CN1195713C - Isomeric paraffin and olefine alkylating method - Google Patents

Isomeric paraffin and olefine alkylating method Download PDF

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CN1195713C
CN1195713C CNB00123515XA CN00123515A CN1195713C CN 1195713 C CN1195713 C CN 1195713C CN B00123515X A CNB00123515X A CN B00123515XA CN 00123515 A CN00123515 A CN 00123515A CN 1195713 C CN1195713 C CN 1195713C
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reaction
isoparaffin
alkylation
catalyst
catalyzer
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CN1339424A (en
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何奕工
杨克勇
贺玉峰
师峰
金欣
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The present invention relates to an alkylation method for isomerized alkane and alkene The method is characterized in that in the method, a reaction product (alkylate) is circulated to an inlet of a reactor to be fed in the reactor together with a raw reaction material to make alkylation reaction and catalyst regeneration simultaneously carried out in the reactor, and the reactivity and the selectivity of a catalyst can be kept for a long period.

Description

The alkylation of a kind of isoparaffin and alkene
The present invention relates to a kind of in the presence of solid acid catalyst isoparaffin and the alkylation reaction technique of the alkylation reaction technique of alkene, particularly Trimethylmethane and butylene.
Be catalyzer with the vitriol oil or hydrofluoric acid in the petrochemical complex industry at present, with isoparaffin, Trimethylmethane particularly, with alkene, particularly butylene carries out the alkylation reaction product that alkylated reaction prepares the trimethylpentane class.This alkylate is the gasoline concoction component of excellent property.This technology is called alkylation process (abbreviation alkylation).But sulfuric acid or hydrofluoric acid have serious pollution and harm to environment, and production unit is had very serious corrodibility.When storing and transporting these strong acid, also there is serious safety problem in addition.Therefore, petrochemical industry urgently wishes to adopt solid acid alkylation catalysts to replace sulfuric acid or hydrofluoric acid, and this has become great research topic in the petrochemical complex catalytic field.
In recent years, be used for the existing many reports of various solid acid catalysts of abovementioned alkyl reaction, as JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, GB1,389,237 disclosed SO 4 2-/ oxide compound super acidic catalyst; US5,220,095, US5,731,256, US5,489,729, US5,364,976, US5,288,685, EP0,714,871 disclosed CF 3SO 3The H/ silicon oxide catalyst; US5,391,527, US5,739,074 disclosed Pt-AlCl 3-KCl/Al 2O 3Catalyzer; US5,157,196, US5,190,904, US5,346,676, US5,221,777, US5,120,897, US5,245,101, US5,012,033, US5,157,197, CN1,062,307, WO95,126,815, disclosed load Lewis acid such as SbF 5, BF 3, AlCl 3Catalyzer; CN1,184,797, CN981,016,170, US5,324,881, US5,475,178 disclosed carried heteropoly acid catalysts; US3,917,738, US4,384,161 disclosed molecular sieve catalysts.
It is as easy as rolling off a log inactivation that solid acid catalyst is used for the greatest problem that alkylated reaction exists, as molecular sieve catalyst, and SO 4 2-/ oxide catalyst is at several hours, even in the several minutes, the alkylation activity (C of catalyzer 4 =Olefin conversion) just drop to very low level from 100%, and the selectivity variation of reaction, cause the octane value of alkylation reaction product-alkylate oil to reduce.Therefore, the regeneration of solid acid alkylation catalysts is a key issue that needs to be resolved hurrily.
At present, many hydrocarbon conversion process that adopt solid acid catalyst are at low temperatures arranged, as alkylation, isomerization, olefin oligomerization, hydroisomerization etc.Some side reactions in these hydrocarbon conversion process, polymerization and hydrogen transfer reactions as molecule, cause some macromolecular alkane or alkene to cover on the surface of catalyzer, different with high temperature, hydrocarbon conversion process (reformation, catalytic cracking etc.), the organic substance that these macromolecule hydrocarbon covertures are ratio of carbon-hydrogen (C/H)＜1 (or claiming the coke precursor), rather than the coke mass of the C/H that produces in the high-temperature technology＞1.This removes this class macromolecule hydrocarbon coverture for solvent washing possibility is provided.
