Catalytic hydrogenation method for carbon nine resin

Abstract

The present invention discloses a catalytic hydrogenation method for carbon nine resin, comprising the following steps: 1) adding a PtWY/?-Al.sub.2O.sub.3 catalyst in the first half of a fixed bed, adding a PdZrNd/?-Al.sub.2O.sub.3 catalyst in the second half of the fixed bed, and feeding hydrogen for reduction; and 2) catalytic hydrogenating the pretreated carbon nine resin in the fixed bed. In the present invention, different catalysts capable of reacting under the same catalytic conditions are added in the first and second halves of the fixed bed, and the two different catalysts play different roles, and can be active and complementary to each other under the same conditions. The synergistic effect of the two catalysts plays a good catalytic role. Moreover, the production process is simplified, and the production cost is saved.

Claims

1. A catalytic hydrogenation method for carbon nine resin, wherein the method comprises the following steps: 1) Preparing a carbon nine resin stream; 2) Pretreating the carbon nine resin stream, thereby producing a pretreated carbon nine resin; 3) Adding a PtWY/?-Al.sub.2O.sub.3 catalyst in the first half of a fixed bed, adding a PdZrNd/?-Al.sub.2O.sub.3 catalyst in the second half of the fixed bed, and feeding hydrogen for reduction of the PtWY/?-Al.sub.2O.sub.3 catalyst and the PdZrNd/?-Al.sub.2O.sub.3 catalysts; and 4) catalytic hydrogenating under catalytic hydrogenation conditions the pretreated carbon nine resin in the fixed bed.

2. The catalytic hydrogenation method of claim 1, wherein the PtWY/?-Al.sub.2O.sub.3 catalyst is prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where a mole ratio of Pt to W is 1:0.1 to 1:0.5, and a ratio of Pt to Y is 1:0.05 to 1:0.1; airing at the room temperature, drying for 5 to 10 hours in a vacuum drying oven at 100? C. to 150? C., roasting for 4 to 8 hours in a muffle furnace at 400? C. to 700? C., and then cooling to the room temperature, and washing with deionized water until the pH is neutral, and drying at 100? C. to 150? C.; and the PdZrNd/?-Al.sub.2O.sub.3 catalyst is prepared by: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where a mole ratio of Pd to Zr is 1:01 to 1:0.5, and a mole ratio of Pd to Nd is 1:0.05 to 1:0.1, airing at the room temperature, drying for 5 to 10 hours in a vacuum drying oven at 100? C. to 150? C., roasting for 4 to 8 hours in a muffle furnace at 400? C. to 700? C., and then cooling to the room temperature, and washing with deionized water until the pH is neutral, and drying at 100? C. to 150? C.

3. The catalytic hydrogenation method of claim 1, wherein conditions for the reduction of having a purity of 99.999% is fed for reduction, a reduction temperature is 200? C. to 400? C., and a reduction time is 2 to 5 hours.

4. The catalytic hydrogenation method of claim 1, wherein the catalytic hydrogenation conditions are as follows: a reaction temperature is 200? C. to 320? C., a reaction pressure is 10 to 25 MPa, a volumetric space velocity is 0.1 to 1.0 h.sup.?1 and a volume ratio of hydrogen to carbon nine resin is 400:1 to 900:1.

5. The catalytic hydrogenation method of claim 1, wherein the carbon nine resin is pretreated under the following conditions: dissolving the carbon nine resin with cyclohexane or ethylcyclohexane at a solubility of 5 wt % to 20 wt %, and passing the solution through a carclazyte or diatomite filtration column.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is an infrared spectrum of a C9 resin before catalytic hydrogenation according to Embodiment 1 of the present invention.

(2) FIG. 2 is an infrared spectrum of the C9 resin after catalytic hydrogenation according to Embodiment 1 of the present invention.

(3) FIG. 3 is an infrared spectrum of the C9 resin before catalytic hydrogenation according to Embodiment 2 of the present invention.

(4) FIG. 4 is an infrared spectrum of the C9 resin after catalytic hydrogenation according to Embodiment 2 of the present invention.

