CN103059912B - Isomerization reaction method of straight-chain paraffin - Google Patents
Isomerization reaction method of straight-chain paraffin Download PDFInfo
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Abstract
An isomerization reaction method of straight-chain paraffin. A straight-chain paraffin raw material is introduced into a reactor in the presence of hydrogen to contact with an isomerization catalyst, so as to generate branched alkane under isomerization reaction conditions. The method is characterized in that the isomerization catalyst is a solid super acid loaded with a hydrogenation / dehydrogenation metal component; the solid superacid acid is a metal oxide supported with ClO<4-> acid radicals; and the hydrogenation / dehydrogenation metal component is one or more selected from Pt, Pd and Ni. The isomerization reaction method of straight-chain paraffin provided by the invention has the characteristics of low reaction temperature, high conversion rate and good selectivity.
Description
Technical field
The present invention relates to isomerization of paraffins reaction method, more particularly, relate to a kind of straight chain alkane isomerization reaction method adopting the Solid superacid bifunctional catalyst of load hydrogenation/dehydrogenation metal component.
Background technology
Straight chain alkane isomerization reaction process is technological process important in petroleum refining industry.In gasoline-range, the octane value of straight-chain paraffin is very low, cannot as effective blend component of gasoline, and the branched paraffin that straight-chain paraffin obtains through skeletal isomerization then has high-octane rating, is the important blend component of reformulated gasoline.In addition, the product Trimethylmethane of Butane isomerization is one of main raw material of alkylation process.
Current straight chain alkane isomerization reaction method generally adopts solid acid or the Solid superacid bifunctional catalyst of load hydrogenation/dehydrogenation metal component, be 150-300 DEG C in temperature, pressure is 1.0-5.0MPa, under there is the condition of hydrogen, straight-chain paraffin and catalyst exposure carry out skeletal isomerization and obtain corresponding branched paraffin.By the difference of isomerization catalyst used, the isomerization method of straight-chain paraffin is mainly divided into three major types: the first kind adopts the chloride alumina catalyst containing hydrogenation/dehydrogenation metal component, the temperature of reaction of this type of isomerization method is low, and the equilibrium conversion of reaction is high, good product selectivity.Equations of The Second Kind adopts the molecular sieve catalyst containing hydrogenation/dehydrogenation metal component, and the temperature of reaction of this kind of isomerization reaction method is high, and because high temperature is unfavorable for that skeletal isomerization reacts, the equilibrium conversion of therefore reacting is low, and selectivity of product is poor.3rd class adopts the solid super-strong acid containing hydrogenation/dehydrogenation metal component (to be generally load SO
4 2-the zirconium white of acid group), temperature during this kind of catalyst reaction is medium, and the equilibrium conversion of therefore reacting is higher, and selectivity of product is better.
US5157199 discloses a kind of C
4-C
6the isomerization reaction method of straight-chain paraffin, the catalyzer of employing is Pt-SO
4 =/ ZrO
2, C
4-C
6straight-chain paraffin temperature be 200 DEG C, pressure is 790Kpa, H
2the mol ratio of/alkane is carry out skeletal isomerization under the condition of 4.5: 1, needs the diamantane (C adding 0.1-0.8wt% in reaction mass
10h
16) as reaction promoter.
US5905181 discloses a kind of C
10-C
40the isomerization reaction method of straight-chain paraffin.Adopt solid acid catalyst, add the nitrogenous compound of 5-50000PPm in reaction mass, as amine.Reaction conditions is: temperature is 250-500 DEG C, and pressure is 1-25000Kpa, H
2the mol ratio of/alkane is (0.1-10): 1.Catalyzer sulfur resistive can be made after adding nitrogenous compound in reaction mass, and improve the selectivity of reaction.
US5057471 discloses a kind of isomerization reaction method of straight-chain paraffin, and the catalyzer of employing is the mordenite of loaded metal platinum Pt.Straight-chain paraffin temperature be 250 DEG C, pressure is 30atm, H
2the mol ratio of/alkane is carry out skeletal isomerization under the condition of 1: 1 to generate branched paraffin.
The beta-molecular sieve of loaded metal platinum and MCM-22 molecular sieve is all adopted to be catalyzer in the method for the isomerization reaction of straight-chain paraffin disclosed in US5095169 and US5107054.Alkylation reaction condition is: temperature is 200-350 DEG C, pressure is 1-70atm, H
2the mol ratio of/alkane is (0.1-10): 1.
