CN1108355C - Isomerization method for C5, C6 paraffine - Google Patents
Isomerization method for C5, C6 paraffine Download PDFInfo
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Abstract
The present invention relates to an isomerization method of light hydrocarbon raw materials containing C5 and C6 normal alkane, which includes the following steps: in the presence of hydrogen gas and under the different isomerization conditions, making the first part of raw materials richly containing C5 hydrocarbon and the second part of raw materials richly containing C6 hydrocarbon respectively carry out contact reaction with an isomerization catalyst; then separating the produced mixture prepared by the isomerization reaction of the two parts of raw materials in a shared gas-liquid separation system to obtain a gas phase hydrocarbon component and a liquid phase isomerization product. The method can effectively regulate isomerization reaction conditions according to the composition of the raw materials to enhance the octane value of products.
Description
The present invention is the isomerization method of the less straight-chain paraffin of a kind of carbon number, specifically, is the isomerization method of a kind of C5, C6 normal paraffin.
The modern gasoline engine requires stop bracket gasoline, and the leaded additive that generally uses banned use of owing to problem of environmental pollution in the past.Therefore, the composition of rearranging blended gasoline becomes the effective way that improves gasoline octane rating to obtain high-octane product.
The final boiling point of blended gasoline fraction is generally less than 205 ℃, and the component of this boiling range scope contains the paraffinic hydrocarbons of C4～C6, and normal paraffin octane value wherein is lower.Improve the octane value of gasoline, low-octane normal paraffin must be converted into high-octane isoparaffin, perhaps utilize reformer that C6 or heavier component are changed into aromatic hydrocarbons.Skellysolve A can not be converted into aromatic hydrocarbons in the blended gasoline fraction, though normal hexane can be converted into aromatic hydrocarbons through the hydrogenation cyclisation, change into aromatic hydrocarbons after, gas yield and fluid density increase, the result causes the volume yield to descend, and therefore generally still the C6 component is carried out isomerization improves its octane value.
Traditional isomerization catalyst is a catalyzer of being made the aluminum chloride type of promotor by hydrogenchloride, the catalyzer that nearest molecular sieve catalyst particularly is carrier with the mordenite is used in a large number, its advantage is insensitive to sulfur impurity and water, and has the desired acidity of isomerization reaction.The active ingredient of isomerization catalyst is the platinum family precious metal.As USP3,932,554 adopt fluorine-containing halon such as CF
4, CCl
3F, CHCl
2F etc. contact with the mordenite catalyst that carries platinum or palladium, make the modified catalyst that fluorine content is at least 0.86 heavy %.Though the catalyzer of above-mentioned chlorine or fluorine modification has good isomerization performance, in the catalyzer use, chlorine or fluorine can run off gradually along with the carrying out of reaction, cause catalyst activity reduction, corrosion of equipment.
USP4,804,803 disclose the one-pass isomerization reaction method of a kind of hydrogen, this method feeds two placed in-line isomerization reactors with the C5/C6 hydrocarbon after hydrogen mixes, and the amounts of hydrogen of regulating adding, making hydrogen hydrocarbon mol ratio is 0.05 or still less, separating isomerism product and gas stream in stabilizer tower then, and described hydrogen does not circulate.The catalyzer that this method is used is the aluminium oxide catalyst that contains the chlorine component, and its active ingredient is the platinum of 0.01～25 heavy %.
USP5,082,989 disclose a kind of C4, C5 and C6 component isomerization combination process, this method is divided into two strands of raw materials with C4～C6 hydrocarbon and carries out isomerization respectively, and first strand of raw material comprises normal butane, and second strand of raw material comprises acyclic C5 and C6 hydrocarbon, two bursts of chargings are respectively with after hydrogen mixes, first strand of raw material fed first conversion zone, react under the butane isomerisation conditions, its temperature is 100～300 ℃, pressure is 0.7～4.0MPa, after again second strand of feedstream and first burst of isomerization reactant heat exchange being heated up, feed second conversion zone, under C5 and C6 hydrocarbon isomerization condition, react, its temperature is 90～225 ℃, and pressure is 2.0～3.0MPa.Above-mentioned two strands of isomerization reactants are fed same separator carry out gas-liquid separation.Its isomerization catalyst system therefor carrier is an aluminum oxide, wherein chloride 2～10 heavy %, platiniferous 0.01～25 heavy %.Though separating C4 from hydrocarbon feed, this method carries out isomerization separately, but C5 and C6 hydrocarbon still mix and carry out isomerization reaction in same reactors, still exist reaction conditions to be difficult to coordinate for C5, raw material that C6 content is big like this and the problem that causes side reaction to increase.
