CN1233602C - Method of producing poly alpha olefine oil using alpha olefine as raw material - Google Patents
Method of producing poly alpha olefine oil using alpha olefine as raw material Download PDFInfo
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- CN1233602C CN1233602C CN 200310120887 CN200310120887A CN1233602C CN 1233602 C CN1233602 C CN 1233602C CN 200310120887 CN200310120887 CN 200310120887 CN 200310120887 A CN200310120887 A CN 200310120887A CN 1233602 C CN1233602 C CN 1233602C
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Abstract
The present invention discloses a method for preparing poly-alpha-alkene oil from alpha-alkene, which belongs to the technical field of petroleum refining processes. Alpha-alkene of C6 to C14 is used as a raw material, alkane of C6 to C14 is used as a solvent, and the oligomerization reaction of the alpha-alkene is carried out at the temperature of 50 to 300 DEG C and under the pressure of 1.0 to 5.0MPa. The poly-alpha-alkene oil is prepared in a suspension bed reactive mode or a fixed bed reactive mode, and AlCl3 solid supported catalysts are used as catalysts. The catalysts have high catalytic activity, selectivity and stability. Compared with mineral oil with the same viscidity, the base oil prepared by the catalytic polymerization of the alpha-alkene has good viscosity-temperature performance, good low temperature fluidity and good high temperature oxidation resistant safety. The poly-alpha-alkene oil has the advantages of little coking, innocuity, good heat resistant performance, good shear stability, good consistency and the like, and is suitable for hydraulic systems of airplanes and missiles.
Description
The invention belongs to the technical field of petroleum processing, and particularly relates to immobilized AlCl3A method for preparing poly α -olefin oil by using α -olefin as a catalyst.
α -base oil prepared by catalytic polymerization of olefin is better than mineral oil with the same viscosity in viscosity-temperature property, low-temperature fluidity and high-temperature oxidation resistance safety, has the advantages of less coking, no toxicity and the like, has good heat resistance, shear stability and compatibility, and can be suitable for hydraulic systems of airplanes and missiles.
α -olefin can be obtained by two methods of paraffin cracking and ethylene oligomerization, crude oil in China generally has high wax content, α -olefin is mainly prepared by high-temperature gas phase cracking under steam dilution at present, and poly α -olefin oil is C as a more ideal raw material9-C12α -olefins, C may also be9-C12α -olefins (distillation range 150 ℃ C. and 250 ℃ C.) and<C8The olefins (initial boiling point-150 ℃) are mixed to be used as raw materials.
AlCl is used as a catalyst for polymerization3With NaCl complexes, in amounts of typically 2 to 2.5% of the olefinic starting material (based on AlCl)3(China refinery technology (second edition), Houdian Main code,P.463-467, China petrochemical Press, 2001).
Schroemeride et al (Lubricants, 2002, 17 (6): 61-64) describe novel α -AlCl for olefin polymerization lubricant base stocks3The activity of the immobilized catalyst is compared with that of 4 catalysts to find AlCl3·NiSO4/γ-Al2O3The catalyst has relatively good effect, and various performances of the catalyst are remarkably enhanced after the catalyst is treated by adding an auxiliary agent, an acidic component and the like. The reaction conditions are that the reaction temperature is 160 ℃, the pressure is 2.0MPa, and the volume space velocity is 0.5-1h-1。
GB 978061 relates to AlCl3Catalyst adsorbed on solid carrier with AlCl pair adsorbed3And adsorbent inactive hydrogen or mixture of hydrogen and nitrogen, methane, ethane, diethyl ether, etc., and carrier including active carbon, porous clay, diatomite, SiO2-Al2O3、SiO2MgO, silica gel, bauxite, Al2O3And corundum, and the like.
JP 58042603 relates to a α -solid catalyst for the polymerization of olefins, aluminum halides, phenyl and/or alkyl radicals and/or C1-8Alkoxysilanes with C1-8The halide of alkyl magnesium (containing organic acid) and titanium tetroxide are reacted to prepare α -solid catalyst for olefin polymerization (suspension type solid catalyst, containing Ti3 wt%).
JP 49116184 relates to the use of stereospecific catalysts for the polymerization of α -olefins, the catalysts being prepared by TiCl3Or TiCl3With AlCl3Co-melt, metal chelate and organoaluminum milling.