US5391532 discloses a kind of isomerization reaction method of straight-chain paraffin.The catalyzer adopted is Pt-heteropolyacid or salt/carrier, and described carrier is selected from SiO
2, γ-Al
2o
3, ZrO
2with unformed SiO
2-Al
2o
3in the mixture of one or more.
US6080904 discloses a kind of isomerization catalyst and method of straight-chain paraffin.Catalyzer used is Pt-w/ZrO
2.Isomerization reaction operational condition is: temperature is 93-425 DEG C, and pressure is 1-7000Kpa, H
2the mol ratio of/alkane is 0.1-10.
EP365147A, EP547791A disclose a kind of preparation method of Solid superacid bifunctional catalyst.First prepare zirconium white, then use ammoniumsulphate soln oxide impregnation zirconium, again with the zirconium white of Platinic chloride dipping sulfate radical load after drying, after super-dry and roasting, be finally prepared into Pt-SO
4 2-/ ZrO
2catalyzer.
CN1093949A discloses a kind of preparation method of the zirconia system super acids for isomerization reaction, that zirconates to be dissolved in water-content be in the aqueous ethanolic solution of the heavy % of 1-100, by ammoniacal liquor adjust ph to 6-7, precipitating zirconium hydroxide, then after filtration, washing, dry, leaching SO
2- 4, roasting, the step such as leaching precious metal obtain group VIII noble metals/SO
2- 4/ ZrO
2system super acids.By the standby super acids of this legal system, precious metal granularity is little, good dispersity, bullion content are low, improves the stability of catalyzer, has good effect to the isomerization reaction of straight-chain paraffin.But the specific surface area of catalyzer prepared by the method is lower, is about 100m
2/ g.
Disclosed straight chain alkane isomerization method does not also find to adopt solid super-strong acid (the load C lO containing hydrogenation/dehydrogenation metal component of the present invention at present
4 -the metal oxide of acid group) as catalyzer.
Summary of the invention
The technical problem that the present invention solves is to provide that a kind of temperature of reaction is low, transformation efficiency is high, the straight chain alkane isomerization reaction method of good product selectivity.
The isomerization reaction method of a kind of straight-chain paraffin provided by the invention, introducing straight-chain paraffin raw material in reactor, depositing in the case of hydrogen, contacting with isomerization catalyst, and under isomerization reaction condition, reaction generates branched paraffin; It is characterized in that, described isomerization catalyst is the solid super-strong acid of load hydrogenation/dehydrogenation metal component, and described solid super-strong acid is load C lO
4 -the metal oxide of acid group, described hydrogenation/dehydrogenation metal component is selected from one or more in Pt, Pd and Ni.
The beneficial effect of the isomerization reaction method of straight-chain paraffin provided by the invention is:
Method provided by the invention adopts the solid super-strong acid of load hydrogenation/dehydrogenation metal component as isomerization catalyst, the grain-size of described catalyzer is little, specific surface area is large, the catalyzer grain-size that such as, in embodiment the present invention adopts is 7.0 ~ 9.0nm, and specific surface area is 132 ~ 177m greatly
2/ g.Described catalyst acid intensity is high, has hydrogenation/dehydrogenation catalytic performance simultaneously.Straight chain alkane isomerization reaction method provided by the invention, the feature that temperature of reaction is low, equilibrium conversion is high, selectivity is good.
Embodiment
The embodiment of straight chain alkane isomerization reaction method provided by the invention is:
Straight chain alkane isomerization reaction method provided by the invention, introducing straight-chain paraffin raw material in reactor, depositing in the case of hydrogen, contacting with isomerization catalyst, and under isomerization reaction condition, reaction generates branched paraffin; It is characterized in that, described isomerization catalyst is the solid super-strong acid of load hydrogenation/dehydrogenation metal component, and described solid super-strong acid is load C lO
4 -the metal oxide of acid group, described hydrogenation/dehydrogenation metal component is selected from one or more in Pt, Pd and Ni.
In method provided by the invention, the condition of described isomerization reaction can be the reaction conditions generally adopted in prior art.Described isomerization reaction condition is: temperature of reaction is 70-450 DEG C, preferred 90-350 DEG C; Reaction pressure is 0.4-10.0MPa, preferred 0.9-6.0MPa; The molar ratio range of hydrogen and normal paraffin is (0.5-10): 1, and preferably (1-8): 1, the weight space velocity of straight-chain paraffin raw material is 0.5-10 hour
-1, preferred 1.0-8.0 hour
-1.
