CN1432550A - Alkane-hygrogenating isomerization reaction process - Google Patents
Alkane-hygrogenating isomerization reaction process Download PDFInfo
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Abstract
The present invention provides a straight chain alkane hydrogenating isomerization reaction process including making straight chain alkane containing material and hydrogen contact with hydrogenating isomerization catalyst in hydrogenation isomerization reaction condition, and features that the material contains compound with strong electronegative element in 5-10000, perferably 10-4000, as reaction assistant. The said hydrogenating isomerization reaction process has relatively high reaction balance converting rate and high isomeric alkane selectivity.
Description
Technical field
The present invention relates to the hygrogenating isomerization reaction process of alkane.The solid acid to contain the hydrogenation/dehydrogenation metal component that is particularly related to a kind of hydrogen and normal paraffin is the hygrogenating isomerization reaction process of catalyzer, and the hygrogenating isomerization reaction process of said hydrogen and alkane is meant that straight-chain paraffin and hydrogen reaction generate the catalytic reaction process of corresponding branched paraffin.
Background technology
The hygrogenating isomerization reaction of straight-chain paraffin is to produce the important process (" Chinese oil Refining Technologies ", Hou Xianglin chief editor, Sinopec press) with high-octane branched paraffin in the petrochemical complex industry.This reaction is that straight-chain paraffin is reacted the alkane that obtains side chain through skeletal isomerization.As everyone knows, C
4-C
6The octane value of straight-chain paraffin very low, can't be as the blend component of gasoline, and their corresponding branched paraffins have high octane value.Therefore, C
4-C
6Branched paraffin be the important blend component of reformulated gasoline.Normal butane isomerization reaction product Trimethylmethane is one of main raw material of alkylated reaction in addition.
The hygrogenating isomerization reaction process of normal paraffin has many courses of industrialization, the Butamer of American UOP company for example, and Penex, (U.S. NPRA can report AM-99-29 to technologies such as TIP, AM-90-12, AM-88-45; " Fuel Processing Technology, 35 (1993) 183).
Reaction method about normal alkane isomerization also has many patent reports:
United States Patent (USP) 5,157,199 have described C
4-C
6The hygrogenating isomerization reaction process of straight-chain paraffin, catalyst system therefor are Pt-SO
4 =/ ZrO
2, the isomerization reaction condition is: temperature is 200 ℃; Pressure is 790kPa; H
2The mol ratio of/alkane is 4.5: 1.And in reaction mass, add the diamantane C of 0.1-0.8 weight %
10H
16As reaction promoter.
United States Patent (USP) 5,905,181 have described C
10-C
40The hygrogenating isomerization reaction process of straight-chain paraffin.The nitrogenous compound resistance agent that has added 5-50000ppm in the reaction mass is as amine.Reaction conditions is: temperature is 250-500 ℃, and pressure is 1-25000Kpa, H
2The mol ratio of/alkane is for being 0.1: 1-10: 1.Can make the anti-sulphur of catalyzer after having added nitrogenous compound in the reaction mass, and improve the selectivity of reaction.
United States Patent (USP) 3,032,599 and European patent 0174,836 employing Pt-SO has also been described
4 =/ ZrO
2For catalyzer carries out C
4-C
6The method of straight-chain paraffin hydroisomerizing reaction.
United States Patent (USP) 5,057,471 have described the method for the hygrogenating isomerization reaction of straight-chain paraffin, and catalyzer is for carrying the mordenite of platinum (Pt).Reaction conditions is: temperature is 250 ℃, and pressure is 30atm, H
2The mol ratio of/alkane is 1: 1.
United States Patent (USP) 5,095,169 and 5,107,054 β zeolite and the MCM-22 molecular sieve of having described employing year platinum is the hygrogenating isomerization reaction process of the straight-chain paraffin of catalyzer.Reaction conditions is: temperature is 200-350 ℃, and pressure is 1-70atm, H
2The mol ratio of/alkane is 0.1: 1 to 10: 1.
United States Patent (USP) 5,256,277 have described the hygrogenating isomerization reaction process of straight-chain paraffin, and catalyst system therefor is the mesoporous molecular sieve material of load hydrogenation component platinum, and reaction conditions is: temperature is 90-430 ℃, and pressure is 1-100atm, H
2The mol ratio of/alkane is for being 0.1: 1 to 10: 1.