(5) FIG. 5 is an infrared spectrum of the C9 resin before catalytic hydrogenation according to Embodiment 3 of the present invention.

(6) FIG. 6 is an infrared spectrum of the C9 resin after catalytic hydrogenation according to Embodiment 3 of the present invention.

(7) FIG. 7 is an infrared spectrum of the C9 resin before catalytic hydrogenation according to Embodiment 4 of the present invention.

(8) FIG. 8 is an infrared spectrum of the C9 resin after catalytic hydrogenation according to Embodiment 4 of the present invention.

(9) FIG. 9 is an infrared spectrum of the C9 resin before catalytic hydrogenation according to Embodiment 5 of the present invention.

(10) FIG. 10 is an infrared spectrum of the C9 resin after catalytic hydrogenation according to Embodiment 5 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(11) The specific implementations of the present invention will be further described in detail by embodiments with reference to the accompanying drawings.

Embodiment 1

(12) The catalytic hydrogenation method for C9 resin comprised the following steps. 1) A PtWY/?-Al.sub.2O.sub.3 catalyst was added in the first half of a fixed bed, a PdZrNd/?-Al.sub.2O.sub.3 catalyst was added in the second half of the fixed bed, hydrogen having a high purity of 99.999% was fed into the fixed bed for reduction, and the reduction was performed at 400? C. for 2 hours.

(13) The PtWY/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where the mole ratio of Pt to W was 1:0.1, and the mole ratio of Pt to Y was 1:0.1; airing at the room temperature, drying for 5 hours in a vacuum drying oven at 150? C., roasting for 4 hours in a muffle furnace at 700? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 150? C.

(14) The PdZrNd/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where the mole ratio of Pd to Zr was 1:0.1, and the mole ratio of Pd to Nd was 1:0.1; airing at the room temperature, drying for 5 hours in a vacuum drying oven at 150? C., roasting for 8 hours in a muffle furnace at 400? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 150? C.

(15) 2) The Pretreated C9 Resin was Catalytic Hydrogenated in the Fixed Bed.

(16) The C9 resin was dissolved with cyclohexane at a solubility of 5 wt %, and the solution was passed through a carclazyte filtration column. Insoluble gel, asphaltene and a small amount of free heavy metal were adsorbed onto the carclazyte, and the pretreated C9 resin solution was catalytic hydrogenated.

(17) The catalytic hydrogenation conditions were as follows: the reaction temperature was 320? C., the reaction pressure was 25 MPa, the volumetric space velocity was 0.1 h.sup.?1, and the volume ratio of hydrogen to C9 resin was 400:1.

(18) As shown in FIG. 2, the carbon-hydrogen absorption peak on the 3019 cm.sup.?1 carbon-carbon double bond was obviously less than that on the 3019 cm.sup.?1 carbon-carbon double bond in FIG. 1, the bromine number of the C9 resin was decreased from 32.5 gBr/100 g to 3.2 gBr/100 g, and the Gardner chromaticity was 2.8. It indicated that the catalysts were effective for the catalytic hydrogenation of the C9 resin.

Embodiment 2

(19) The catalytic hydrogenation method for C9 resin comprised the following steps. 1) A PtWY/?-Al.sub.2O.sub.3 catalyst was added in the first half of a fixed bed, a PdZrNd/?-Al.sub.2O.sub.3 catalyst was added in the second half of the fixed bed, hydrogen having a high purity of 99.999% was fed into the fixed bed for reduction, and the reduction was performed at 200? C. for 5 hours.

(20) The PtWY/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where the mole ratio of Pt to W was 1:0.5, and the mole ratio of Pt to Y was 1:0.05; airing at the room temperature, drying for 10 hours in a vacuum drying oven at 100? C., roasting for 8 hours in a muffle furnace at 400? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 100? C.

(21) The PdZrNd/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where the mole ratio of Pd to Zr was 1:0.5, and the mole ratio of Pd to Nd was 1:0.05; airing at the room temperature, drying for 10 hours in a vacuum drying oven at 100? C., roasting for 8 hours in a muffle furnace at 700? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 100? C.

