CN1142123C - Solid acid catalytic process for alkylating paraffin and olefin - Google Patents

Abstract

The present invention relates to an alkylation method for isomerized alkane and alkene. The method comprises the following steps: a mixture of a raw material prepared from C4 to C6 isomerized alkane and C3 to C6 single-bond alkene is in contact with a solid acid catalyst under the condition of alkylation reaction. The method is characterized in that the raw material contains 10 to 3000 ppm of compound containing strong electronegative elements, preferably hydrogen halide used as a reaction assistant. The method has the advantages of high yield of alkylate and high selectivity of reaction.

Description

A kind of isoparaffin of solid acid catalysis and the alkylation of alkene

The present invention relates to a kind of is the alkylation of the isoparaffin of catalyzer and the alkylation of alkene, particularly Trimethylmethane and butylene with the solid acid.

At present, many hydrocarbon conversion process that adopt solid acid catalyst are at low temperatures arranged, as alkylation (alkylation of the alkylation of isoparaffin and alkene, benzene and alkene), isomerization (C ₄, C ₅, C ₆The isomerization of low-carbon (LC) normal paraffin, the isomerization of low-carbon alkene), olefin oligomerization, hydroisomerization etc.In these low temperature hydrocarbon conversion reaction technologies, need to adopt solid acid catalyst with strong acid character, as: carried heteropoly acid catalyst, carried heteropoly acid salt catalyst, zeolite [molecular sieve, SO 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 or acid-treated oxide compound of Lewis or molecular sieve catalyst.These solid acid catalysts all carry out hydrocarbon conversion reaction by the carbonium ion reaction mechanism in hydrocarbon conversion reaction.

The alkylation reaction method of said isoparaffin and alkene is meant C ₄-C ₆Isoparaffin and C ₃-C ₆The singly-bound olefine reaction generate the long chain alkane of isomery.The product of this alkylated reaction is as the C of Trimethylmethane and butene alkylation generation ₈Octane-iso has high octane value and low Reid vapour pressure, is a kind of gasoline blend component of excellent performance.

The catalyzer of the alkylation process that is used for above-mentioned isoparaffin and alkene of present industrial employing is that concentration is about 95% H ₂SO ₄Or HF.H wherein ₂SO ₄Alkylation carries out under low temperature (about 10 ℃ of temperature of reaction), can prevent the building-up reactions of alkene.H ₂SO ₄To produce a large amount of spent acid in the method alkylation process, more difficult giving birth to used, if discharging will cause serious environmental to pollute.The HF method is also carried out under lesser temps (being generally 20～40 ℃).HF is more volatile, causes environmental pollution and equipment corrosion easily.Industrial employing H ₂SO ₄Produce alkylate oil existing decades of history with the HF method, visible " the Alkylation of isobutane with C of detailed discussion ₄Olefins ", Ind.Eng.Chem.Res., 27,381-379 (1988), Handbook of Petroleum Refining Processes, 1,23-28 (1986) and " Chinese oil Refining Technologies ", Sinopec press, 206～217 (1991).

Because H ₂SO ₄With HF liquid strong acid serious environment pollution, adopt solid acid replaces them has become investigators in the catalytic field in the world as the catalyzer of alkylated reaction great research topic.In recent years, be used for the existing many reports of various solid acid catalysts of abovementioned alkyl method, 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 Lewis acid such as SbF ₅, BF ₃, AlCl ₃The catalyzer of load; CN1184797A, CN1232814A, US5,324,881, US5,475,178 disclosed carried heteropoly acid catalysts; US3,549,557,3,644,565,3,647,916,3,917,738,4,384,161 disclosed molecular sieve catalysts etc.

WO94/03415 discloses the alkylation of a kind of alkane and alkene, this method is included under the alkylation reaction condition, in the presence of a kind of crystalline microporous body, a kind of olefin feedstock that contains is contacted with a kind of raw material that contains isoparaffin, alkylation reaction condition comprises temperature in the critical temperature of described raw material main ingredient or more than the critical temperature, and pressure is in the emergent pressure of described raw material main ingredient or more than the emergent pressure.Described crystalline microporous body comprises various zeolites and stratified material, and described zeolite comprises ZSM series zeolite, offretite zeolite, MCM zeolite, mordenite, REY zeolite etc., and layered material comprises layered silicate, laminated clay etc.When being catalyzer, adopting this method can improve the transformation efficiency of butylene and improve activity of such catalysts stability, but adopt this method olefin conversion still lower with the MCM series zeolite.