US5,326,923 and CN1,076,386A discloses a kind of method that is used for the lewis acidic acidic hydrocarbon conversion catalysts of solvent extraction regeneration load, and this method comprises isolates catalyzer earlier from reaction system, then with being selected from SO 2, phenols and aromatic oxide solvent contact with the lewis acidic alkylation catalyst of load, and remove the reaction residue that is attached on the catalyst surface, make catalyzer recover initial performance.
US5,925,801 disclose a kind of metal complex that uses is the isoparaffin of catalyzer and the alkylation of alkene, wherein mention the catalyzer that comes regeneration of deactivated with the solvent extraction method, promptly adopt inorganic or organic solvent contacts with catalyzer, and remove the reaction residue that is attached on the catalyst surface, make catalyzer recover initial performance; Wherein inorganic solvent comprises carbonic acid gas and sulfurous gas, and organic solvent comprises aromatic hydrocarbon, contains oxygen organic mixture, halogen-containing organic compound etc.
Te Kaiping 8-281118 discloses a kind of method for regenerating solvent of solid heteropoly compound.This method adopts polarity or non-polar solvent, under normal temperature, the normal pressure, particularly under action of ultrasonic waves, handles solid heteropoly acid salt or heteropolyacid alkylation catalyst in container, makes the solid Heterocompound catalyst partly recover active.Wherein polar solvent comprises water, alcohol, ether, CS 2Deng, non-polar solvent comprises aromatic hydrocarbons, naphthenic hydrocarbon, C 4-C 10Aliphatic saturated hydrocarbon etc.
US5,489,732 and CN1,144, what 141A disclosed a kind of solid acid alkylation catalysts faces the hydrogen renovation process.This method adopts hydrogen at 10-300 ℃, under 6.9-3790 kPa the hydrogen partial pressure, with the alkylation catalyst Pt-KCl-AlCl that contains hydrogenation activity constituent element Pt 3/ Al 2O 3Contact, C on the selective hydrogenation catalyst surface 4 +The coverture of hydrocarbon molecules makes catalyzer recover active.
US5,523,503 disclose a kind of processing method with the saturated hydrocarbon polymer moving-bed regeneration solid acid alkylation catalysts of hydrogen.This method is with saturated Trimethylmethane of hydrogen and the solid acid alkylation catalysts (Pt-KCl-AlCl that contains Pt 3/ Al 2O 3) contact, the saturated desorption of macromolecule hydrocarbon molecule hydrogenation that catalyst surface is covered makes catalyzer recover active.
US3,855,343 disclose a kind of employing BF 3-resin is the isoparaffin of catalyzer and the alkylation of alkene, and this method is to feed isoparaffin, alkene and BF in the reactor that resin catalyst is housed 3, and, can adopt batch operation or operate continuously mode with polar solvent such as water, ethers and the alcohols employed resin catalyst of regenerating.When adopting the operate continuously mode, be to contain alkylate, unreacted reactant, BF 3From reactor, take out and enter revivifier with the slurries of resin catalyst, in this revivifier, feed polar solvent and contact with resin catalyst and make catalyst regeneration, will contain solvent, alkylate, unreacted reactant, BF in the revivifier 3Take out and the feeding distiller with the slurries of resin catalyst, in distiller, isolate solvent and after condensation, return revivifier, contain alkylate, unreacted reactant, BF in the distiller 3Enter reactor again with the slurries of regenerated resin catalyst, in reactor, take out the hydrocarbon product mixture and feed BF 3Stripping tower is isolated BF in stripping tower 3And return BF 3The bottoms that head tank, stripping tower obtain enters rectifier and isolates alkylate and unreacted isoparaffin reactant, and with unreacted isoparaffin reactant Returning reactor.The shortcoming of this method is to need a plurality of tripping devices, and can only use polar solvent, and non-polar solvent does not have effect to the regeneration of resin catalyst.
US5,365,010 disclose solid acid alkylation catalysts high temperature roast renovation process.This method is Lewis acid, particularly BF 3, the alkylation catalyst (BF of load 3/ Al 2O 3) roast under the temperature about 600 ℃, remove the hydro carbons coverture on the catalyst surface, reach the purpose of catalyst regeneration.