The purpose of this invention is to provide a kind of hydrocarbon feed isomerization that will contain normal paraffin with effective raw material octane value that improves, improve the method for isomerization reaction transformation efficiency.
We find, the deficiency of isomerization reaction technology in the past is to adopt the parallel feeding of C5/C6 fraction, under same reaction conditions, carry out isomerization reaction, though this method is simple, but because the C5 fraction is than the isomerization reaction difficulty of C6 fraction, need higher isomerisation temperature, and the C6 fraction is easy to take place side reactions such as cracking and influences product yield under higher isomerisation temperature, and produce carbon distribution and influence catalyst life, so C5, the C6 fraction carries out isomerization reaction under identical conditions is difficult to regulate appropriate reaction conditions and makes the normal paraffin in the raw material be converted into isoparaffin to greatest extent.If C5 in the raw material and C6 fraction are separated, carry out isomerization reaction respectively, then help adjusting the reaction conditions of C5 and C6 fraction, mainly be the transformation efficiency that temperature of reaction improves normal paraffin.
Specifically, the isomerization method of the light hydrocarbon feedstocks of the C5 of containing provided by the invention, C6 normal paraffin comprises the steps:,
(1) first strand of raw material that will be rich in the C5 hydrocarbon be in the presence of hydrogen, under C5 hydrocarbon isomerization condition with the isomerization catalyst contact reacts,
(2) second strand of raw material that will be rich in the C6 hydrocarbon be in the presence of hydrogen, under C6 hydrocarbon isomerization condition with the isomerization catalyst contact reacts,
(3) product that above-mentioned two strands of raw materials are obtained through isomerization reaction mixes the formation mixture,
(4) mixture is carried out Separate System of Water-jet, obtain the isomerization product of gas phase hydrocarbon component and liquid phase.
Described first strand of raw material is that carbon number is lower than 6 hydro carbons, and wherein the content of Skellysolve A should be no less than 40 heavy %, preferably is no less than 50 heavy %, and the content of C5 hydrocarbon is no less than 85 heavy %, preferably is no less than 90 heavy %, also contains the C4 hydrocarbon of 1～10 heavy % in this strand raw material.In addition,, also should contain a certain amount of hydrogen in the raw material, because scission reaction does not take place the C5 hydrocarbon substantially, so hydrogen hydrocarbon mol ratio is 0.05～2.6 to get final product in the C5 isomerization reaction under isomerisation temperature for avoiding the generation of side reaction.
Owing to do not contain the C6 component in first strand of raw material, so temperature of reaction suitably can be improved increasing the isomerization rate of Skellysolve A, suitable C5 isomerisation conditions is that 230～350 ℃, 1.0～3.0MPa, raw material feed weight air speed are 0.2～10.0 hour
-1, preferred 0.5～3.0 hour
-1
The content of C6 hydrocarbon should be no less than 85 heavy % in described second strand of raw material, preferably contain a large amount of normal paraffins and the isomer of single methyl, the amount of normal paraffin should be no less than 30 heavy %, preferably is no less than 50 heavy %, and wherein the summation of normal paraffin and single methyl isomer should be no less than 70 heavy %.The C5 hydrocarbon content should be less than 10 heavy % in this strand raw material, otherwise is unfavorable for adjusting reaction conditions.Because there is cracking side-reaction in the C6 hydrocarbon under isomerisation conditions, therefore the content of hydrogen should suitably increase in this strand material, suitable hydrogen hydrocarbon mol ratio is 2.5～4.0, if too little being difficult to of amounts of hydrogen then can cause the system energy consumption to increase to suppress scission reaction too much.
In addition, second gang of C that raw material contains
7 +Therefore component will increase the coking of catalyzer, require its content should be less than 3.5 heavy %, and the unsaturated hydro carbons that this material contains also will under isomerisation conditions cracking reaction take place and increase the hydrogen consumption, so require unsaturated hydro carbons content in the raw material less than 10 weight %.
