Process for the preparation of a bicyclic fused-ring alkane

Abstract

A process for preparation of a bicyclic fused-ring alkane. In the presence of a bifunctional solid catalyst, one or more cyclitols undergo a CC coupling reaction with itself or each other at a temperature and in a nitrogen gas atmosphere, to produce a bicyclic alkane precursor mixture; then, the nitrogen gas is replaced by hydrogen gas, and the bicyclic alkane precursor mixture is hydrogenated or hydrodeoxygenated at a temperature and under a pressure, to produce the bicyclic fused-ring alkane. The proportion of the bicyclic fused-ring alkane in the product as prepared according to the process is not lower than 80 wt %.

Claims

1. A process for preparation of a bicyclic fused-ring alkane, comprising: producing a bicyclic alkane precursor mixture by a CC coupling reaction of one or more compounds with itself or each other at a first temperature and in a nitrogen gas atmosphere in presence of a bifunctional solid catalyst; then, replacing nitrogen gas of the nitrogen gas atmosphere by hydrogen gas, and hydrogenating or hydrodeoxygenating the bicyclic alkane precursor mixture at a second temperature and under a pressure, to produce the bicyclic fused-ring alkane, wherein the one or more compounds is one or more selected from the group consisting of cyclopentanol, methyl cyclopentanol, dimethyl cyclopentanol, ethyl cyclopentanol, propyl cyclopentanol, cyclohexanol, methyl cyclohexanol, dimethyl cyclohexanol, ethyl cyclohexanol, propyl cyclohexanol, cycloheptanol, methyl cycloheptanol, dimethyl cycloheptanol, ethyl cycloheptanol, propyl cycloheptanol and 5-ethyl-3-methyl cycloheptanol, the bifunctional solid catalyst is one or more selected from the group consisting of Pd/SAPO, CoMo/HY, Ni/HZSM-5, CuCo/H, Ir/Al-SBA-15, PtNi/Al-SBA-16, Ru/Ti-MCM-41, Pt/H-ZSM-5, PdFe/H-ZSM-5, Au/LaY, Pt/Al-SBA-16 and Pt/H, an acidity H.sub.0 of the bifunctional solid catalyst is not lower than 3.5, and the bifunctional solid catalyst is added in an amount from 1 wt % to 20 wt % based on a total weight of reactants of the one or more compounds, and the bicyclic fused-ring alkane is decalin or alkyl substituted decalin.

2. The process according to claim 1, wherein, the acidity H.sub.0 of the bifunctional solid catalyst is in a range from 4.4 to 12.

3. The process according to claim 1, wherein, the first temperature of the CC coupling reaction ranges from 100 C. to 250 C.; the second temperature is in a range from 90 C. to 160 C., and the pressure of the hydrogen gas is in a range from 2 MPa to 6 MPa.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIGURE is the GC-MS diagram of the bicyclic alkane precursor and bicyclic alkane product as prepared in Example 1 of the invention from cyclopentanol in the presence of the catalyst Pt/H.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(2) The following examples are provided with the purpose of illustrating the contents of the invention, but not of further limiting the protection scope of the invention.

Example 1

(3) 33.25 g cyclopentanol and 1.67 g Pt/H (the H.sub.0 of Pt/H is 4.4) were simultaneously added to a high pressure reactor with mechanical stirring, and under the protection with nitrogen gas, the reaction mixture was kept at the temperature 200 C. for carrying out the reaction for 10 hours. Then, the temperature was decreased to 120 C. At this time, the atmosphere was replaced by hydrogen gas, and the corresponding pressure was kept at 4 MPa to go on the reaction for 5 hours, thereby to provide a product.

(4) As shown by analyzing the materials in the reaction procedure, the conversion of the cyclopentanol in the nitrogen gas atmosphere is 100%, and the yield of the bicyclic alkane precursor mixture is 90%. In the hydrogen gas atmosphere, the bicyclic alkane precursor mixture is fully converted, and the yield of the bicyclic alkane is 98%. Hence, in the whole procedure, the conversion of the cyclopentanol is 100%, and the yield of the bicyclic alkane is 88%, wherein the yield of the fused-ring naphthalene-derived alkane is not lower than 80%. The GC-MS spectra of the bicyclic alkane precursor and bicyclic alkane as produced by hydrogenating the bicyclic alkane precursor mixture in the example is shown in FIGURE.

