CN100496724C - Solid phosphoric acid catalyst and methods of dimerizing olefin with the same - Google Patents
Solid phosphoric acid catalyst and methods of dimerizing olefin with the same Download PDFInfo
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Abstract
A solid phosphoric acid catalyst which attains high activity and dimer selectivity in olefin dimerization reactions; and efficient methods for olefin dimerization which comprise using the catalyst. The solid phosphoric acid catalyst comprises a siliceous support and one or more phosphoric acids deposited thereon, the proportion of orthophosphoric acid in the phosphoric acids deposited being 60 mol% or higher in terms of phosphorus atom amount. The solid phosphoric acid catalyst is prepared by contacting a siliceous support with an aqueous phosphoric acid solution and then drying the support, the preparation steps being conducted at a temperature lower than 100 DEG C. Also provided is a method in which an olefin-containing raw material is brought into contact with the catalyst. Furthermore provided are: the method in which the olefin-containing raw material is regulated so as to contain water in an amount of 10-1,000 mass ppm; the method in which the olefin-containing raw material is brought into contact with the solid phosphoric acid catalyst in a liquid phase; and the method in which the olefin is a C3-7 monoolefin.
Description
Technical field
The present invention relates to comprise the solid phosphoric acid catalyst that loads on the phosphoric acid on the carrier, and relate to this solid phosphoric acid catalyst of use carries out selective dimerisationization to alkene method.
Background technology
The oligomer of alkene is used for various uses, particularly, the dimer of low molecular weight olefins (for example propylene, n-butene, isobutene, amylene etc.) is important as the high-octane rating raw material for producing gasoline, also is being important aspect the chemical intermediate raw material perhaps.The low dimerization that comprises dimerizing olefinsization is to use acid catalyst to implement, and this has been made a lot of researchs.The conventional example of acid catalyst comprises sulfuric acid, hydrofluoric acid, phosphoric acid, aluminium chloride, boron fluoride, amorphous or crystalline aluminosilicate, clay, ion exchange resin, composite oxides and such as the solid acid that loads on the acid on the solid carrier, and also solid phosphoric acid catalyst has been done various detections, it provides cheap and simple chemical production processes.
Disclose the use solid phosphoric acid with oligomeric acrylamideization, described solid phosphoric acid is (patent documentation 1) for preparing under 100 ℃ or higher calcination condition; Also disclose the use catalyst with oligomeric acrylamideization, described catalyst is to be (catalyst of being made up of orthophosphoric acid silicon and pyrophosphoric acid silicon) (patent documentation 2) for preparing by the amorphous mixture crystallization that makes phosphoric acid and siliceous raw material under the condition of 3-50mol% at 250-450 ℃ and water vapor concentration.
Known now, the condensation level of the phosphoric acid in the solid phosphoric acid catalyst influences the activity of the oligomerization of alkene, and also disclose and used catalyst to make the example of the olefin oligomerizationization of C3, C4 etc., the mass ratio less (with regard to the phosphorus atoms amount, the ortho-phosphoric ratio in the phosphoric acid of institute's load is about 46mol% at the most) (patent documentation 3 and non-patent literature 1) of the free phosphoric acid composition (such as the non-condensation or the low condensation phosphoric acid of orthophosphoric acid or pyrophosphoric acid) that wash-out goes out when solid phosphoric acid catalyst is under water and catalyst wherein.
But, using above-mentioned traditional phosphoric acid catalyst is not the dimerization that is used for alkene to the main purpose that alkene hangs down dimerization, and use the conventional solid phosphoric acid catalyst to relate to the accessory substance of the high polymerizating product of alkene inevitably, therefore, optionally provide the dimer of alkene comparatively difficult.