Because of containing a large amount of C6 in second strand of raw material, so can carry out isomerization reaction under lower temperature, avoiding cracking side-reaction, the isomerized suitable condition of C6 is that 200～300 ℃, 1.0～3.0MPa, raw material feed weight air speed are 0.2～10.0 hour
-1, preferred 0.5～3.0 hour
-1
For guaranteeing catalyst activity stability, should remove the detrimental impurity in the isomerization raw material, should be as sulphur content in the isomerization raw material less than 30PPm, water-content should be less than 50PPm.Remove the method that the method for sulphur and water-content can adopt those skilled in the art to be familiar with in the raw material, remove sulphur in the raw material, adopt molecular sieve adsorption to remove water as adopting hydrodesulfurization.
Above-mentioned two strands of materials are after isomerization reaction, and products therefrom mixes the back and forms mixture, and mixture obtains the isomerization product of gas phase hydrocarbon component and liquid phase through gas-liquid separation.
When the mol ratio of hydrogen and hydrocarbon in the isomerization product mixture greater than 0.05 the time, need hydrogen is told from mixture, mixes back recycle with first strand and second strand of raw material respectively, the higher hydrogen yield of the purity of this hydrogen stream reaches 95 heavily more than the %.Isolate liquid stream behind the hydrogen obtains gas phase hydrocarbon component and liquid phase through gas-liquid separation isomerization product.
The gas phase hydrocarbon component that above-mentioned reaction mixture obtains through gas-liquid separation is mainly hydro carbons and a spot of hydrogen below the C4, separates the liquid product that obtains and is isomerization product.
The inventive method can be used the different isomerization catalysts of forming.The activity of such catalysts component is a VIII family metal, and VIII family metal comprises platinum, palladium, germanium, ruthenium, rhodium, osmium, iridium, and its amount that contains in catalyzer is 0.01～2.0 heavy %.Support of the catalyst can be an aluminum oxide, wherein contains a certain amount of chlorine, and the content of chlorine in catalyzer is 5～15 heavy %; Support of the catalyst is the complex carrier formed of aluminum oxide, mordenite also, also can further contain the β zeolite in this complex carrier.The isomerization catalyst that preferred embodiment of the inventive method is used contains 0.01～2.0 heavy %, the VIII family metal of preferred 0.15～0.8 heavy %, wherein carrier is made up of the β zeolite of 20～80 heavy %, the mordenite of 10～70 heavy % and the aluminum oxide of 10～50 heavy %, and each components contents is preferably in the carrier: β zeolite 40～60 heavy %, mordenite 10～50 heavy %, aluminum oxide 10～30 heavy %.Preferred platinum of VIII family metal or palladium in the catalyzer.
The silica of β zeolite and mordenite in the described isomerization catalyst, promptly silica alumina ratio is 5～80, and is preferred 10～60, and more preferably 15～40.Mordenite can be natural or the synthetic mordenite.The sodium content of mordenite and β zeolite all should be less than 0.3 heavy %, and the sodium content of two kinds of zeolites is preferably in the scope of 0.01～0.08 heavy %.
The high purity aluminium oxide that the used preferred aluminum alkoxide hydrolysis of aluminum oxide makes in the heterogeneous catalyst, this high purity aluminium oxide is selected from high-carbon (C
4Above) aluminum alkoxide the hydrolysis high purity aluminium oxide or the low-carbon (LC) (C that make
4Below) high purity aluminium oxide that makes of aluminum alkoxide hydrolysis, or the mixture of the two, the method preparation that the high purity aluminium oxide that described low-carbon alkoxy aluminium hydrolysis makes adopts CN1032951A to announce.
The preparation method of the preferred isomerization catalyst of the inventive method comprises:
(1) h-mordenite, Hydrogen β zeolite and aluminum oxide are mixed by the butt weight ratio, pinch through mixing, moulding, roasting make Zeolite support,
(2) with the above-mentioned Zeolite support of solution impregnation that contains VIII family metal, dry, roasting makes catalyzer.
The h-mordenite in (1) step or Hydrogen β zeolite all can adopt conventional ion-exchange techniques to be prepared by na-pretreated zeolite in the described method.As na-pretreated zeolite is carried out ion-exchange with acid or acidic salt solution under 90～95 ℃,, be preferably less than the h-type zeolite of 0.08 heavy % to make sodium content less than 0.3 heavy %.Hydrochloric acid is generally selected in acid used in the ion exchange process for use, and its concentration is preferably 0.1～5.0 mol, and used acidic salt solution is generally selected ammonium chloride solution for use.Described ion exchange process can repeat repeatedly, till the sodium content of zeolite reaches requirement.