In method provided by the invention, described straight-chain paraffin raw material is C
4-C
6normal paraffin, the mixture of one or more namely in normal butane, Skellysolve A and normal hexane, or containing C
4-C
6normal paraffin in the hydrocarbon fraction of one or more.
In method provided by the invention, described reactor can carry out for various reactor, and the present invention is not limited in this respect.Such as fixed-bed reactor, batch tank reactor, moving-burden bed reactor, liquefied bed reactor or three-phase slurry bed reactor.The flow pattern of material can be upstriker also can be downstriker.
Method provided by the invention, in described isomerization catalyst, metal oxide can be selected from the oxide compound of the metallic element in periodic table of elements IIB, IVB, VB, VIB, VIIB, VII, VIII and group III A, is preferably the mixture of one or more in the oxide compound of Zr, Ti, Fe, V, Cr, Mo, W and Mn.
In method provided by the invention, take total catalyst weight as benchmark, in described isomerization catalyst, the charge capacity of hydrogenation/dehydrogenation metal component is the heavy % of 0.05-5.0, the preferably heavy % of 0.1-3.0; With the gross weight of solid super-strong acid for benchmark, described ClO
4 -the charge capacity of acid group is the heavy % of the heavy % of 0.1-12.0, preferred 0.5-9.0.
In method provided by the invention, the preferred Pt of hydrogenation/dehydrogenation metal component in described isomerization catalyst.
In method provided by the invention, the solid super acid catalyst of described load hydrogenation/dehydrogenation metal component is prepared by following steps:
(1) the chloride metal-salt of solubility is mixed with the aqueous solution that concentration is 0.1 ~ 10.0 mol/L, preferably 0.2 ~ 5.0 mol/L, in same solution, add water soluble alkali precipitation agent, the concentration of alkali precipitation agent is 0.1 ~ 5.0 mol/L, preferably 0.1 ~ 4.0 mol/L; By the mixing solutions of metal-salt and water soluble alkali precipitation agent in enclosed system, be hydrolyzed reaction at strong mixing and 60 ~ 190 DEG C, obtains the hydrogel of metal-salt and carry out ripening; To the hydrogel stratification of the metal-salt after ripening, remove supernatant liquid, lower sediment thing is dry, roasting, obtains ClO
4 -/ metal oxide; Wherein, described water soluble alkali precipitation agent for not make solution alkaline when normal-temperature dissolution is in the aqueous solution, and decompose under hydrothermal conditions make the aqueous solution be alkalescence organic or inorganic compound;
(2) by ClO that step (1) obtains
4 -/ metal oxide impregnated is in ammonium perchlorate soln, and fully after dipping, after filtration, dry, roasting obtains ClO
4 -the metal oxide of acid group load.
(3) by ClO that step (2) obtains
4 -the metal oxide impregnated of acid group load, in the aqueous solution of the compound of soluble hydrogenation/dehydrogenation metal component, is fully flooded, and then filtration, dry, roasting, obtain the ClO containing hydrogenation/dehydrogenation metal component
4 -the metal oxide catalyst of acid group load, wherein said hydrogenation/dehydrogenation metal component is selected from one or more in Pt, Pd and Ni.
Preferred scheme is the amount of the raw material that preparation Solid superacid bifunctional catalyst adopts, after making to be prepared as catalyzer, with Solid superacid bifunctional catalyst total weight, in catalyzer, the charge capacity of hydrogenation/dehydrogenation metal component is the heavy % of 0.05-5.0, the preferably heavy % of 0.1-3.0; With ClO
4 -/ metal oxide total weight, described ClO
4 -the charge capacity of acid group is the heavy % of 0.1-12.0, the preferably heavy % of 0.5-9.0.
Preferred scheme is the kind of the raw material that preparation Solid superacid bifunctional catalyst adopts, and makes to be prepared as load hydrogenation/dehydrogenation metal component ClO
4 -after/metal oxide catalyst, the mixture of one or more preferably in the oxide compound of Zr, Ti, Fe, V, Cr, Mo, W and Mn of described metal oxide.
