WO2021169016A1 - 一种碳九树脂的加氢催化方法 - Google Patents

一种碳九树脂的加氢催化方法 Download PDF

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WO2021169016A1
WO2021169016A1 PCT/CN2020/086585 CN2020086585W WO2021169016A1 WO 2021169016 A1 WO2021169016 A1 WO 2021169016A1 CN 2020086585 W CN2020086585 W CN 2020086585W WO 2021169016 A1 WO2021169016 A1 WO 2021169016A1
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resin
nitrate
carbon
solution
silica gel
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French (fr)
Chinese (zh)
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胡敏杰
黄辉
徐卫红
李颖
张皓荐
肖勋文
王斌
房江华
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宁波工程学院
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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
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • 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
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to the hydrogenation catalysis of petroleum resin, in particular to a hydrogenation catalysis method of carbon nine resin.
  • C9 resin is a by-product from cracking to produce ethylene.
  • C9 resin hydrogenation catalyzes the double bond and part of the benzene ring in the resin to be saturated, and the halogen element remaining in the resin polymerization process is removed, which improves the resin's chromaticity, light and heat stability, oxidation stability and UV resistance It improves product quality and expands its use.
  • adhesive and sealant applications especially transparent pressure-sensitive tapes, outdoor sealants, disposable sanitary products, medical tapes, road marking paints, and polyolefin modifiers, applications need light color, odorless and stable Petroleum resin with good properties, and carbon nine resin is one of them. Therefore, the market demand for hydrogenated carbon nine resin is growing rapidly, which also promotes the development of hydrogenation catalytic technology of carbon nine resin, and the choice of catalyst is an influence
  • C9 resin is the key to the quality of the finished product after hydrogenation.
  • Resin hydrogenation catalysts are mainly divided into two types of catalysts: precious metals and non-precious metals.
  • the precious metal catalysts are mainly palladium series. Compared with palladium-platinum catalysts, the catalysts of this series have the advantages of high activity, low starting temperature, high product yield and good quality, but the disadvantages are that they are sensitive to poisons such as sulfur and are very easy to be poisoned and deactivated.
  • Non-precious metal catalysts are mostly nickel-based catalysts supported on diatomaceous earth or alumina-diatomite, nickel-tungsten or nickel-molybdenum sulfide catalysts.
  • This type of catalyst has strong sulfur resistance, but the catalyst is not enough to be a catalyst
  • the activity of the product is not high, the bromine value of the product is still high, the hydrogenation degradation is relatively serious, the resin yield of the product is only about 80%, the softening point is reduced from 120°C to 90°C, and the catalyst life is short. Therefore, in the prior art, an unused catalyst is used for the stepwise hydrogenation catalysis of the C9 resin.
  • Chinese patent CN102924659A discloses a two-stage fixed-bed resin hydrogenation method.
  • the first stage catalyst is Ni/Al 2 O 3 , mainly for removing sulfur from the raw resin.
  • the second stage is the precious metal Pt-Pd/Al 2 O 3 hydrogenation catalyst, which is mainly hydrodecolorization treatment;
  • the hydrogenation reaction pressure of the first stage hydrodesulfurization is 2.0 ⁇ 6.0MPa
  • the reaction temperature is 250 ⁇ 350°C
  • the liquid space velocity is 1 ⁇ 5h -1
  • Sec hydrogenation decoloration hydrogenation reaction pressure of 6.0 ⁇ 12.0MPa the reaction temperature is 250 ⁇ 350 °C
  • LHSV 1 ⁇ 5h -1 the high pressure fixed bed catalytic hydrotreatment.
  • the method takes full advantage of the two-stage catalyst and improves the life of the precious metal catalyst. But the disadvantage is that the activity of the catalyst still needs to be improved; the use of Al 2 O 3 as a supporting carrier leads to uneven dispersion of the catalyst on it, resulting in poor catalytic effect; the two-stage catalyst adopts different pressurization conditions and cannot be completed in the same fixed bed. , The production efficiency is low, and there is pressure interference in the actual operation process, which affects the final carbon nine resin quality.
  • the current carbon nine resin hydrogenation catalysts have problems such as uneven dispersion of the catalyst on the support and poor catalytic effect. Therefore, it is necessary to develop a C9 resin hydrogenation catalytic method with high catalytic efficiency and simple process.
  • the technical problem to be solved by the present invention is to provide a hydrogenation catalyst method for preparing carbon nine resin with good chromaticity, low bromine value and simple process in view of the current state of the art.
  • a carbon nine resin hydrogenation catalysis method which is characterized in that: Ni-Nd-Gd/silica gel co-precipitation catalyst is placed in the second half of the bed, and hydrogen is introduced for reduction; 2) the pretreated carbon nine resin is hydrogenated and catalyzed in the fixed bed.