With h-mordenite, Hydrogen β zeolite and aluminum oxide in proportion behind the mixing, adding rare nitric acid or extrusion aids such as acetic acid, citric acid mixes and pinches, and then extrusion moulding, room temperature～150 ℃ drying, 450～850 ℃, preferably 500～600 ℃, roasting makes the composite zeolite carrier, and the carrier of extrusion moulding is stripe shape preferably, also can be other shape, as sheet shape, cloverleaf pattern.The method of carrier moulding also can adopt the method for dripping ball or spin to make the ball-type carrier except that extrusion moulding.
The preferred Platinic chloride of solution, the acid of chlorine palladium, the platinum ammonium complex ion that contain VIII family metal described in the catalyst preparation step (2), the amount of flooding the solution of the used VIII of containing family metal should make bullion content wherein satisfy desired content in the catalyzer.During dipping, the volume ratio of steeping fluid and carrier is preferably 3～1.2: 1.Dipping back carrier promptly gets isomerization catalyst in room temperature～150 ℃ drying, 450～850 ℃ of roastings.
Described drying of above-mentioned preparation catalyzer and roasting time are 1～8 hour, are preferably 3～6 hours.
Below accompanying drawing is described.
Fig. 1 is a C5/C6 isomerization method schematic flow sheet provided by the invention.
Fig. 2 is the schema that simplifies the operation of the inventive method.
Fig. 3 is a prior art C5/C6 parallel feeding alienation general flow chart.
For ease of understanding the present invention, only list major equipment among the figure, other utility appliance such as valve, pump, instrument etc. are ignored.
As shown in Figure 1, the inventive method comprises pentane isomerization part, isomeric hexaneization part and shared product separation facility.The first strand of raw material that is rich in the C5 hydrocarbon enters system by pipeline 10, through interchanger 15 heat exchange after pipeline 11 enters process furnace 12 heating, entering C5 isomerization reactor 13 through pipeline 23 again contacts with isomerization catalyst and carries out isomerization reaction, the isomerization product that is produced is discharged by pipeline 14, after interchanger 15 carries out heat exchange, enter condenser 22 coolings with feed stream, send into knockout drum 24 then.
The second strand of raw material that is rich in the C6 hydrocarbon enters system by pipeline 16, through interchanger 21 heat exchange, enter process furnace 18 heating through pipeline 17, entering C6 isomerization reactor 19 through pipeline 27 again contacts with isomerization catalyst and carries out isomerization reaction, the isomerization product that is produced flows out through pipeline 20, carry out heat exchange with feed stream at interchanger 21, the isomerization product with pipeline 14 mixes again, enters knockout drum 24 after condenser 22 coolings.
The gas composition of being told by knockout drum 24 is mainly hydrogen and not liquescent carburet hydrogens such as minute quantity C2 and C3, after this hydrogen stream is discharged by separating tank 24 tops, divide two strands by compressor 30 pressurization back, respectively through pipeline 28 and pipeline 29 and recycle after first strand of raw material and second strand of raw material mix.The separating tank temperature is controlled to be 10～40 ℃, and working pressure is controlled to be 1.3～2.8MPa and gets final product.
Isomerization product after gas-liquid separation is discharged by separating tank 24 bottoms, through interchanger 31 heat exchange, temperature raises after pipeline 26 enters stabilizer tower 32 by the middle part, stabilizer tower 32 tower top temperatures are controlled to be 60～80 ℃, column bottom temperature is controlled to be 140～170 ℃, pressure is 1.0～1.7MPa, stablizing the light constituent of cat head is discharged by pipeline 33, through entering basin 34 after condenser 38 coolings, non-condensable gas is discharged by pipeline 35, discharged by pipeline 36 by a liquefied gas part of discharging at the bottom of the jar, another part loops back cat head.Enter interchanger 31 by a product part of discharging at the bottom of the stabilizer tower through pipeline 37 and reduce the back as the isomerization product discharge, contain C in this product with tower feed stream temperature after heat exchange
4The isomerization product of above heavy constituent; Another part material of discharging at the bottom of the tower returns the gas phase section of stabilizer tower after condenser 39 condensations.