USP5,523, orthokinetic bed solid catalyst alkylation process of a kind of while is disclosed in 503, the a plurality of reactors of this process using, be divided into reaction zone and breeding blanket, change the position of reaction zone and breeding blanket by the inlet point of control feed stream and regeneration, so circulation is switched, and reaches successive reaction-regenerated purpose; The reaction raw materials of reaction zone has passed through the reaction bed more than two in this method, the i.e. logistics that contains unreacting material and product of coming out from first reaction bed enters second bed again or enters the 3rd bed again, and the used regeneration of catalyst regeneration is for being dissolved with H 2Raw material isoparaffin liquid, need and separate H 2Step, and because H arranged 2Existence, Gu gas-liquid-three-phase system has increased operation easier and insecurity.
The method that the purpose of this invention is to provide the alkylation production high-octane rating gasoline alkylate of a kind of isoparaffin and alkene makes and adopts comparatively simple technological process just can realize the reactive behavior and the selectivity of long period ground maintenance catalyzer.
The alkylation of isoparaffin provided by the invention and alkene is to contain isoparaffin and C 3～C 6The raw material for alkylation of monoolefine reacts under alkylation reaction condition in the presence of a kind of solid acid catalyst; The 5-50 weight % that it is characterized in that product alkylate oil that reaction is obtained, preferred 10-40 weight % loops back reactor inlet as regenerated solvent and enters reactor with reaction raw materials, and alkylated reaction and catalyst regeneration are carried out in reactor simultaneously.
The said product alkylate oil that loops back reactor inlet as regenerated solvent can be the not separated logistics that contains unreacted reactant (as isoparaffin) of coming out from reactor in the method provided by the invention, also can be through the isolating pure alkylate oil of separation column, but from the consideration that reduces cost, the preferably not separated logistics that contains unreacted reactant (as isoparaffin) of coming out from reactor.
Said C in the method provided by the invention 4～C 6Isoparaffin is most preferred to be Trimethylmethane, said C 3～C 6Singly-bound alkene is most preferred to be butene-1 or butene-2 or its mixture.
Said alkylation reaction condition has no particular limits in the method provided by the invention, preferably adopt existing alkylation reaction condition in the prior art, for example temperature of reaction is 10-350 ℃, reaction pressure is 0.5-10.0MPa, the molar ratio range of isoparaffin and alkene is 2-100, and the weight space velocity of reaction raw materials is 0.1-20 hour -1
Said alkylation reaction condition more preferably adopts supercritical reaction conditions in the method provided by the invention, be that temperature of reaction is from the critical temperature to 300 of isoparaffin ℃, preferably from the critical temperature to 250 of isoparaffin ℃, more preferably from the critical temperature to 200 of isoparaffin ℃; Reaction pressure be emergent pressure from isoparaffin to 10.0MPa, preferably from the emergent pressure of isoparaffin to 9.0MPa, more preferably from the emergent pressure of isoparaffin to 6.0MPa; The scope of the mol ratio of isoparaffin and alkene is 2.0-100, preferred 10-90; The scope of the weight space velocity of reaction raw materials (WHSV) is 0.1-20 hour -1, preferred 0.5-8.0 hour -1
Said solid acid catalyst can be the disclosed various solid acid catalysts that are used for the alkylated reaction of isoparaffin and alkene in the prior art in the method provided by the invention, comprises heteropolyacid salt catalyst, zeolite [molecular sieve, the SO of carried heteropoly acid catalyst, load or not load 4 2-/ oxide compound super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst, solid polymerization ion exchange resin and Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst.In these catalyzer, the preferably heteropolyacid salt catalyst of carried heteropoly acid catalyst, load or not load, loading type Br nsted-Lewis conjugation solid super acid catalyst and the acid-treated oxide catalyst of Lewis, more preferably carried heteropoly acid catalyst and loading type Br nsted-Lewis conjugation solid super acid catalyst.
Said carried heteropoly acid catalyst is made up of porous inorganic carrier and a kind of heteropolyacid 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; This catalyzer is existing the description in CN1232814A, this with the document as reference of the present invention.The heteropolyacid salt catalyst of said load or not load and above-mentioned catalyzer are similar in the method provided by the invention, and different is the alkali metal salts or ammonium salt that wherein said heteropolyacid salt is above-mentioned heteropolyacid.