  • the preparation of the Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust a saturated sodium silicate solution with 5-7 mol/L nitric acid to a pH value of 1-2, and pour in zirconium nitrate, molybdenum nitrate and Yttrium nitrate aqueous solution, Zr:Mo molar ratio is 1:0.1 ⁇ 1:0.5, Zr:Y molar ratio is 1:0.05 ⁇ 1:0.3, the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 5-10% of the weight of sodium silicate, adjust the prepared solution to pH 9-10 with saturated sodium carbonate solution to form a precipitate.
  • the precipitate is separated by centrifugation, and the separated precipitate is washed with deionized water.
  • the precipitate is dried at 100-150°C for 3 to 5 hours, and the dried precipitate is roasted in a muffle furnace at 500-700°C for 3 to 5 hours;
  • the preparation of the Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1-2 with 5-7 mol/L nitric acid, and pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate , Ni:Nd molar ratio is 1:0.03 ⁇ 1:0.1, Ni:Gd molar ratio is 1:0.01 ⁇ 1:0.08, the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is sodium silicate 5-10% of the weight, adjust the prepared solution to pH 9-10 with saturated sodium carbonate solution to form a precipitate.
  • the precipitate is separated by centrifugation, and the separated precipitate is washed with deionized water until it is neutral and precipitates.
  • the product is dried at 100-150°C for 3 to 5 hours, and the dried precipitate is calcined in a muffle furnace at 500-700°C for 3 to 5 hours.
  • the hydrogen reduction conditions of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel co-precipitation catalyst are: high-purity hydrogen gas is introduced for reduction, the reduction temperature is 350-500°C, and the reduction time is 5-10 hours .
  • the hydrogenation catalytic conditions are: reaction temperature 250-450°C, reaction pressure 10-25MPa, volumetric space velocity 0.1-1.0h -1 , and the volume ratio of hydrogen to carbon nine resin is 400:1-900:1 .
  • the pretreatment condition of the carbon nona resin is: the carbon nona resin is dissolved with cyclohexane or ethylcyclohexane at a solubility of 5-20% by weight, and the solution is passed through a clay or diatomaceous earth filter column.
  • the surface area of the Zr-Mo-Y/silica gel and Ni-Nd-Gd/silica gel co-precipitation catalyst is 90-150 square meters/g, and the pore diameter of 50-100 nm accounts for 10-20%.
  • the present invention has the advantages of: 1) Putting different catalysts capable of reacting under the same catalytic conditions in the front and back sections of the fixed bed, the Zr-Mo-Y/silica gel catalyst can remove C9 resin Most of the sulfur and halogen in the resin also have a certain effect of removing bromine, and the Ni-Nd-Gd/silica gel catalyst is mainly used for deep hydrogenation, and has the effect of further removing other heteroatoms, which can continue to remove the carbon nine resin. For the residual sulfur and nitrogen, the two different catalysts have different focus points, but they can be active under the same conditions and have complementary effects. The synergy of the two catalysts has a good catalytic effect and simplified The production process is improved, and the production cost is saved.
  • Fig. 1 is an infrared spectrogram of Example 1 C9 resin before hydrogenation catalysis.
  • Fig. 2 is an infrared spectrogram after hydrogenation catalysis of C9 resin in Example 1 of the present invention.
  • Fig. 3 is an infrared spectrogram of Example 2 of the present invention before carbon nine resin hydrogenation catalysis.
  • Fig. 4 is an infrared spectrogram of Example 2 of the present invention after C9 resin hydrogenation catalyzed.
  • Fig. 5 is an infrared spectrogram of Example 3 of the present invention before carbon nine resin hydrogenation catalysis.
  • Fig. 6 is an infrared spectrogram of Example 3 of the present invention after C9 resin hydrogenation catalyzed.
  • Fig. 7 is an infrared spectrogram before hydrogenation catalysis of C9 resin in Example 4 of the present invention.
  • Fig. 8 is an infrared spectrogram of Example 4 of the present invention after C9 resin hydrogenation catalyzed.
  • Fig. 9 is an infrared spectrogram of Example 5 C9 resin before hydrogenation catalysis.
  • Fig. 10 is an infrared spectrogram after hydrogenation catalysis of C9 resin in Example 5 of the present invention.
  • the hydrogenation catalysis method of C9 resin includes the following steps: 1) Put the Zr-Mo-Y/silica co-precipitation catalyst in the first half of the fixed bed, and put the Ni-Nd-Gd/silica co-precipitation catalyst in the second half of the fixed bed ,
  • the fixed bed is reduced by introducing 99.999% high-purity hydrogen gas, the reduction temperature is 350°C, and the reduction time is 10 hours.