In the phosphate aqueous solution load operation, although be subjected to effects of operation conditions such as operating time or temperature, the ortho-phosphoric condensation of institute's load is more easily carried out in the dry run.In case even after load, be easy to carry out in a like fashion condensation.As hereinafter described, particularly, the low orthophosphoric acid concentration in total phosphoric acid helps carrying out condensation.Equally, as described in patent documentation 3, through the only dissolving (patent documentation 3, the aft section of paragraph 0036) very lentamente in water of highly condensed phosphoric acid of condensation.That is to say that the hydrolysis of highly condensed phosphoric acid is carried out slowlyer in fact.
In other words, in traditional phosphate aqueous solution load operation, because therefore the low orthophosphoric acid concentration in total phosphoric acid etc. be easy to carry out condensation, and certainly will improve the load capacity of highly condensed phosphoric acid.Therefore, under above-mentioned situation (with regard to the phosphorus atoms amount, the ortho-phosphoric ratio in the phosphoric acid of institute's load is about 46mol% at the most), even output orthophosphoric acid, ortho-phosphoric actual ratio will be much smaller than the maximum as theoretical value (about 46mol%), because condensation is being carried out.Highly condensed phosphoric acid for condensation in dry run and load is difficult for turning back to orthophosphoric acid, though with its then with reaction system in liquid state or vaporous water contact and hydrolysis.In addition, in the orthophosphoric acid of institute's load, can carry out condensation to orthophosphoric acid, even Zong the orthophosphoric acid concentration in the phosphoric acid is higher and lower according to reaction condition.
Patent documentation 1: special fair 8-29251 number public Reported
Patent documentation 2: special fair 7-59301 number public Reported
Patent documentation 3: the spy opens public Reported 2001-199907 number
Non-patent literature 1: " Applied Catalysis A:General ", 1993,97, p.177-196
Summary of the invention
The invention provides and in dimerizing olefins reaction, demonstrate high activity and dimer optionally solid phosphoric acid catalyst and the effective ways that alkene carried out dimerization.
According to a first aspect of the invention, described solid phosphoric acid catalyst comprises that the phosphoric acid that loads on the carrier (comprises the material that can become phosphoric acid by hydrolysis, Hereinafter the same go up), with regard to the phosphorus atoms amount, the ortho-phosphoric ratio in the phosphoric acid of institute's load is 60mol% or higher.
According to a second aspect of the invention, carry out drying then and prepare by phosphate aqueous solution being contacted described carrier, implement this preparation process being lower than under 100 ℃ the temperature according to the solid phosphoric acid catalyst of first aspect.
According to a third aspect of the invention we, the method that alkene is carried out dimerization comprises and will contain the olefin feedstock contact according to first or the solid phosphoric acid catalyst of second aspect.
According to a forth aspect of the invention, in method, describedly contain the water that olefin feedstock comprises 10 to 1000 quality ppm according to the third aspect.
According to a fifth aspect of the invention, according to the 3rd or the method for fourth aspect in, the described olefin feedstock that contains contacts with solid phosphoric acid catalyst in the liquid phase.
According to a sixth aspect of the invention, in the method according to either side in aspect the 3rd to the 5th, described alkene is the monoolefine of C3-C7.
The invention effect
Solid phosphoric acid catalyst of the present invention is particularly suitable for dimerizing olefins reaction, and can generate olefin dimers effectively, because its catalytic life that has high activity and dimer selectivity and have prolongation in reaction.
Implement the best approach of the present invention
To describe the present invention below.
Carrier for the solid phosphoric acid catalyst that uses in the present invention, can use can load phosphoric acid any carrier, it preferably includes but is not limited to the mechanograph of siliceous supports (for example diatomite (diatomite), trichomonad soil (infusorial earth), infusorial earth (ciliate earth), diatomite (kieselguhr), kaolin, bleaching earth and artificial porous tripoli and their mixture).In the molding process of carrier, can under any temperature conditions, implement calcining, thereby make it have enough intensity, space capacity and specific area.Shape to method of moulding and mechanograph has no particular limits, and for example can form the various mechanographs of granular, sheet or spherical form by granulation in compressing tablet, extrusion molding, spray-drying, rotating granulation or the oil, and particle diameter is about 0.5 to 5mm.
