CN1339424A - Isomeric paraffin and olefine alkylating method - Google Patents

Abstract

The invention relates to a method for alkylation of isoparaffins and olefins, which is characterized in that the method is to circulate the reaction product (alkylated oil) back to the reactor inlet together with the reaction raw materials into the reactor, so that the alkylation reaction and Catalyst regeneration is carried out in the reactor at the same time, so as to maintain the reactivity and selectivity of the catalyst for a long period of time.

Description

A kind of alkylation method of isoparaffin and olefin

The invention relates to an alkylation reaction process of isoparaffins and olefins in the presence of a solid acid catalyst, in particular to an alkylation reaction process of isobutane and butene.

At present, in the petrochemical industry, concentrated sulfuric acid or hydrofluoric acid is used as a catalyst to alkylate isoparaffins, especially isobutane, and olefins, especially butene, to prepare trimethylpentanes. reaction product. This alkylation product is an excellent gasoline blending component. This process is called the alkylation process (referred to as alkylation). However, sulfuric acid or hydrofluoric acid has serious pollution and harm to the environment, and is very corrosive to production equipment. In addition, there are serious safety problems in the storage and transportation of these strong acids. Therefore, the petrochemical industry is eager to use solid acid alkylation catalysts to replace sulfuric acid or hydrofluoric acid, which has become a major research topic in the field of petrochemical catalysis.

In recent years, there have been many reports on various solid acid catalysts used in the above-mentioned alkylation reactions, such ^as JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, and _GB1,389,237 . Superacid catalyst; US5,220,095, US5,731,256, US5,489,729, US5,364,976, US5,288,685, EP0,714,871 disclosed CF ₃ SO ₃ H/silica catalyst; US5,391,527, US5,739,074 disclosed Pt- AlCl ₃ -KCl/Al ₂ O ₃ catalyst; , disclosed supported Lewis acid catalysts such as SbF ₅ , BF ₃ , AlCl ₃ ; CN1,184,797, CN981,016,170, US5,324,881, US5,475,178 disclosed supported heteropolyacid catalysts; US3,917,738, US4,384,161 disclosed molecular sieve catalysts.

The biggest problem in the use of solid acid catalysts in the alkylation reaction is that they are extremely easy to deactivate, such as molecular sieve catalysts, SO ₄ ^2- /oxide catalysts, within hours or even minutes, the catalyst's alkylation reaction activity (C ₄ ⁼ olefin conversion) drops from 100% to a very low level, and the selectivity of the reaction becomes poor, resulting in a decrease in the octane number of the product of the alkylation reaction, the alkylate. Therefore, the regeneration of solid acid alkylation catalyst is a key problem to be solved urgently.

Currently, there are many hydrocarbon conversion processes using solid acid catalysts at low temperature, such as alkylation, isomerization, olefin oligomerization, hydroisomerization, etc. Some side reactions in these hydrocarbon conversion processes, such as molecular polymerization and hydrogen transfer reactions, lead to some macromolecular alkanes or olefins covering the surface of the catalyst. Unlike high-temperature hydrocarbon conversion processes (reforming, catalytic cracking, etc.), these Macromolecular hydrocarbon coverings are organic substances (or coke precursors) with a carbon-to-hydrogen ratio (C/H)<1, rather than coke substances with C/H>1 produced in high-temperature processes. This opens up the possibility of solvent flushing to remove such macromolecular hydrocarbon coatings.

US5,326,923 and CN1,076,386A disclose a kind of method for the acidic hydrocarbon conversion catalyst that is used for solvent extraction regenerating load Lewis acid, and this method comprises first separating catalyst from reaction system, then using SO ₂ , phenols The solvent and aromatic ether contact the alkylation catalyst loaded with Lewis acid to remove the reaction residue adhering to the surface of the catalyst and restore the original performance of the catalyst.

US5,925,801 discloses a method for the alkylation of isoparaffins and olefins using a metal complex as a catalyst, wherein it is mentioned that a solvent extraction method is used to regenerate a deactivated catalyst, that is, an inorganic or organic solvent is used to contact the catalyst , and remove the reaction residue adhering to the surface of the catalyst to restore the original performance of the catalyst; the inorganic solvents include carbon dioxide and sulfur dioxide, and the organic solvents include aromatic hydrocarbons, oxygen-containing organic compounds, halogen-containing organic compounds, etc.

