CN1144615C - Solid super acid catalyst for alkylation - Google Patents

Abstract

The present invention provides a catalyst used for alkylation, which comprises inorganic or organic porous carriers and main components of heteropoly acid and Lewis acid. The present invention provides a preparation method of the catalyst and the application of the catalyst on catalytic alkylation of isoparaffin when at least one kind of olefin whose each molecule has 3 to 5 carbon atoms exists. The solid acid catalyst has high olefin conversion rate, high alkylate oil yield and high catalytic activity stability in the alkylation reaction. The C8 saturated hydrocarbon content in the catalyzed generation alkylate oil is larger than 75%, and the oil yield counted by olefin weight is from 175 to 205%.

Description

Be used for alkylating solid super acid catalyst

The present invention relates to a kind of solid super acid catalyst, particularly relate to a kind of solid super acid catalyst that is used for isoparaffin and olefin alkylation reaction.

Alkylation process is meant that an organic molecular species and a kind of reactive organic molecule generation that has alkyl group have the more process of HMW branched material, and reacting at the industrial alkene that is often referred to iso-butane and C3～C5 generates the process of alkylate oil.This gasoline alkylate has high octane number owing to it, low sensitiveness, and no aromatic hydrocarbons component has high shock resistance and pollution-free characteristics as engine fuel, thereby can be used as the ideal blending component of high-knock rating gasoline.

The present industrial traditional alkylation process before 50 years that still adopts, promptly sulfuric acid process and hydrofluoric acid method are that catalyst is by iso-butane and alkene synthesis of alkyl carburetion with sulfuric acid and hydrofluoric acid mainly.There are a large amount of spent acid dischargings in the sulfuric acid process, the problem of serious environment pollution; Hydrofluoric acid is volatile hypertoxic chemicals, in case reveal will give production environment and on every side ecology cause serious harm, also problems such as production equipment are corroded in existence in addition.Therefore from the sixties, the experts and scholars of countries in the world just focus onto on the solid acid, explore new catalyst to replace this two kinds of catalyst.

For carrying out the isobutane alkylation catalyst for reaction, many different types of new catalysts had been proposed with alkene.Used molecular sieve catalyst, as US 3251902, US 3647916, US 4377721, US 4384161; Super acids (SO ₄ ^2-/ ZrO ₂), as JP-01245854-A, JP-01245853, JP-61242641-A, US 4116880; Highly cross-linked resin is as US 3855342, US 3855343 and US 3879489; Liquid superacid and support type Lewis acid are catalyst as materials such as US 3852371, US 3855342, WO94/24075.But these researchs are not success so far.This is because above-mentioned these molecular sieve catalysts and solid super acid catalyst are when catalytic alkylation reaction carries out, the side reaction of alkene oligomerization takes place, produce macromolecule product, thereby make catalyst promptly tie the charcoal inactivation after several hours in reaction, this is the total problem (A.Corma of solid acid catalyst, A.Martinez, Catal.Rev-Sci.Eng.35 (4) 483-570,1994).Because the solid acid catalyst of being made up of oxide generally all need just have enough activity under higher reaction temperature, at this moment will cause olefinic polymerization, produce macromolecule product and make catalyst junction charcoal inactivation, the catalyst of therefore seeking new synthesizing alkylated gasoline has been regarded as one of several problem demanding prompt solutions in a global difficult problem and the catalytic field.Just present, also there is not the satisfied alkylation catalyst that can replace sulfuric acid, hydrofluoric acid.

US 4992616, US 5221777 discloses support type Lewis acid as catalyst and has been used for alkylated reaction, this catalyst uses halide to load on the carrier, because a little less than halide and the carrier interphase interaction, the problem that exists halide to run off finally will inevitably cause activity and long term stability problem.

Chinese patent CN1125639A has narrated the heteropolyacid catalyst of iso-butane and butene alkylated usefulness, is to be dissolved in the mixed liquor equal solvent of low carbon fatty acid, fat, ketone, ether, alcohol and fatty alcohol and fatty alcohol ester with heteropoly acid, makes catalyst.Though it has good alkylation catalytic activity, but still belongs to homogeneous catalyst, existence separates incomplete problem with product.