The ripening time described in step (1) is 5 ~ 100 hours, preferably 12 ~ 80 hours; Said dry optimum condition is vacuum-drying, and temperature is 45 ~ 95 DEG C, preferably 50 ~ 90 DEG C; Said maturing temperature is 200 ~ 700 DEG C, preferably 300 ~ 600 DEG C.Described water soluble alkali precipitation agent for normal-temperature dissolution in the aqueous solution time do not make solution alkaline, and decompose under hydrothermal conditions can make the aqueous solution be alkalescence organic or inorganic compound.Described water soluble alkali precipitation agent is preferably urea (H
2nCONH
2), urea and chloride metal-salt are dissolved completely in same water solution system, and when system temperature raises gradually, from 60 DEG C, urea has a small amount of decomposition, and time more than 100 DEG C, urea starts to decomposite ammonia (NH
3), when temperature is more than 130 DEG C, urea decomposes completely, its ammonia decomposed completely makes the aqueous solution be strong basicity in confined reaction system, there is hydrolytic precipitation reaction in chloride metal-salt, the reaction process of this hydrolytic precipitation occurs in the very uniform water solution system of a dispersion in strong alkaline aqueous solution medium.
The concentration of the ammonium perchlorate soln described in step (2) is 0.5-2.5 mol/L.
Step (2) and the abundant dipping described in step (3) refer to dipping method conventional in this area, usually, and at room temperature at least 1.0 hours; Described drying means is drying means conventional in this area, preferably drying more than 2 hours under the condition of 80-120 DEG C.Described roasting method is this area conventional bake method, preferably under the environment of air existence, and 200 ~ 700 DEG C, preferably 300 ~ 600 DEG C roasting 2-4 hour.
Straight chain alkane isomerization reaction method provided by the invention, adopt Solid superacid bifunctional catalyst, i.e. the load solid super-strong acid of hydrogenation/dehydrogenation metal component, in the presence of hydrogen, catalysis straight-chain paraffin carries out skeletal isomerization, generates corresponding branched paraffin.Have the advantages that temperature of reaction is low, equilibrium conversion is high, selectivity is good.
The following examples will be further described specifically the present invention, but they can not be interpreted as limiting the scope of the present invention.
In embodiment and comparative example:
The strength of acid H of prepared sample
omeasure with indicator method.Measuring method is as follows: just roasting sample is put into weighing bottle, covers tightly, and puts into moisture eliminator and is cooled to room temperature, takes out about 0.3g and puts on little watch-glass, drips on sample with the indicator corresponding to different strength of acid, observes color sample changing conditions.If correspond to the indicator generation colour-change of a certain strength of acid, then show that sample has this strength of acid.Indicator be with dried hexanaphthene be solvent preparation solution.
The grain-size of prepared sample calculates (H.P. Klug and L.E.Alexander by Scherrer method, " X-ray Diffraction Procedure for Polycrystalline and AmorphousMaterials ", 2nd Ed., Wiley, 1974), said Scherrer equation is:
in formula: λ is the beam wavelength of X-ray target
b is the halfwidth (I of hkj diffraction peak
max, in units of radian); θ
bfor 1/2 of 2 θ of hkj diffraction peak.
The specific surface area nitrogen adsorption methods of prepared sample measures.
In embodiment and comparative example, the straight chain alkane isomerization reaction related to carries out in the fixed bed reaction system of 40 milliliters of catalyzer a set of dress.Reactive system is made up of three parts below:
1, charging metering system: straight-chain paraffin pumps in the water trap of plural serial stage and removes moisture by precision metering pump from head tank, ensure that the water-content in straight-chain paraffin material is less than 5PPm, then enter in a solution-air material mixer, hydrogen enters mass flowmeter by reducing valve, according to the mol ratio of hydrogen/alkane that reaction requires, control its flow by mass flowmeter and also enter solution-air mixer, enter again in fixed-bed reactor after fully mixed with alkane and carry out isomerization reaction.The inlet amount of straight-chain paraffin is measured by the precision electronic balance under material pot, ensures stable, inlet amount accurately.
2, reactive system: fixed-bed reactor can fill 40 milliliters of catalyzer, and the temperature of catalyst reactor bed is controlled by temperature control instrument, ensures the homogeneous and constant of reaction bed temperature.The pressure of reactor is controlled by precision pressure controller, and in guarantee reactor, pressure is stable and accurate.
3, product separation and analytical system: the reaction product of outflow reactor and unreacted material are through two-stage gas-liquid separator by liquid-phase reaction product, gas-phase product and hydrogen separately.Gas-phase product is by online gas-chromatography timing analysis, and by an other stratographic analysis, it forms entirely in liquid-phase isomerization reaction product timing taking-up.
