbon feedstocks and character
The employed light hydrocarbon feedstocks of this Comparative Examples is identical with embodiment 1 employed light hydrocarbon feedstocks.
2. isomerization principal reaction condition
The temperature in of anterior reactor, ℃ 250
The inlet pressure of anterior reactor, MPa 1.95
Charging is the interior weight hourly space velocity of reactor forwardly, h
-11.0
Hydrogen/oil mol ratio 2.6 in the anterior reactor
The temperature in of rear portion reactor, ℃ 250
The inlet pressure of rear portion reactor, MPa 1.85
The weight hourly space velocity of charging in the reactor of rear portion, h
-11.0
Hydrogen/oil mol ratio 2.6 in the reactor of rear portion
The circulation ratio 0 of rear portion gas-liquid separator liquid phase stream
3. the composition of isomerization product and character
The weight of isomerization product is composed as follows:
The following alkane of C3, heavy % 3.1
Normal butane, heavy %3.7
Trimethylmethane, heavy %0.4
Skellysolve A, heavy %12.0
Iso-pentane, heavy %20.7
Pentamethylene, heavy %1.4
Normal hexane, heavy %5.0
Isohexane, heavy %47.2
Hexanaphthene and methylcyclopentane, heavy %5.6
Benzene, heavy %0.5
C7 and above hydro carbons, heavy %0.4
The research octane number (RON) of isomerization product after gasoline stabilizer removes light constituent is 81.0, its research octane number (RON) is compared the raising that also has by a relatively large margin with the octane value of light hydrocarbon feedstocks, but because the rear portion isomerization reaction product is the equilibrium products under rear portion isomerization reaction condition, wherein contain a certain amount of C6 normal paraffin, when directly effluxing as isomerization product, its research octane number (RON) has been compared a certain distance with the present invention.
Comparative Examples 2
In this Comparative Examples, also be to adopt the technical process that proposes among the ZL03102218.9, the liquid phase major part of the gas-liquid separator of rear portion isomerization reaction system loops back takes off the isoparaffin tower, sub-fraction is gone the gasoline stable system as isomerization product, and the circulation ratio of rear portion gas-liquid separator liquid phase stream is 61.6 heavy %.Describe from several aspects such as the composition of the composition of light hydrocarbon feedstocks and character, isomerization principal reaction condition and isomerization product and character below:
1. the composition of light hydrocarbon feedstocks and character
The employed light hydrocarbon feedstocks of this Comparative Examples is identical with embodiment 1 employed light hydrocarbon feedstocks.
2. isomerization principal reaction condition
The temperature in of anterior reactor, ℃ 250
The inlet pressure of anterior reactor, MPa 1.95
Charging is the interior weight hourly space velocity of reactor forwardly, h
-11.0
Hydrogen/oil mol ratio 2.6 in the anterior reactor
The temperature in of rear portion reactor, ℃ 250
The inlet pressure of rear portion reactor, MPa 1.85
The weight hourly space velocity of charging in the reactor of rear portion, h
-11.0
Hydrogen/oil mol ratio 2.6 in the reactor of rear portion
The circulation ratio of rear portion gas-liquid separator liquid phase stream, heavy %61.6
3. the composition of isomerization product and character
The weight of isomerization product is composed as follows:
The following alkane of C3, heavy % 3.3
Normal butane, heavy %3.7
Trimethylmethane, heavy %0.4
Skellysolve A, heavy %12.0
Iso-pentane, heavy %20.8
Pentamethylene, heavy %1.4
Normal hexane, heavy %3.1
Isohexane, heavy %49.0
Hexanaphthene and methylcyclopentane, heavy %5.4
Benzene, heavy %0.5
C7 and above hydro carbons, heavy %0.4
The research octane number (RON) of isomerization product after gasoline stabilizer removes light constituent is 82.4, owing to increased the circulation ratio of the gas-liquid separator liquid phase stream of rear portion reactive system, its research octane number (RON) is compared with Comparative Examples 1 and is significantly improved, but for Comparative Examples 2, can not accomplish the recycle to extinction of liquid phase stream of the gas-liquid separator of rear portion reactive system, in order to prevent C7 and the accumulation of above hydro carbons in reactive system, must there be a certain proportion of liquid phase stream to efflux as isomerization product, and this thigh effluxes and can contain a certain proportion of C6 normal paraffin in the logistics surely, thereby has limited the further raising of isomerization product octane value.
Claims (9)
1. isomerization method for light hydrocarbon, it is characterized in that light hydrocarbon feedstocks forwardly in the isomerization reactor isomerization reaction takes place earlier, the outlet logistics of anterior reactor is after gas-liquid separation, the gained liquid phase stream separates in taking off the isohexane tower, serve as the main overhead stream of forming and serve as the main tower base stream mixing of forming with C 5 fraction and dimethyl C6 alkane with C7 and above cut, go the gasoline stable system as isomerization product, with C6 normal paraffin and monomethyl C6 alkane serves as that the side-stream of the main tower of forming is introduced in the rear portion isomerization reactor, the reactant flow of rear portion isomerization reactor is after gas-liquid separation, the gained liquid phase stream all returns and mixes with the liquid phase stream of the gas-liquid separator of anterior isomerization reaction system, common as the charging of taking off the isohexane tower, said light hydrocarbon feedstocks is one or more in C4～C7 hydro carbons.