United States Patent (USP) 5,391,532 have described the hygrogenating isomerization reaction process of straight-chain paraffin.Catalyst system therefor is Pt-heteropolyacid or heteropolyacid salt/carrier (SiO
2, γ-Al
2O
3, ZrO
2, unformed SiO
2-Al
2O
3Deng).
United States Patent (USP) 6,080,904 have described the hygrogenating isomerization reaction process of straight-chain paraffin.Catalyst system therefor is Pt-W/ZrO
2Reaction conditions is: temperature is 93-425 ℃, and pressure is 1-7000Kpa, H
2The mol ratio of/alkane is for being 0.1: 1 to 10: 1.
Above-mentioned patent related to the present invention does not all relate to and add the micro-compound that contains the strong electronegativity element carries out isomerization reaction as reaction promoter technology among the present invention in the hygrogenating isomerization reaction raw material of straight-chain paraffin.
Summary of the invention
The hygrogenating isomerization reaction process that the purpose of this invention is to provide a kind of straight-chain paraffin.Adopt this method to have higher molecular balance transformation efficiency and isoparaffin selectivity preferably.
The present inventor is surprised to find that, if in isomerization reaction raw material straight-chain paraffin, add and contain the organic or inorganic compound of strong electronegativity element as reaction promoter, and select proper reaction conditions to carry out hygrogenating isomerization reaction, can improve the equilibrium conversion of reaction significantly, and prolong life of catalyst.We studies show that: add the auxiliary agent contain the strong electronegativity element in the mixture of reaction mass, when these auxiliary agents contact with the acid sites of the solid acid catalyst of load platinum in isomerization reaction, can interact.Its result has changed the original acid properties of solid acid catalyst, particularly strength of acid H significantly
oWith acid site density.Thereby changed the catalytic property of solid acid catalyst in the straight-chain paraffin hygrogenating isomerization reaction of load platinum significantly.
The method of the hygrogenating isomerization reaction of straight-chain paraffin provided by the present invention comprises a kind of raw material that contains straight-chain paraffin is contacted with a kind of hydroisomerization catalyst under the hydroisomerizing reaction conditions with hydrogen, it is characterized in that in said raw material, containing 5-10000ppm, preferred 10-4000ppm, more preferably the compound that contains the strong electronegativity element of 10-2000ppm is as reaction promoter.
When adopting the inventive method to carry out hygrogenating isomerization reaction, can obtain higher molecular balance transformation efficiency and isoparaffin selectivity preferably.
Embodiment
Said strong electronegativity element halogen preferably in the method provided by the invention, the said organic or inorganic compound that contains the strong electronegativity element be hydrogen halide or can be decomposed into the inorganic or organic compound of hydrogen halide under alkylation conditions preferably.In general all inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions may be used to the present invention, but preferred mineral compound is hydrogen halide such as HF, HCl, HBr and HI, is more preferably HF or HCl; Preferred organic compound is the halogen-containing organic compound with 2～8 carbon atoms.The said organic or inorganic compound that contains the strong electronegativity element also can be two or more the mixture in the above-claimed cpd.
Said organic compound includes, but not limited to have one or dihalogenated alkane of 2～8 carbon atoms, for example a fluoroethane in the method provided by the invention, monochlorethane, 1-fluoropropane, n-propyl chloride, 2-fluoropropane, 1-fluorine butane, 1-chlorobutane, 1-n-butyl bromide, 2-fluorine butane, 1,3-difluoro butane, 1,3-dichlorobutane, 1-fluorine iso-pentane, 1-fluorine hexane, 2-fluorine hexane, 1-fluorine heptane, n octyl fluoride, 2-fluoro-octane, 1-chloro-octane, fluoro octane-iso etc.
The said organic or inorganic compound that contains the strong electronegativity element is most preferred in the method provided by the invention is hydrogen fluoride or hydrogenchloride.
Said straight-chain paraffin is C in the method provided by the invention
4-C
6Straight-chain paraffin, as normal butane, Skellysolve A and normal hexane, or their mixture.