Isomerization reaction product analytical procedure: the composition adopting Agilent-5890 gas-chromatography on-line analysis gas-phase product, chromatographic column is the OV-01 kapillary crosslinking column of 50m × 0.2mm, with the full composition of Agilent-7890 gas chromatographic analysis hydroisomerization reaction product.Chromatographic column is the OV-01 capillary column of 50m × 0.2mm.
Embodiment 1
Embodiment 1 illustrates Pt-ClO
4 -/ ZrO
2catalysts and its preparation method.
(1) by 108.8gZrOCl
28H
2o (Beijing Chemical Plant, analytical pure) is dissolved in 250ml deionized water, stirs after solution is completely limpid, is made into the ZrOCl that concentration is 1.35 mol/L
2solution.At ZrOCl
225.0gH is added in solution
2nCONH
2-urea (Beijing Yili Fine Chemicals Co., Ltd., analytical pure), stirring and dissolving, urea concentration is in the solution 1.67 mol/L.
(2) pour above-mentioned solution into 500ml autoclave, heat up 150 DEG C under vigorous stirring, now the pH value of gel mother liqueur is 10.6.Ageing mother liquor under 150 DEG C and Hydro-thermal pressure, the time of ageing process is 45 hours.Mother liquor after ageing terminates, through leaving standstill 5 hours, then outwells supernatant liquid, by lower sediment thing in vacuum drying oven, at the vacuum tightness of 0.09MPa and 70 DEG C dry 24 hours, obtains ClO
4 -/ Zr (OH)
4.
(3) by the ClO of porphyrize
4 -/ Zr (OH)
4, put into muffle furnace 200 DEG C of flowing air atmosphere roasting 8.5 hours, the ClO obtained
4 -/ ZrO
2sample is denoted as Cl-Zr-I.
(4) in a beaker, 20.0 grams of Cl-Zr-I are put into, then be that the ammonium perchlorate soln of 1.5 mol/L adds in beaker by 150 ml concns, room temperature immersion 1.5 hours, then cross and filter redundant solution, filter cake, 100 DEG C of dryings 3.0 hours, is put into muffle furnace and within 3.5 hours, is obtained ClO 350 DEG C of air atmosphere roastings
4 -the ZrO of acid group load
2, be denoted as Cl-Zr-II.
(5) by 0.168gH
2[PtCl
6] Platinic chloride is dissolved in 30ml deionized water, 10.0gCl-Zr-II is immersed in platinum acid chloride solution, floods 1.5 hours under room temperature, then 100 DEG C of dryings 3.0 hours, 350 ° of roastings 2.0 hours in air atmosphere, obtain the Pt-ClO that platinum content is 0.8 heavy %
4 -/ ZrO
2catalyzer, is denoted as PCZ-1 respectively.Its physico-chemical property is as shown in table 1.
The PCZ sample prepared is carried out chlorine Cl content analysis, and converses ClO
4 -content.Cl content analysis is that adopt scanning quantitation method to measure, result is as shown in table 1 with Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Embodiment 2
Embodiment 2 illustrates Pt-ClO
4 -/ Fe
3o
4catalysts and its preparation method.
The catalyst preparing operation steps of embodiment 2 and analytical procedure identical with embodiment 1, difference is, metallic compound used in step (1) is (FeCl
39H
2o); Ammonium perchlorate soln's concentration in step (4) described in steeping fluid is 0.8 mol/L; By 0.063gH in step (5)
2[PtCl
6] Platinic chloride is dissolved in 30ml deionized water and makes steeping fluid; The Pt-ClO obtained
4 -/ Fe
3o
4catalyzer, is denoted as C-2.Its physico-chemical property is as shown in table 1.
Embodiment 3
Embodiment 3 illustrates Pt-ClO
4 -/ CrO
2catalysts and its preparation method.
The catalyst preparing operation steps of embodiment 3 and analytical procedure identical with embodiment 1, difference is, metallic compound used in step (1) is 40gCrCl
39H
2o; Ammonium perchlorate soln's concentration in step (4) described in steeping fluid is 2.5 mol/L.The Pt-ClO obtained
4 -/ CrO
2catalyzer, is denoted as C-3.Its physico-chemical property is as shown in table 1.
