CN112604692B - High-fluorine-content C9 resin hydrogenation catalyst, and preparation method and application thereof - Google Patents

High-fluorine-content C9 resin hydrogenation catalyst, and preparation method and application thereof Download PDF

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CN112604692B
CN112604692B CN202110036900.1A CN202110036900A CN112604692B CN 112604692 B CN112604692 B CN 112604692B CN 202110036900 A CN202110036900 A CN 202110036900A CN 112604692 B CN112604692 B CN 112604692B
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张先茂
吴阳春
王泽�
王瑜
王国兴
夏大寒
周正
赵志杰
彭渺
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Wuhan Kelin Chemical Industry Group Co ltd
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    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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    • C08F8/04—Reduction, e.g. hydrogenation

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Abstract

A high-fluorine C9 resin hydrogenating catalyst is prepared from active component M1Auxiliary component M2And a carrier component M3And (4) forming. M is calculated by the total weight of the catalyst being 100 percent1The content of the components is 37% -54%, M2The content of the components is 4 to 6 percent, and the balance is M3And (4) components. M1The component contains Ni, Mo, Cu, Al and M2The component contains Sm, Na and M3The component is amorphous silicon-aluminum-MgAl2O4A composite oxide. The invention also discloses a preparation method and application of the catalyst. The catalyst provided by the invention is used for removing fluorine and sulfur in C9 resin by hydrogenation, and can effectively delay the poisoning of fluorine and sulfur of a rear-section hydrogenation catalyst.

