CN111574645B - Hydrogenation method for high-sulfur petroleum resin - Google Patents
Hydrogenation method for high-sulfur petroleum resin Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 118
- 239000011347 resin Substances 0.000 title claims abstract description 118
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 66
- 239000003208 petroleum Substances 0.000 title claims abstract description 37
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 32
- 239000011593 sulfur Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 92
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000004042 decolorization Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 22
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 22
- 229910000510 noble metal Inorganic materials 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 12
- 102000002322 Egg Proteins Human genes 0.000 claims description 11
- 108010000912 Egg Proteins Proteins 0.000 claims description 11
- 210000003278 egg shell Anatomy 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 5
- 150000001924 cycloalkanes Chemical class 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 4
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- 229910021126 PdPt Inorganic materials 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical class C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
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- 229910017061 Fe Co Inorganic materials 0.000 description 1
- 101100135888 Mus musculus Pdia5 gene Proteins 0.000 description 1
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 229910021132 PdIr Inorganic materials 0.000 description 1
- 229910007676 ZnO—SiO2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000003682 fluorination reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000007670 refining Methods 0.000 description 1
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- 239000012266 salt solution Substances 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
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Abstract
The invention discloses a method for hydrogenating high-sulfur petroleum resin, belonging to the technical field of polymer hydrogenation. The method is characterized in that a supported bimetallic alloy catalyst is used as a pre-hydrogenation desulfurization catalyst, a supported metal catalyst is used as a hydrogenation decolorization catalyst, and a two-section fixed bed continuous hydrogenation mode is adopted to carry out hydrogenation reaction on resin, so that the obtained hydrogenated resin has the advantages that the color phase of the resin is improved to be water white, and the resin has good thermal stability. The invention has the advantages of simple process, high catalyst activity, good stability, improved resin chromaticity, improved thermal stability, slightly reduced softening point, good economic benefit and good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of polymer hydrogenation, and relates to a method for hydrogenating high-sulfur petroleum resin.
Background
The petroleum resin has a large molecular weight, polymer molecules extend on the surface of the catalyst to form high steric hindrance, and the hydrogenation difficulty of the petroleum resin is determined by the molecular structure of the polymer molecules. The petroleum resin hydrogenation process is designed under harsh operating conditions, and the process types vary according to the production scale and the product requirements. At present, the representative of the foreign petroleum resin hydrogenation modification is American Exxon, Ismann, Japan crude and Japan bright dipping companies. At present, hydrogenated petroleum resin is more and more popular in the market, a catalyst is the key of the hydrogenated petroleum resin technology, a palladium catalyst and a nickel catalyst are mostly used abroad, and the development direction of the hydrogenation catalyst in the future is to improve the activity and the stability of the catalyst, prolong the service life of the catalyst, reduce side reactions and properly reduce the manufacturing cost. China should accelerate the research of petroleum resin hydrogenation catalysts and the localization of hydrogenation catalysts, and further promote the popularization of hydrogenated petroleum resin technology and the reduction of product cost.
The raw materials for producing petroleum resins mainly come from C5 and C9 fractions of an ethylene cracking unit. At present, the main raw material for ethylene cracking in China is naphtha, which accounts for about 60 percent. The typical recovery of ethylene from naphtha is approximately 33% in China, and then 300 million tons of naphtha are required for 100 million tons of ethylene. With the global oil upgrading and high sulfur content, naphtha S content produced by oil refining is high, and consequently sulfur content in C5 and C9 fractions as by-products of ethylene cracking is high, so that the S content of petroleum resin polymerized from C5 and C9 fractions is also increasing. Therefore, the hydrogenation of petroleum resin is not only based on the structural characteristics, but also takes into consideration the influence of impurities on the catalyst.