Embodiment 4
Embodiment 4 illustrates Pt-ClO
4 -/ (Mo
2o
3) x (MnO) y Catalysts and its preparation method.
The catalyst preparing operation steps of embodiment 3 and analytical procedure identical with embodiment 1, difference is, metallic compound used in step (1) is Na
2moO
42H
2o and MnCl
24H
2o, mol ratio is 1: 2; Ammonium perchlorate soln's concentration in step (4) described in steeping fluid is 2.5 mol/L.The Pt-ClO obtained
4 -/ (Mo
2o
3) x (MnO) y, x: y=1: 2, catalyzer, is denoted as C-4.Its physico-chemical property is as shown in table 1.
Embodiment 5
Embodiment 5 illustrates Pt-ClO
4 -/ TiO
2catalysts and its preparation method.
The catalyst preparing operation steps of embodiment 5 and analytical procedure identical with embodiment 1, difference is, metallic compound used in step (1) is 40gTiCl
46H
2o; Ammonium perchlorate soln's concentration in step (4) described in steeping fluid is 3.5 mol/L; By 0.336gH in step (5)
2[PtCl
6] Platinic chloride is dissolved in 30ml deionized water and makes steeping fluid.The Pt-ClO obtained
4 -/ TiO
2catalyzer, is denoted as C-5.Its physico-chemical property is as shown in table 1.
Embodiment 6
Embodiment 6 illustrates the effect of straight chain alkane isomerization reaction method provided by the invention.
By the catalyst Pt-ClO of preparation
4 -/ ZrO
2(PCZ-1) powder compressing tablet, fragmentation, the 20-40 object particle 5.0g obtained that sieves load in fixed-bed reactor, first carry out the reduction of catalyzer, under hydrogen flowing quantity is 150ml/ minute condition, is warmed up to 280 DEG C of reduction 5.0 hours with 4 DEG C/min, completes the reduction process of catalyzer.After the temperature of reactor is dropped to temperature of reaction, pass into hydrogen and boost to reaction pressure, pump into n-pentane reaction material with volume pump according to predetermined amount of flow, start to react, after stable reaction, the composition of analytical reaction tail gas, and take out product liquid analysis it forms entirely on time.Isomerization reaction condition and result as shown in table 2.
Embodiment 7
Embodiment 7 illustrates the effect of straight chain alkane isomerization reaction method provided by the invention.
Isomerization method testing apparatus, operation steps and analytical procedure used is with embodiment 6, and straight-chain paraffin raw material is Skellysolve A as different from Example 6, adopts the catalyst Pt-ClO prepared in embodiment 2
4 -/ Fe
3o
4, i.e. C-2, isomerization reaction condition and result as shown in table 2.
Embodiment 8
Embodiment 8 illustrates the effect of straight chain alkane isomerization reaction method provided by the invention.
Isomerization method testing apparatus, operation steps and analytical procedure used is with embodiment 6, and straight-chain paraffin raw material is Skellysolve A as different from Example 6, adopts the catalyst Pt-ClO prepared in embodiment 5
4 -/ TiO
2, i.e. C-2, isomerization reaction condition and result as shown in table 2.
Embodiment 9
Embodiment 9 illustrates the effect of straight chain alkane isomerization reaction method provided by the invention.
Isomerization method testing apparatus, operation steps and analytical procedure used is with embodiment 6, and straight-chain paraffin raw material is normal hexane as different from Example 6, adopts the catalyst Pt-ClO prepared in embodiment 3
4 -/ CrO
2i.e. C-3, isomerization reaction condition and result as shown in table 3.
Embodiment 10
Embodiment 10 illustrates the effect of straight chain alkane isomerization reaction method provided by the invention.
Isomerization method testing apparatus, operation steps and analytical procedure used is with embodiment 6, and straight-chain paraffin raw material is the mixture of 60 heavy % Skellysolve As and 40 heavy % normal hexanes as different from Example 6, adopts the catalyst Pt-ClO prepared in embodiment 4
4 -/ (Mo
2o
3)
x(MnO)
y, x: y=1: 2, i.e. C-4, isomerization reaction condition and result as shown in table 4.