  • the preparation of the Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1 with 6 mol/L nitric acid, pour into the aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, Zr: Mo The molar ratio is 1:0.1, and the Zr:Y molar ratio is 1:0.3.
  • the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 5% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate
  • the solution is adjusted to pH 9 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Baking in a furnace at 500°C for 3 hours;
  • the preparation of Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 2 with 6 mol/L nitric acid, pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate, Ni:Nd
  • the molar ratio is 1:0.1
  • the molar ratio of Ni:Gd is 1:0.01.
  • the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 10% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution is adjusted to pH 10 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Firing in a furnace at 700°C for 5 hours.
  • the carbon nine resin was dissolved with cyclohexane at a solubility of 5 wt%, and the solution was passed through a clay filter column.
  • the insoluble gel, asphaltene and a small amount of free heavy metals are absorbed on the clay, and the pretreated carbon nine resin solution enters the catalytic hydrogenation.
  • the hydrogenation catalysis conditions are: reaction temperature 450°C, reaction pressure 10MPa, volumetric space velocity 0.1h -1 , and the volume ratio of hydrogen to carbon nine resin is 400:1.
  • the hydrogenation catalysis method of C9 resin includes the following steps: 1) Put the Zr-Mo-Y/silica co-precipitation catalyst in the first half of the fixed bed, and put the Ni-Nd-Gd/silica co-precipitation catalyst in the second half of the fixed bed ,
  • the fixed bed is reduced by introducing 99.999% high-purity hydrogen gas, the reduction temperature is 500°C, and the reduction time is 5 hours.
  • the preparation of Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 2 with 6 mol/L nitric acid, pour into the aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, Zr: Mo
  • the molar ratio is 1:0.5
  • the Zr:Y molar ratio is 1:0.05.
  • the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 10% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution is adjusted to pH 10 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Baking in a furnace at 700°C for 5 hours;
  • the preparation of Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1 with 6 mol/L nitric acid, pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate, Ni:Nd
  • the molar ratio is 1:0.03, and the molar ratio of Ni:Gd is 1:0.08.
  • the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 5% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution is adjusted to pH 9 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Firing in a furnace at 500°C for 3 hours.
  • the carbon nine resin was dissolved with ethyl cyclohexane at a solubility of 20 wt%, and the solution was passed through a clay filter column.
  • the insoluble gel, asphaltene and a small amount of free heavy metals are absorbed on the clay, and the pretreated carbon nine resin solution enters the catalytic hydrogenation.
  • the hydrogenation catalysis conditions are: reaction temperature 250°C, reaction pressure 25MPa, volumetric space velocity 1.0h -1 , and the volume ratio of hydrogen to carbon nine resin is 900:1.
  • the hydrogenation catalysis method of C9 resin includes the following steps: 1) Put the Zr-Mo-Y/silica co-precipitation catalyst in the first half of the fixed bed, and put the Ni-Nd-Gd/silica co-precipitation catalyst in the second half of the fixed bed ,
  • the fixed bed is reduced by introducing 99.999% high-purity hydrogen gas, the reduction temperature is 400 DEG C, and the reduction time is 7 hours.
  • the preparation of Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1.5 with 6 mol/L nitric acid, pour into the aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, Zr: Mo The molar ratio is 1:0.2, and the Zr:Y molar ratio is 1:0.1.
  • the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 7% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate
  • the solution was adjusted to pH 9.5 to form a precipitate.
  • the precipitate was separated by centrifugation.
  • the separated precipitate was washed with deionized water to neutrality.
  • the precipitate was dried at 125°C for 4 hours. Baking in a furnace at 600°C for 4 hours;
  • the preparation of Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1.5 with 6 mol/L nitric acid, pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate, Ni:Nd
  • the molar ratio is 1:0.06, and the molar ratio of Ni:Gd is 1:0.05.
  • the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution was adjusted to pH 9.7 to form a precipitate.
  • the precipitate was separated by centrifugation.
  • the separated precipitate was washed with deionized water to neutrality.
  • the precipitate was dried at 125°C for 4 hours. Firing in a furnace at 550°C for 4 hours.
  • the carbon nine resin was dissolved with cyclohexane at a solubility of 15 wt%, and the solution was passed through a clay filter column.
  • the insoluble gel, asphaltene and a small amount of free heavy metals are absorbed on the clay, and the pretreated carbon nine resin solution enters the catalytic hydrogenation.
  • the hydrogenation catalysis conditions are: reaction temperature 350°C, reaction pressure 18MPa, volumetric space velocity 0.6h -1 , and the volume ratio of hydrogen to carbon nine resin is 600:1.