Chinese patent CN1125640A has narrated iso-butane and butene alkylated solid heteropoly acid salt catalyzer, select by the synthetic alkali metal of phosphorus tungsten, phosphorus molybdenum, silicon tungsten, four kinds of heteropoly acids of silicon molybdenum (Cs, K) and ammonium (NH ₄ ⁺, N (C ₂H ₅) ₄ ⁺) salt is as catalyst.When adopting this catalyst to carry out alkylated reaction, its alkylate oil yield is lower, and can not keep activity of such catalysts stability.In addition, as if the improvement of merely making catalyst gained result with heteropoly acid and heteropolyacid salt is not sufficient to compensate the expense that the use because of this expensive reagent causes and raises.

U.S. Pat 5324881 has been narrated iso-butane and butene alkylated method, and this method is included under the alkylation conditions, and catalyst system therefor is a kind of carried heteropoly acid catalyst.Alleged according to the example, catalyst is all being handled more than 350 ℃, and olefin conversion is the highest to have only 87 (weight) %, and the alkylate oil yield is the highest to have only 140 (heavy, based on alkene) %, experimental results show that this method of employing, and catalyst activity stability is still bad.

The objective of the invention is to solve the existing problem of liquid acid catalyst aspect environmental protection; and the olefin conversion and the low bad shortcoming of activity stability that reaches of alkylate oil yield that remedy existing solid acid catalyst; the solid super acid catalyst of a kind of active height, good stability is provided, and another object of the present invention is to provide a kind of this Preparation of catalysts method.

Solid super acid catalyst of the present invention is while carried heteropoly acid and Lewis on porous carrier, and by weight, heteropoly acid accounts for the 10w%～55w% of carrier, and Lewis acid accounts for the 1w%～5w% of carrier.The specific area of catalyst is 50～1000m ²G ^-1, be preferably in 100～800m ²G ^-1Between, the porosity of catalyst is 0.05～3cm ³G ^-1, average pore size is between 1.0～80.0nm.Super acids is the also strong acid of sulfuric acid (Ho＜-11.93) than 100%, the invention provides Ha Meite (Hammett) acid strength Ho＜-12 of catalyst, belongs to solid super-strong acid.

Be applicable to that the carrier that solid super-strong acid of the present invention uses is inorganic or organic porous carrier, as zirconium dioxide, titanium dioxide, silica, aluminium oxide, natural or artificial synthetic zeolite, in the molecular sieve one or more.Described zeolite, molecular sieve can be one or more mixtures in A type zeolite, X type zeolite, y-type zeolite, modenite, ZSM-series zeolite Beta zeolite, phosphorus aluminium zeolite, the Ti-Si zeolite.When using these porous carrier materials, may contain some impurity, such as picture oxide, bases, alkali earths, aluminium compound or known other the various impurity of this area professional, the total amount of these impurity preferably is no more than 2w%.The specific area of carrier is 50～1000m ²G ^-1, be preferably 100～800m ²G ^-1, porosity is 0.05～3cm ³G ^-1, average pore size is between 1.0～80.0nm.

Heteropoly acid used in the present invention has following chemical expression:

H _kYW _mMo _12-mO ₄₀·nH ₂O

Wherein, H represents hydrogen atom, and k represents the number of hydrogen atom, round numbers 3 and 4; Y is selected from phosphorus atoms, silicon atom; W represents tungsten atom, and m represents the number of tungsten atom, is 0～12 positive integer; Mo represents molybdenum atom, and 12-m represents the number of molybdenum atom; The O represention oxygen atom; N represents the number of the crystallization water, gets any number greater than 0 to 12.

Above-mentioned Lewis acid comprises halogenation boron, aluminum halide, and aikyl aluminum halide, antimony halides, halogenated titanium and its mixture are as in boron trifluoride, antimony pentafluoride, Antimony pentachloride or the alchlor one or more.

Catalyst of the present invention can adopt following method preparation:

1, under agitation a certain amount of heteropoly acid is added in water or the organic solvent and dissolves,, carry out drying then with the baked inorganic or organic porous carrier of heteropoly acid solution impregnation.Can use the known various technology of this area professional in order to carry out this step.Generally, be preferably in 110～250 ℃,, dry the used time to be generally 12～30hr such as under 120 ℃ temperature, drying soaked carrier surpassing 100 ℃.Can dry in the presence of air or air/nitrogen mixture, its flow is 10～10000cm ³Hr ^-1G ^-1

2, adopt gas phase adsorption method load Lewis acid (BF by 1 gained material ₃, SbF ₅, SbCl ₅Or AlCl ₃).With nitrogen is that the Lewis acid vapour is carried in carrier gas, or the inorganic or organic porous carrier behind the carried heteropoly acid is in the pure Lewis acid vapour atmosphere, and Lewis acid fully is adsorbed.After absorption finishes at room temperature vacuum extract superfluous Lewis acid.