Said loading type Br nsted-Lewis conjugation solid super acid catalyst such as CN1246467A describe in the method provided by the invention, this with the document as reference of the present invention; Wherein preferably formed by 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; The definition of wherein said heteropolyacid and porous inorganic carrier is identical with top definition to 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.This catalyzer is existing the description in CN1246467A, this with the document as reference of the present invention.
Other catalyzer described in the method provided by the invention all are catalyzer that are used for low-carbon (LC) isoparaffin and olefin alkylation reaction of disclosed routine in the prior art, and the present invention has no particular limits it.For example, can use JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, GB1,389,237 disclosed SO 4 2-/ oxide compound super acidic catalyst; US5,220,095, US5,731,256, US5,489,729, US5,364,976, US5,288,685, EP0,714,871 disclosed CF 3SO 3The H/ silicon oxide catalyst; US5,391,527, US5,739,074 disclosed Pt-AlCl 3-KCl/Al 2O 3Catalyzer; US5,157,196, US5,190,904, US5,346,676, US5,221,777, US5,120,897, US5,245,101, US5,012,033, US5,157,197, CN1,062,307, WO95,126,815 disclosed Lewis acid such as SbF 5, BF 3, AlCl 3The oxide catalyst of load; US3,549,557,3,644,565,3,647,916,3,917,738,4,384, the 161 disclosed catalyzer that contain β, ZSM-5 equimolecular sieve etc.; These documents at this all as reference of the present invention.
The alkylation of isoparaffin provided by the invention and alkene can carry out in various reactors, as fixed-bed reactor, intermittently tank reactor, moving-burden bed reactor, fluidized-bed reactor or three-phase slurry bed reactor, preferably fixed-bed reactor.The flow pattern of material can be that upstriker also can be a downstriker.Reaction mass can be also can be from different beds punishment section feedings from catalyzer top layer or bottom one section feeding.
Fig. 1 is the basic flow sheet according to a kind of embodiment of the present invention.Under alkylation reaction condition, alkylated reaction material (Trimethylmethane and butylene) enters reactor and begins reaction.The reactant flow that a part contains product alkylate oil and unreacted reactant such as Trimethylmethane is circulated back to reactor inlet by pump 1, separates and most of reaction product enters separation column with unreacted reactant.Loop back reactor inlet at the isolated Trimethylmethane of cat head by pump 2, obtain product-alkylate oil at the bottom of the tower.Fresh reaction raw materials (mixture of Trimethylmethane and butylene), the alkylate oil that is circulated back to reactor inlet and unreacted Trimethylmethane enter reactor jointly and participate in reaction and regeneration together.
Fig. 2 is the basic flow sheet according to another kind of embodiment of the present invention.Under alkylation reaction condition, the beds that alkylated reaction material (Trimethylmethane and butylene) segmentation enters reactor begins reaction.Other technological processs are identical with Fig. 1.
Fig. 3 is the basic flow sheet according to another kind of embodiment more of the present invention.Under alkylation reaction condition, alkylated reaction material (Trimethylmethane and butylene) enters reactor and begins reaction.Reaction product enters separation column with unreacted Trimethylmethane and separates.Loop back reactor inlet at the isolated Trimethylmethane of cat head by pump 4, obtain product (alkylate oil) at the bottom of the tower.Part alkylate oil loops back reactor inlet by pump 3.Fresh reaction raw materials (mixture of Trimethylmethane and butylene), the alkylate oil that is circulated back to reactor inlet and unreacted Trimethylmethane enter reactor jointly and participate in reaction and regeneration together.
Fig. 4 is the situation of 30 days the ACTIVITY CHANGE OF FT of alkylated reaction operate continuously operation in the embodiment of the invention 1.
Fig. 5 is that the octane value of the reaction product (alkylate oil) in the embodiment of the invention 1 moves 30 days changing conditions in operate continuously.
The following examples will the present invention is described further, but the present invention is not subjected to the restriction of these embodiment.In these embodiment and Comparative Examples, alkylation process is to overlap in the fixed bed reaction system that can adorn the 50ml catalyzer one to carry out.This reactive system is made up of following three parts:
1, charging metering system: adopt in the mixture input reactor of precision metering pump (U.S. TSP company product) with Trimethylmethane and butylene from the reaction raw materials jar.Inlet amount is by the precise electronic balance under reaction raw materials jar metering, guaranteed stable, inlet amount accurately.