The instantiation of phosphoric acid comprises orthophosphoric acid and condensation product (pyrophosphoric acid, polyphosphoric acid etc.) thereof.In load operation, can also use hydrolyzable to become the material (phosphoric acid precursor) of phosphoric acid, for example C1 to C8 alcohol phosphate.Can also use their mixture.
In catalyst, the ratio of phosphoric acid and carrier is 10 to 200 quality %, be preferably 30 to 120 quality % (with phosphoric acid in orthophosphoric acid, the ortho-phosphoric amount that is generated when perhaps the phosphoric acid beyond the orthophosphoric acid being changed into complete hydrolysis; The back is referred to as " phosphoric acid load capacity ").In dimerizing olefins reaction, less load capacity causes low activity, and bigger load capacity increases the wash-out of phosphoric acid in the reaction solution, thereby causes the undesirable corrosion to device and equipment.
In the present invention, the ratio that loads on orthophosphoric acid in the phosphoric acid on the carrier and other condensation polyphosphoric acid etc. is very important.That is to say, with regard to the phosphorus atoms amount, when the ortho-phosphoric ratio in the phosphoric acid be 60mol% or higher, be preferably 70mol% or higher, more preferably for 80mol% or when higher, can in the dimerizing olefins reaction, provide high activity and dimer selectivity.
Though with regard to the phosphorus atoms amount when the ortho-phosphoric ratio in the phosphoric acid be 60mol% or when higher ortho-phosphoric condensation progress extremely slow, but when ratio during less than 60mol%, progress is faster showed in ortho-phosphoric condensation, thereby causes activity to reduce suddenly in the dimerizing olefins reaction.For high activity and dimer selectivity are kept a long-time section in the dimerizing olefins reaction, be very important with the alkene contact catalyst, the ortho-phosphoric ratio in this catalyst in the phosphoric acid is 60mol% or higher.
The method that is used for the ortho-phosphoric ratio in the catalyst phosphoric acid of measuring is had no particular limits, but phosphorus nuclear (
31P) solid-state nuclear magnetic resonance spectrum is only method.According to condensation level, the chemical displacement value of the phosphorus of phosphoric acid nuclear is shifted to higher magnetic field, and when ortho-phosphoric shift value is made as 0ppm, observes the shift value of pyrophosphoric acid and polyphosphoric acid at pact-11.8ppm peace treaty-24.3ppm place respectively.Determine the area ratio thereby these signals separate through waveform, can measure phosphoric acid condensation composition thus.
In measuring process or preparing (preliminary treatment) in the stage, need avoid catalyst to contact with moisture.When catalyst in measuring process or preparing (preliminary treatment) when contacting with moisture in the stage, the phosphoric acid partial hydrolysis of condensation in the catalyst, and become orthophosphoric acid.Therefore, can not implement to measure accurately.
For carrying method, preferably catalyst is immersed in the phosphate aqueous solution, carry out drying subsequently, perhaps will be undertaken moldedly by mixing paste that siliceous supports and phosphate aqueous solution obtained, carry out drying subsequently.
Above method is particularly preferred, because when being eluted to the phosphoric acid amount that reduces institute's load in the reaction solution owing to the phosphoric acid in the catalyst in the dimerization reaction process, can suitably supply with phosphoric acid by catalyst is flooded once more.In following method, can adopt and method of moulding identical during carrier is molded and identical mechanograph shape.
For Preparation of catalysts, carrier is immersed in the carrying method that carries out drying in the phosphate aqueous solution subsequently with specifically describing.The device that is used to prepare catalyst is had no particular limits, can use common groove at intermittence.Be used to implement the reactor that dimerizing olefins reacts by use, can when Preparation of Catalyst, implement the filling of catalyst simultaneously.Concentration to the phosphate aqueous solution that is used to flood has no particular limits, but generally is made as about 10 to 80 quality %.Can change concentration according to the phosphoric acid load capacity of expection.