Description

High-fluorine-content C9 resin hydrogenation catalyst, and preparation method and application thereof
Technical Field
The invention relates to a high fluorine-containing C9 resin hydrogenation catalyst, a preparation method of the catalyst, and application of the catalyst in hydrogenation of high fluorine-containing C9 resin.
Background
The C9 resin is a thermoplastic resin obtained by heating polymerization or catalytic polymerization reaction of C9 fraction which is a byproduct in the production of industrial ethylene, and is widely used in the industries of adhesives, road finishes, printing inks, rubber and the like due to strong tackifying property and good compatibility with other oils and resins. The C9 fraction generally contains impurities such as sulfur, nitrogen, olefins, etc., and BF is used in catalytic polymerization of C9 resin3The catalyst causes C9 resin to contain high fluorine, and the impurities cause high resin chroma and poor photo-thermal stability, so that the application of the resin is limited. At present, the methodThe hydrogenation modification of the C9 resin is the most common and effective method, the added value of the hydrogenated C9 resin is improved, and the economic benefit is obvious.
At present, the domestic resin hydrogenation mainly adopts a fixed bed hydrogenation process, and because the C9 resin contains a certain amount of sulfur and nitrogen impurities, BF is particularly used3The C9 resin for catalytic polymerization contains high fluorine, and the fluorine content can reach 100-400ppm according to the difference of resin polymerization process, and the poisons have poisoning effect on both noble metal catalysts and nickel catalysts. At present, impurities such as sulfur, nitrogen and the like in a resin raw material are generally removed by adopting a diatomite adsorption or hydrogenation pretreatment mode in the hydrogenation of the C9 resin, so that a subsequent main hydrogenation catalyst is protected from being deactivated due to poisoning, but the treatment of fluorine in the resin is less reported at present.
Patent CN102746458A describes a preparation method of hydrogenated C9 resin, which adopts two-stage hydrogenation process, wherein the first-stage hydrogenation catalyst uses macroporous zeolite or diatom as carrier, and cobalt and molybdenum as active ingredients, wherein cobalt accounts for 15-45%, molybdenum accounts for 5-15%. The catalyst is in a sulfuration state, has good sulfur poisoning resistance, can remove sulfur in the resin liquid to 2ppm under the optimal condition, and avoids rapid inactivation of the subsequent hydrogenation catalyst due to sulfur poisoning.
Patent CN106008819A introduces a production device and a production method of low-chroma carbon nine petroleum resin, wherein the cold-polymerized C9 resin is treated by a two-stage hydrogenation process, the first-stage hydrogenation process adopts a nickel-based catalyst, the Ni content is 15-30%, refractory alumina and silica are used as carriers, impurities such as sulfur, chlorine, gel and the like in the resin can be removed under the conditions of 150-200 ℃ and 5-20 MPa, and the activity and the service life of the catalyst of the second-stage hydrogenation are ensured.
Patent CN105175633A describes a combined petroleum resin hydrotreating method, which uses alumina and activated carbon to adsorb resin liquid at high temperature to remove sulfur and chlorine impurities in the resin, and then carries out two-stage hydrotreating.
Patent CN102850491A describes a method for removing fluorine before hydrogenation of petroleum resin, wherein the method comprises the steps of preheating the dissolved resin, adding the preheated resin into a reaction kettle, adding a DTBHQ polymerization inhibitor, sealing the reaction kettle, adding a surfactant polyoxyethylene cetyl ether into the reaction kettle, introducing high-pressure steam, starting stirring, keeping for 5-15min, reducing the temperature in the reaction kettle to 20-70 ℃, standing to separate oil from water, and removing a water layer to obtain the fluorine-removed petroleum resin. The method can control the fluorine content in the resin liquid within 50ppm, so that the total resin treatment amount of a unit catalyst is greatly improved, and the service life of the catalyst is prolonged.
In summary, it can be seen that the pretreatment of resin hydrogenation generally comprises the removal of sulfur, nitrogen and chlorine, and aims at using BF3The pretreatment of the catalytic polymerization resin with high fluorine content is less researched, and the research of the existing defluorination adopts a process of adding a surfactant for washing, so that the defluorination precision is not high, and the process flow is complex.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a high fluorine-containing C9 resin hydrogenation catalyst, and a preparation method and application thereof.
The catalyst provided by the invention consists of an active component M1Auxiliary component M2And a carrier component M3The catalyst is used for removing fluorine and sulfur in the C9 resin by hydrogenation. M is calculated by the total weight of the catalyst being 100 percent1The content of the components is 37% -54%, M2The content of the components is 4 to 6 percent, and the balance is M3And (4) components. M1The component contains Ni, Mo, Cu, Al and M2The component contains Sm, Na and M3The component is amorphous silicon-aluminum-MgAl2O4A composite oxide. With M1Component (B) M, 100% of the total weight of the component1The NiO content in the components is 47 to 72 percent, and the MoO311-15 percent of CuO, 6-9 percent of CuO and the balance of Al2O3With M2Component (B) M, 100% of the total weight of the component2Sm in the component2O327% -48% of Na2The content of O is 52 to 73 percent, calculated as M3The content of amorphous silicon-aluminum is 74-88 percent, MgAl is calculated by 100 percent of the total weight of the components2O4The content is 12-26%.
The invention also provides a preparation method of the C9 resin hydrogenation catalyst, which comprises the following specific steps:
(1) adding soluble salts of Ni, Cu and Al into water to prepare a solution I, slowly adding a precipitator into the solution I, controlling the reaction temperature to be 50-80 ℃, controlling the pH value of the system to be 9-10, and continuously stirring at constant temperature for 3-5h after precipitation is finished to obtain slurry for later use;
(2) dissolving soluble salt of Mo in water, adding surfactant to prepare solution II, stirring and heating to 50-80 ℃, then adding the slurry obtained in the step (1) into the solution II, carrying out reflux reaction at 80-120 ℃ for 3-5h, filtering, washing and drying the obtained product to obtain a component M1A precursor of (a);