Aiming at the problem of resource utilization of rich high-sulfur petroleum resin, a sulfur-resistant eggshell-type noble metal alloy catalyst is used as a hydrodesulfurization catalyst, a supported metal catalyst is used as a two-stage hydrogenation and decoloration catalyst, the resin is subjected to hydrogenation reaction by adopting a two-stage fixed bed continuous hydrogenation mode, the catalyst is stable and ideal, the hue of the prepared hydrogenated petroleum resin is improved to be water white, the hydrogenated petroleum resin has good thermal stability, and the softening point is reduced little. The following known techniques all have some disadvantages:
chinese patent, publication No.: CN102633941A introduces a method for preparing high-grade resin by catalytic hydrogenation, which takes supported noble metal palladium as a first-stage hydrogenation catalyst and skeletal nickel as a second-stage hydrogenation catalyst, and adopts a two-stage kettle type or fixed bed continuous hydrogenation mode to carry out hydrogenation reaction on the resin. The reaction process and the catalyst are not suitable for resin containing high impurity, and the utilization rate of the first-stage noble metal Pd is low.
Chinese patent, publication No.: CN103386302A discloses a petroleum resin hydrogenation catalyst, namely Al2O3Is used as a carrier and is used as a carrier,the supported noble metal Pd and the oxide auxiliary agent account for more than 90 percent of metal palladium microcrystal with the grain diameter less than 3nm, and the defect is that the catalyst has impurity S2-The catalyst is susceptible to poisoning and deactivation due to poor tolerance, and the catalyst life is affected.
Chinese patent, publication No.: CN104959136A introduces a preparation method for a resin hydrogenation eggshell type catalyst, noble metal particles are uniformly distributed on the surface of a carrier, the use amount of noble metals of a petroleum resin hydrogenation catalyst is reduced, and the cost of the catalyst is effectively reduced. Only the requirements of the resin structure on the catalyst structure are considered, but the influence of resin impurities on the catalyst is not considered.
Chinese patent, publication No.: CN104877077A introduces a method for preparing hydrogenated C9 petroleum resin, which takes Ni/ZnO catalyst as hydrogenation adsorption desulfurization and supported metal catalyst as hydrogenation decolorization catalyst, and adopts a two-section fixed bed continuous hydrogenation mode to carry out hydrogenation reaction on the resin. The sulfur capacity content of the hydrogenation adsorption desulfurization catalyst is limited and only accounts for 10-15% of the weight of the catalyst, the active center of the catalyst can be converted into NiS, and hydrogen sulfide is adsorbed on the carrier to generate acidity, so that the resin is promoted to crack, and the yield of the hydrogenated resin is reduced.
Chinese patent, publication No.: CN105367714A describes a method for preparing hydrogenated DCPD resin by using supported Ni/ZnO-SiO2The catalyst is used as a pre-hydrogenation catalyst, the eggshell type Pd catalyst is used as a hydrogenation and decoloration catalyst, and the resin is subjected to hydrogenation reaction by adopting a two-section fixed bed continuous hydrogenation mode, so that the hydrogenated DCPD resin is prepared, the resin hue is improved to be water white, and the hydrogenated DCPD resin has good thermal stability. The colloid blocks the pore channel of the prehydrogenation catalyst, so that the catalyst is quickly deactivated.
Disclosure of Invention
The invention provides a method for hydrogenating high-sulfur petroleum resin, which solves the problem of quick inactivation of a resin hydrogenation catalyst. The invention has wide raw material range, takes high-grade hydrogenated resin as a target product, improves the chroma of the resin, improves the heat stability, slightly reduces the softening point rate of the resin and obviously improves the product yield.