For isomerization reaction is carried out fully, general isomerization reaction zone is all selected the system that has two reactors at least for use, and for the present invention, C5 and C6 isomerization reaction Duan Junke comprise two to a plurality of reactors.For the multistage reactive system, the catalyzer evenly distribute can be several sections, generally be that two reactors in series are used.Two reactors in series are used can make to be reflected under the lower temperature of reaction and are carried out, especially to the C6 hydrocarbon, owing to exist the side reaction of heat releases such as hydrogenation, therefore in first reactor, flow out high-temperature material and can under lower temperature, carry out, be beneficial to generate more isomer through entering second reactor after cooling.Because the C5 hydrocarbon is difficult for carrying out hydrocracking,, and do not need the intercooling step of product under same temperature so two reactors of C5 isomerization zone can be operated.
In the flow process of Fig. 1, when hydrogen-hydrocarbon ratio less than 0.05 the time, can directly discharge system from the light constituent that separating tank 24 is told, no longer circulation is reclaimed and is used.Isolate isomerization product discharge system through stabilizer tower again by the heavy constituent that separating tank 24 is told.
The inventive method is separated C5 with the C6 component, and according to C5, C6 isomerization reaction characteristic separately, under not quite identical condition, carry out isomerization reaction respectively, make the isomerization rate of raw material increase, thereby can make isomerization product with higher octane.In addition, the isomerization catalyst acidity that the present invention uses is higher, has higher isomerization activity, and chlorine-containing components not, helps reducing in reaction process equipment corrosion.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
The preparation isomerization catalyst.
Get 100 gram sodium type mordenites (Fushun No.3 Petroleum Factory's production) and be put in the three-necked bottle, its composition sees Table 1, adds the NH of 800 milliliter of 1 mol in three-necked bottle
4Cl solution was 90～95 ℃ of exchanges 3 hours, filter, the gained solid washs with deionized water, 120 ℃ of dryings 3 hours, twice of repetitive operation, HCl with 800 milliliter of 1 mol handled 3 hours at 90～95 ℃ again, filter, wash to filtrate with deionized water and be neutral, 600 ℃ of roastings 6 hours, making sodium content is 0.03 heavy %, silica alumina ratio is 23.4 h-mordenite, the sodium content fluorescence spectrum method for measuring.
Get 100 gram sodium type β zeolites (Fushun No.3 Petroleum Factory's production), its composition sees Table 1, and making sodium content by above-mentioned ammonium switching method is that 0.03 heavy %, silica alumina ratio are 28.6 Hydrogen β zeolite.
With above-mentioned h-mordenite, Hydrogen β zeolite and high purity aluminium oxide (SB powder, Germany CONDEA company produces) to press 20: 60: 20 mixed of butt weight ratio even, the salpeter solution that added volume ratio and be 1: 1 mixes to be pinched, add nitric acid and solid powder volume ratio be 1: 1.6, extruded moulding, 120 ℃ of dryings 2 hours, 550 ℃ of roastings made the composite zeolite carrier in 4 hours.
Get composite zeolite carrier 100 gram, with the platinum acid chloride solution room temperature dipping of 45 milliliter of 8.6 mol 24 hours, 120 ℃ of dryings 4 hours, roasting made isomerization catalyst in 4 hours in 550 ℃ of air, and wherein platinum content is 0.35 weight %.
Example 2
Simplify flow process by the inventive method shown in Figure 2 and carry out isomerization reaction.Wherein the C5 raw material is a Skellysolve A, and the C6 raw material is a normal hexane.
Be respectively charged into catalyzer 111 grams (150 milliliters) of example 1 preparation in reactor 13 and 19, and the temperature of reactor 13 is risen to 275 ℃, the temperature of reactor 19 rises to 260 ℃.
Press the flow process of Fig. 2, high pressure hydrogen with 5.9 liters/time air speed enter system by pipeline 11, Skellysolve A was with 1.0 o'clock
-1Weight space velocity enter system by pipeline 10, hydrogen hydrocarbon mol ratio is 2.6.Mixed hydrogen and Skellysolve A are heated to 275 ℃ by well heater 12, send into reactor 13 tops by pipeline 14 again.Carry out the isomerization reaction of Skellysolve A under the condition of 275 ℃ of degree, 1.8MPa, resultant of reaction is discharged from reactor 13 bottoms and is entered pipeline 27 through pipeline 16.The n-pentane isomerization rate is 68.9 heavy % under these conditions.