JP-P-8-281118 discloses a solvent regeneration method for solid heteropoly compounds. The method adopts polar or non-polar solvents, under normal temperature and normal pressure, especially under the action of ultrasonic waves, to process solid heteropoly acid salt or heteropoly acid alkylation catalyst in a container, so that the solid heteropoly compound catalyst part Rejuvenate. The polar solvents include water, alcohol, ether, CS2 _, etc., and the non-polar solvents include aromatic hydrocarbons, naphthenes, _C4 - _C10 saturated aliphatic hydrocarbons, etc.

US5,489,732 and CN1,144,141A disclose a hydrogenation regeneration method of a solid acid alkylation catalyst. In this method, hydrogen is contacted with an alkylation catalyst Pt-KCl-AlCl ₃ /Al ₂ O ₃ containing hydrogenation active component Pt at 10-300°C and a hydrogen partial pressure of 6.9-3790 kPa, and the selective addition A covering of _C4 ⁺ hydrocarbon molecules on the surface of the hydrogen catalyst, reactivating the catalyst.

US5,523,503 discloses a process for regenerating a solid acid alkylation catalyst with a hydrogen-saturated hydrocarbon moving bed. In this method, hydrogen-saturated isobutane is contacted with a Pt-containing solid acid alkylation catalyst (Pt-KCl-AlCl ₃ /Al ₂ O ₃ ), so that the macromolecular hydrocarbon molecules covered by the catalyst surface are hydrogenated and desorbed, Reactivate the catalyst.

US3,855,343 discloses a method for _the alkylation of isoparaffins and olefins using BF ₃ -resin as a catalyst, the method is to feed isoparaffins, olefins and BF into a reactor equipped with a resin catalyst, and use Polar solvents such as water, ethers and alcohols are used to regenerate the used resin catalysts, and batch operation or continuous operation can be adopted. When the continuous operation mode is adopted, the slurry containing the alkylation product, unreacted reactants, BF ₃ and resin catalyst is taken out from the reactor and enters the regenerator, and the polar solvent and resin are introduced into the regenerator The catalyst is contacted to regenerate the catalyst. The slurry containing solvent, alkylation product, unreacted reactant, _BF3 and resin catalyst in the regenerator is taken out and passed into the distiller, and the solvent is separated and condensed in the distiller Return to the regenerator, the slurry containing alkylation products, unreacted reactants, _BF3 and regenerated resin catalyst in the distiller enters the reactor again, and the hydrocarbon product mixture is taken out in the reactor and passed into the _BF3 stripper, The BF ₃ is separated in the stripping tower and returned to the BF ₃ raw material tank, the bottom product obtained from the stripping tower enters the rectifier to separate the alkylation product and unreacted isoparaffin reactants, and the unreacted isoparaffin The alkanes reactants are returned to the reactor. The disadvantage of this method is that multiple separation devices are required, and only polar solvents can be used, and non-polar solvents have no effect on the regeneration of the resin catalyst.

US5,365,010 discloses a high-temperature firing regeneration method for a solid acid alkylation catalyst. In this method, Lewis acid, especially BF ₃ , supported alkylation catalyst (BF ₃ /Al ₂ O ₃ ) is burned at a temperature of about 600°C to remove the hydrocarbon covering on the catalyst surface and achieve the goal of catalyst regeneration. Purpose.

Disclosed in USP5,523,503 is a kind of simultaneous moving bed solid catalyst alkylation process, this process adopts a plurality of reactors, is divided into reaction zone and regeneration zone, changes reaction zone by controlling the entry point of raw material stream and regeneration stream and the position of the regeneration zone, so as to achieve the purpose of continuous reaction-regeneration; in this method, the reaction raw materials in the reaction zone have passed through more than two reaction beds, that is, the unreacted raw materials and The stream of the product enters the second bed layer or the third bed layer again, and the regeneration stream used for catalyst regeneration is the raw material isoparaffin liquid dissolved with H ₂ , which requires a step of separating H ₂ , and due to the presence of H ₂ , The gas-liquid-solid three-phase system increases the difficulty and safety of operation.