In order to ensure the phosphoric acid load capacity of 70 quality %, for example generally the concentration of phosphate aqueous solution is made as 35 to 45 quality %, though it changes according to the performance such as surface area of carrier.Generally dip time can be set to about 1 hour or longer.Dipping temperature is set to is lower than 100 ℃, preferably be not higher than 50 ℃.100 ℃ or higher hot conditions are not preferred, because the ortho-phosphoric ratio in the phosphoric acid may be lower.In addition,, can not flood,, more preferably be set to 15 ℃ or higher so temperature preferably is set to 0 ℃ or higher because low excessively temperature causes solidifying.
After dipping,, can suitably remove redundant moisture by evaporation drying or by being in the atmosphere or by the use air-flow by after removing unnecessary phosphate aqueous solution such as the conventional method that filters.For being used for dry gas, can use any gas that under drying condition, becomes gaseous state, and be not particularly limited, and the saturated hydrocarbon of air, nitrogen, hydrogen and C1 to C5 is suitable.Gas can comprise saturation capacity or steam still less.For example can at room temperature use the gas that comprises 2.5 volume % or steam still less to implement drying.Baking temperature is set to is lower than 100 ℃, preferably be not higher than 50 ℃.Under 100 ℃ or higher temperature, cause the quick condensation of phosphoric acid, cause the ortho-phosphoric ratio in the phosphoric acid to reduce, be not preferred therefore.Reduce drying efficiency because cross low temperature,, more preferably be set to 5 ℃ or higher so baking temperature preferably is set to 0 ℃ or higher.Suitably adjust the drying time and the flow velocity of gas, thereby the ortho-phosphoric ratio in the phosphoric acid becomes in above-mentioned scope, for example with regard to the phosphorus atoms amount, is not less than 60mol%, guarantees that simultaneously phosphoric acid carries out condensation by drying.Can highly condensed phosphoric acid catalyst be turned back to low condensation state (having 60mol% or higher orthophosphoric acid ratio) by impregnation process once more and use the highly condensed phosphoric acid catalyst that has through the phosphoric acid of condensation in advance.
For the alkene that contains olefin feedstock, can use the monoolefine of C3 to C7, can be used alone or in combination linear alkene, branched-chain alkene and cycloolefin according to the expection product.Its instantiation comprises propylene, butylene (1-butylene, suitable-the 2-butylene, anti--the 2-butylene, isobutene), positive amylene, iso-amylene, cyclopentene, n-hexylene, dissident's alkene, cyclohexene, nhepene, iso-heptene, cycloheptene etc.The dimerization of alkene means that 2 moles raw material olefin generates 1 mole alkene by reaction (under the situation of mixed olefin feedstock, comprising the reaction between the different material alkene).
In the present invention, as raw material olefin, for example be fit to use butylene.
In the dimer that butylene produced, isooctene is useful as the high-octane rating raw material for producing gasoline.High-purity diisobutene can be used as the raw material such as the functionalized chemical product of octyl phenol and different n-nonanoic acid.
In the production of the dimer of butylene, can be used alone butylene, but the mixture that also can use several butylene to mix mutually with any ratio.Preferably adjust the composition of butylene according to the desirable characteristics (octane number etc.) of the dimerization product of using and being produced.Satisfying under the scope of desirable characteristics, wherein can comprise other alkene, for example propylene, straight chain amylene, side chain amylene, cyclopentene, hexene, heptene etc.