CN1125639A discloses the alkylation of a kind of Trimethylmethane and alkene, and this method comprises PW ₁₂, PMo ₁₂, SiW ₁₂, PW ₁₂Mo _12-n(n=1-11) etc. heteropolyacid is dissolved in by 10-70% in the mixed solution equal solvent of low carbon fatty acid, ester, ketone, ether, alcohol or lipid acid and Fatty Alcohol(C12-C14 and C12-C18) and makes the alkylated reaction that catalyzer is used for catalyzing iso-butane alkane and butylene, be reflected at 10-70 ℃ and carry out, alkane alkene is than being 1.5-18.Though when adopting this method to avoid sulfuric acid or hydrofluoric acid to make catalyzer to the deep-etching of equipment, carry out but be reflected in the liquid phase, brought the problem of reaction product and described separated from solvent, olefin conversion and alkylate oil yield are lower when carrying out the alkylated reaction of Trimethylmethane and butylene with this method simultaneously.

CN1184797A discloses the alkylation of a kind of Trimethylmethane and butylene, it is catalyzer that this method adopts the basic metal or the ammonium salt of phosphorus tungsten, phosphorus molybdenum, silicon tungsten, silicon-molybdenum heteropoly acid, the mobility scale of alkalimetal ion and ammonium ion (mol) is phosphorus series 0.5-3.0, silicon series 0.5-4.0.

US5,324,881 disclose the alkylation of a kind of isoparaffin and alkene, and this method is included under the alkylation conditions, in the presence of a kind of carried heteropoly acid catalyst, isoparaffin and alkene is reacted, and obtains alkylate.Described heteropolyacid contains and at least aly is selected from down element in the group as its central element: P, Si, B, Ge, As, Ti, Zr, Mn, F, V, Ce, Th, and contains and at least aly be selected from down element in organizing as its coordination element: Mo, W, V, Mn, Co, Ni, Cu, Zn, Fe.

CN1232814A discloses the alkylation of a kind of low-carbon (LC) isoparaffin and alkene, this method working load type heteropolyacid catalyst, and be not less than the critical temperature of isoparaffin in temperature, pressure is not less than under the condition of emergent pressure of isoparaffin and reacts, have olefin conversion and alkylate oil yield advantage of higher, activity of such catalysts stability makes moderate progress simultaneously.

CN1246467A discloses the alkylation of a kind of low-carbon (LC) isoparaffin and alkene, it is characterized in that employed catalyzer is made up of a kind of Lewis acid institute of a kind of Br nsted acid of a kind of porous inorganic carrier of 40～95 heavy % and load 1～60 heavy % on it and 0.3～15 heavy %, wherein said Br nsted acid is a kind of heteropolyacid or a kind of inorganic mineral acid, and said Lewis acid is selected from AlCl ₃, BF ₃Perhaps XF ₅, wherein X is P, As, Sb or Bi.The catalyst activity component be difficult for to run off when adopting this method, and reaction conversion ratio and selectivity are all higher.

The objective of the invention is to provide on the basis of existing technology a kind of isoparaffin of solid acid catalysis and the alkylation of alkene, the selectivity that the makes alkylated reaction especially yield of trimethylpentane can be significantly improved.

The present inventor is surprised to find that, if in the reaction mass mixture of alkylated reaction, add the organic or inorganic compound contain the strong electronegativity element or its mixture as reaction promoter, and select proper reaction conditions to carry out the alkylated reaction of isoparaffin and alkene, the selectivity that can improve reaction significantly is the yield of trimethylpentane especially, and can improve the yield of alkylate oil, the running period of improving catalyzer simultaneously.

The alkylation of isoparaffin provided by the present invention and alkene comprises C ₄～C ₆Isoparaffin and C ₃～C ₆The raw mix that singly-bound alkene is formed contacts with a kind of solid acid catalyst under alkylation reaction condition, it is characterized in that in said raw material, containing 5-5000ppm, preferred 10-3000ppm, more preferably the organic or inorganic compound that contains the strong electronegativity element or its mixture of 10-2000ppm.