The purpose of the present invention is to provide a method for producing high-octane alkylated gasoline by alkylation of isoparaffins and olefins, so that the reaction activity and selectivity of the catalyst can be maintained for a long period of time by using a relatively simple process .

The method for alkylating isoparaffins and olefins provided by the invention is to react the alkylation raw materials containing isoparaffins and _C3 - _C6 monoolefins in the presence of a solid acid catalyst under alkylation reaction conditions ; It is characterized in that 5-50% by weight of the product alkylate obtained by the reaction, preferably 10-40% by weight, is used as a regeneration solvent to circulate back to the reactor inlet and enter the reactor together with the reaction raw materials, so that the alkylation reaction and the catalyst are regenerated simultaneously in the reactor.

In the method provided by the present invention, said product alkylate that is recycled back to the reactor inlet as the regeneration solvent can be the unseparated stream that contains unreacted reactants (such as isoparaffins) from the reactor, or can be It is pure alkylate separated by a fractionation tower, but in view of cost reduction, it is preferably the unseparated stream containing unreacted reactants (such as isoparaffins) from the reactor.

In the method provided by the present invention, the most preferred C ₄ -C ₆ isomeric alkane is isobutane, and the most preferred C ₃ -C ₆ single bond olefin is butene-1 or butene-2 or a mixture thereof .

The alkylation reaction conditions mentioned in the method provided by the present invention are not particularly limited. It is preferred to adopt the existing alkylation reaction conditions in the prior art, for example, the reaction temperature is 10-350° C., and the reaction pressure is 0.5-10.0 MPa, the molar ratio range of isoparaffin to olefin is 2-100, and the weight space velocity of the reaction raw material is 0.1-20 hr ^-1 .

Said alkylation reaction conditions in the method provided by the present invention are more preferably supercritical reaction conditions, that is, the reaction temperature is from the critical temperature of isoparaffins to 300°C, preferably from the critical temperature of isoparaffins to 250°C, More preferably from the critical temperature of isoparaffins to 200°C; the reaction pressure is from the critical pressure of isoparaffins to 10.0MPa, preferably from the critical pressure of isoparaffins to 9.0MPa, more preferably from the critical pressure of isoparaffins to 6.0 MPa; the molar ratio of isoparaffins to olefins is in the range of 2.0-100, preferably 10-90; the weight space velocity (WHSV) of the reaction raw materials is in the range of 0.1-20 hours ^-1 , preferably 0.5-8.0 hours ^-1 .

Said solid acid catalyst in the method provided by the invention can be various solid acid catalysts disclosed in the prior art for the alkylation reaction of isoparaffins and olefins, including supported heteropolyacid catalysts, supported or not Supported heteropolyacid salt catalyst, zeolite molecular sieve catalyst, SO ₄ ^2- /oxide superacid catalyst, supported Brnsted-Lewis conjugated solid superacid catalyst, solid polymeric ion exchange resin, and Brnsted acid or Lewis Acid-treated oxide or molecular sieve catalysts. Among these catalysts, preferred are supported heteropolyacid catalysts, supported or unsupported heteropolyacid salt catalysts, supported Brönsted-Lewis conjugated solid superacid catalysts, and Lewis acid-treated oxide catalysts, more Preferred are supported heteropolyacid catalysts and supported Brönsted-Lewis conjugated solid superacid catalysts.

In the method provided by the present invention, the supported heteropolyacid catalyst is composed of a porous inorganic carrier and a heteropolyacid, wherein the general formula of the heteropolyacid is H _8-n [AM ₁₂ O ₄₀ ], wherein A is P or Si, M is W or Mo, n is the valence state of A, and its value is 4 or 5; said porous inorganic carrier is a conventional porous inorganic carrier, including activated carbon, silicon oxide, aluminum oxide, magnesium oxide, titanium oxide, Natural or synthetic aluminosilicate zeolite, carbon fiber, natural clay, etc., or their mixtures, wherein silicon oxide, aluminum oxide or their mixtures are preferred; this catalyst has been described in CN1232814A, and will This document is incorporated herein by reference. The supported or unsupported heteropolyacid salt catalyst in the method provided by the present invention is similar to the above-mentioned catalyst, except that the heteropolyacid salt is the alkali metal salt or ammonium salt of the above-mentioned heteropolyacid.