The technical scheme of the invention is as follows:
a method for hydrogenating petroleum resin with high sulfur content uses a sulfur-resistant eggshell-shaped noble metal alloy as a first-stage hydrodesulfurization catalyst and a supported metal catalyst as a second-stage hydrogenation decolorization catalyst, and adopts a two-stage hydrogenation mode to carry out hydrogenation reaction on the resin to prepare hydrogenated resin, wherein the color phase of the resin is improved to be water white, and the softening point is reduced; the method comprises the following steps:
heating the solvent to 130-150 ℃, uniformly dissolving the solvent and the molten high-sulfur petroleum resin in a dynamic mixer, wherein the high-sulfur petroleum resin accounts for 10-30% of the mass ratio of the mixed substances, and then entering an impurity removal reactor filled with a colloid absorbing adsorbent to remove colloid, partial chlorine or fluorine; then mixing with hydrogen and injecting the mixture into a hydrodesulfurization tower filled with a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst removes sulfur, chlorine or fluorine in the resin, the feeding temperature is 260-300 ℃, the hydrogen partial pressure is 2-4MPa, and the volume space velocity is 1-4h-1The volume ratio of hydrogen to oil is 100-200: 1; the hydrodesulfurization catalyst is an eggshell type noble metal alloy catalyst; the resin solution after hydrodesulfurization enters a stripping gas-liquid separation tower, the content of dissolved hydrogen sulfide in the resin solution is reduced through hydrogen stripping, and the separated hydrogen is washed and recycled; the resin solution after hydrodesulfurization is pressurized and mixed with hydrogen to enter a deep hydrogenation tower for hydrogenation and decolorization, wherein the feeding temperature is 240-280 ℃, the hydrogen partial pressure is 8-18MPa, and the volume space velocity is 0.5-1.5h-1The volume ratio of hydrogen to oil is 200-600: 1; the catalyst used for hydrogenation and decoloration is a supported metal catalyst; injecting the resin solution subjected to hydrogenation and decoloration into a solvent removal tower, distilling the resin solution at normal pressure, circularly dissolving the high-sulfur petroleum resin by using a product solvent distilled from the top of the tower, allowing a product at the bottom of the tower to enter a devolatilization tower, performing negative pressure operation on the devolatilization tower, and ejecting high-boiling-point oligomers generated by petroleum resin cracking in the hydrogenation and decoloration process out of the devolatilization tower; hydrogenated resin is discharged from the bottom of the devolatilization tower, the color phase of the resin is improved to be water white, and the softening point is reduced.
The colloid-absorbing adsorbent is Ca/Al2O3Wherein the mesopore volume accounts for more than 80% of the total pore volume, the pore diameter is 20-50nm, and Ca is added2+Mass ofThe content is 0.3 to 1.0 percent. Ca2+The introduction of (2) is beneficial to the removal of chlorine/fluorine in the residual initiator of the synthetic resin.
In the eggshell type noble metal alloy catalyst, the noble metal alloy is PdM, and M is one or more than two of Ir, Re, Pt, Ru, Au and Ag.
M is Pt or Ir, the molar ratio of Pd to M is 4:1, the mass content of Pd is 0.3-1.0%, and the carrier is Al2O3、SiO2、TiO2、SiO2-Al2O3Or Al2O3-TiO2。
The supported metal catalyst is a noble metal catalyst, a high nickel catalyst or a skeletal nickel catalyst. Preferably selecting a high nickel catalyst and a skeleton nickel catalyst, wherein the mass content of metal nickel in the high nickel catalyst is more than 30 percent; the skeletal nickel catalyst needs to be dealuminized, and the removal rate of aluminum needs to be more than 95 percent.
The solvent is a mixture of cycloalkane and straight-chain alkane, the cycloalkane accounts for 30-70% of the solvent by mass, and the proportion of the cycloalkane to the solvent is determined according to the solubility of the resin.
The invention has the beneficial effects that: the resin and the solvent are dynamically mixed, and the continuous operation of adsorption impurity removal, hydrodesulfurization, stripping desolventizing hydrogen sulfide, gas purification, hydrodecolorization, solvent removal and devolatilization is carried out. The method provided by the invention improves the impurity resistance, the reaction activity and the selectivity due to the use of a two-stage hydrogenation method. The method has wide adaptability to resin raw materials, and is particularly suitable for high-sulfur petroleum resin. The petroleum resin obtained by thermal polymerization or catalytic polymerization can be subjected to two-step hydrotreating by the method provided by the invention to obtain high-performance hydrogenated resin no matter the content of impurities in the resin solution is high, especially when the content of sulfur or fluorine/chlorine in the resin solution is high. Through first-stage hydrodesulfurization, sulfur, chlorine/fluorine in the resin are removed by using a sulfur-resistant eggshell type noble metal alloy catalyst, so that the second-stage hydrogenation metal catalyst is effectively protected, and the service life of the catalyst is greatly prolonged. Therefore, the invention has the advantages of simple process, high catalyst activity, good stability, improved resin chromaticity, improved resin thermal stability, slightly reduced softening point and good economic benefit.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention.