The condition of said hygrogenating isomerization reaction can be the reaction conditions that generally adopts in the prior art in the method provided by the invention, and for example temperature of reaction is 50-400 ℃, preferred 70-350 ℃; Pressure is 0.5-8.0MPa, preferred 2-7MPa; The molar ratio range of hydrogen and alkane is 0.5-10, preferred 1.0-5.0; The raw material weight air speed is 0.5-10 hour
-1, preferred 1.5-7.5 hour
-1
Said hydroisomerization catalyst is the corresponding catalyst of the hygrogenating isomerization reaction that is used for straight-chain paraffin of disclosed routine in the prior art in the method provided by the invention, and the present invention has no particular limits it.This catalyzer generally is the solid acid catalyst that contains the hydrogenation/dehydrogenation metal component, for example contains the solid acid catalyst of VIIIA family metallic element.As the example of this catalyzer, can enumerate, for example, contain heteropolyacid catalyst, heteropolyacid salt catalyst, carried heteropoly acid catalyst, carried heteropoly acid salt catalyst, zeolite [molecular sieve, the SO of Pt, Pa or Ni
4 2-/ oxide compound super acidic catalyst, loading type Br nsted-Lewis (being called for short B-L) conjugation solid super acid catalyst, solid polymerization ion exchange resin and with Br nsted or acid-treated oxide compound of Lewis or molecular sieve catalyst etc.In these catalyzer, particularly preferably be the carried heteropoly acid catalyst that contains Pt, Pa or Ni and contain the loading type Br nsted-Lewis conjugation solid super acid catalyst of Pt, Pa or Ni.
Said carried heteropoly acid catalyst is that porous inorganic carrier and a kind of heteropolyacid are formed in the method provided by the invention, and wherein said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is conventional porous inorganic carrier, comprise aluminosilicate zeolite, carbon fiber, natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic etc., or their mixture, wherein preferably silicon oxide, aluminum oxide or their mixture.
The said loading type B-L of method provided by the invention conjugation solid super acid catalyst preferably is made up of a kind of heteropolyacid of a kind of porous inorganic carrier of the heavy % of 40-95 and the load heavy % of 1-60 on it and a kind of Lewis acid of the heavy % of 0.3-15; Identical in the definition of said heteropolyacid and porous inorganic carrier and the explanation carried heteropoly acid class catalyzer to the definition of heteropolyacid and porous inorganic carrier; Said Lewis acid is selected from AlCl
3, BF
3Perhaps XF
5, wherein X is P, As, Sb or Bi.
The method of the hygrogenating isomerization reaction of straight-chain paraffin provided by the invention can be carried out in various reactors, as fixed-bed reactor, intermittently tank reactor, moving-burden bed reactor, liquefied bed reactor or three-phase slurry bed reactor etc.The flow pattern of material can be that upstriker also can be a downstriker.
The following examples will be further described specifically the present invention, but they can not be interpreted as the qualification to protection domain of the present invention.
In each embodiment and Comparative Examples, the hygrogenating isomerization reaction of said straight-chain paraffin carries out in autoclave.Analytical procedure: adopt the composition of SP-3420 chromatogram on-line analysis gas-phase product, chromatographic column is the OV-01 kapillary crosslinking column of 50m * 0.2mm, uses HP-5890 (hewlette-packard product) stratographic analysis isomerization product from C
5～C
10Full composition.Chromatographic column is the OV-01 capillary column of 50m * 0.2mm.
Embodiment 1
Carry out the hygrogenating isomerization reaction of Skellysolve A and hydrogen according to method provided by the invention.
Take by weighing 5.24g phospho-wolframic acid (H
3PW
12O
40.22H
2O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 35ml deionized water, be made into H
3PW
12O
40The aqueous solution.With the 18.5g granularity is 40-60 purpose silica gel (SiO
2, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing
3PW
12O
40Solution flooded 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtained containing 20 weight %H
3PW
12O
40With 80 weight %SiO
2Carried heteropoly acid catalyst, be designated as 20%H
3PW
12O
40/ SiO
2, the specific surface area of catalyzer is 380m
2/ g.The specific surface of catalyzer adopts cryogenic nitrogen absorption BET method to measure.The preparation method of other carried heteropoly acid catalyst is same as described above.
With 0.156g Platinic chloride H
2[PtCl
6] be dissolved in the 27ml deionized water, with 15.0g 20%H
3PW
12O
40/ SiO
2Be immersed in the above-mentioned platinum acid chloride solution, dipping is 3.0 hours under the room temperature, then 85 ℃ of dryings 10 hours.300 ℃ of roastings are 2.0 hours under air atmosphere, continue to obtain the Pt-H that platinum content is 0.5 weight % 400 ℃ of roastings 2.0 hours
3PW
12O
40/ SiO
2Catalyzer.