Said loaded Brnsted-Lewis conjugated solid superacid catalyst in the method provided by the invention is as described in CN1246467A, this document is used as the reference of the present invention at this; Wherein it is preferably by a kind of 40-95 weight % The porous inorganic carrier is composed of 1-60% by weight of a heteropolyacid and 0.3-15% by weight of a Lewis acid loaded thereon; Polyacid and porous inorganic carrier have the same definition; said Lewis acid is selected from AlCl ₃ , BF ₃ or XF ₅ , wherein X is P, As, Sb or Bi. This catalyst has been described in CN1246467A, which is hereby incorporated by reference in the present invention.

The other catalysts described in the method provided by the present invention are conventional catalysts disclosed in the prior art for the alkylation reaction of low-carbon isoparaffins and olefins, and the present invention has no special limitation thereon. For example, JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, GB1,389,237 disclosed SO ₄ ^2- /oxide superacid catalyst; US5,220,095, US5,731,256, US5,489,729, US5, 364,976, US5,288,685, EP0,714,871 disclosed CF ₃ SO ₃ H/silica catalyst; US5,391,527, US5,739,074 disclosed Pt-AlCl ₃ -KCl/Al ₂ O ₃ catalyst; 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 ₃ supported oxide catalyst US 3,549,557, 3,644,565, 3,647,916, 3,917,738, 4,384,161 disclose catalysts containing molecular sieves such as β, ZSM-5, etc.; these documents are hereby referred to as the present invention.

The alkylation method of isoparaffins and olefins provided by the present invention can be carried out in various reactors, such as fixed bed reactors, batch reactors, moving bed reactors, fluidized bed reactors or three-phase mud beds The reactor is preferably a fixed bed reactor. The flow of materials can be either upward or downward. The reaction materials can be fed from the top layer or the bottom layer of the catalyst in one stage, or from different catalyst bed layers in stages.

Fig. 1 is a basic flow diagram according to an embodiment of the present invention. Under the conditions of the alkylation reaction, the alkylation reaction materials (isobutane and butene) enter the reactor to start the reaction. A portion of the reactant stream containing product alkylate and unreacted reactants such as isobutane is recycled back to the reactor inlet through pump 1, while most of the reaction products and unreacted reactants enter the fractionation column for separation. The isobutane separated at the top of the tower is recycled back to the reactor inlet by the pump 2, and the product—alkylated oil is obtained at the bottom of the tower. Fresh reaction raw materials (mixture of isobutane and butene), alkylate recycled back to the reactor inlet and unreacted isobutane enter the reactor together to participate in the reaction and regeneration.

Fig. 2 is a basic flowchart according to another embodiment of the present invention. Under the conditions of the alkylation reaction, the alkylation reaction materials (isobutane and butene) enter the catalyst bed layer of the reactor in stages to start the reaction. Other processes are the same as in Figure 1.

Fig. 3 is a basic flowchart according to yet another embodiment of the present invention. Under the conditions of the alkylation reaction, the alkylation reaction materials (isobutane and butene) enter the reactor to start the reaction. The reaction product and unreacted isobutane enter the fractionation tower for separation. The isobutane separated at the top of the tower is recycled back to the reactor inlet by pump 4, and the product (alkylate) is obtained at the bottom of the tower. A portion of the alkylate is recycled by pump 3 back to the reactor inlet. Fresh reaction raw materials (mixture of isobutane and butene), alkylate recycled back to the reactor inlet and unreacted isobutane enter the reactor together to participate in the reaction and regeneration.

Fig. 4 shows the changes in the reaction activity of the alkylation reaction in Example 1 of the present invention, which has been operated continuously for 30 days.

Fig. 5 shows the variation of the octane number of the reaction product (alkylate) in Example 1 of the present invention during continuous operation for 30 days.

The following examples will further illustrate the present invention, but the present invention is not limited by these examples. In these examples and comparative examples, the alkylation reaction process is carried out in a fixed-bed reaction system which can hold 50 ml of catalyst. The reaction system consists of the following three parts:

1. Feed metering system: A precision metering pump (produced by American TSP Company) is used to feed the mixture of isobutane and butene into the reactor from the reaction raw material tank. The feed amount is measured by the precision electronic balance under the reaction raw material tank, which ensures a stable and accurate feed amount.