Said strong electronegativity element halogen preferably in the method provided by the invention, the said organic or inorganic compound that contains the strong electronegativity element be hydrogen halide or can be decomposed into the inorganic or organic compound of hydrogen halide under alkylation conditions preferably.In general all inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions may be used to the present invention, but preferred mineral compound is hydrogen halide such as HF, HCl, HBr and HI, is more preferably HF or HCl; Preferred organic compound is the halogen-containing organic compound with 2～8 carbon atoms.The said organic or inorganic compound that contains the strong electronegativity element also can be two or more the mixture in the above-claimed cpd.

Said organic compound includes, but not limited to have one or dihalogenated alkane of 2～8 carbon atoms, for example a fluoroethane in the method provided by the invention, monochlorethane, 1-fluoropropane, n-propyl chloride, 2-fluoropropane, 1-fluorine butane, 1-chlorobutane, 1-n-butyl bromide, 2-fluorine butane, 1,3-difluoro butane, 1,3-dichlorobutane, 1-fluorine iso-pentane, 1-fluorine hexane, 2-fluorine hexane, 1-fluorine heptane, n octyl fluoride, 2-fluoro-octane, 1-chloro-octane, fluoro octane-iso etc.;

The said organic or inorganic compound that contains the strong electronegativity element is most preferred in the method provided by the invention is hydrogen fluoride or hydrogenchloride.

Said 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.The flow pattern of material can be that upstriker also can be a downstriker.

The alkylation of isoparaffin provided by the invention and alkene is owing to add the auxiliary agent that contains the strong electronegativity element in reacting material mixture, when reaction raw materials contacts with solid acid catalyst in alkylated reaction, the auxiliary agent and the acid active centre that contain the strong electronegativity element interact, improved the original acid properties of solid acid catalyst, as strength of acid, acid distribution and acid site density etc.; Consequently changed the catalytic performance of solid acid catalyst in alkylated reaction, make alkylated reaction selectivity especially the yield of trimethylpentane obviously improve, and can improve the yield of alkylate oil; Content owing to alkene in the product alkylate oil reduces simultaneously, has reduced the carbon deposit of catalyst surface, thus the running period that can improve catalyzer.

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 1-3

Carry out the alkylated reaction of Trimethylmethane and butylene according to method provided by the invention.

Take by weighing 5.24g phospho-wolframic acid (H ₃PW ₁₂O ₄₀22H ₂O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 35ml deionized water, be made into H ₃PW ₁₂O ₄₀The aqueous solution.With the 18.5g granularity is 20-40 purpose silica gel (SiO ₂, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing ₃PW ₁₂O ₄₀Solution stirring is even, floods 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtains containing 20 heavy %H ₃PW ₁₂O ₄₀Carried heteropoly acid catalyst with 80 heavy % silica gel is designated as 20%H ₃PW ₁₂O ₄₀/ SiO ₂, the specific surface of this catalyzer is 380m ²/ g.The specific surface of catalyzer adopts cryogenic nitrogen absorption BET method to measure (down together).

Take by weighing the above-mentioned 20%H of 10.0g ₃PW ₁₂O ₄₀/ 5iO 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, with the listed Trimethylmethane of table 1 and butene feedstock by required alkane alkene mixed in molar ratio evenly after, pump into according to predetermined amount of flow with precision metering pump that reactor reacts and close nitrogen gas stream simultaneously, after stable reaction, with the composition of SP-3420 gas chromatograph (chromatographic column is the OV-01 kapillary crosslinking column of 50m * 0.2mm) timing analysis reaction end gas, and take out product liquid on time and analyze its composition with HP-5890 gas chromatograph (chromatographic column is the OV-01 capillary column of 50m * 0.2mm).The reaction conditions of each embodiment is as shown in table 2, and wherein said raw material alkane alkene is than the actual mol ratio that is meant isoparaffin and monoolefine in the mixed raw material.In reacting material mixture, add the HF of 100ppm as reaction promoter.