(22) 2) The Pretreated C9 Resin was Catalytic Hydrogenated in the Fixed Bed.

(23) The C9 resin was dissolved with cyclohexane at a solubility of 20 wt %, and the solution was passed through a diatomite filtration column. Insoluble gel, asphaltene and a small amount of free heavy metal were adsorbed onto the diatomite, and the pretreated C9 resin solution was catalytic hydrogenated.

(24) The catalytic hydrogenation conditions were as follows: the reaction temperature was 200? C., the reaction pressure was 10 MPa, the volumetric space velocity was 1.0 h.sup.?1, and the volume ratio of hydrogen to C9 resin was 900:1.

(25) As shown in FIG. 4, the carbon-hydrogen absorption peak on the 3019 cm.sup.?1 carbon-carbon double bond was obviously less than that on the 3019 cm.sup.?1 carbon-carbon double bond in FIG. 3, the bromine number of the C9 resin was decreased from 32.5 gBr/100 g to 1.8 gBr/100 g, and the Gardner chromaticity was 1.9. It indicated that the catalysts were effective for the catalytic hydrogenation of the C9 resin.

Embodiment 3

(26) The catalytic hydrogenation method for C9 resin comprised the following steps. 1) A PtWY/?-Al.sub.2O.sub.3 catalyst was added in the first half of a fixed bed, a PdZrNd/?-Al.sub.2O.sub.3 catalyst was added in the second half of the fixed bed, hydrogen having a high purity of 99.999% was fed into the fixed bed for reduction, and the reduction was performed at 300? C. for 3 hours.

(27) The PtWY/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where the mole ratio of Pt to W was 1:0.3, and the mole ratio of Pt to Y was 1:0.07; airing at the room temperature, drying for 7 hours in a vacuum drying oven at 130? C., roasting for 7 hours in a muffle furnace at 600? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 120? C.

(28) The PdZrNd/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where the mole ratio of Pd to Zr was 1:0.2, and the mole ratio of Pd to Nd was 1:0.08; airing at the room temperature, drying for 6 hours in a vacuum drying oven at 140? C., roasting for 6 hours in a muffle furnace at 500? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 130? C.

(29) 2) The Pretreated C9 Resin was Catalytic Hydrogenated in the Fixed Bed.

(30) The C9 resin was dissolved with ethylcyclohexane at a solubility of 20 wt %, and the solution was passed through a diatomite filtration column. Insoluble gel, asphaltene and a small amount of free heavy metal were adsorbed onto the diatomite, and the pretreated C9 resin solution was catalytic hydrogenated.

(31) The catalytic hydrogenation conditions were as follows: the reaction temperature was 300? C., the reaction pressure was 20 MPa, the volumetric space velocity was 0.7 h.sup.?1, and the volume ratio of hydrogen to C9 resin was 600:1.

(32) As shown in FIG. 6, the carbon-hydrogen absorption peak on the 3019 cm.sup.?1 carbon-carbon double bond was obviously less than that on the 3019 cm.sup.?1 carbon-carbon double bond in FIG. 5, the bromine number of the C9 resin was decreased from 32.5 gBr/100 g to 0.9 gBr/100 g, and the Gardner chromaticity was 0.6. It indicated that the catalysts were effective for the catalytic hydrogenation of the C9 resin.

Embodiment 4

(33) The catalytic hydrogenation method for C9 resin comprised the following steps. 1) A PtWY/?-Al.sub.2O.sub.3 catalyst was added in the first half of a fixed bed, a PdZrNd/?-Al.sub.2O.sub.3 catalyst was added in the second half of the fixed bed, hydrogen having a high purity of 99.999% was fed into the fixed bed for reduction, and the reduction was performed at 350? C. for 3 hours.

(34) The PtWY/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where the mole ratio of Pt to W was 1:0.4, and the mole ratio of Pt to Y was 1:0.06; airing at the room temperature, drying for 9 hours in a vacuum drying oven at 120? C., roasting for 5 hours in a muffle furnace at 500? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 130? C.