3, the moulding of catalyst can be adopted two kinds of methods.A kind of is the binder free type, and catalyst fines is got 8～30 orders in the pressure lower sheeting moulding of 5-30 ton; Another kind is the adding additives type, and used binding agent is Al ₂O ₃, kaolin, silica gel etc., consumption accounts for 10～50% of gross weight, extruded moulding.

Introduce application conditions and the effect of catalyst of the present invention in alkylated reaction below.

In the presence of the catalyst of the present invention and under isoparaffin and the olefin alkylation reaction condition, make to contain isoparaffin and olefine reaction raw material and contact with catalyst and finish alkylated reaction.

Described isoparaffin can be the isoparaffin of C4～C7, and iso-butane preferably, alkene are to contain the material that the alkene of 3～5 carbon atoms is formed at least a each molecule, and it is 1-butylene, 2-butylene or their mixture that this alkene is preferably selected.The reaction raw materials that contains isoparaffin can be pure iso-butane, also can contain other component that does not influence alkylated reaction.In order to limit alkene oligomerization, can make iso-butane excessive to alkene, the mol ratio of isoparaffin/alkene is generally 1～100 in the raw material, and more preferably 3～50, be preferably 8～30, most preferably be 8～18.According to catalyst provided by the invention, should guarantee that heteropoly acid crystallization water number is not more than 12 in the catalyst, preferably be not more than 8, in order to avoid influence the super acids character of catalyst, the amount of the crystallization water adopts thermogravimetry commonly used to measure in the heteropoly acid.Therefore, the content of water be should give control in the described reaction raw materials, and the content of water should not be higher than 200 μ gg ^-1, preferably be not higher than 100 μ gg ^-1

The alkylated reaction temperature is being lower than 40 ℃, perhaps is higher than under the iso-butane critical-temperature and carries out.When reaction temperature is lower than 40 ℃, be similar to the process conditions that existing commercial plant adopts, the pressure of reactor should make the hydrocarbon in the reactor remain on liquid state.When under being higher than the iso-butane critical-temperature, reacting, promptly be to select supercritical reaction conditions, selected temperature is not less than the critical-temperature of iso-butane, but be not higher than 300 ℃, preferably between 136～250 ℃, described reaction pressure is not less than the critical pressure of iso-butane, can select 3.6～9.0MPa, preferably selects between 3.6～6.0MPa.Alkylated reaction is with 0.1～15h ^-1Weight space velocity (WHSV) carry out 2～8hr ^-1Be suitable, 2～5hr preferably ^-1

Catalyst of the present invention can be used in the various reactors and carry out, as fixed bed reactors, moving-burden bed reactor, fluidized-bed reactor or tank reactor etc. intermittently.

The present invention is used for the solid super acid catalyst of alkylated reaction, by the Br nsted (B) of heteropoly acid acid and the common conjugation super acids of forming of Lewis (L) acid as catalyst, working in coordination, interact in two kinds of acid catalyst centers, can obtain quite high catalytic activity and selectivity under appropriate processing condition.Having improved existing circle acid catalyst activity, improved activity stability greatly with optionally simultaneously.

Its analysis of components of the alkylate oil that the present invention obtains is better than the alkylate oil composition that obtains with sulfuric acid process.In addition, make alkylated reaction and compare with solid acid catalyst with existing, the solid catalyst among the present invention has very high olefin conversion and alkylate oil yield in alkylated reaction, and good stability of catalytic activity.To the generation selectivity height of the trimethylpentane of high-octane rating composition in the alkylate oil, the C8 saturated hydrocarbon content is 175-205% greater than 75% in the oily yield of alkene weight in the alkylate oil that catalyst generates.Mainly be trimethylpentane (TMP) in the product, wherein the product of concentration maximum is 2,2,4-trimethylpentane (isooctane).Under supercritical reaction conditions, solid acid catalyst of the present invention keeps 100% olefin conversion in reaction especially, and non-inactivation in long-time, the catalytic stability height.Because iso-butane is excessive in material, utilize the supercritical fluid of reactant itself to have stronger solubility property, can remove the coke precursor that catalyst surface generates, avoided burnt matter precursor further to generate coke, thereby prevented catalysqt deactivation, helped commercial Application.