Table 1

Isobutane feedstock is formed (heavy %)		Butene feedstock is formed (heavy %)
				Propane	2.31	1-butylene+iso-butylene	2.91
Trimethylmethane	95.1	Normal butane	11.54
				Normal butane	1.54	Maleic-2	59.03
Butylene	1.95	Anti-butene-2	25.66
						Trimethylmethane	0.86
Impurity		Impurity
				H 2O	34ppm	H 2O	40ppm
S	＜1.0mg/m 3	S	＜1.0mg/m 3
				Divinyl	75ppm	Divinyl	5ppm

Reaction result is listed in the table 2.Alkylated reaction is through after 720 hours as can be seen, catalyst activity (C ₄Olefin conversion) still keeps 100%.RON and MON value are according to document Huston and Logan " Estimate Alkyl Yield and Quality ", hydrocarbon processing, and in September, 1975, the method for 107-108 page or leaf is drawn by gas chromatographic analysis.By table 2 result as can be known, the C in solid acid alkylating reaction product-alkylate oil ₈The amount of isoparaffin component even be higher than sulfuric acid alkylation method (seeing Comparative Examples 1).Compare with the alkylated reaction result who does not contain reaction promoter in the reaction mass (seeing Comparative Examples 2), the selectivity of alkylated reaction is good, generates more purpose C ₈Product.

Comparative Examples 1

The alkylating result of Trimethylmethane and butylene is carried out in the explanation of this Comparative Examples as catalyzer with sulfuric acid.

With 73.3g (40m1) concentration 95% H ₂SO ₄Be catalyzer, in tank reactor, carry out the alkylated reaction of Trimethylmethane and butylene.At reactor pressure (nitrogen pressure) is under the 7.0atm, adds the 18.0g Trimethylmethane.When temperature of reaction is 10 ℃ under violent stirring then, add the 3.48g butylene.Reaction continued to carry out 3.0 hours, then the composition of gas phase composition and liquid product in the usefulness gas chromatographic analysis still.Reaction mass sees Table 1.The results are shown in Table 2 in reaction.

Comparative Examples 2

Alkylation effect when not containing electronegative element as reaction promoter in this Comparative Examples explanation raw material.

Catalyzer, reaction conditions and process are with embodiment 1, and reaction mass is the reaction mass among the embodiment 1, but do not contain the HF reaction promoter.The results are shown in Table 2 in reaction.

Table 2

		Embodiment 1	Embodiment 2	Embodiment 3	Comparative Examples 1	Comparative Examples 2
							Reaction conditions	Temperature, ℃	145	50	230	10	145
Pressure, MPa	4.0	2.5	6.0	0.7	4.0
						Weight space velocity, hour -1		3.5	3.5	3.5	--	3.5
Alkane/alkene mol ratio	22.0	22.0	22.0		22.0
						HF in the raw material, ppm		100	100	100	0	0
Sample time, hour		48	400	720	3								150
						C 4 ＝Olefin conversion, weight %		100.0	100.0	100.0	100.0	100.0
The alkylate oil yield, g/g		2.02	2.00	2.01	2.01								1.98
						Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH *		4.25 3.40 5.42 84.64 2.82 0.00 5.45	2.05 4.29 4.42 84.23 5.51 0.00 5.40	4.51 3.23 6.25 82.27 3.74 0.00 5.31	5.63 6.05 5.63 77.79 4.90 0.00 5.64	4.12 4.20 6.21 70.87 14.6 0.0 3.01

^*: TMP: trimethylpentane; DMH: dimethylhexane

Embodiment 4

The HF that adds 1500ppm in the mixture of alkylated reaction raw material alkane shown in the table 1 and alkene carries out alkylated reaction according to the listed reaction conditions of table 3 with the reactions steps identical with embodiment 1, and the results are shown in Table 3 for gained.

Embodiment 5

The fluorobutane that adds 500ppm in the mixture of alkylated reaction raw material alkane shown in the table 1 and alkene carries out alkylated reaction according to the listed reaction conditions of table 3 with the reactions steps identical with embodiment 1, and the results are shown in Table 3 for gained.