Normal hexane after the pressurization was with 0.67 o'clock
-1Weight space velocity enter system through pipeline 20, high pressure hydrogen with 3.4 liters/time air speed enter system by pipeline 17, hydrogen hydrocarbon mol ratio is 2.6.Mixed normal hexane and hydrogen are heated to 260 ℃ by well heater 18, enter the top of reactor 19 again through pipeline 24.Carry out the normal hexane isomerization reaction under 260 ℃ of temperature, 1.8MPa condition, the reactor resultant is discharged by reactor 19 bottoms and is entered pipeline 27 through pipeline 26.Two kinds of isomerization reaction logistics mix in pipeline 27, enter knockout drum 24 and carry out gas-liquid separation after condenser 22 coolings.The isomerization rate of normal hexane is 83.5% under these conditions.
Discharged by pipeline 25 by the light constituent after knockout drum 24 separation, the liquid isomerization product is discharged by pipeline 31, and its composition sees Table 2, and research octane number (RON) (RON) is 81.3.The operational condition of separating tank 24 is 40 ℃, 1.7MPa.Be preferably in separating tank top placement separation tray for improving separation efficiency.
Comparative Examples 1
By prior art processes flow process shown in Figure 3, be that raw material carries out isomerization reaction with Skellysolve A and normal hexane mixture.
Catalyzer 74 grams (100 milliliters) of filling example 1 preparation in reactor 13, and reactor batch temperature is risen to 260 ℃ gradually.With high pressure hydrogen with 54 liters/time air speed by pipeline 11 feeding systems, Skellysolve A and normal hexane mix the back with 1.0 o'clock by 1.5: 1 weight ratio
-1Weight space velocity enter system by pipeline 10, hydrogen hydrocarbon mol ratio is 2.6, the mixture that enters system is heated to 260 ℃ by well heater 12, send into reactor 13 through pipeline 14, under 260 ℃ of temperature, 1.8MPa condition, carry out the alkane isomerization reaction, resultant of reaction is flowed out through pipeline 16 by reactor 13 bottoms and enters condenser 22 coolings, enter knockout drum 24 then, the light constituent that produces is discharged by pipeline 25, the liquid isomerization product is discharged by pipeline 31, the composition of gained isomerization product sees Table 2, and RON is 80.3.
Example 3
This example is investigated the isomerization stability of catalyzer to hexane.
Carrying out on fixed-bed reactor, is raw material with the normal hexane, 260 ℃ of temperature of reaction, and feed weight air speed 1.0 hours
-1, 1.8MPa, carry out isomerization reaction under the condition of hydrogen hydrocarbon mol ratio 2.6.Continuous operation 108 hours, reaction result sees Table 3, and catalyst stability can be good.
Example 4
This example is investigated the isomerization stability of catalyzer to pentane.
Carrying out on fixed-bed reactor, is raw material with C5 fraction oil, at 270 ℃, and raw material feed weight air speed 1.0 hours
-1, 1.8MPa, carry out isomerization reaction under the condition of hydrogen hydrocarbon mol ratio 2.6, continuous operation 1000 hours, reaction result sees Table 4, table 4 data show that catalyst stability can be good.
Testing the oil composition of used C5 fraction is: C4 14.96 heavy %, Skellysolve A 33.40 heavy %, iso-pentane 51.64 heavy %.
Example 5
Method by example 2 is carried out isomerization reaction, and different is that reaction raw materials replaces Skellysolve A with C5 fraction oil, replaces normal hexane with C6 fraction oil.C5 and C6 fraction weight of oil were than 1.5: 1.Test used fraction oil and reaction gained product liquid composition and character and see Table 5.
Comparative Examples 2
Example 5 described C5 are mixed as raw material by 1.5: 1 weight ratios with C6 fraction oil, carry out isomerization reaction by the method for Comparative Examples 1, its liquid product composition sees Table 5.