Wherein, show each reaction parameter in 2-4 to be defined as follows:
Transformation efficiency=(weight of the initial normal paraffin of the normal paraffin weight transformed in reaction/react) × 100% of reaction
Selectivity=(the normal paraffin weight transformed in the isoparaffin weight/reaction of generation) × 100% of reaction
Yield=(in the isoparaffin weight/reaction of generation initial normal paraffin weight) × 100% of reaction
Comparative example 1
Comparative example 1 illustrates a kind of Solid superacid bifunctional catalyst Pt-SO in prior art
4 2-/ ZrO
2and preparation method thereof.
According to the preparation method described in European patent EP 365147A and EP547791A, first prepare zirconium white, then use ammoniumsulphate soln oxide impregnation zirconium, again with the zirconium white of Platinic chloride dipping sulfate radical load after drying, through super-dry and roasting, be finally prepared into Pt-SO
4 2-/ ZrO
2catalyzer is as a comparison sample.
By ZrOCl
2be made into the solution that concentration is 1.0 mol/L.By ammoniacal liquor (25 ~ 28%NH
3) be made into the solution that concentration is 2.0 mol/L.Under agitation, ammonia soln is added dropwise to ZrOCl lentamente
2in solution, obtain milky gel mother liqueur.At 50 DEG C, ageing mother liquor 24 hours, then repeatedly filters, washs, obtain without Cl
-the filter cake of ion, 100 DEG C of dryings 4 hours, obtain Zr (OH)
4.Be that the ammonium sulfate of 2.0 mol/L adds and fills 30.0gZr (OH) by 300 ml concns
4beaker in, room temperature immersion 1.5 hours, then crosses and filters redundant solution, and filter cake was 100 DEG C of dryings 4.0 hours, and then 650 DEG C of roastings 3.5 hours, obtain the zirconium white SO of sulfate radical load
4 2-/ ZrO
2.
By 0.250gH
2[PtCl
6] Platinic chloride is dissolved in 38ml deionized water, by 15.0gSO
4 2-/ ZrO
2be immersed in platinum acid chloride solution, flood 2.5 hours under room temperature, then 100 DEG C of dryings 4.0 hours, 350 ° of roastings 3.0 hours in air atmosphere, obtain the Pt-SO that platinum content is 0.8 heavy %
4 2-/ ZrO
2catalyzer, the comparative catalyst's sample obtained is denoted as PSZ-DB.
Sulphur S content analysis is carried out to the PSZ-DB sample prepared, and converses SO
4 2-content.S content analysis is that adopt scanning quantitation method to measure, result is as shown in table 1 with Rigaku Electric Co., Ltd 3271E type Xray fluorescence spectrometer.
Comparative example 2
Comparative example 2 illustrates in prior art and adopts Pt-SO
4 2-/ ZrO
2the effect of n-pentane isomerization method is used for as catalyzer.
Isomerization method testing apparatus, operation steps and analytical procedure used, with embodiment 6, adopts the catalyst Pt-SO prepared in comparative example 1 as different from Example 6
4 2-/ ZrO
2, i.e. PSZ-DB.Isomerization reaction condition and result as shown in table 2.
Comparative example 3
Comparative example 3 illustrates in prior art and adopts Pt-SO
4 2-/ ZrO
2the effect of Isomerization of Hexane method is used for as catalyzer.
Isomerization method testing apparatus, operation steps and analytical procedure used is with comparative example 2, and straight-chain paraffin raw material is normal hexane as different from Example 6.Isomerization reaction condition and result as shown in table 3.
Comparative example 4
Comparative example 3 illustrates in prior art and adopts Pt-SO
4 2-/ ZrO
2the effect of straight chain mixed alkanes isomerization method is used for as catalyzer.
Isomerization method testing apparatus, operation steps and analytical procedure used is with comparative example 2, and straight-chain paraffin raw material is the mixture of 60 heavy % Skellysolve As and 40 heavy % normal hexanes as different from Example 6.Isomerization reaction condition and result as shown in table 4.
Table 1Pt-ClO
4 -the physico-chemical property of/metal oxide catalyst
*: S content; *: SO
4 2-content
The isomerization reaction result of table 2 Skellysolve A
The isomerization reaction result of table 3 normal hexane
The isomerization reaction result of table 4 mixed alkanes
From table 1, in straight chain alkane isomerization method provided by the invention, the specific surface area of the Solid superacid bifunctional catalyst adopted is 132-177m
2/ g, comparative example is 106m
2/ g; Grain-size is 7-9nm, much smaller than the grain-size (58nm) of the catalyzer prepared by comparative example.From table 2-4, compared with straight chain alkane isomerization reaction method of the prior art, C provided by the invention
4-C
6straight chain alkane isomerization reaction method, under the same reaction conditions, transformation efficiency improves about 0.93-3.1 percentage point, and selectivity improves 0.5-1.6 percentage point, and product yield improves 1.3-4.1 percentage point.