US 6002060 relates to a process for oligomerizing olefins using supported AlCl3/SiO2The catalyst takes organic aluminum as an auxiliary agent, takes allene as a raw material, and is stirred for 0.5h at the temperature of 100 ℃ under the reaction condition, the conversion rate is 99%, and the obtained product contains 16% of dimer, 11.5% of trimer, 16% of tetramer, 16% of pentamer and 40% of hexamer.
US 4795852 relates to the preparation of olefin oligomers and catalysts used. The catalyst used is prepared by reacting a compound containing a certain amount of iron group metal with catalytic action, a certain amount of alkyl aluminium compound with catalytic action and an alkoxy aluminium compound with catalytic action, which are loaded on a porous carrier.
The invention aims to provide a method for preparing poly α -olefin oil by using α -olefin as a raw material.
The technical solution of the invention is that the raw material is C6-C14α -olefin of (1), the solvent being C6-C14The reaction temperature of the alkane is 50-300℃,The oligomerization of α -olefin is carried out under the reaction pressure of 1.0-5.0 MPa, and AlCl is used as a catalyst3The catalyst is immobilized.
The oligomerization reaction adopts a suspension bed or fixed bed reaction mode.
AlCl used3The immobilized catalyst is fresh AlCl3Vapor prepared, at 450 ℃ and 550 ℃, CCl4In N2High purity gamma-Al under carrier2O3Reacting to generate AlCl3The reaction stoichiometry is:
AlCl in terms of Al3The yield is more than 95mol percent, and AlCl3The steam concentration is 0.28-0.70 mol/L.
Adopts a double-pore structure gamma-Al with mesopores and macropores2O3The specific surface area is 110 to 140m2The pore volume is 1.2-1.8 cm3G, pore volume 1.53cm3(iv)/g, the pore distribution is 25-35 (v)% of d 5-20 nm, and the pore diameter d is 40-50 (v)% of 500-1500 nm; subjecting 10-200 mesh gamma-Al2O3The carrier is roasted for 3 hours at 400 ℃ in advance, and the adsorption water is completely removed; from N2Carrier tape AlCl3Steam is mixed with gamma-Al at 200-600 DEG C2O3Carrying out immobilization reaction for 0.5-4.0 h; after the immobilization reaction is finished, N is used at the temperature of 250-450 DEG C2Purging for 1h, and then cooling to room temperature; the active component AlClxThe catalyst contains 6.0 to 9.0 (m)%, wherein x is 2.0 to 2.3.
1-C6 ＝、1-C12 ＝In a liquid-solid two-phase stirring reaction mode, heptane is used as a solvent, oligomerization reaction is carried out under the conditions that the reaction temperature is 80-100 ℃ and the reaction pressure is 1.0MPa, and the conversion rate of olefin is more than 55%.
The invention has the beneficial effects that the base oil prepared by catalytic polymerization of α -olefin instead of natural mineral oil has better viscosity-temperature property, low-temperature fluidity and high-temperature oxidation resistance safety than mineral oil with the same viscosity, has the advantages of less coking, no toxicity and the like, and also has good heat resistance, shear stability and compatibility.
The present invention will be further described with reference to the following embodiments.
Example 1
In AlCl3The generator is filled with 20mL of high-purity gamma-Al2O3(spherical d ═ 1.8 to 2.0mm), heated to 500 ℃ and N was passed through at 40mL/min and 2.0mL/h, respectively2And CCl4To produce AlCl3Steam 27.8 mmol/h; fixed bed AlCl3The immobilized reactor is filled with gamma-Al with mesoporous and macroporous double-pore structure2O310mL (3.13g) (60-200 mesh), dewatering and heat treating at 500 deg.C for 2h, cooling to 300 deg.C, and adding N at 40mL/min2Carrying the lower handle AlCl3Introducing AlCl through steam3Reacting in an immobilized reactor at 300 ℃ for 4.0h, and then reacting with N at 400 DEG C2Purging for 1h, and then cooling to the normal temperature. 3.36g of ACGZC, in which AlCl is presentx(x ═ 2.2) accounted for 7.5 (m)%.