2. according to the method for claim 1, it is characterized in that described light hydrocarbon feedstocks is one or more in C5～C6 hydro carbons.
3. according to the method for claim 1, it is characterized in that the temperature of reaction in the anterior isomerization reactor is 100～400 ℃, reaction pressure is 0.5～5.0MPa, and raw material feed weight air speed is 0.2～10.0h-1, and hydrogen/oil mol ratio is 0.05～5.0.
4. according to the method for claim 3, it is characterized in that the temperature of reaction in the anterior isomerization reactor is 230～300 ℃, reaction pressure is 1.0～3.0MPa, and raw material feed weight air speed is 0.5～3.0h
-1, hydrogen/oil mol ratio is 0.1～3.0.
5. according to the method for claim 1, it is characterized in that the temperature of reaction in the isomerization reactor of rear portion is 100～380 ℃, reaction pressure is 0.5～5.0MPa, and raw material feed weight air speed is 0.2～10.0h, and hydrogen/oil mol ratio is 0.05～5.0.
6. according to the method for claim 5, it is characterized in that the temperature of reaction in the isomerization reactor of rear portion is 230～290 ℃, reaction pressure is 1.0～3.0MPa, and raw material feed weight air speed is 0.5～3.0h
-1, hydrogen/oil mol ratio is 0.1～3.0.
7. according to claim 1,3,4,5 or 6 method, the temperature of reaction that it is characterized in that the rear portion isomerization reactor is than low 5～20 ℃ of the temperature of reaction of anterior isomerization reactor.
8. according to the method for claim 1, it is characterized in that front portion, the rear portion isomerization reactor outlet shared gas-liquid separator of logistics or difference are respectively with a gas-liquid separator.
9. according to the method for claim 1, it is characterized in that front portion, rear portion isomerization reaction system gas-liquid separator the shared recycle compressor of gas phase or a recycle compressor is set respectively.
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| CN200810057264A CN101497815B (en) | 2008-01-31 | 2008-01-31 | Isomerization method for light hydrocarbon |
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| CN104220157A (en) * | 2012-03-29 | 2014-12-17 | 环球油品公司 | Process for controlling a temperature in an isomerization zone |
| CN104945212A (en) * | 2015-06-03 | 2015-09-30 | 上海河图工程股份有限公司 | C5/C6 alkane low-temperature isomerization method |
| CN105820838A (en) * | 2015-01-07 | 2016-08-03 | 中国石油化工股份有限公司 | Method for isomerization of light hydrocarbon |
| CN107916131A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method that isomerization gasoline and aromatic hydrocarbons are produced by alkane |
| CN108238838A (en) * | 2016-12-26 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method of C6 alkane high yield benzene |
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| CN1634812A (en) * | 2003-12-25 | 2005-07-06 | 中国石油化工股份有限公司 | Method for separating n-alkane from C5 to C6 alkane isomerized products |
| CN1840513A (en) * | 2005-03-31 | 2006-10-04 | 中国石油化工股份有限公司 | Method for isomerization of light hydrocarbon |
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| CN1286782C (en) * | 2003-01-30 | 2006-11-29 | 中国石油化工股份有限公司 | Method for isomerization of light hydrocarbon |
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| US20030010679A1 (en) * | 2001-02-05 | 2003-01-16 | Petroleum Energy Center | Solid acid catalyst, production method thereof, and method for hydrodesulfurizing and isomerizing light hydrocarbon oil using the same |
| CN1634812A (en) * | 2003-12-25 | 2005-07-06 | 中国石油化工股份有限公司 | Method for separating n-alkane from C5 to C6 alkane isomerized products |
| CN1840513A (en) * | 2005-03-31 | 2006-10-04 | 中国石油化工股份有限公司 | Method for isomerization of light hydrocarbon |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104220157A (en) * | 2012-03-29 | 2014-12-17 | 环球油品公司 | Process for controlling a temperature in an isomerization zone |
| CN105820838A (en) * | 2015-01-07 | 2016-08-03 | 中国石油化工股份有限公司 | Method for isomerization of light hydrocarbon |
| CN105820838B (en) * | 2015-01-07 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of isomerization method for light hydrocarbon |
| CN104945212A (en) * | 2015-06-03 | 2015-09-30 | 上海河图工程股份有限公司 | C5/C6 alkane low-temperature isomerization method |
| CN107916131A (en) * | 2016-10-11 | 2018-04-17 | 中国石油化工股份有限公司 | A kind of method that isomerization gasoline and aromatic hydrocarbons are produced by alkane |
| CN107916131B (en) * | 2016-10-11 | 2021-04-06 | 中国石油化工股份有限公司 | Method for producing isomerized gasoline and aromatic hydrocarbon from alkane |
| CN108238838A (en) * | 2016-12-26 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of method of C6 alkane high yield benzene |
| CN108238838B (en) * | 2016-12-26 | 2021-02-05 | 中国石油化工股份有限公司 | Method for producing benzene with high yield by using C6 alkane |
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| CN101497815B (en) | 2012-09-12 |
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