Claims (8)
1. an isomerization reaction method for straight-chain paraffin, introducing straight-chain paraffin raw material in reactor, depositing in the case of hydrogen, contacting with isomerization catalyst, and under isomerization reaction condition, reaction generates branched paraffin; It is characterized in that, described isomerization catalyst is the solid super-strong acid of load hydrogenation/dehydrogenation metal component, and described solid super-strong acid is load C lO
4 -the metal oxide of acid group, described hydrogenation/dehydrogenation metal component is selected from one or more in Pt, Pd and Ni, and the solid super acid catalyst of described load hydrogenation/dehydrogenation metal component is prepared by following steps:
(1) the chloride metal-salt of solubility is mixed with the aqueous solution that concentration is 0.1 ~ 10.0 mol/L, adds water soluble alkali precipitation agent in same solution, the concentration of alkali precipitation agent is 0.1 ~ 5.0 mol/L; By the mixing solutions of metal-salt and water soluble alkali precipitation agent in enclosed system, be hydrolyzed reaction at strong mixing and 60 ~ 190 DEG C, obtains the hydrogel of metal-salt and carry out ripening; To the hydrogel stratification of the metal-salt after ripening, remove supernatant liquid, lower sediment thing is dry, roasting, obtains ClO
4 -/ metal oxide; Wherein, described water soluble alkali precipitation agent for not make solution alkaline when normal-temperature dissolution is in the aqueous solution, and decompose under hydrothermal conditions make the aqueous solution be alkalescence organic or inorganic compound;
(2) by ClO that step (1) obtains
4 -/ metal oxide impregnated is in ammonium perchlorate soln, and fully after dipping, after filtration, dry, roasting obtains ClO
4 -the metal oxide of acid group load;
(3) by ClO that step (2) obtains
4 -the metal oxide impregnated of acid group load, in the aqueous solution of the compound of soluble hydrogenation/dehydrogenation metal component, is fully flooded, and then filtration, dry, roasting, obtain the ClO containing hydrogenation/dehydrogenation metal component
4 -the metal oxide catalyst of acid group load.
2. according to the method for claim 1, it is characterized in that, described isomerization reaction condition is: temperature of reaction is 70-450 DEG C, and pressure is 0.4-10.0MPa, the mol ratio of hydrogen and straight-chain paraffin raw material is (1-10): 1, and the weight hourly space velocity of straight-chain paraffin raw material is 0.5-10.0 hour
-1.
3. according to the method for claim 2, it is characterized in that, described isomerization reaction condition is: temperature of reaction 90-350 DEG C, and pressure is 0.9-6.0MPa, the mol ratio of hydrogen and straight-chain paraffin raw material is (1-8): 1, and the weight hourly space velocity of straight-chain paraffin raw material is 1.0-8.0 hour
-1.
4. according to the method for claim 1, it is characterized in that, described straight-chain paraffin raw material is C
4-C
6normal paraffin in the mixture of one or more, or containing C
4-C
6normal paraffin in the hydrocarbon fraction of one or more.
5. according to any one method in claim 1-4, it is characterized in that, take total catalyst weight as benchmark, and in described isomerization catalyst, the charge capacity of hydrogenation/dehydrogenation metal component is the heavy % of 0.05-5.0; With solid super-strong acid gross weight for benchmark, described ClO
4 -the charge capacity of acid group is the heavy % of 0.1-12.0.
6. according to the method for claim 5, it is characterized in that, take total catalyst weight as benchmark, and in described isomerization catalyst, the charge capacity of hydrogenation/dehydrogenation metal component is the heavy % of 0.1-3.0; With solid super-strong acid gross weight for benchmark, described ClO
4 -the charge capacity of acid group is the heavy % of 0.5-9.0.
7. according to any one method in claim 1-4, it is characterized in that, in described isomerization catalyst, described metal oxide is selected from the mixture of one or more in the oxide compound of Zr, Ti, Fe, V, Cr, Mo, W and Mn.
8. according to any one method in claim 1-4, it is characterized in that, in described isomerization catalyst, hydrogenation/dehydrogenation metal component is Pt.
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