When (, when carrying out under Pc=3.59MPa), also promptly selecting supercritical reaction conditions for use being higher than the iso-butane critical-temperature for iso-butane: Tc=135.0 ℃.Iso-butane and olefin alkylation reaction are heat releases and subtract molecular reaction, consider that from the thermodynamics angle low temperature and high pressure help the direction that thermodynamic (al) balance is tending towards product.But the too high requirement of withstand voltage height to reactor of reaction pressure is unfavorable for commercial Application.

This solid super acid catalyst provided by the invention has pollution-free, environment amenable characteristics, it does not have the severe corrosive and the harmfulness of sulfuric acid and hydrofluoric acid, and the catalytic performance that is higher than these two kinds of acid is arranged again, and being expected to replace sulfuric acid and hydrofluoric acid is the catalyst of alkylated reaction.Compare with existing solid acid catalyst, its olefin conversion and alkane yield height, the C8 saturated hydrocarbon content is greater than 75% in the alkylate oil that catalyst generates, and to the generation selectivity height of the trimethylpentane of high-octane rating composition in the alkylate oil, and stability of catalytic activity is good.

Below each example further specify the present invention, yet the invention is not restricted to this.

An alkylated reaction raw material part is taken from the alkylation commercial plant of Fushun second branch factory of oil in the example, other has the raw material that contains iso-butane of taking from the production of Tianjin petrochemical industry two factories, raw material with separate sources mixes the reaction raw materials that just can obtain certain alkane alkene mol ratio, and the composition of used isoparaffin and alkene is listed in the table 1.

Table 1

Take from the Fushun second branch factory of oil		Tianjin petrochemical industry two factories
				Component	Content, W%	Component	Content, W%
Propane iso-butane normal butane 1-butylene Cis2-butylene Trans2-butylene water, μ g.g -1	1.1 68.8 6.5 19.2 2.6 1.8 45	Propane iso-butane normal butane butylene water, μ g.g -1	0.8 95.0 2.8 1.4 12

Data are to adopt Ha Meite (Hammett) indicator method commonly used in the table 2, measure the catalyst Ha Meite acid strength Ho value gained result among the part embodiment and Comparative Examples among the present invention.

Table 2 acid strength measurement result

The catalyst numbering	PW- SbF/SiO 2	SiW- SbF/SiO 2	PW- SbCl/HY	SbCl/ HY	PW/ HY
						Anthraquinone (Ho=-8.2)	(+)	(+)	(+)	(+)	(+)
Para-nitrotoluene (Ho=-11.35)	(+)	(+)	(+)	(+)	(-)
						Nitrobenzene (Ho=-12.14)	(+)	(+)	(+)	(+)	(-)
M-chloronitrobenzene (Ho=-13.16)	(+)	(-)	(+)	(+)	(-)
						2,4-dinitrotoluene (DNT) (Ho=-15.60)	(-)	(-)	(-)	(+)	(-)
1,3,5-trinitrobenzen (Ho=-16.12)	(-)	(-)	(-)	(-)	(-)

(+)-expression indicator color changes, and (-)-expression indicator color does not change

The anthraquinone of used indicator and para-nitrotoluene are benzole soln, and nitrobenzene and m-chloronitrobenzene are cyclohexane solution, 2, and 4-dinitrotoluene (DNT) and 1,3,5-trinitrobenzen are thionyl chloride solution.

Embodiment provided by the invention is as follows:

Embodiment 1:

Used anhydrous heteropoly acid is with commodity heteropoly acid H in the example ₃PW ₁₂O ₄₀.31H ₂O (PW ₁₂), H ₄SiW ₁₂O ₄₀.29H ₂O (SiW ₁₂) at 400 ℃ of following roasting 4hr gained, place under the drying nitrogen to store.

Accurately take by weighing 20g phosphotungstic acid (PW ₁₂) place a beaker, add in the 100g distilled water, phosphotungstic acid is dissolved fully, left standstill then 24 hours, make PW ₁₂The aqueous solution.100g be impregnated in the Salkowski's solution at 70～230 order SiO 2 powders of 400 ℃ of down dry 24hr in advance, leave standstill 8hr after, at 120 ℃ of dry 24hr, obtain containing 20 (weight) %PW ₁₂6H ₂O/SiO ₂(expression PW ₁₂Weight account for the percentage of vehicle weight, following representation class with).