2. Reaction system: The reactor can hold 25ml of catalyst, and the constant temperature area of the heating furnace ensures that the temperature of the catalyst bed is uniform and constant. The temperature of the catalyst bed in the reactor is controlled by a British West temperature control instrument. The pressure of the reactor is controlled by a high-precision pressure controller (produced by Anaheim, USA). This ensures the stability and accuracy of the temperature and pressure in the reactor.

3. Separation and analysis system: The reaction products and unreacted materials are separated by high-pressure and low-pressure two-stage separators to separate liquid-phase reaction products (alkylate oil) and gas-phase unreacted materials (isobutane and olefins). The material is regularly analyzed by online gas chromatography, and the alkylate oil is regularly taken out and analyzed by another chromatograph.

Analysis method: adopt SP-3420 chromatography to analyze the composition of gas phase products online, the chromatographic column is OV-01 capillary cross-linked column of 50m × 0.2mm, and use HP-5890 (produced by Hewlett-Packard Company of the United States) to analyze the alkylate oil from _C3 ~ Full composition of C ₁₂ . The chromatographic column is a 50m×0.2mm OV-01 capillary column.

Example 1

According to the method provided by the invention, the cyclic alkylation reaction of isobutane and butene is carried out.

Weigh 5.24g of phosphotungstic acid (H ₃ PW ₁₂ O ₄₀ .22H ₂ O, analytically pure, produced by Beijing Chemical Plant) and dissolve it in 35ml of deionized water to prepare H ₃ PWO ₄₀ aqueous solution. Put 18.5g of 20-40 mesh silica gel (SiO ₂ , produced by Qingdao Ocean Chemical Factory) into a suction filter bottle, treat it at 0.095 MPa vacuum and 75°C for 1.0 hour, cool down to room temperature, and add A good H ₃ PW ₁₂ O ₄₀ solution, impregnated for 1.0 hour, then vacuum dried at 160°C for 4 hours, yielded a supported heteropolyacid catalyst containing 20% by weight H ₃ PW ₁₂ O ₄₀ .2H ₂ O and 80% by weight silica gel , recorded as 20% H ₃ PW ₁₂ O ₄₀ .2H ₂ O/SiO ₂ , the specific surface area of the catalyst is 350m ² /g. The specific surface area of the catalyst was determined by low-temperature nitrogen adsorption BET method.

The alkylation reaction was carried out according to the process shown in Fig. 1 . Weigh 10.0 g of the above-mentioned 20% H ₃ PW ₁₂ O ₄₀ .2H ₂ O/SiO ₂ catalyst, put it into a 50 ml fixed-bed reactor, and feed it with nitrogen flow. Raise the temperature and pressure to the temperature and pressure required for the reaction, and use a high-pressure precision metering pump to pump the mixture containing isobutane and butene according to the required alkene ratio (isoparaffin/olefin, molar ratio) in the reaction material. The starting material was reacted while turning off the nitrogen flow. Use a high-pressure metering pump at the outlet of the reactor according to the required reaction cycle ratio (defined as: the weight of the reaction product recycled to the inlet of the reactor/the weight of the entire reaction product) and the ratio of alkene to part of the reaction product and part of the unreacted Isobutane was recycled back to the reactor inlet. After the reaction is stable, use the HP-3420 gas chromatograph to regularly analyze the reaction tail gas, and regularly take out the liquid product and use the HP-5890 gas chromatograph to analyze its octane number. The composition of the reaction raw materials is shown in Table 1.

Table 1. Isobutane material composition Butene material composition Component Content (weight%) Component Content (weight%) Propane Isobutane n-Butane Butene Impurity H ₂ OS Butadiene 2.3195.11.541.9534ppm＜1mg/m ³ 75ppm Normal and isomeric butene n-butane cis-2-butene trans-2-butene isobutane impurity H ₂ OS butadiene 2.9111.5459.0325.660.8640ppm＜1mg/m ³ 5ppm

The reaction conditions are: temperature 136° C., pressure 5.0 MPa, alkanes/enes = 20 (molar ratio), circulation ratio 0.3, and weight space velocity 2.30 hours ⁻¹ ; the reaction results are shown in Fig. 4 and Fig. 5 . After 720 hours (30 days) of the alkylation reaction, the catalyst activity ( _C4 ⁼ olefin conversion) remained 100%. The alkylation reaction product, the alkylate, had an octane number RON of 95.0 (research octane number); MON of 93.0 (motor octane number) and remained stable during the thirty day reaction period. This shows that the selectivity of the alkylation reaction remains unchanged. RON and MON values were obtained by gas chromatographic analysis according to the literature (Hutson and Logan "Estimate Alkyl Yield and Quanlity", Hydrocarbon Processing, September 1975, pp. 107-108).