Before reacting, carry out the reduction of catalyzer earlier, the 5.0g catalyzer is packed in the autoclave of 250ml, at hydrogen flowing quantity is under the 200 ml/min conditions, be warmed up to 260 ℃ with 5 ℃/minute,, finish the reduction process of catalyzer 260 ℃ of reduction 5.0 hours.Under temperature of reaction, promptly can carry out isomerization reaction.
After the reduction of carrying out above-mentioned catalyzer, add the Skellysolve A (chemical pure, the Beijing Chemical Plant produces) that 10.0g contains 100ppm HF with high-pressure metering pump, arrive 5.0MPa with pressurized with hydrogen then, under the strong mixing (2000 rev/mins), be warmed up to 140 ℃ and react, react after 60 minutes stopped reaction.To be cooled to room temperature, with the gaseous product amount of accurate under meter metering reaction, the composition of chromatographically liquid reacting product, reaction result is listed in the table 1.
Each parameter-definition is as follows in each table of table 1 and back:
The transformation efficiency of reaction=(the normal paraffin weight/reaction that has transformed in the reaction initially just
The weight of structure alkane) * 100%
The selectivity of reaction=(transformed in the isoparaffin weight/reaction of generation
Normal paraffin weight) * 100%
The productive rate of isoparaffin=(the initial N-alkanes of the isoparaffin weight that generates in the reaction/react
The weight of hydrocarbon) * 100%
Table 1.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??76.4????68.1 |
| The optional wt % of iso-pentane | ??97.6????96.7 |
| The productive rate weight % of iso-pentane | ??74.5????65.8 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0 MPa; H
2/ alkane: 2.52 (mol ratios);
Reaction times: 60 minutes
Comparative Examples 1
Catalyzer, reaction conditions and reaction process are with embodiment 1, and reaction mass is the reaction mass among the embodiment 1, but do not contain any compound of strong electrolyte element that contains as reaction promoter.The results are shown among the embodiment 1-5 as a comparison of reaction.
Embodiment 2
In Skellysolve A, add the HF of 2000ppm as reaction promoter.Identical among the catalyzer that carries out hygrogenating isomerization reaction and process and the embodiment 1, reaction conditions sees Table 2, and reaction result is listed in the table 2.
Table 2.
| Reaction promoter ppm | ??2000????0 |
| Reaction conversion ratio weight % | ??77.6????68.1 |
| The optional wt % of iso-pentane | ??98.2????96.7 |
| The productive rate weight % of iso-pentane | ??76.2????65.8 |
Reaction conditions: temperature: 140 ℃; Pressure: 2.0MPa; H
2/ alkane: 1.02 (mol ratios);
Reaction times: 90 minutes
Embodiment 3
In the reaction raw materials Skellysolve A, add organic fluoride-butyl fluoride of 500ppm as reaction promoter.Identical among catalyzer, reaction conditions and the process of carrying out hygrogenating isomerization reaction and the embodiment 1, reaction result is listed in the table 3.
Table 3.
| Reaction promoter ppm | ??500?????0 |
| Reaction conversion ratio weight % | ??75.2????68.1 |
| The optional wt % of iso-pentane | ??98.2????96.7 |
| The productive rate weight % of iso-pentane | ??738?????65.8 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0Mpa; H
2/ alkane: 2.52;
Reaction times: 60 minutes
Embodiment 4-5
Catalyzer changes alkylation reaction condition and is condition 1: 90 ℃ of temperature of reaction, condition 2: 250 ℃ of temperature of reaction with embodiment 1.Identical among other reaction masses and auxiliary agent, reaction method and process and the embodiment 1, reaction result is listed in the table 4.
Table 4.
| Temperature of reaction ℃ | ??90??????250 |
| Reaction conversion ratio weight % | ??73.3????84.1 |
| The optional wt % of iso-pentane | ??98.8????82.5 |
| The productive rate weight % of iso-pentane | ??72.4????69.4 |
Reaction pressure: 5.0Mpa; Reaction times: 60 minutes
Embodiment 6
Silicotungstic acid catalyst (0.5%Pt-20%H with 6.0g load platinum
4SiW
12O
40/ SiO
2, the preparation method is with embodiment 1) and in the reactor of packing into, identical among the reaction mass, reaction conditions that carries out hygrogenating isomerization reaction and process and the embodiment 1, reaction result is listed in the table 5.