The supply source that contains olefin feedstock is had no particular limits, and the example is included in the olefine fraction produced in the FCC technology, by removing olefine fraction that diene component obtained, coking fraction of exhaust gas, products of dehydrogenation reactions etc. and by with any ratio their being mixed the mixture that is obtained from extract or select the cut that hydrogenation generates the naphtha pyrolysis stove.The content that can improve and reduce specific cut by the known method of use such as distillation further it adjusts.For example can use the isobutene-iso-butane cut that contains the high concentration isobutene, it can obtain by distillation (or reaction distillation) the removal n-butene and the normal butane of FCC-C4 cut; Perhaps can use by extracting the residual fraction that butadiene obtains in the C 4 fraction that from the naphtha pyrolysis stove, generates.
When these cuts were used for the dimerization reaction of butylene, only otherwise the influence reaction, they can contain the impurity of trace, for example butadiene.
In order to remove reaction heat, can use the olefin feedstock that contains that contains solvent.Can use in the dimerization reaction condition and be liquid and be nonactive any solvent substantially solid phosphoric acid catalyst.For example can use hydrocarbon such as n-alkane, isoparaffin, cycloalkane and aromatic hydrocarbon.Saturated hydrocarbon such as the butane in residue or the C 4 fraction also can be used as solvent.Adjusting the amount of solvent, is 1 to 70 quality % thereby make alkene and the ratio that contains the olefin feedstock total amount that contains this alkene and solvent, is preferably 10 to 65 quality %, more preferably is 15 to 60 quality %.Cross a large amount of solvents and reduce productivity ratio, reduce the heat abstraction rate and cross solvent in a small amount.
In the present invention, preferably will contain olefin feedstock contacts with solid phosphoric acid catalyst in the liquid phase.In gas phase, the coking meeting causes active and the reduction of dimer selectivity in the dimerizing olefins reaction, and shortens catalyst life.
Reactor and the reaction type that is used for the dimerizing olefins reaction had no particular limits, can use intermittence, semi-batch or continuous flowing type reaction, also can adopt continuous flowing type reaction by fixed bed, fluid bed and moving bed flow reactor by the container type reactor.Reaction temperature is set to 0 to 300 ℃, preferably is set to 20 to 200 ℃.Enough reaction rates can not be guaranteed being lower than under 0 ℃ the temperature, and side reaction can be increased being higher than under 300 ℃ the temperature.Reaction pressure preferably is set to from atmosphere is pressed onto 20MPa, because reaction system can not keep liquid phase under lower pressure, and equipment cost can increase under elevated pressures.WHSV (per hour the carrier of per unit mass supply raw materials quality) is set to from 0.1 to 300hr
-1, preferably from 1 to 150hr
-1Under the situation of less WHSV, production efficiency is lower, and under the situation of bigger WHSV, reaction is not carried out.
As mentioned above, though when the ortho-phosphoric ratio in the phosphoric acid with regard to the phosphorus atoms amount be 60mol% or when higher ortho-phosphoric condensation progress extremely slow, ortho-phosphoric condensation can progressively be carried out along with the carrying out of dimerization reaction according to reaction condition in the catalyst.
In order to prevent that orthophosphoric acid carries out condensation in the catalyst, moisture is coexisted as in the reaction system.Provide the method for moisture to have no particular limits to being used to, can the water of scheduled volume be dissolved in by mixing apparatus and contain in the olefin feedstock, and offer reactor.Contain that moisture is 10 to 1000 quality ppm in the olefin feedstock, preferred 30 to 50 quality ppm, more preferably 50 to 300 quality ppm.
When moisture during less than above-mentioned scope, the catalyst regeneration frequency increases, and is lower than 60mol% because the orthophosphoric acid ratio in the catalyst in the phosphoric acid was reduced in the short relatively time, thereby causes productivity ratio to reduce.On the other hand, when moisture was big, excessive moisture (particularly, the water yield surpasses the saturation water component of material solution) washed away the phosphoric acid in the catalyst, thus active can undesirably the reduction.When the phosphoric acid in the catalyst washes away when reducing by this mode, can continue to add phosphoric acid, and suitably offer reaction system (catalyst bed).