Table 3

		Embodiment 4	Embodiment 5
				Reaction conditions	Temperature, ℃	145	145
Pressure, MPa	4.0	4.0
			Weight space velocity, hour -1		5.5	1.5
Alkane/alkene mol ratio	60.0	22.0
			Auxiliary agent content in the raw material		HF，1500ppm	Butyl fluoride, 500ppm
Sample time, hour		160					180
			C 4 ＝Olefin conversion, weight %		100.0	100.0
The alkylate oil yield, g/g		2.01					2.02
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH *		4.05 3.79 6.42 83.23 2.51 0.00 5.31	4.11 3.13 5.86 83.87 3.03 0.00 5.29

Embodiment 6-7

Take by weighing 5.24g silicotungstic acid (H ₄SiW ₁₂O ₄₀22H ₂O, analytical pure, the Beijing Chemical Plant produces) be dissolved in the 35ml deionized water, be made into H ₄SiW ₁₂O ₄₀The aqueous solution.With the 18.5g granularity is 20-40 purpose silica gel (SiO ₂, Haiyang Chemical Plant, Qingdao produces) and put into filter flask, handled 1.0 hours down 0.095 MPa vacuum tightness and 75 ℃, cool to room temperature, under the condition that keeps vacuum, add the H for preparing ₄SiW ₁₂O ₄₀Solution stirring is even, floods 1.0 hours, then 100 ℃ of vacuum-dryings 4 hours, obtains containing 20 heavy %H ₄SiW ₁₂O ₄₀Carried heteropoly acid catalyst with 80 heavy % silica gel is designated as 20%H ₄SiW ₁₂O ₄₀/ SiO ₂, the specific surface of catalyzer is 376m ²/ g.

With the above-mentioned 20%H of 10.0g ₄SiW ₁₂O ₄₀/ SiO ₂As catalyzer, in the mixture of alkylated reaction raw material alkane shown in the table 1 and alkene, add the HCl of 100ppm or the n octyl fluoride of 800ppm, carry out alkylated reaction according to the listed reaction conditions of table 4 with the reactions steps identical with embodiment 1, the results are shown in Table 4 for gained.

Table 4

		Embodiment 6	Embodiment 7
				Reaction conditions	Temperature, ℃	175	145
Pressure, MPa	5.0	4.0
			Weight space velocity, hour -1		3.5	3.5
Alkane/alkene mol ratio	22.0	22.0
			Auxiliary agent content in the raw material		HCl，100ppm	N octyl fluoride, 800ppm
Sample time, hour		48					200
			C 4 ＝Olefin conversion, weight %		100.0	100.0
The alkylate oil yield, g/g		2.01					2.00
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH		3.89 4.19 5.47 82.36 4.09 0.00 5.39	4.01 4.45 5.68 81.48 4.38 0.00 5.27

Embodiment 8

With preparation Cs _2.5H _0.5PW ₁₂O ₄₀Be example, the preparation method of various heteropolyacid salts and the effect of alkylated reaction are described.

With 22.81g phospho-wolframic acid (H ₃PW ₁₂O ₄₀21H ₂O, chemical reagent factory of Beijing Xinhua product, analytical pure) and 2.85gCs ₂CO ₃(northern Tonghua factory products, analytical pure) is made into the solution of 0.35 and 0.87 volumetric molar concentration respectively, under violent stirring, with Cs ₂CO ₃Solution is added dropwise to H lentamente ₃PW ₁₂O ₄₀In the solution, treat Cs ₂CO ₃After solution dropwises, continue to stir 30 minutes, then with the white precipitate that obtains 50 ℃ of dryings 24 hours, obtaining molecular formula is Cs _2.5H _0.5PW ₁₂O ₄₀8H ₂The heteropolyacid salt of O.With this Cs for preparing _2.5H _0.5PW ₁₂O ₄₀8H ₂O is levigate, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 20～40 purpose particles and is used for alkylated reaction as catalyzer.

Repeat the alkylated reaction step of embodiment 1, different is wherein catalyzer is with the Cs of above-mentioned preparation _2.5H _0.5PW ₁₂O ₄₀8H ₂The O catalyzer replaces.The gained reaction result is all listed in the table 5.

Comparative Examples 3

Repeat the alkylated reaction step of embodiment 8, different is not contain HF in the raw material for alkylation.The results are shown in Table 5 for gained.