Comparative Examples 2
Catalyzer, reaction conditions and the reaction process of carrying out hygrogenating isomerization reaction are with embodiment 6, and reaction mass is the reaction mass among the embodiment 6, but do not contain any compound of strong electrolyte element that contains as reaction promoter.The results are shown in Table 5 in reaction as a comparison.
Table 5.
| Reaction promoter ppm | ??150?????0 |
| Reaction conversion ratio weight % | ??76.8????67.1 |
| The optional wt % of iso-pentane | ??97.1????96.7 |
| The productive rate weight % of iso-pentane | ??74.6????64.9 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0MPa; H
2/ alkane: 2.52;
Reaction times: 60 minutes
Embodiment 7
With preparation C
S2.5H
0.5PW
12O
40Be example, the preparation method of various heteropolyacid salts be described:
With 22.81g phospho-wolframic acid (H
3PW
12O
40.21H
2O, chemical reagent factory of Beijing Xinhua product, analytical pure) and 2.85gC
S2CO
3(northern Tonghua factory products, analytical pure) is made into the solution of 0.35 and 0.87 volumetric molar concentration respectively by above-mentioned stoichiometric equation weighing, under violent stirring, with C
S2CO
3Solution is added dropwise to H very lentamente
3PW
12O
40In the solution, C
S2CO
3After solution dropwises, continue to stir 30 minutes, then with the white precipitate that obtains 50 ℃ of dryings 24 hours, obtain C
S2.5H
0.5PW
12O
40.8H
2The O heteropolyacid salt.With the C for preparing
S2.5H
0.5PW
12O
40.8H
2O is levigate, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 40～60 purpose particles as catalyzer.
The method of load platinum obtains 0.5 weight %Pt-C with embodiment 1
S2.5H
0.5PW
12O
40Catalyzer.
Identical among reaction mass, reaction conditions and the process of carrying out hygrogenating isomerization reaction and the embodiment 1.Reaction result is listed in the table 6.
Comparative Examples 3
Catalyzer, reaction conditions and the reaction process of carrying out hygrogenating isomerization reaction are with embodiment 7, and reaction mass is the reaction mass among the embodiment 7, but do not contain any compound of strong electrolyte element that contains as reaction promoter.The results are shown in Table 6 in reaction as a comparison.
Table 6.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??77.9????67.3 |
| The optional wt % of iso-pentane | ??98.7????95.5 |
| The productive rate weight % of iso-pentane | ??76.9????64.3 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0Mpa; H
2/ alkane: 2.52;
Reaction times: 60 minutes
Embodiment 8
Solid acid alkylation catalysts among this embodiment is that (B:Br nsted acid is H to B-L conjugation super acids here
3PW
12O
40L:Lewis acid is SbF here
5).This Preparation of catalysts method is as follows: the method for pressing among the embodiment 1 prepares 20%H earlier
3PW
12O
40/ SiO
2Catalyzer is then with this 20%H of 10.0g
3PW
12O
40/ SiO
2Packing in the reactor, is 120 hours with air speed
-1Nitrogen gas stream handled 4 hours at 100 ℃, cool to 50 ℃ then, make nitrogen gas stream SbF is housed through one
5Storage bottle, carry SbF
5The above-mentioned catalyzer of flowing through makes SbF
5Obtain B-L acid with the heteropolyacid interaction, purged 1.0 hours with nitrogen gas stream at last, finish preparation.The gained catalyzer is designated as H
3PW
12O
40-SbF
5/ SiO
2Catalyzer.
The method of load platinum obtains 0.5 weight %Pt-H with embodiment 1
3PW
12O
40-SbF
5/ SiO
2Catalyzer.
Identical among the reaction mass that carries out hygrogenating isomerization reaction and auxiliary agent, reaction process and the embodiment 1, reaction conditions and the results are shown in Table 7.
Comparative Examples 4
Catalyzer, reaction conditions and the reaction process of carrying out hygrogenating isomerization reaction are with embodiment 8, and reaction mass is the reaction mass among the embodiment 8, but do not contain any compound of strong electrolyte element that contains as reaction promoter.The results are shown in Table 7 in reaction as a comparison.