2, reactive system: reactor can be adorned the 25ml catalyzer, the temperature homogeneous of the constant temperature zone assurance beds of process furnace and constant.The temperature of catalyst reactor bed is controlled by Britain West temperature control instrument.The pressure of reactor is controlled by high-accuracy pressure controller (U.S. Anaheim company product).Guaranteed the stable of temperature and pressure in the reactor and accurately.
3, separation and analytical system: reaction product and unreacted material separate liquid-phase reaction product (alkylate oil) and the unreacted material of gas phase (Trimethylmethane and alkene) through high pressure and low pressure two-stage separator, unreacted material is by online gas-chromatography timing analysis, and alkylate oil regularly takes out by an other stratographic analysis to be formed entirely.
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 alkylate oil from C 3～C 12Full composition.Chromatographic column is the OV-01 capillary column of 50m * 0.2mm.
Embodiment 1
Carry out the circulation alkylated reaction of Trimethylmethane and butylene 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 3PWO 40The aqueous solution.With 18.5g20-40 order 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 160 ℃ of vacuum-dryings 4 hours, obtained containing 20% heavy H 3PW 12O 40.2H 2The carried heteropoly acid catalyst of O and 80% heavy silica gel is designated as 20%H 3PW 12O 40.2H 2O/SiO 2, the specific surface area of catalyzer is 350m 2/ g.The specific surface of catalyzer adopts cryogenic nitrogen absorption BET method to measure.
Carry out alkylated reaction according to flow process shown in Figure 1.Take by weighing the above-mentioned 20%H of 10.0 grams 3PW 12O 40.2H 2O/SiO 2Catalyzer in the 50ml fixed-bed reactor of packing into, feeds nitrogen gas stream.Heat up, boost to the required temperature and pressure of reaction, pump into the reaction raw material that contains Trimethylmethane and butylene and close nitrogen gas stream simultaneously than (isoparaffin/alkene, mol ratio) with the alkane alkene of a high voltage precision volume pump by requirement in the reaction mass.At reactor outlet with high-pressure metering pump reaction cycle on request the weight that loops back the reaction product weight/total overall reaction product of reactor inlet) and alkane alkene ratio than (being defined as:, partial reaction product and the unreacted Trimethylmethane of part are looped back the inlet of reactor.After the stable reaction, with HP-3420 gas chromatograph timing analysis reaction end gas, and regularly taking out product liquid analyzes its octane value with the HP-5890 gas chromatograph.The composition of reaction raw materials sees Table 1.
Table 1.
The Trimethylmethane material is formed The butylene material is formed
Component Content (heavy %) Component Content (heavy %)
Propane Trimethylmethane normal butane butylene impurity H 2O S divinyl ?2.31 ?95.1 ?1.54 ?1.95 ?34ppm ?＜1mg/m 3?75ppm Just, the trans 2-butylene Trimethylmethane of isomery butylene normal butane cis 2-butylene impurity H 2O S divinyl ?2.91 ?11.54 ?59.03 ?25.66 ?0.86 ?40ppm ?＜1mg/m 3?5ppm
Reaction conditions is: 136 ℃ of temperature, pressure 5.0MPa, alkane/alkene=20 (mol ratio), recycle ratio 0.3, weight space velocity 2.30 hours -1Reaction result is listed among Fig. 4 and Fig. 5.Alkylated reaction through 720 hours (30 days) after, catalyst activity (C 4 =Olefin conversion) keeps 100%.The octane value RON of alkylation reaction product-alkylate oil is 95.0 (research octane number (RON)s); MON is 93.0 (motor-method octane numbers), and keeps stable between 30 days reaction period.The selectivity of this explanation alkylated reaction remains unchanged.RON and MON value be according to document (Hutson and Logan " Estimate AlkylYield and Quanlity ", hydrocarbon processing, in September, 1975 the 107-108 page or leaf) method, draw by gas chromatographic analysis.
The processing method of continuous round-robin solid acid Trimethylmethane provided by the invention and butene alkylation loops back reactor inlet and reaction mass with partial reaction product (alkylate oil) and together enters reactor and carry out alkylated reaction, and remove macromole coverture on the catalyst surface simultaneously, reach the clean surface that keeps catalyzer, thereby make alkylation activity and the stable purpose of selectivity.