In the figure: 1a dynamic mixer; 2, removing impurities in a reaction tower; 3, a hydrodesulfurization reaction tower; 4 steam stripping gas-liquid separation tower; 5, washing the tower with water; 6, a deep hydrogenation tower; 7a desolventizing tower; 8 a devolatilization tower.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1: with calcium nitrate as precursor, mesoporous Al2O3As a carrier, Ca/Al is prepared2O3The amount of Ca supported was 2%, and the introduction of Ca into the reaction was examined2+Influence on dechlorination/fluorination effect. C9 petroleum resin with S content of 480ppm is used as raw material, and the mixture of C8-C14 naphthenic hydrocarbon and straight-chain alkane is used, wherein the mass ratio of the naphthenic hydrocarbon is 40%. The dissolved resin concentration was 20%. Operating conditions of the impurity removal reaction tower: operating at normal pressure; the reaction temperature is 200 ℃ and 220 ℃, and the liquid space velocity is 0.2h-1. See table 1 below for resin raw materials and resin properties after adsorption and impurity removal.
| Raw materials | Al2O3 | Ca/Al2O3 | |
| Softening point | 115 | 115 | 115 |
| Color number | 9 | 10 | 10 |
| Gum content | 0.32％ | 0.11％ | 0.07 |
| Bromine number | 52 | 64 | 65 |
| Sulfur content | 480 | 420 | 417 |
| Content of F | 48 | 21 | 5 |
The chromaticity measurement is that the resin is prepared into 50 wt% toluene solution to be compared with standard Fe-Co colorimetric solution;
the content of colloid is determined by adopting an adsorption weighing method;
f content determination the content of F in the resin is determined by oxygen bomb combustion-ion chromatography;
the sulfur content and the F content are relative to the resin;
as can be seen from Table 1, in the mesoporous Al2O3Ca-loaded2+After that, the removal of F was significantly increased.
Example 2: impregnating the ball with an inducing agentDrying the carrier, adding the dried carrier into a double noble metal salt solution, controlling the deposition of double noble metal alloy nano particles on the surface of the carrier through surface rapid reduction reaction and solution viscosity after a metal ion and an initiator form a double gold complex, filtering, washing, and heating and drying in an inert atmosphere to form the stable eggshell type noble metal alloy (PdM) catalyst. M is Ir, Re, Pt, Ru, Au and Ag, the mole ratio of Pd/M is 4:1, and the Pd loading amount PdM @ Al of 0.5 percent of Pd2O3For the hydrodesulfurization catalyst, the hydrodesulfurization effect of the bimetallic alloy catalyst was examined using the resin liquid obtained after the defluorination in example 1 as a raw material. The reaction conditions are that the feeding temperature is 280 ℃, the hydrogen partial pressure is 3MPa, and the volume space velocity is 2h-1Hydrogen-oil volume ratio 100: 1, resin concentration 20%. See table 2 below for resin properties after hydrodesulfurization.
| PdIr | PdRe | PdPt | PdRu | PdAu | PdAg | |
| Softening point | 113 | 108 | 111 | 107 | 112 | 111 |
| |
3 | 3 | 3 | 3 | 3 | 3 |
| Bromine number | 3.7 | 2.4 | 2.1 | 4.8 | 5.8 | 6.1 |
| Sulfur content | 31 | 37 | 23 | 45 | 38 | 59 |
| Content of |
4 | 4 | 4 | 4 | 4 | 5 |
As can be seen from Table 1, the eggshell-type bimetallic alloy as the hydrodesulfurization catalyst can significantly reduce the S content, bromine number and color number. However, the fluorine content and the softening point of the resin were not greatly changed. The resin solution after the hydrogen stripping reaction can further reduce the content of S. Taking PdPt as an example, the S content can be reduced to about 10ppm by hydrogen stripping.