Example 2
3.36g of ACGZC is added into a 75mL stainless steel autoclave with magnetic stirring, and 1-C with the total volume of 50mL is added6 ＝With heptane (1-C)6 ＝The heptane is 3: 7 in mass ratio) is reacted for 6h under the conditions that the reaction temperature is 80 ℃ and the reaction pressure is 1.0MPa, and the experimental result shows that the 1-C is6 ＝Conversion 58%, 1-C6 ＝The distribution of oligomerization reaction products is as follows: dimer 51.3%, trimer 41.6%, tetramer 7.1%.
Example 3
3.36g of ACGZC is added into a 75mL stainless steel autoclave with magnetic stirring, and 1-C with the total volume of 50mL is added12 ＝With heptane (1-C)12 ＝3: 7/heptane, mass ratio) at a reaction temperature of 100 ℃ and a reaction pressure of 1. Reaction under the condition of 0MPa6h, the experimental result shows that 1-C12 ＝The conversion was 52% and the dimer selectivity was 98%.
Example 4
3.36g of ACGZC is added into a 75mL stainless steel autoclave with magnetic stirring, and 1-C with the total volume of 50mL is added12 ＝With heptane (1-C)12 ＝The heptane is 3: 7 in mass ratio) is reacted for 10 hours under the conditions that the reaction temperature is 150 ℃ and the reaction pressure is 1.0MPa, and the experimental result shows that the 1-C is12 ＝The conversion was 75% and the dimer selectivity was 95%.
Comparative example 1
75mL stainless steel autoclave with magnetic stirring was charged with H-USY zeolite (SiO)2/Al2O380) catalyst 0.5g, 50mL of 1-C was added12 ＝With heptane (1-C)12 ＝3/7 in terms of weight ratio) under the conditions of reaction temperature of 150 ℃ and reaction pressure of 1.0MPa for 6h, 1-C12 ＝Substantially unreacted.
Claims (4)
1. A method for preparing poly α -olefin oil by using α -olefin as a raw material is characterized in that the raw material is C6-C14α -olefin of (1), the solvent being C6-C14Alkane is reacted in a suspension bed or fixed bed mode, and the volume ratio of the catalyst to the raw material is 0.05-0.5 or the volume space velocity is 0.2-2.0 h-1In the range, the oligomerization reaction of α -olefin is carried out under the conditions that the reaction temperature is 50-300 ℃ and the reaction pressure is 1.0-5.0 MPa, and the catalyst is AlCl3The supported catalyst adopts a double-pore structure gamma-Al with mesopores and macropores2O3。
2. The method of claim 1, wherein the poly α -olefin oil is prepared from α -olefins3The immobilized catalyst is fresh AlCl3Vapor prepared, at 450-550 ℃,CCl4in N2High purity gamma-Al under carrier2O3Reacting to generate AlCl3The reaction stoichiometry is:
AlCl in terms of Al3The yield is more than 95mol percent, and AlCl3The steam concentration is 0.28-0.70 mol/L.
3. The method for preparing poly α -olefin oil from α -olefin as claimed in claim 1, wherein said method comprises using γ -Al having a mesoporous structure with mesopores and macropores2O3The specific surface area is 110 to 140m2The pore volume is 1.2-1.8 cm3The pore distribution is that d is 25-35% of 5-20 nm and the pore diameter d is 40-50% of 500-1500 nm according to volume percentage; subjecting 10-200 mesh gamma-Al2O3The carrier is roasted for 3 hours at 400 ℃ in advance, and the adsorption water is completely removed; from N2Carrier tape AlCl3Steam is mixed with gamma-Al at 200-600 DEG C2O3Carrying out immobilization reaction for 0.5-4.0 h; after the immobilization reaction was completed, N was added thereto at 400 ℃2Purging for 1h, and then cooling to room temperature; according to the mass percentage, the active component AlClxThe catalyst contains 6.0-9.0% of x which is 2.0-2.3.
4. The method for producing poly α -olefin oil from α -olefin as claimed in claim 1, 2 or 3, wherein the raw material is C6-C14α -olefin of (1), the solvent being C6-C14The volume ratio of the alkane, the catalyst and the raw material is 0.05-0.5 or the volume space velocity is 0.2-2.0 h-1In the range, the oligomerization reaction of α -olefin is carried out under the conditions that the reaction temperature is 50-300 ℃ and the reaction pressure is 1.0-5.0 MPa, and the conversion rate of the olefin can reach more than 50%.
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