Examples 2-13

(5) Just as Example 1, Pd/SAPO, CoMo/HY, Ni/HZSM-5, CuCo/H, Ir/Al-SBA-15, PtNi/Al-SBA-16, Ru/Ti-MCM-41, Pt/H-ZSM-5, PdFe/H-ZSM-5, Au/LaY, Pt/Al-SBA-16, and Pt/H (the H.sub.0 of these catalyst is in the range from 4.4 to 1.2) were used as the catalyst, and one or more cyclitols were used as the reactants. The results with regard to the reactant and amount thereof, the catalyst and amount thereof, the reaction temperature, the reaction time, the conversion of the reactant and the yield of the bicyclic alkane are shown in the following table:

(6) TABLE-US-00001 Yield of bicyclic Acid Temperature Time of Time of Temperature alkanes (%) strength Mass Mass of C-C C-C Hydrogen hydroge- of hydro- Bicyclic of Acidic of of raw coupling coupling gas nation genation fused- Linear supporters catalyst material reaction reaction pressure reaction reaction ring bicyclic Entyy Catalysts (-H0) (g) Raw materials (g) ( C.) (h) (MPa) (h) ( C.) alkanes alkanes 2 Pd/SAPO 5 2.8 Cyclopentanol 28 240 18 2 5 100 85 5 3 CoMo/HY 4.4 2.5 Cyclohexanol 32.0 250 25 3 3 120 82 8 4 Ni/H-ZSM- 7 2.7 20% 35 140 20 5 5 150 84 9 5 Cyclohexanol 80% Cyclopentanol 5 CuCo/H 5 3.7 Dimethyl 33 170 18 6 4 160 83 2 cyclopentanol 6 Ir/Al-SBA- 7.7 3.2 Ethyl 35 140 16 3 5 100 81 8 15 cyclopentanol 7 PtNi/Al- 6.5 3.4 Propyl 32 150 20 3 4 150 80 12 SBA-16 cyclohexanol 8 Ru/Ti- 7 3.8 Butyl 35 100 5 2 5 140 80 5 MCM-41 cyclopentanol 9 Pt/H-ZSM- 7.2 5.5 Ethyl 38 110 8 2 4 100 83 8 5 cyclohexanol 10 PdFe/H- 6.7 6 Dimethyl 40 180 15 3 2 110 80 7 ZSM-5 cycloheptanol 11 Au/LaY 4.5 5 Cycloheptanol 40 120 5 2.5 5 100 82 5 12 Pt/Al-SBA- 6 6 Propyl 30 150 10 5 5 90 80 15 16 cycloheptanol 13 Pt/H 7.7 5 30% 25 140 18 3 10 100 85 5 Cyclopentanol 30% Methyl cyclopentanol 40% Propyl cyclopentanol

(7) As seen from Examples 1-13, in the presence of the catalysts Pd/SAPO, CoMo/HY, Ni/HZSM-5, CuCo/H, Ir/Al-SBA-15, PtNi/Al-SBA-16, Ru/Ti-MCM-41, Pt/H-ZSM-5, PdFe/H-ZSM-5, Au/LaY, Pt/Al-SBA-16, and Pt/H, a cyclitol underwent the CC coupling reaction at a temperature ranging from 100 C. to 250 C. in a nitrogen gas atmosphere; the resultant coupling products were hydrogenated or hydrodeoxygenated by hydrogen from 2 to 6 MPa and at a temperature ranging from 90 to 160 C. The conversion of the raw material can reach 100%, and the yield of the resultant bicyclic fused-ring alkane is not lower than 80%. After the above reaction, the catalyst is tested by thermogravimetric analysis (TGA) to find out that in the above catalyst, almost no coking and coal-aggregating phenomena occurs.

(8) As for the product as prepared in Example 1, the density is measured to be 0.89 g/mL according to GB2540-81 Petroleum products-Determination of density-Pyknometer method; the freezing point is measured to be lower than 60 C. as determined according to GB2430-81 Determination of the Ice Point of Jet Fuel; the dynamic viscosity is measured to be 2.69 mm.sup.2/s (20 C.) according to GB265-88 Petroleum products-Determination kinematic viscosity and dynamic viscosity; and the net heat value is measured to be 37.0 MJ/L according to GB/T 384-81 Determination of caloric value of petroleum products. Obviously, the bicyclic fused-ring alkanes as prepared in the invention are high-density fuels having advantages in high density, high net volume caloric value, and low freezing point.