Table 7.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??78.2????67.6 |
| The optional wt % of iso-pentane | ??97.8????95.7 |
| The productive rate weight % of iso-pentane | ??76.4????64.7 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0 Mpa; H
2/ alkane: 2.52;
Reaction times: 60 minutes
Embodiment 9
With 20.0g zirconium oxychloride (ZrOCl
2.8H
2O, analytical pure, Beijing Chemical Plant) be dissolved in the 180ml water, room temperature under the agitation condition, slowly splashes into 25% ammonia soln, is 10.5 until the pH of solution value, stops dropping ammonia and stirring, aged at room temperature 24 hours, then with distilled water wash, be filtered to no Cl
-Ion, 100 ℃ of dryings 5 hours obtain Zr (OH)
4With the Zr behind the platinum acid chloride solution impregnation drying (OH)
4, method is with embodiment 1.The Zr (OH) of Platinic chloride will have been flooded
4100 ℃ of dryings 3 hours.Preparation 1.0M sulphuric acid soln is pressed 10ml acid solution/1gPt-Zr (OH)
4Ratio with 1.0M sulphuric acid soln dipping Pt-Zr (OH)
4Solid 4.0 hours filters out unnecessary acid solution, and 100 ℃ of dryings 3 hours 650 ℃ of roasts 4.0 hours, obtain 0.5 weight %Pt-SO then
4 =/ ZrO
2Catalyzer.With the Pt-SO for preparing
4 =/ ZrO
2Catalyzer is worn into fine powder, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 20～40 purpose particles as catalyzer.
Identical among catalyst reduction and reaction process and the embodiment 1, identical among the reaction mass that carries out hygrogenating isomerization reaction and auxiliary agent, reaction process and the embodiment 1, reaction conditions and the results are shown in Table 8.
Comparative Examples 5
Catalyzer, reaction conditions and the reaction process of carrying out hygrogenating isomerization reaction are with embodiment 9, and reaction mass is the reaction mass among the embodiment 9, but do not contain any compound of strong electrolyte element that contains as reaction promoter.The results are shown in Table 8 in reaction as a comparison.
Table 8.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??74.4????69.7 |
| The optional wt % of iso-pentane | ??98.6????98.9 |
| The productive rate weight % of iso-pentane | ??73.4????68.9 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0Mpa; H
2/ alkane: 2.52;
Reaction times: 60 minutes
Embodiment 10
Carry out the hygrogenating isomerization reaction of hexane and hydrogen according to method provided by the invention.Catalyzer, reaction conditions and reaction process change reaction mass into the normal hexane reaction result and list in the table 9 with embodiment 1.
Table 9.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??89.4????80.9 |
| The optional wt % of isohexane | ??96.6????94.7 |
| The productive rate weight % of isohexane | ??86.4????76.6 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0MPa; H
2/ alkane: 3.02;
Reaction times: 90 minutes
Embodiment 11
Carry out the hygrogenating isomerization reaction of hexane and pentane admixture and hydrogen according to method provided by the invention.
Catalyzer, reaction conditions and reaction process change reaction mass in the mixture of 50% normal hexane and 50% Skellysolve A with embodiment 1.Reaction result is listed in the table 10.
Table 10.
| Reaction promoter ppm | ??100?????0 |
| Reaction conversion ratio weight % | ??84.6????79.4 |
| Isoparaffin optional wt % | ??98.6????94.1 |
| The productive rate weight % of isoparaffin | ??83.4????74.7 |
Reaction conditions: temperature: 140 ℃; Pressure: 5.0Mpa; H
2/ alkane: 2.75;
Reaction times: 90 minutes
Claims (15)
1, a kind of straight-chain paraffin hygrogenating isomerization reaction process, comprise a kind of raw material that contains straight-chain paraffin is contacted with a kind of hydroisomerization catalyst under the hydroisomerizing reaction conditions with hydrogen, it is characterized in that in said raw material, containing the compound that contains the strong electronegativity element of 5-10000ppm as reaction promoter.
2,, it is characterized in that in said raw material, containing the compound that contains the strong electronegativity element of 10-4000ppm as reaction promoter according to the method for claim 1.