Silica behind the dipping is positioned over then in the nitrogen stream that carries antimony pentafluoride and handles 5hr, nitrogen flow 1000cm ³Hr ^-1G ^-1, wherein the molar content of antimony pentafluoride is 20%.Make that antimony pentafluoride is saturated to be adsorbed on the silica.After absorption finishes at room temperature vacuum extract superfluous Lewis acid.Contained antimony pentafluoride weight accounts for 5% of vehicle weight in the catalyst that obtains like this.

Powder after above-mentioned processing is in 5 tons pressure lower sheeting moulding, and note is numbered PW-SbF/SiO ₂

Having obtained a specific area like this is 280m ²G ^-1, pore volume is 0.60cm ³G ^-1, average pore size is the catalyst of 14.0nm.The Ha Meite acid strength Ho value that adopts Ha Meite (Hammett) indicator method mensuration catalyst commonly used the results are shown in Table 2 less than-12.The infrared acid measurement result of the original position pyridine adsorption of catalyst shows, has the acid centre of B acid type and L acid type on the catalyst simultaneously.

Take by weighing 10gPW-SbF/SiO ₂Catalyst grinds to 40 orders, and 25cm packs into ³In the fixed bed reactors, in 120 ℃ of nitrogen streams, activate 3hr in advance, transfer to desired reaction temperature, reaction pressure, use precision metering pump with 25cm ³Hr ^-1Amount send into the raw material that contains iso-butane and alkene, the online chromatography that degass of every 1hr sampling is analyzed its composition.Reaction condition and reaction result see Table 3.Its analysis of components of the alkylate oil that the present invention obtains is better than the alkylate oil composition that obtains with sulfuric acid process.

Comparative Examples 1

With the concentrated sulfuric acid is the alkylated reaction that catalyst carries out iso-butane and alkene, takes by weighing the heavy sulfuric acid (analyzing pure) of 84g98% and adds in the high pressure tank reactor, 12 ℃ of reaction temperatures, under reaction pressure 0.5MPa and the strong agitation, add reaction raw materials, reaction 2hr gets product analysis.Reaction condition and reaction result see Table 3.

Table 3

Catalyst	PW-SbF/SiO 2				98% sulfuric acid
						Reaction temperature, ℃	25		136		12
Reaction pressure, MPa	0.5		4.5		0.5
						Alkane alkene mol ratio	20		12		8.0
WHSV，hr -1	1.6		1.6		-
						Reaction time, hr	2	4	2	4	2
C 4 ＝Olefin conversion, heavy %	100	100	100	100	100
						The alkylate oil yield, % (based on alkene)	178	180	200	201	198
C 5 +Product distributes, heavy % C 5 C 6 C 7 C 8 C 9 + C 8 ＝	1.90 1.24 6.58 75.12 15.16 0.00	1.72 1.81 5.98 75.45 15.04 0.00	1.32 1.26 3.98 78.34 15.10 0.00	1.07 1.46 2.75 79.56 15.16 0.00	1.22 2.10 3.00 73.60 20.08 0.00
						MON	-	92.4	-	94.0	92.3
RON	-	93.8	-	96.2	93.4

Embodiment 2

Accurately take by weighing 50g silico-tungstic acid (SiW ₁₂) place a beaker, add in the 100g distilled water, silico-tungstic acid is dissolved fully, leave standstill 24hr then, make SiW ₁₂The aqueous solution.100g be impregnated in SiW at 70～230 order SiO 2 powders of 400 ℃ of down dry 24hr in advance ₁₂In the solution, leave standstill 8hr after, at 120 ℃ of dry 24hr, obtain containing 50 (weight) %SiW ₁₂6H ₂O/SiO ₂

Silica behind the dipping is positioned over then in the nitrogen stream that carries antimony pentafluoride and handles 5hr, nitrogen flow 1cm ³Hr ^-1G ^-1, wherein the molar content of antimony pentafluoride is 20%.Make that antimony pentafluoride is saturated to be adsorbed on the silica.After absorption finishes at room temperature vacuum extract superfluous Lewis acid.Contained antimony pentafluoride weight accounts for 5% of vehicle weight in the catalyst that obtains like this.