Comparative Examples 1
Catalyzer, reaction mass and reaction conditions be with embodiment 1, but reaction product is not looped back reactor inlet in the reaction process.Alkylated reaction is through after 300 hours, catalyst activity (C 4 =Olefin conversion) though still keep 100%, the octane value RON of alkylation reaction product (alkylate oil) reduces to 94.1 (research octane number (RON)s); MON reduces to 92.2 (motor-method octane numbers).This result shows that the selectivity of the alkylated reaction of catalyzer has begun variation, and passivation phenomenon appears in catalyzer.
Embodiment 2
The solid acid alkylation catalysts of using among this embodiment is that (B:Bronsted acid is H to B-L conjugation super acids here 3PW 12O 40L:Lewis acid is SbF here 5).The Preparation of catalysts method is as follows: the method for pressing among the embodiment 1 prepares 20%H earlier 3PW 12O 40/ SiO 2, then with 10.0g20%H 3PW 12O 40/ SiO 2Packing in the fixed-bed reactor, is 120 hours with air speed -1Nitrogen gas stream handled 4 hours at 100 ℃, cool to 50 ℃ then, make carrier 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, used nitrogen purging at last 1.0 hours, finish preparation.Be designated as H 3PW 12O 40-SbF 5/ SiO 2Catalyzer.
Method by Trimethylmethane among the embodiment 1 and butene alkylation is carried out alkylated reaction.Reaction conditions is: 135 ℃ of temperature of reaction; Pressure 5.0MPa; Weight space velocity 2.3 hours -1Alkane alkene is than 20 (mol ratios); Recycle ratio 0.35.Reaction result is the result of Fig. 4 and Fig. 5 in the similar embodiment 1 very.Alkylated reaction through 820 hours (34 days) after, catalyst activity (C 4 =Olefin conversion) keeps 100%.The octane value RON of alkylation reaction product (alkylate oil) is 95.6 (research octane number (RON)s); MON is 93.4 (motor-method octane numbers), and keeps stable between 30 days reaction period.This B-L conjugation solid super-strong acid alkylation catalyst that shows circulating reaction is obtained good alkylated reaction effect.
Embodiment 3
Same procedure according to embodiment 1 is carried out alkylated reaction, and different is to carry out alkylated reaction according to the flow process of Fig. 3, and a part of reaction product (alkylate oil) of soon coming out from separation column loops back reactor inlet.Reaction conditions is: 137 ℃ of temperature, pressure 5.0MPa, alkane/alkene=19 (mol ratio), recycle ratio 0.25, weight space velocity 2.30 hours -1Reaction result is the result of Fig. 4 and Fig. 5 in the similar embodiment 1 very.Alkylated reaction through 720 hours (30 days) after, catalyst activity (C 4 =Olefin conversion) keeps 100%.The octane value RON of alkylation reaction product (alkylate oil) is 95.1 (research octane number (RON)s); MON is 93.2 (motor-method octane numbers), and keeps stable between 30 days reaction period.The selectivity of this explanation alkylated reaction remains unchanged.

Claims (16)

1, the alkylation of a kind of isoparaffin and alkene, this method are to contain C 4～C 6Isoparaffin and C 3～C 6The raw material for alkylation of monoolefine reacts under alkylation reaction condition in the presence of a kind of solid acid catalyst, it is characterized in that this method adopts fixed-bed reactor; The 5-50 weight % of the product alkylate oil that reaction is obtained loops back reactor inlet as regenerated solvent and enters reactor with reaction raw materials, and alkylated reaction and catalyst regeneration are carried out in reactor simultaneously.
2,, it is characterized in that the 10-40 weight % of product alkylate oil that reaction is obtained loops back reactor inlet as regenerated solvent according to the alkylation of claim 1.
3, according to the method for claim 1 or 2, the wherein said product alkylate oil that loops back reactor inlet as regenerated solvent is the not separated logistics that contains unreacted reactant of coming out from reactor, or through the isolating pure alkylate oil of separation column.
4, according to the method for claim 3, the wherein said product alkylate oil that loops back reactor inlet as regenerated solvent is the not separated logistics that contains unreacted reactant of coming out from reactor.