Embodiment 1
Extrusion die goods (1.6mm ф * 2mm) be immersed in the 31 quality % phosphate aqueous solutions of the 60ml in the 100ml beaker with 12.0g diatomite (diatomite).After dipping reaches 1 hour, by granular membrane the aqueous solution is removed, the indoor enforcement standing and drying with 25 ℃ temperature and humidity of 50% 2 hours, thereby prepare solid phosphoric acid catalyst A.Adopt the solid-state nuclear magnetic resonance spectrum to catalyst carry out phosphorus (
31P) analyze the composition (mol%, with regard to the phosphorus atoms amount, the back is the same) that draws institute's load phosphoric acid and comprise orthophosphoric acid 85% and pyrophosphoric acid 15%, and do not comprise polyphosphoric acid.Record by acid-base titration, with regard to the orthophosphoric acid amount, phosphoric acid amount is 20 quality % in the catalyst, and by washing with water after catalyst removes phosphoric acid, then carries out drying, and the ratio of carrier is 77.5 quality % in the catalyst.Therefore, the phosphoric acid load capacity is 25.8 quality %.
With 2g solid phosphoric acid catalyst A be loaded on the tubular type stainless steel reactor (internal diameter: 8mm), and dimerization reaction implemented 30 days continuously, simultaneously from the top of reactor with 40g/h (WHSV=26h
-1) the speed supply contain the raw material (isobutene is 30 quality %, and n-butene is 5 quality %, and n-hexane is 65 quality %, and water is 250mass ppm) of isobutene, and extract reaction product solution out from the bottom of reactor.Under the catalyst bed temperature of the pressure of 1.0MPa and 80 ℃, keep liquid phase state.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 2
(1mm ф * 2mm) is loaded on tubular type stainless steel reactor (internal diameter: 8mm) with the diatomaceous extrusion die goods of 3.0g.Only can enough all flooding the phosphate aqueous solution that diatomaceous amount is introduced 31 quality %, and phosphate aqueous solution is removed in the bottom from reactor after one hour from the bottom of reactor.When room temperature (25 ℃) down and with the speed of 1L/H is introduced the moisture that contains 2 volume % from the top of reactor nitrogen is 90 minutes then, then it is discharged from the bottom, implement drying with this.The solid phosphoric acid catalyst B that part from reactor is taken out with the mode identical with embodiment 1 analyzes.Found that the composition of the phosphoric acid of institute's load comprises orthophosphoric acid 87% and pyrophosphoric acid 13%, and does not comprise polyphosphoric acid.The amount of phosphoric acid in the catalyst (with regard to the orthophosphoric acid amount) is 19 quality %, and the ratio of carrier is 77.7 quality % in the catalyst, so the phosphoric acid load capacity is 24.4 quality %.The amount of remaining catalyst is 1.86g in reactor.
Then, dimerization reaction continue was implemented 30 days, simultaneously from the top of reactor with 40g/h (WHSV=28h
-1) speed introduce the raw material (isobutene is 30 quality %, and n-butene is 5 quality %, and n-hexane is 65 quality %, and water is 250 quality ppm) contain isobutene, and extract reaction product solution out from the bottom.Under the catalyst bed temperature of the pressure of 1.0MPa and 80 ℃, keep liquid phase state.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 3
Except using the raw material of forming by the water of the n-hexane of the isobutene of 35 quality %, 65 quality % and 250 quality ppm, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 4
Except using the raw material formed by the water of the n-hexane of the n-butene of the isobutene of 8 quality %, 27 quality %, 65 quality % and 250 quality ppm and pressure being set to 2.0MPa and the catalyst bed temperature is set to 145 ℃, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 5
Except using the raw material formed by the water of the n-hexane of the n-butene of 35 quality %, 65 quality % and 250 quality ppm and pressure being set to 2.0MPa and the catalyst bed temperature is set to 145 ℃, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
The comparative example 6
(1mm ф * 2mm) is loaded on tubular type stainless steel reactor (internal diameter: 8mm) with the diatomaceous extrusion die goods of 3.0g, only can enough all flooding the phosphate aqueous solution that diatomaceous amount is introduced 31 quality %, and phosphate aqueous solution is removed in the bottom from reactor after one hour from the bottom of reactor.When room temperature (25 ℃) is introduced dried nitrogen from the top of reactor and is down and with the speed of 1L/H 60 minutes then, then it is discharged from the bottom, implement drying with this.The solid phosphoric acid catalyst C that part from reactor is taken out with the mode identical with embodiment 1 analyzes.Found that the composition of the phosphoric acid of institute's load comprises orthophosphoric acid 80% and pyrophosphoric acid 20%, and does not comprise polyphosphoric acid.The amount of phosphoric acid in the catalyst (with regard to the orthophosphoric acid amount) is 19 quality %, and the ratio of carrier is 78.3 quality % in the catalyst, so the phosphoric acid load capacity is 24.3 quality %.The amount of remaining catalyst is 1.93g in reactor.