Powder after above-mentioned processing is in 5 tons pressure lower sheeting moulding, and note is numbered SiW-SbF/SiO ₂

Having obtained a specific area like this is 285m ²G ^-1Catalyst.The Ha Meite acid strength Ho value that adopts Ha Meite (Hammett) indicator method mensuration catalyst commonly used the results are shown in Table 2 less than-12.The infrared acid measurement result of the original position pyridine adsorption of catalyst shows, has the acid centre of B acid type and L acid type on the catalyst simultaneously.

Take by weighing 10gSiW-SbF/SiO ₂Catalyst grinds to 40 orders, and 25cm packs into ³In the fixed bed reactors, in 120 ℃ of nitrogen streams, activate 3hr in advance, transfer to super critical condition desired reaction temperature, reaction pressure, use precision metering pump with 25cm ³Hr ^-1Amount send into the raw material that contains iso-butane and alkene, the online chromatography that degass of every 1hr sampling is analyzed its composition.Reaction condition and reaction result see Table 4.

Table 4

The catalyst numbering	SiW-SbF/SiO 2
					Reaction temperature, ℃	136		190
Reaction pressure, MPa	4.5		5.5
					Alkane alkene mol ratio	18		18
WHSV，hr -1	1.6		1.6
					Reaction time, hr	24	100	24	48
C 4 ＝Olefin conversion, heavy %	100	100	100	100
					The alkylate oil yield, % (based on alkene)	198	200	200	201
C 5 +Product distributes, heavy % C 5 C 6 C 7 C 8 C 9 + C 8 ＝	1.09 1.24 4.58 75.22 17.87 0.00	1.70 1.84 3.98 75.45 17.03 0.00	1.32 1.20 3.95 77.34 16.19 0.00	1.07 1.45 3.75 78.54 15.19 0.00
					The C8 product distributes, %			-	-
Trimethylpentane (TMP)	80	77	-	-
					Dimethyl pentane (DMP)	20	20	-	-
2，2，4-TMP/TMP	42	44	-	-

2,2,4-TMP/TMP---2,2,4-TMP shared percentage composition in the trimethylpentane component

Embodiment 3:

Accurately take by weighing 20g phosphotungstic acid (PW ₁₂) place a beaker, add in the 100g distilled water, phosphotungstic acid is dissolved fully, leave standstill 24hr then, make PW ₁₂The aqueous solution.With 100g in advance at 70～230 order Hydrogen Y molecular sieve powder impregnations of 400 ℃ of down dry 24hr in Salkowski's solution, leave standstill 8hr after, at 160 ℃ of dry 24hr, obtain containing 20 (weight) %PW ₁₂2H ₂O/HY.

HY molecular sieve behind the dipping is positioned in the reaction tube, adds behind the 5g Antimony pentachloride in 120 ℃ constant temperature air bath heating 5 hours, Antimony pentachloride is gasified totally and is uniformly distributed on the carrier.After absorption finishes at room temperature vacuum extract superfluous Lewis acid.Contained Antimony pentachloride weight accounts for about 3% of vehicle weight in the catalyst that obtains like this.

Powder after above-mentioned processing adds adhesive and the extrusion aid extruded moulding of about 25 (weight) %, and note is numbered PW-SbCl/HY.。

Having obtained a specific area like this is 580m ²G ^-1, pore volume is 0.31cm ³G ^-1, average pore size is the catalyst of 2.1m.The Ha Meite acid strength Ho value that adopts Ha Meite (Hammett) indicator method mensuration catalyst commonly used the results are shown in Table 2 less than-12.The infrared acid measurement result of the original position pyridine adsorption of catalyst shows, has the acid centre of B acid type and L acid type on the catalyst simultaneously.

Take by weighing 10gPW-SbCl/SiO ₂Catalyst grinds to 40 orders, and 25cm packs into ³In the fixed bed reactors, in 160 ℃ of nitrogen streams, activate 3hr in advance, adopt supercritical reaction conditions to carry out alkylated reaction, transfer to desired reaction temperature, reaction pressure, use precision metering pump with 25cm ³Hr ^-1Amount send into the raw material that contains iso-butane and alkene, the online chromatography that degass of every 1hr sampling is analyzed its composition.Reaction condition and reaction result see Table 5.