5, according to the process of claim 1 wherein said C 4～C 6Isoparaffin is a Trimethylmethane, said C 3～C 6Singly-bound alkene is butene-1 or butene-2 or its mixture.
6, according to the process of claim 1 wherein that said alkylation reaction condition is that temperature of reaction is 10-350 ℃, reaction pressure is 0.5-10.0MPa, and the molar ratio range of isoparaffin and alkene is 2-100, and the weight space velocity of reaction raw materials is 0.1-20 hour -1
7, according to the method for claim 6, wherein said alkylation reaction condition is that temperature of reaction is from the critical temperature to 300 of isoparaffin ℃, reaction pressure is that emergent pressure from isoparaffin is to 10.0MPa, the scope of the mol ratio of isoparaffin and alkene is 2.0～100, and the scope of the weight space velocity of reaction raw materials is 0.1～20 hour -1
8, according to the method for claim 7, wherein said reaction conditions is that temperature of reaction is from the critical temperature to 250 of isoparaffin ℃, reaction pressure is that emergent pressure from isoparaffin is to 9.0MPa, the scope of the mol ratio of isoparaffin and alkene is 10～90, and the scope of the weight space velocity of reaction raw materials is 0.5～8.0 hour -1
9, according to the method for claim 8, wherein temperature of reaction is from the critical temperature to 200 of isoparaffin ℃, and reaction pressure is that emergent pressure from isoparaffin is to 6.0MPa.
10, according to the process of claim 1 wherein that said catalyzer is carried heteropoly acid class catalyzer, zeolite [molecular sieve, SO 4 2-/ oxide compound super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst, ion exchange resin or acid-treated oxide compound of Louis or molecular sieve catalyst.
11, according to the method for claim 10, wherein said catalyzer is carried heteropoly acid class catalyzer, loading type B-L conjugation solid super acid catalyst or solid polymerization ion exchange resin.
12, according to the method for claim 11, wherein said catalyzer is a carried heteropoly acid class catalyzer.
13, according to the method for claim 12, wherein said carried heteropoly acid class catalyzer 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 the porous inorganic carrier of routine that comprises aluminosilicate zeolite, carbon fiber and the natural clay of gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic, or their mixture.
14, according to the method for claim 13, wherein said porous inorganic carrier is silicon oxide, aluminum oxide or their mixture.
15, according to the method for claim 10, wherein said loading type B-L 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; Identical in the definition of said heteropolyacid and porous inorganic carrier and the claim 13 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.
16, be from catalyzer top layer or bottom one section feeding according to the reaction mass that the process of claim 1 wherein, or from different beds punishment section feedings.
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CN101244972B (en) * 2008-01-31 2012-05-02 北京华福工程有限公司 Alkylation reaction method with ion liquid as catalyst and reactor
CN102191081B (en) * 2010-03-11 2014-04-30 中国石油化工股份有限公司 Alkylation method of solid acid
CN103361121A (en) * 2012-04-05 2013-10-23 中国石油天然气股份有限公司 Production method of high-octane gasoline blending component
CN106281432B (en) * 2015-05-21 2017-11-17 北京化工大学 It is a kind of to utilize the system and device and production method that sulfuric acid is catalyst preparation alkylate oil
CN105061129B (en) * 2015-09-18 2017-11-14 中石化炼化工程（集团）股份有限公司 A kind of alkylation and its device of isoparaffin and alkene
CN106631655B (en) * 2015-10-28 2019-05-21 中国石油化工股份有限公司 A kind of alkylation reaction method
CN107649188B (en) * 2016-07-25 2021-01-08 中国石油化工股份有限公司 Regeneration method of solid acid catalyst and method for preparing alkylate oil
CN107974277B (en) * 2016-10-25 2020-03-24 中国石油化工股份有限公司 Solid acid alkylation equipment and method
CN109718723B (en) * 2017-10-30 2022-07-15 中国石油化工股份有限公司 Fixed bed isoparaffin synthesis reactor, multistage feeding equipment thereof and isoparaffin synthesis method
CN110655436B (en) * 2018-06-28 2022-07-15 中国石油化工股份有限公司 Solid acid alkylation method
CN110655435B (en) * 2018-06-28 2022-06-24 中国石油化工股份有限公司 Solid acid alkylation reaction method and reaction device

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