Table 5

	Embodiment 8	Comparative Examples 3
			Sample time, hour	120	130
HF content in the raw material, ppm	100	0
			C 4 ＝Olefin conversion, weight %	100.0	100.0
The alkylate oil yield, g/g	2.01	1.98
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH	3.15 3.99 5.72 77.63 9.51 0.00 4.81	4.33 3.83 6.88 68.93 16.03 0.00 3.29

Embodiment 9

The solid acid alkylation catalysts that this embodiment uses is that (B:Br nsted acid is H to B-L conjugation super acids here ₃PW ₁₂O ₄₀L:Lewis acid is SbF here ₅) catalyzer.This Preparation of catalysts method is as follows: the method for pressing among the embodiment 1 prepares 20%H earlier ₃PW ₁₂O ₄₀/ SiO ₂Catalyzer is then with this 20%H of 10.0g ₃PW ₁₂O ₄₀/ SiO ₂Packing in the fixed-bed reactor, is 120 hours with air speed ^-1Nitrogen gas stream handled 4 hours at 100 ℃, cool to 50 ℃ then, make nitrogen gas stream SbF is housed through one ₅Storage bottle, carry SbF ₅The above-mentioned catalyzer of flowing through, the time is 3.5 hours, makes SbF ₅Obtain B-L acid with the heteropolyacid interaction, purged 1.0 hours with nitrogen gas stream at last, make H ₃PW ₁₂O ₄₀-SbF ₅/ SiO ₂Catalyzer is used for alkylated reaction.

Use above-mentioned H ₃PW _I2O ₄₀-SbF ₅/ SiO ₂Catalyzer carries out alkylated reaction according to the listed reaction conditions of table 6 with the reactions steps identical with embodiment 1, and the results are shown in Table 6 for gained.

Comparative Examples 4

Repeat the alkylated reaction step of embodiment 9, different is not contain HF in the raw material for alkylation.The results are shown in Table 6 for gained.

Table 6

		Embodiment 9	Comparative Examples 4
				Reaction conditions	Temperature of reaction, ℃	30	30
Reaction pressure, MPa	2.5	2.5
			Weight space velocity, hour -1		3.10	2.81
Alkane/alkene mol ratio	22.0	22.0
			HF content in the raw material, ppm		100	0
Sample time, hour		50					100 *
			C 4 ＝Olefin conversion, weight %		100.0	100.0
The alkylate oil yield, g/g		2.02					1.99
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH		3.41 3.56 4.89 84.23 3.91 0.00 5.44	2.99 3.54 5.12 73.77 14.58 0.00 4.01

Embodiment 10

With 20.0gZrOCl ₂8H ₂O zirconyl chloride (analytical pure, Beijing Chemical Plant) is dissolved in the 180ml water, under room temperature and agitation condition to wherein slowly splashing into 25% ammonia soln, until the pH of solution value is 10.5, stop dropping ammonia and stirring, aged at room temperature 24 hours, then with distilled water wash, be filtered to no Cl ^-Ion, 100 ℃ of dryings 5 hours obtain solid Zr (OH) ₄Preparation 1.0M sulphuric acid soln is pressed 10ml sulphuric acid soln/1gZr (OH) ₄Ratio with 1.0M sulphuric acid soln dipping Zr (OH) ₄Solid 4.0 hours filters out unnecessary acid solution, and 100 ℃ of dryings 3 hours 550 ℃ of roasts 4.0 hours, obtain SO then ₄ ⁼/ ZrO ₂Solid super-strong acid.With the SO for preparing ₄ ⁼/ ZrO ₂Solid super-strong acid is worn into fine powder, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets the catalyzer of 20～40 purpose particles as alkylated reaction.

With above-mentioned SO ₄ ⁼/ ZrO ₂Solid super-strong acid is a catalyzer, carries out alkylated reaction according to the reactions steps identical with embodiment 1, and the results are shown in Table 7 for gained.

Comparative Examples 5

Repeat the alkylated reaction step of embodiment 10, different is not contain HF in the raw material for alkylation.The results are shown in Table 7 for gained.