Comparative Examples 2

Carry out the alkylated reaction of iso-butane and alkene by the reaction condition of embodiment 3, different is the load that catalyst system therefor does not carry out heteropoly acid, has only adopted the load of Antimony pentachloride.The catalyst numbering is designated as SbCl/HY.Adopt Ha Meite (Hammett) indicator method commonly used to measure the Ha Meite acid strength of catalyst, the results are shown in Table 2.The infrared acid measurement result of the original position pyridine adsorption of catalyst shows, only occurs the acid centre of L acid type on the catalyst.The alkylated reaction of iso-butane and alkene the results are shown in Table 5.

Comparative Examples 3

Carry out the alkylated reaction of iso-butane and alkene by the reaction condition of embodiment 3, different is the Gas Phase Adsorption that catalyst system therefor does not carry out lewis acid.Only adopted the load of heteropoly acid.The catalyst numbering is designated as PW/HY.The contained crystallization water number of heteropoly acid is not in scope of the present invention in this Comparative Examples catalyst, and catalyst final drying temperature is 60 ℃, drying time 4hr.Adopt Ha Meite (Hammett) indicator method commonly used to measure the Ha Meite acid strength of catalyst, the results are shown in Table 2.The alkylated reaction of iso-butane and alkene the results are shown in Table 5.

Table 5

Catalyst	PW-SbCl/HY		SbCl/HY		PW/HY
							Reaction temperature, ℃	136		136		136
Reaction pressure, MPa	4.5		4.5		4.5
							Alkane alkene mol ratio	12		12		12
WHSV，hr -1	1.6		1.6		1.6
							Reaction time, hr	4	18	2	4	4	18
C 4 ＝Olefin conversion, heavy %	100	100	100	65	100	78
							The alkylate oil yield, % (based on alkene)	200	201	158	-	182	152
C 5 +Product distributes, heavy % C 5 C 6 C 7 C 8 C 9 + C 8 ＝	0.89 1.44 4.88 78.12 14.67 0.00	0.72 1.41 5.08 79.45 13.34 0.00	0.82 1.26 3.99 78.34 15.59 0.00	1.08 3.45 6.75 28.56 45.15 15.01	1.63 2.24 3.44 64.12 22.57 6.00	0.92 1.63 3.56 53.60 22.08 18.21

Embodiment 4～5:

Accurately take by weighing phosphotungstic acid (PW ₁₂) 10g and 50 the gram place beaker, each adds in the 100g distilled water, and phosphotungstic acid is dissolved fully, leaves standstill 24hr then, makes PW ₁₂The aqueous solution.With 100g in advance at 70～230 order Hydrogen Y molecular sieve powder impregnations of 400 ℃ of down dry 24hr in Salkowski's solution, leave standstill 8hr after, at 160 ℃ of dry 24hr, obtain containing 10 (weight) %PW ₁₂2H ₂O/HY and 50 (weight) %PW ₁₂2H ₂O/HY.

HY molecular sieve behind the dipping is positioned in the reaction tube, heats 5hr after adding the 2g Antimony pentachloride in 120 ℃ constant temperature air bath, Antimony pentachloride is gasified totally and is uniformly distributed on the carrier.After absorption finishes at room temperature vacuum extract superfluous Lewis acid.Contained antimony pentafluoride weight accounts for 1% of vehicle weight in the catalyst that obtains like this.

Powder after above-mentioned processing adds alumina adhesive and the extrusion aid extruded moulding of about 25 (weight) %, and note is numbered 10PW-SbCl/HY and 50PW-SbCl/HY.Its specific area is respectively 603m ²G ^-1And 575m ²G ^-1

Take by weighing 10PW-SbCl/HY and each 10g of 50PW-SbCl/HY catalyst, carry out iso-butane and olefin alkylation reaction by embodiment 3 described methods, reaction raw materials, reaction unit and catalyst amount are with embodiment 3.Reaction condition and reaction result see Table 6.