3, according to the method for claim 1 or 2, wherein said strong electronegativity element is a halogen.
4, according to the method for claim 1 or 2, the wherein said compound that contains the strong electronegativity element is hydrogen halide or the inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions.
5, according to the method for claim 4, wherein said organic compound is one or a dihalogenated alkane with 2～8 carbon atoms.
6, according to the process of claim 1 wherein that the said compound that contains the strong electronegativity element is hydrogen fluoride or hydrogenchloride.
7, according to the process of claim 1 wherein that said straight-chain paraffin is normal butane, Skellysolve A or normal hexane, or their mixture.
8, according to the process of claim 1 wherein that the condition of said hygrogenating isomerization reaction is that temperature of reaction is 50-400 ℃, pressure is 0.5-8.0MPa, and the molar ratio range of hydrogen and alkane is 0.5-10, and the raw material weight air speed is 0.5-10 hour
-1
9, according to the method for claim 8, wherein the condition of said hygrogenating isomerization reaction is that temperature of reaction is 70-350 ℃, and pressure is 2-7MPa, and the molar ratio range of hydrogen and alkane is 1.0-5.0, and the raw material weight air speed is 1.5-7.5 hour
-1
10, according to the process of claim 1 wherein that said hydroisomerization catalyst is heteropolyacid catalyst, heteropolyacid salt catalyst, carried heteropoly acid catalyst, carried heteropoly acid salt catalyst, zeolite [molecular sieve, the SO that contains Pt, Pa or Ni
4 2-/ oxide compound super acidic catalyst, loading type Br nsted-Lewis (being called for short B-L) conjugation solid super acid catalyst, solid polymerization ion exchange resin or with Br nsted or acid-treated oxide compound of Lewis or molecular sieve catalyst.
11, according to the process of claim 1 wherein that said hydroisomerization catalyst is the loading type Br nsted-Lewis conjugation solid super acid catalyst that contains the carried heteropoly acid catalyst of Pt, Pa or Ni or contain Pt, Pa or Ni.
12, according to the method for claim 10 or 11, wherein said carried heteropoly acid catalyst is made up of porous inorganic carrier and a kind of heteropolyacid, and wherein said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is aluminosilicate zeolite, carbon fiber or the natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic, or their mixture.
13, according to the method for claim 12, wherein said porous inorganic carrier is silicon oxide, aluminum oxide or their mixture.
14, according to the method for claim 10 or 11, wherein said loading type Br nsted-Lewis conjugation solid super acid catalyst is made up of a kind of heteropolyacid of a kind of porous inorganic carrier of the heavy % of 40-95 and the load heavy % of 1-60 on it and a kind of Lewis acid of the heavy % of 0.3-15; Wherein said heteropolyacid general formula is H
8-n[AM
12O
40], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is aluminosilicate zeolite, carbon fiber or the natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic, or their mixture; Said Lewis acid is selected from AlCl
3, BF
3Perhaps XF
5, wherein X is P, As, Sb or Bi.
15, according to the method for claim 14, wherein said porous inorganic carrier is silicon oxide, aluminum oxide or their mixture.
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| CN106334570A (en) * | 2015-07-09 | 2017-01-18 | 中国石油化工股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
| CN106964398A (en) * | 2017-03-09 | 2017-07-21 | 武汉凯迪工程技术研究总院有限公司 | Hydroisomerizing dewaxing catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3577479A (en) * | 1968-08-09 | 1971-05-04 | Sun Oil Co | Aluminum halide isomerization of saturated hydrocarbons |
| US3848019A (en) * | 1970-12-24 | 1974-11-12 | Phillips Petroleum Co | Catalytic conversion of hydrocarbons using a rhenium-alumina catalyst |
| FR2206124B1 (en) * | 1972-11-10 | 1976-08-20 | Inst Francais Du Petrole | |
| US5591689A (en) * | 1995-06-23 | 1997-01-07 | Phillips Petroleum Company | Preparation of isomerization catalyst composition |
| US6090992A (en) * | 1998-12-08 | 2000-07-18 | Phillips Petroleum Company | Isomerization catalyst system, method of making and method of using such catalyst system in the isomerization of saturated hydrocarbons |
-
2002
- 2002-01-10 CN CNB02100238XA patent/CN100425583C/en not_active Expired - Lifetime
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