Table 7

	Embodiment 10	Comparative Examples 5
			Sample time, hour	40	40
HF content in the raw material, ppm	100	0
			C 4 ＝Olefin conversion, weight %	100.0	100.0
The alkylate oil yield, g/g	2.00	1.98
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH	4.22 4.17 6.42 72.44 12.75 0.00 4.25	4.39 4.59 6.98 65.11 18.93 0.00 3.01

Embodiment 11

30.0gNa beta-molecular sieve (Fushun No.3 Petroleum Factory's catalyst plant is produced) and ammonium nitrate and water were mixed into slurries by 1: 0.5: 10, and 90 ℃ are stirred exchange 0.5 hour, filter then, wash.The ammonium exchange process that triplicate is same 110 ℃ of dryings 3 hours, 550 ℃ of roasts 6 hours, obtains the H beta-molecular sieve with filter cake then.The H beta-molecular sieve for preparing is worn into fine powder, and compressing tablet on tabletting machine is broken into small-particle then, sieves, and gets 20～40 purpose particles as alkylation catalyst.

With above-mentioned H beta-molecular sieve is catalyzer, carries out alkylated reaction according to the reactions steps identical with embodiment 1, and the results are shown in Table 8 for gained.

Comparative Examples 6

Repeat the alkylated reaction step of embodiment 11, different is not contain HF in the raw material for alkylation.The results are shown in Table 8 for gained.

Table 8

	Embodiment 11	Comparative Examples 6
			Sample time, hour	36	36
HF content in the raw material, ppm	100	0
			C 4 ＝Olefin conversion, weight %	100.0	100.0
The alkylate oil yield, g/g	2.00	1.95
			Products distribution, weight % C 5C 6C 7C 8C 9 +C 8 ＝TMP/DMH	4.79 5.14 6.62 70.88 11.98 0.59 3.37	5.01 5.25 7.25 60.07 20.53 1.89 2.78

Claims (12)

1, the alkylation of a kind of isoparaffin and alkene, this method comprises C ₄～C ₆Isoparaffin and C ₃～C ₆The raw mix that singly-bound alkene is formed contacts with a kind of solid acid catalyst under alkylation reaction condition, it is characterized in that containing the halogen-containing compound of 10-3000ppm as reaction promoter in said raw material.

2, according to the process of claim 1 wherein that said halogen-containing compound is hydrogen halide or the inorganic or organic compound that can be decomposed into hydrogen halide under alkylation conditions.

3, according to the method for claim 2, wherein said organic compound is one or a dihalogenated alkane with 2～8 carbon atoms.

4, according to the method for claim 1 or 2, wherein said halogen-containing compound is hydrogen fluoride or hydrogenchloride.

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 butylene.

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 mol ratio 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 mol ratio of isoparaffin and alkene is 10-90, and the weight space velocity of reaction raw materials is 0.5-8.0 hour ^-1

8, according to the process of claim 1 wherein that said solid acid catalyst is heteropolyacid salt catalyst, zeolite [molecular sieve, the SO of carried heteropoly acid catalyst, load or not load ₄ ^2-/ oxide solid super acidic catalyst, loading type Br nsted-Lewis conjugation solid super acid catalyst or Br nsted acid or acid-treated oxide compound of Lewis or molecular sieve catalyst.

9, according to the method for claim 8, the heteropolyacid salt catalyst that wherein said solid acid catalyst is carried heteropoly acid catalyst, load or not load, loading type Br nsted-Lewis conjugation solid super acid catalyst or the acid-treated oxide catalyst of Lewis.

10, according to the method for claim 8, wherein said carried heteropoly acid catalyst is made up of porous inorganic carrier and a kind of heteropolyacid, and wherein said heteropolyacid general formula is H _8-n[AM ₁₂O ₄₀], wherein A is P or Si, and M is W or Mo, and n is the valence state of A, and its value is 4 or 5; Said porous inorganic carrier is the porous inorganic carrier of the aluminosilicate zeolite that comprises gac, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, natural or synthetic, carbon fiber, natural clay etc., or their mixture.

11, according to the method for claim 10, wherein said porous inorganic carrier is silicon oxide, aluminum oxide or their mixture.

12, according to the method for claim 8, wherein said loading type Br nsted-Lewis conjugation solid super acid catalyst is made up of a kind of heteropolyacid of a kind of porous inorganic carrier of the heavy % of 40-95 and the load heavy % of 1-60 on it and a kind of Lewis acid of the heavy % of 0.3-15; Identical in the definition of wherein said heteropolyacid and porous inorganic carrier and the claim 11 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.