Table 1
Table 2
Table 3
| Product liquid is formed, heavy % | Reaction times, hour | ||||||||
| 3 | 8 | 27 | 39 | 51 | 63 | 80 | 93 | 108 | |
| Isohexane | 80.5 | 80.6 | 80.7 | 80.4 | 80.5 | 80.0 | 80.4 | 80.6 | 80.4 |
| Normal hexane | 17.8 | 17.7 | 17.6 | 18.1 | 17.9 | 17.7 | 18.1 | 17.8 | 17.4 |
Table 4
| Product liquid is formed, heavy % | Reaction times, hour | ||||||||
| 46 | 96 | 190 | 290 | 410 | 500 | 643 | 787 | 1000 | |
| Iso-pentane | 66.7 | 67.1 | 67.1 | 65.3 | 68.4 | 68.3 | 67.9 | 67.8 | 66.8 |
| Skellysolve A | 33.3 | 32.9 | 32.9 | 34.7 | 31.6 | 31.7 | 32.1 | 32.2 | 33.2 |
Table 5
Claims (11)
1, a kind of isomerization method that contains the light hydrocarbon feedstocks of C5, C6 normal paraffin comprises the steps:
(1) first strand of raw material that will be rich in the C5 hydrocarbon be in the presence of hydrogen, under C5 hydrocarbon isomerization condition with the isomerization catalyst contact reacts,
(2) second strand of raw material that will be rich in the C6 hydrocarbon be in the presence of hydrogen, under C6 hydrocarbon isomerization condition with the isomerization catalyst contact reacts,
(3) product that above-mentioned two strands of raw materials are obtained through isomerization reaction mixes the formation mixture,
(4) mixture is carried out gas-liquid separation, obtain the isomerization product of gas phase hydrocarbon component and liquid phase.
2, in accordance with the method for claim 1, it is characterized in that first strand of raw material is carbon number less than 6 hydro carbons, wherein the content of Skellysolve A is more than or equal to 40 heavy %, and the C5 hydrocarbon content is more than or equal to 85 heavy %, and hydrogen hydrocarbon mol ratio is 0.05～2.6.
3, in accordance with the method for claim 1, the content that it is characterized in that C6 normal paraffin in second strand of raw material is more than or equal to 30 heavy %, and the C6 hydrocarbon content is more than or equal to 85 heavy %, and hydrogen hydrocarbon mol ratio is 2.5～4.0.
4, in accordance with the method for claim 1, the isomerisation conditions that it is characterized in that the C5 hydrocarbon is that 230～350 ℃, 1.0～3.0MPa, feed weight air speed are 0.2～10.0 hour
-1
5, in accordance with the method for claim 1, the isomerisation conditions that it is characterized in that the C6 hydrocarbon is that 200～300 ℃, 1.0～3.0MPa, feed weight air speed are 0.2～10.0 hour
-1
6, in accordance with the method for claim 1, it is characterized in that when in (3) step in the isomerization product mixture mol ratio of hydrogen and hydrocarbon greater than 0.05 the time, need hydrogen is told from mixture, mix the back recycle with first strand and second strand of raw material respectively, isolate liquid stream behind the hydrogen obtains gas phase hydrocarbon component and liquid phase through gas-liquid separation isomerization product.
7,, it is characterized in that the gas phase hydrocarbon component that isomerization reaction product obtains through separation is hydrogen and the hydro carbons below the C4 according to claim 1 or 6 described methods.
8, in accordance with the method for claim 1, it is characterized in that described isomerization catalyst is made up of VIII family metal and the carrier of 0.01～2.0 heavy %, described carrier is made up of the aluminum oxide of β zeolite, 10～70 heavy % mordenites and 10～50 weight % of 20～80 heavy %.
9, in accordance with the method for claim 8, it is characterized in that described VIII family metal is platinum or palladium, its content is 0.15～0.8 heavy %.
10,, it is characterized in that described isomerization catalyst carrier is made up of the mordenite of the β zeolite of 40～60 heavy %, 10～50 heavy % and the aluminum oxide of 10～30 heavy % according to claim 8 or 9 described methods.
11,, it is characterized in that the silica of β zeolite and mordenite is 5～80 in the described isomerization catalyst according to claim 8 or 9 described methods.
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| CN104945212B (en) * | 2015-06-03 | 2017-01-11 | 上海河图工程股份有限公司 | C5/C6 alkane low-temperature isomerization method |
| CN115725332A (en) * | 2021-08-27 | 2023-03-03 | 中国石化工程建设有限公司 | Light hydrocarbon isomerization device and light hydrocarbon isomerization method |
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2000
- 2000-09-28 CN CN 00124668 patent/CN1108355C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386139C (en) * | 2005-06-03 | 2008-05-07 | 中国石油天然气股份有限公司 | Method and device for establishing gas phase circulation by pushing narrow fraction liquid phase hydrocarbon inert gas |
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| CN1345914A (en) | 2002-04-24 |
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