Table 6

The catalyst numbering	10PW-SbCl/HY		50PW-SbCl/HY
					Reaction temperature, ℃	136		136
Reaction pressure, MPa	4.5		4.5
					Alkane alkene mol ratio	18		18
WHSV, hr -1	1.6		1.6
					Reaction time, hr	24	48	24	48
Olefin conversion, %	100	100	100	100
					Alkylate oil yield (based on alkene), %	199	196	200	201
C 5 +Product distributes.% C 5C 6C 7C 8C 9 +C 8 =	1.72 5.81 8.98 79.45 4.04 0.00	1.64 5.78 8.80 76.64 7.14 0.00	1.79 4.97 6.84 79.63 6.77 0.00	1.81 5.06 6.83 81.72 4.41 0.00
					The C8 product distributes, % trimethylpentane (TMP) dimethyl pentane (DMP) 2,2,4-TMP/TMP	79 21 40	77 22 38	83 17 44	81 18 45

2,2,4-TMP/TMP---2,2,4-TMP shared percentage composition in the trimethylpentane component

The result by this support type conjugation super acidic catalyst that embodiment among the present invention draws, maintains 100% olefin conversion, the catalytic stability height as can be seen in alkylated reaction from above-mentioned table.The C8 saturated hydrocarbon content is greater than 75% in the alkylate oil that catalysis generates, and is 175-205% in the oily yield of alkene weight.Mainly be trimethylpentane (TMP) in the product, wherein the product of concentration maximum is 2,2,4-trimethylpentane (isooctane).

Claims (12)

1, the method for a kind of isoparaffin and olefin alkylation is characterized in that using a kind of solid acid catalyst, and isoparaffin and alkene carry out alkylated reaction under the super critical condition of isoparaffin; Described solid acid catalyst is carried heteropoly acid and Lewis acid simultaneously on porous carrier, and heteropoly acid accounts for the 10w%～55w% of carrier by weight, and Lewis acid accounts for the 1w%～5w% of carrier, and wherein said heteropoly acid has following chemical expression:

H _kYW _mMo _12-mO ₄₀·nH ₂O

Wherein, H represents hydrogen atom, and k represents the number of hydrogen atom, round numbers 3 and 4; Y is selected from phosphorus atoms, silicon atom; W represents tungsten atom, and m represents the number of tungsten atom, is 0～12 positive integer; Mo represents molybdenum atom, and 12-m represents the number of molybdenum atom; The O represention oxygen atom; N represents the number of the crystallization water, gets any number of 0 to 12; Described Lewis acid comprises halogenation boron, aluminum halide, aikyl aluminum halide, antimony halides, halogenated titanium and its mixture; Described alkylation reaction condition is that reaction temperature is 136～250 ℃, and reaction pressure 3.6～9.0MPa, weight space velocity are 0.1～15h ^-1Described isoparaffin is C ₄～C ₇In the isoparaffin one or more, alkene are C ₃～C ₅Alkene in one or more, wherein the mol ratio of isoparaffin/alkene is 1～100 in the reaction raw materials.

2, in accordance with the method for claim 1, it is characterized in that described isoparaffin is an iso-butane, described alkene is 1-butylene or 2-butylene or its mixture.

3, in accordance with the method for claim 1, it is characterized in that the mol ratio of isoparaffin/alkene in the reaction raw materials is 8～30, the content of water should be lower than 200 μ gg in the reaction raw materials ^-1

4, in accordance with the method for claim 1, the mol ratio that it is characterized in that isoparaffin/alkene in the reaction raw materials is 8～18.

5, in accordance with the method for claim 1, the specific area that it is characterized in that described solid acid catalyst is 50～1000m ²G ^-1, the porosity of catalyst is 0.05～3cm ³G ^-1, average pore size is between 1.0～80.0nm.

6, in accordance with the method for claim 5, the specific area that it is characterized in that described solid acid catalyst is 100～800m ²G ^-1

7, in accordance with the method for claim 1, Ha Meite acid strength Ho＜-12 that it is characterized in that described catalyst.

8, in accordance with the method for claim 1, it is characterized in that described porous carrier is to be selected from zirconium dioxide, titanium dioxide, silica, aluminium oxide, the molecular sieve one or more.

9, in accordance with the method for claim 8, its feature can be selected from A type zeolite, X type zeolite, y-type zeolite, modenite, ZSM-series zeolite, Beta zeolite, phosphorus aluminium zeolite, the Ti-Si zeolite one or more mixture at described molecular sieve.

10, according to claim 1,8 or 9 described methods, the specific area that it is characterized in that described carrier is 50～1000m ²G ^-1, porosity is 0.05～3cm ³G ^-1, average pore size is between 1.0～80.0nm.

11, in accordance with the method for claim 10, the specific area that it is characterized in that described carrier is 100～800m ²G ^-1

12, in accordance with the method for claim 1, it is characterized in that described Lewis acid is selected from one or more in boron trifluoride, antimony pentafluoride, Antimony pentachloride or the alchlor.