Example 3: PdPt is used as an active component, and the effect of the carrier on hydrodesulfurization is investigated. The reaction conditions are that the feeding temperature is 280 ℃, the hydrogen partial pressure is 3MPa, and the volume space velocity is 2h-1Hydrogen-oil volume ratio 100: 1, resin concentration 20%. See table 3 below for resin properties after hydrodesulfurization.
As can be seen from Table 3, the eggshell catalyst is a hydrodesulfurization catalyst, and the influence of the carrier on the hydrodecolorization effect is not obvious. SiO carrier2-Al2O3And Al2O3-TiO2The best hydrodesulfurization effect is shown.
Example 4: by PtPd @ Al2O3For the hydrodesulfurization catalyst, the influence of the reaction conditions on the hydrodesulfurization effect was examined. See table 4 below for resin properties after hydrodesulfurization.
As can be seen from Table 4, the effect of hydrodesulfurization is greatly influenced by the reaction temperature and space velocity, and the desulfurization effect is hardly influenced by the reaction pressure and the gas oil ratio.
Example 5: by PtPd @ Al2O3The catalyst is a hydrodesulfurization catalyst, and the reaction conditions are that the feeding temperature is 260 ℃, the hydrogen partial pressure is 3MPa, and the volume space velocity is 2h-1Hydrogen-oil volume ratio 100: 1, resin concentration 20%. Table 5 below shows the properties of the products obtained after 1000 hours of operation.
From Table 5, the results of the 1000 hour test in PtPd @ Al2O3The sulfur and bromine values on the hydrodesulfurization catalyst were substantially unchanged from the initial experiment, indicating that the technique has good stability.
Example 6: respectively using eggshell type Pd @ Al2O3(Pd content: 1%) catalyst, Ni/Al2O3(Ni content 40%) and dealuminated skeleton nickel (dealumination rate is greater than 95%) as deep hydrogenation catalyst. The effect of different catalysts on the hydrodecolorization effect was compared on the basis of example 5. Table 6 below shows the reaction process conditions and the properties of the hydrogenated resin product obtained at the end.
Table 6 shows eggshell type Pd @ Al2O3Catalyst, Ni/Al2O3And the skeletal nickel is used as a deep hydrogenation catalyst to show a good hydrogenation and decoloration effect, and a two-stage fixed bed hydrogenation mode is adopted to carry out hydrogenation reaction on the resin to prepare the hydrogenated resin, so that the color phase of the resin is improved to be water white, the softening point is slightly reduced, and the hydrogenated resin has good thermal stability.
Example 7: using resin liquid obtained after hydrodesulfurization and hydrogen stripping as raw material, and using Ni/Al2O3(Ni content 40%) is a deep hydrogenation catalyst. On the basis of example 5 and example 6, the reaction conditions were: the feeding temperature is 260 ℃, the hydrogen partial pressure is 15MPa, and the volume space velocity is 0.6h-1Hydrogen-oil volume ratio 400: 1, resin concentration 20%. The properties of the hydrogenated resin after 1000 hours of hydrodecoloration are shown in Table 7 below.
From Table 7, the results of the 1000h run of the process are reported in PdPt @ Al2O3For hydrodesulphurisation catalysts, Ni/Al2O3The hydrogenation and decoloration catalyst is a hydrogenation and decoloration catalyst, a two-section fixed bed hydrogenation mode is adopted to carry out hydrogenation reaction on resin to prepare hydrogenated resin, the color phase of the resin is improved to be water white, the softening point is slightly reduced, and the hydrogenated resin has good thermal stability. The results show that the technology of the invention has good stability and long service life of the catalyst.