The process for the continuous circulation of solid acid isobutane and butene alkylation reaction provided by the present invention circulates part of the reaction product (alkylated oil) back to the reactor inlet and enters the reactor together with the reaction materials to carry out the alkylation reaction. And at the same time remove the macromolecule covering on the surface of the catalyst to maintain the clean surface of the catalyst, thereby stabilizing the activity and selectivity of the alkylation reaction.

Comparative example 1

Catalyst, reaction mass and reaction conditions are the same as in Example 1, but the reaction product is not recycled back to the reactor inlet during the reaction. After 300 hours of the alkylation reaction, the catalyst activity (C ₄ ⁼ olefin conversion) remained at 100%, but the octane number RON of the alkylation reaction product (alkylate oil) dropped to 94.1 (research octane value); MON dropped to 92.2 (motor octane number). This result indicates that the selectivity of the catalyst for the alkylation reaction has begun to deteriorate, and the catalyst is deactivated.

Example 2

The solid acid alkylation catalyst used in this example is a BL conjugated superacid (B: Bronsted acid, here H ₃ PW ₁₂ O ₄₀ ; L: Lewis acid, here SbF ₅ ). The preparation method of the catalyst is as follows: first prepare 20% H ₃ PW ₁₂ O ₄₀ /SiO ₂ according to the method in Example 1, then put 10.0g of 20% H ₃ PW ₁₂ O ₄₀ /SiO ₂ into the fixed bed reactor, and use The nitrogen flow with a space velocity of 120 hours ^-1 was treated at 100°C for 4 hours, then cooled to 50°C, and the carrier gas was passed through a storage bottle filled with _SbF5 , and the _SbF5 was carried through the above-mentioned catalyst to make _SbF5 and heteropoly Acid interaction gave BL acid, and a final nitrogen purge for 1.0 h completed the preparation. Recorded as H ₃ PW ₁₂ O ₄₀ -SbF ₅ /SiO ₂ catalyst.

The alkylation reaction was carried out according to the method for the alkylation reaction of isobutane and butene in Example 1. The reaction conditions are: reaction temperature 135° C.; pressure 5.0 MPa; weight space velocity 2.3 hours ⁻¹ ; alkene ratio 20 (molar ratio); circulation ratio 0.35. The reaction results are very similar to those in Figure 4 and Figure 5 in Example 1. After 820 hours (34 days) of the alkylation reaction, the catalyst activity ( _C4 ⁼ olefin conversion) remained 100%. The alkylation reaction product (alkylate) had an octane number RON of 95.6 (research octane number); MON of 93.4 (motor octane number) and remained stable during the thirty day reaction period. This shows that the BL conjugated solid superacid alkylation catalyst with cyclic reaction has achieved good alkylation reaction effect.

Example 3

The alkylation reaction was carried out in the same manner as in Example 1, except that the alkylation reaction was carried out according to the flow chart in Figure 3, that is, a part of the reaction product (alkylated oil) from the fractionating tower was recycled back to the reactor inlet. The reaction conditions are: temperature 137° C., pressure 5.0 MPa, alkane/ene=19 (molar ratio), circulation ratio 0.25, and weight space velocity 2.30 h ⁻¹ ; the reaction results are very similar to those shown in Figure 4 and Figure 5 in Example 1. After 720 hours (30 days) of the alkylation reaction, the catalyst activity ( _C4 ⁼ olefin conversion) remained 100%. The octane number RON of the alkylation reaction product (alkylate) was 95.1 (research octane number); MON was 93.2 (motor octane number) and remained stable during the thirty day reaction period. This shows that the selectivity of the alkylation reaction remains unchanged.

Claims (17)

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; The 5-50 weight % that it is characterized in that 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, according to the method for claim 1, this method adopts fixed-bed reactor.

17, 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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