Then, dimerization reaction continue was implemented 30 days, simultaneously from the top of reactor with 40g/h (WHSV=26h
-1) speed introduce do not comprise water substantially contain isobutene raw material (isobutene is 30 quality %, and n-butene is 5 quality %, and n-hexane is 65 quality %), and extract out from reactor lower part.Under the catalyst bed temperature of the pressure of 1.0MPa and 80 ℃, keep liquid phase state.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 7
Except using the raw material formed by the water of the pentane of the cyclopentene of the positive amylene of the iso-amylene of 20 quality %, 20 quality %, 10 quality %, 50 quality % and 250 quality ppm and pressure being set to 2.0MPa and the catalyst bed temperature is set to 145 ℃, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
Embodiment 8
Except using the raw material formed by the water of the n-hexane of the positive amylene of the iso-amylene of the n-butene of the isobutene of 20 quality %, 3 quality %, 7 quality %, 10 quality %, 60 quality % and 250 quality ppm and pressure being set to 1.5MPa and the catalyst bed temperature is set to 120 ℃, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 1 and the table 3 respectively on reaction result and the reaction front and back catalyst.
[comparative example 1]
Except after removing phosphate aqueous solution, in 110 ℃ drying oven, implementing to implement and embodiment 1 identical operations, thereby prepare solid phosphoric acid catalyst D the drying process.Analyze this catalyst with the mode identical with embodiment 1.Found that the composition of the phosphoric acid of institute's load comprises orthophosphoric acid 57%, pyrophosphoric acid 38% and polyphosphoric acid 5%.The amount of phosphoric acid in the catalyst (with regard to the orthophosphoric acid amount) is 20 quality %, and the ratio of carrier is 80.5 quality % in the catalyst, so the phosphoric acid load capacity is 24.8 quality %.Use solid phosphoric acid catalyst D, use the mode identical to implement dimerization reaction with embodiment 1.The composition of phosphoric acid is shown in table 2 and the table 4 respectively on reaction result and the reaction front and back catalyst.
[comparative example 2]
Except removing behind the phosphate aqueous solution, implement and embodiment 2 identical operations by 200 ℃ nitrogen being supplied with when implementing drying process by the prepared support materials of dipping in phosphate aqueous solution and using the method identical to remove the aqueous solution with the speed of 1L/H to be 1 hour (and discharge its bottom) from reactor from the top of reactor with embodiment 2.With the mode identical the solid phosphoric acid catalyst E that takes out from reactor is analyzed with embodiment 1.Found that the composition of the phosphoric acid of institute's load comprises orthophosphoric acid 25%, pyrophosphoric acid 39% and polyphosphoric acid 36%.The amount of phosphoric acid in the catalyst (with regard to the orthophosphoric acid amount) is 18 quality %, and the ratio of carrier is 83.3 quality % in the catalyst, so the phosphoric acid load capacity is 21.6 quality %.