(35) The PdZrNd/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where the mole ratio of Pd to Zr was 1:0.3, and the mole ratio of Pd to Nd was 1:0.07; airing at the room temperature, drying for 7 hours in a vacuum drying oven at 130? C., roasting for 7 hours in a muffle furnace at 600? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 100? C.

(36) 2) The Pretreated C9 Resin was Catalytic Hydrogenated in the Fixed Bed.

(37) The C9 resin was dissolved with ethylcyclohexane at a solubility of 10 wt %, and the solution was passed through a diatomite filtration column. Insoluble gel, asphaltene and a small amount of free heavy metal were adsorbed onto the diatomite, and the pretreated C9 resin solution was catalytic hydrogenated.

(38) The catalytic hydrogenation conditions were as follows: the reaction temperature was 280? C., the reaction pressure was 18 MPa, the volumetric space velocity was 0.6 h.sup.?1, and the volume ratio of hydrogen to C9 resin was 700:1.

(39) As shown in FIG. 8, the carbon-hydrogen absorption peak on the 3019 cm.sup.?1 carbon-carbon double bond was obviously less than that on the 3019 cm.sup.?1 carbon-carbon double bond in FIG. 7, the bromine number of the C9 resin was decreased from 32.5 gBr/100 g to 1.1 gBr/100 g, and the Gardner chromaticity was 0.9. It indicated that the catalysts were effective for the catalytic hydrogenation of the C9 resin.

Embodiment 5

(40) The catalytic hydrogenation method for C9 resin comprised the following steps. 1) A PtWY/?-Al.sub.2O.sub.3 catalyst was added in the first half of a fixed bed, a PdZrNd/?-Al.sub.2O.sub.3 catalyst was added in the second half of the fixed bed, hydrogen having a high purity of 99.999% was fed into the fixed bed for reduction, and the reduction was performed at 350? C. for 4 hours.

(41) The PtWY/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of platinum nitrate, tungsten nitrate and yttrium nitrate, where the mole ratio of Pt to W was 1:0.2, and the mole ratio of Pt to Y was 1:0.06; airing at the room temperature, drying for 6 hours in a vacuum drying oven at 110? C., roasting for 6 hours in a muffle furnace at 650? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 110? C.

(42) The PdZrNd/?-Al.sub.2O.sub.3 catalyst was prepared by dipping: dipping a ?-Al.sub.2O.sub.3 carrier into an aqueous solution of palladium nitrate, zirconium nitrate and neodymium nitrate, where the mole ratio of Pd to Zr was 1:0.2, and the mole ratio of Pd to Nd was 1:0.06; airing at the room temperature, drying for 9 hours in a vacuum drying oven at 100? C., roasting for 5 hours in a muffle furnace at 600? C., and then cooling to the room temperature; and, washing with deionized water until the pH was neutral, and drying at 110? C.

(43) 2) The Pretreated C9 Resin was Catalytic Hydrogenated in the Fixed Bed.

(44) The C9 resin was dissolved with ethylcyclohexane at a solubility of 10 wt %, and the solution was passed through a diatomite filtration column. Insoluble gel, asphaltene and a small amount of free heavy metal were adsorbed onto the diatomite, and the pretreated C9 resin solution was catalytic hydrogenated.

(45) The catalytic hydrogenation conditions were as follows: the reaction temperature was 250? C., the reaction pressure was 15 MPa, the volumetric space velocity was 0.5 h.sup.?1, and the volume ratio of hydrogen to C9 resin was 800:1.

(46) As shown in FIG. 10, the carbon-hydrogen absorption peak on the 3019 cm.sup.?1 carbon-carbon double bond was obviously less than that on the 3019 cm.sup.?1 carbon-carbon double bond in FIG. 9, the bromine number of the C9 resin was decreased from 32.5 gBr/100 g to 1.5 gBr/100 g, and the Gardner chromaticity was 1.7. It indicated that the catalysts were effective for the catalytic hydrogenation of the C9 resin.