  • the hydrogenation catalysis method of C9 resin includes the following steps: 1) Put the Zr-Mo-Y/silica co-precipitation catalyst in the first half of the fixed bed, and put the Ni-Nd-Gd/silica co-precipitation catalyst in the second half of the fixed bed ,
  • the fixed bed is reduced by introducing 99.999% high-purity hydrogen gas, the reduction temperature is 500°C, and the reduction time is 8 hours.
  • the preparation of the Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1 with 6 mol/L nitric acid, pour into the aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, Zr: Mo
  • the molar ratio is 1:0.3
  • the Zr:Y molar ratio is 1:0.09.
  • the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 6% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate
  • the solution was adjusted to pH 9.5 to form a precipitate.
  • the precipitate was separated by centrifugation.
  • the separated precipitate was washed with deionized water to neutrality.
  • the precipitate was dried at 125°C for 4 hours. Baking in a furnace at 650°C for
  • the preparation of Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 2 with 6 mol/L nitric acid, pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate, Ni:Nd
  • the molar ratio is 1:0.08, and the molar ratio of Ni:Gd is 1:0.06.
  • the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 8% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution is adjusted to pH 10 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Firing in a furnace at 600°C for 4 hours.
  • the carbon nine resin was dissolved with cyclohexane at a solubility of 10% by weight, and the solution was passed through a clay filter column.
  • the insoluble gel, asphaltene and a small amount of free heavy metals are absorbed on the clay, and the pretreated carbon nine resin solution enters the catalytic hydrogenation.
  • the hydrogenation catalysis conditions are: reaction temperature 400°C, reaction pressure 20MPa, volumetric space velocity 0.7h -1 , and the volume ratio of hydrogen to carbon nine resin is 700:1.
  • the hydrogenation catalysis method of C9 resin includes the following steps: 1) Put the Zr-Mo-Y/silica co-precipitation catalyst in the first half of the fixed bed, and put the Ni-Nd-Gd/silica co-precipitation catalyst in the second half of the fixed bed ,
  • the fixed bed is reduced by introducing 99.999% high-purity hydrogen gas, the reduction temperature is 450°C, and the reduction time is 6 hours.
  • the preparation of Zr-Mo-Y/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1.5 with 6 mol/L nitric acid, pour into the aqueous solutions of zirconium nitrate, molybdenum nitrate and yttrium nitrate, Zr: Mo
  • the molar ratio is 1:0.3
  • the Zr:Y molar ratio is 1:0.02.
  • the weight of zirconium nitrate, molybdenum nitrate and yttrium nitrate in the prepared solution is 9% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate
  • the solution is adjusted to pH 10 to form a precipitate.
  • the precipitate is separated by centrifugation.
  • the separated precipitate is washed with deionized water to neutrality.
  • the precipitate is dried at 125°C for 4 hours. Baking in a furnace at 600°C for 5 hours;
  • the preparation of Ni-Nd-Gd/silica gel co-precipitation catalyst includes the following steps: adjust the saturated sodium silicate solution to pH 1 with 6 mol/L nitric acid, pour into the aqueous solution of nickel nitrate, neodymium nitrate and gadolinium nitrate, Ni:Nd
  • the molar ratio is 1:0.08, and the molar ratio of Ni:Gd is 1:0.07.
  • the weight of nickel nitrate, neodymium nitrate and gadolinium nitrate in the prepared solution is 6% of the weight of sodium silicate, and the prepared solution is saturated with sodium carbonate.
  • the solution was adjusted to pH 9.5 to form a precipitate.
  • the precipitate was separated by centrifugation.
  • the separated precipitate was washed with deionized water to neutrality.
  • the precipitate was dried at 125°C for 4 hours. Firing in a furnace at 550°C for 4 hours.
  • the carbon nine resin was dissolved with ethyl cyclohexane at a solubility of 15 wt%, and the solution was passed through a clay filter column.
  • the insoluble gel, asphaltene and a small amount of free heavy metals are absorbed on the clay, and the pretreated carbon nine resin solution enters the catalytic hydrogenation.
  • the hydrogenation catalysis conditions are: reaction temperature 300°C, reaction pressure 20MPa, volumetric space velocity 0.8h -1 , and the volume ratio of hydrogen to carbon nine resin is 700:1.

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PCT/CN2020/086585 2020-02-28 2020-04-24 一种碳九树脂的加氢催化方法 WO2021169016A1 (zh)

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JP2021518761A JP7079380B2 (ja) 2020-02-28 2020-04-24 Ｃ９樹脂の接触水素化方法
DE112020000194.6T DE112020000194B4 (de) 2020-02-28 2020-04-24 Hydrierungskatalyseverfahren für C9-Harz

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