Claims (3)
1. A method for hydrogenating petroleum resin with high sulfur content uses a sulfur-resistant eggshell-shaped noble metal alloy as a first-stage hydrodesulfurization catalyst and a supported metal catalyst as a second-stage hydrogenation decolorization catalyst, and adopts a two-stage hydrogenation mode to carry out hydrogenation reaction on the resin to prepare hydrogenated resin, wherein the color phase of the resin is improved to be water white, and the softening point is reduced; the method is characterized by comprising the following steps:
heating the solvent to 130-150 ℃, uniformly dissolving the solvent and the molten high-sulfur petroleum resin in a dynamic mixer, wherein the high-sulfur petroleum resin accounts for 10-30% of the mass ratio of the mixed substances, and then entering an impurity removal reactor filled with a colloid absorbing adsorbent to remove colloid, partial chlorine or fluorine; then mixing with hydrogen and injecting the mixture into a hydrodesulfurization tower filled with a hydrodesulfurization catalyst, wherein the hydrodesulfurization catalyst removes sulfur, chlorine or fluorine in the resin, the feeding temperature is 260-300 ℃, the hydrogen partial pressure is 2-4MPa, and the volume space velocity is 1-4h-1The volume ratio of hydrogen to oil is 100-200: 1; the hydrodesulfurization catalyst is an eggshell type noble metal alloy catalyst; the resin solution after hydrodesulfurization enters a stripping gas-liquid separation tower, the content of dissolved hydrogen sulfide in the resin solution is reduced through hydrogen stripping, and the separated hydrogen is washed and recycled; the resin solution after hydrodesulfurization is pressurized and mixed with hydrogen to enter a deep hydrogenation tower for hydrogenation and decolorization, wherein the feeding temperature is 240-280 ℃, the hydrogen partial pressure is 8-18MPa, and the volume space velocity is 0.5-1.5h-1The volume ratio of hydrogen to oil is 200-600: 1; the catalyst used for hydrogenation and decoloration is a supported metal catalyst; the resin solution after hydrogenation and decoloration is injected into the solution for desolventizingThe solvent of the product distilled from the top of the tower is recycled to re-dissolve the high-sulfur petroleum resin after atmospheric distillation, the product at the bottom of the tower enters a devolatilization tower, the devolatilization tower is operated at negative pressure, and high-boiling-point oligomers generated by petroleum resin cracking in the process of hydrogenation and decoloration are ejected from the devolatilization tower; hydrogenated resin is discharged from the bottom of the devolatilization tower, the color phase of the resin is improved to be water white, and the softening point is reduced; the colloid-absorbing adsorbent is Ca/Al2O3Wherein the mesopore volume accounts for more than 80% of the total pore volume, the pore diameter is 20-50nm, and Ca is added2+The mass content of (A) is 0.3-1.0%; in the eggshell type noble metal alloy catalyst, the noble metal alloy is PdM, and M is one or more than two of Ir, Re, Pt, Ru, Au and Ag; the supported metal catalyst is a noble metal catalyst, a high nickel catalyst or a skeletal nickel catalyst.
2. The method for hydrogenating high-sulfur petroleum resin according to claim 1, wherein the hydrogenation comprises: m is Pt or Ir, the molar ratio of Pd to M is 4:1, the mass content of Pd is 0.3-1.0%, and the carrier is Al2O3、SiO2、TiO2、SiO2-Al2O3Or Al2O3-TiO2。
3. The method for hydrogenating high-sulfur petroleum resin according to claim 1 or 2, wherein the hydrogenation comprises: the solvent is a mixture of cycloalkane and straight-chain alkane, and the cycloalkane accounts for 30-70% of the solvent by mass.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389119A2 (en) * | 1989-03-14 | 1990-09-26 | Exxon Chemical Patents Inc. | Halogen resistant hydrotreating process and catalyst |
| CN104877077A (en) * | 2015-06-24 | 2015-09-02 | 大连理工大学 | Method for preparing hydrogenated C9 petroleum resin |
| CN105367714A (en) * | 2015-12-03 | 2016-03-02 | 大连理工大学 | Method for preparing hydrogenated DCPD resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0389119A2 (en) * | 1989-03-14 | 1990-09-26 | Exxon Chemical Patents Inc. | Halogen resistant hydrotreating process and catalyst |
| CN104877077A (en) * | 2015-06-24 | 2015-09-02 | 大连理工大学 | Method for preparing hydrogenated C9 petroleum resin |
| CN105367714A (en) * | 2015-12-03 | 2016-03-02 | 大连理工大学 | Method for preparing hydrogenated DCPD resin |
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