Then, use remaining 1.8g catalyst E in reactor, use the mode identical to implement dimerization reaction with embodiment 2.The composition of phosphoric acid is shown in table 2 and the table 4 respectively on reaction result and the reaction front and back catalyst.
[comparative example 3]
Except use comprises the raw material of water of the n-hexane of isobutene, 65 quality % of 35 quality % and 250 quality ppm, use the mode identical to implement dimerization reaction with comparative example 1.The composition of phosphoric acid is shown in table 2 and the table 4 respectively on reaction result and the reaction front and back catalyst.
[comparative example 4]
Except use comprise the n-hexane of n-butene, 65 quality % of isobutene, the 27 quality % of 8 quality % and 250 quality ppm water raw material and pressure is set to 2.0MPa and the catalyst bed temperature is set to 145 ℃, use the mode identical to implement dimerization reaction with comparative example 1.The composition of phosphoric acid is shown in table 2 and the table 4 respectively on reaction result and the reaction front and back catalyst.
[comparative example 5]
Except use comprise the n-hexane of n-butene, 65 quality % of 35 quality % and 250 quality ppm water raw material and pressure is set to 2.0MPa and the catalyst bed temperature is set to 145 ℃, use the mode identical to implement dimerization reaction with comparative example 2.Because do not obtain the product of dimerization, thus after 5 hours cessation reaction.The composition of phosphoric acid is shown in table 2 and the table 4 respectively on reaction result and the reaction front and back catalyst.
Table 1: reaction result
Table 2: reaction result
Table 3: phosphoric acid composition (mol% is with regard to the phosphorus atoms amount) in the catalyst before and after the reaction
Table 4: phosphoric acid composition (mol% is with regard to the phosphorus atoms amount) in the catalyst before and after the reaction
Industrial applicability
Solid phosphoric acid catalyst of the present invention can be used in the various reactions of using acid catalyst, For example except dimerizing olefins, it also can be used for the hydration reaction of alkene, the alkane of aromatic Change reaction.
Claims (4)
1, a kind of solid phosphoric acid catalyst that is used for dimerizing olefinsization, it is then to carry out drying by the aqueous solution contact siliceous supports of the phosphoric acid precursor that becomes phosphoric acid with phosphate aqueous solution or hydrolyzable to prepare, wherein implement described preparation process under 100 ℃ the temperature being lower than, with regard to phosphorus atoms quantity, the ortho-phosphoric ratio in the phosphoric acid of institute's load is 60mol% or higher.
2, a kind of method that is used for dimerizing olefinsization, it comprise will contain the olefin feedstock contact according to the solid phosphoric acid catalyst of claim 1, wherein saidly contain the water that olefin feedstock comprises 10 to 1000 quality ppm.
3, according to the method for claim 2, the wherein said olefin feedstock that contains contacts with described solid phosphoric acid catalyst in the liquid phase.
4, according to the method for claim 2 or 3, wherein said alkene is to have the monoolefine of 3 to 7 carbon atoms or the mixture of these monoolefines.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004210743 | 2004-07-16 | ||
| JP210743/2004 | 2004-07-16 | ||
| JP152696/2005 | 2005-05-25 |
Publications (2)
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| CN100496724C true CN100496724C (en) | 2009-06-10 |
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| JP5336239B2 (en) * | 2009-03-26 | 2013-11-06 | Ｊｘ日鉱日石エネルギー株式会社 | Process for producing olefin dimer, olefin dimer |
| CN112745184B (en) * | 2019-10-31 | 2022-08-12 | 中国石油化工股份有限公司 | Method for producing isooctene by overlapping mixed C4 raw material with high olefin content |
| CN112495404B (en) * | 2020-11-19 | 2022-07-12 | 万华化学集团股份有限公司 | Solid phosphoric acid catalyst, preparation method and recovery method of Saucy-Marbet reaction light component |
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