(3) adding sodium metaaluminate solution, sodium silicate solution and aluminum sulfate solution into a reaction container in a concurrent flow manner, keeping the reaction temperature at 20-50 ℃, keeping the pH value of the system at 6.5-9.5, reacting for 0.5-2.5 h, then heating to 60-90 ℃, aging for 0.5-3h to obtain amorphous silicon-aluminum slurry, and then adding MgAl into the slurry2O4Stirring uniformly, filtering the obtained product, washing and drying to obtain a component M3A precursor of (a);
(4) dissolving soluble salts of Na and Sm in water to obtain component M2And then adding M to the solution of1Precursor and component M of3The precursors are mixed evenly and then M is added2The solution of (A) is extruded into strips by sesbania powder and nitric acid aqueous solution, and the high fluorine-containing C9 resin hydrogenation catalyst is obtained after drying, roasting and forming.
In the preparation method of the catalyst, the Ni salt is selected from one of nickel nitrate and nickel chloride, the Mo salt is selected from one of ammonium heptamolybdate and ammonium tetramolybdate, the Cu salt is selected from one of copper nitrate and copper chloride, the aluminum salt is selected from one of aluminum nitrate and aluminum sulfate, the Sm salt is samarium nitrate, the sodium salt is selected from one of sodium nitrate and sodium sulfate, the precipitant is selected from one of sodium hydroxide and ammonia water, and the surfactant is selected from one of sodium dodecyl sulfonate and dodecyl trimethyl ammonium bromide.
The catalyst provided by the invention is used for hydrogenating high fluorine-containing C9 resin to remove fluorine and sulfur impurities in the resin, and is reduced by hydrogen at 430 ℃ and has the reaction pressure of 6.0-8.0MPa and the reaction temperature of 210 ℃ and 330 DEG CThe volume ratio of hydrogen to oil is 300-600, and the volume space velocity is 0.5-1.5h-1When the catalyst is used under the condition, the defluorination rate is more than 86 percent, and the desulfurization rate is more than 97 percent.
Compared with the prior art, the invention has the following advantages:
(1) catalyst active component M1Firstly, preparing M of Ni, Cu and Al by adopting a precipitation method1The active component precursor is used for introducing Mo into the catalyst in an anion exchange mode, so that the high dispersion of active metal is realized, more active centers are formed, and the formed catalyst has higher activity.
(2) The introduction of active component Cu can reduce NiAl2O4The amount of spinel increases the amount of highly dispersed NiO, and the active center of the catalyst is mainly highly dispersed NiO, so that the utilization rate of the active component Ni can be improved by adding Cu. In addition, after Cu is added, CuO is firstly reduced into copper crystal nuclei in a hydrogen environment in the catalyst reduction process to form a copper-rich alloy, and then the copper crystal nuclei are used as the crystal nuclei of nickel oxide adjacent to the copper crystal nuclei, so that the nucleation rate of the nickel oxide can be increased, the reduction of the nickel oxide is promoted, the reduction temperature of NiO on the catalyst is reduced, and the hydrogenation activity of the catalyst after low-temperature reduction is improved.
(3) The existence of Mo can lead the catalyst to adsorb a part of sulfur on the catalyst in the hydrogenation process, reduce the contact chance of the sulfide and Ni, and cause the reduction of the adsorption capacity of the sulfide on the Ni, thereby improving the sulfur poisoning resistance of the catalyst. In addition, Mo and Ni will form nickel molybdate or nickel polymolybdate during the calcination process, and Al2O3Compete for Ni and inhibit NiAl to a certain extent2O4And forming spinel.
(4) The auxiliary agent Sm can increase the electronegativity of Ni to make nucleophilic S2-Difficult to adsorb and enhances the sulfur resistance of the catalyst. The Sm is transferred to the surface of Ni atoms during reduction activation of Sm-added catalyst due to Ni nicking and hydrogen overflow2O3Reducing part of the reaction product to Sm<3+Low cost Sm<3+Easily transfer electrons to Ni atoms, increase the electron cloud density of the Ni atoms, reduce the electron binding energy, and reduce the electron binding energyThe activation energy of the reaction is improved, and the hydrogenation reaction activity is improved. The auxiliary agent Na can adjust the acidity of the catalyst, so that the catalyst has moderate acid strength, fluoride can be adsorbed to a certain degree, the contact chance of the fluoride and Ni is reduced, and the hydrogenation activity of the catalyst is ensured.
(5) The amorphous silicon-aluminum has large aperture, is more suitable for a hydrogenation raw material of C9 resin with relatively high molecular weight, can effectively slow down the internal diffusion influence in the hydrogenation process, and MgAl2The O spinel structure has good acid resistance to HF, and can ensure that the carrier is not damaged and corroded by too high HF in the hydrogenation process, thereby causing the collapse of the catalyst structure.
Detailed Description
The characteristics of the catalyst, the preparation method and the catalytic performance of the catalyst of the present invention will be described in detail with reference to the following specific examples, but the present invention is not limited to these examples and does not limit the scope of the present invention.
Example 1:
adding 86.1g of nickel nitrate, 3.8g of copper chloride and 23.5g of aluminum sulfate into water to prepare a solution I, then dropwise adding 0.5mol/L sodium hydroxide solution into the solution I, controlling the reaction temperature to be 65 ℃, controlling the pH of the system to be 9, and continuously stirring at constant temperature for 4 hours after the precipitation is finished to obtain slurry for later use. Dissolving 6.9g of ammonium heptamolybdate in water, adding 2g of sodium dodecyl sulfate to prepare a solution II, stirring and heating to 80 ℃, adding the obtained slurry into the solution II, carrying out reflux reaction at 120 ℃ for 4 hours, filtering, washing and drying the obtained product to obtain a component M1The precursor of (1).
24g of sodium metaaluminate, 100g of sodium silicate (25% SiO)2Content), 33.5g of aluminum sulfate are respectively prepared into solutions, the solutions are added into a reaction vessel in parallel, the reaction temperature is kept at 35 ℃, the pH value is 6.5, the reaction is carried out for 0.5h, then the solution is heated to 60 ℃, the aging is carried out for 3h to obtain amorphous silicon-aluminum slurry, and 6.8g of MgAl is added into the slurry2O4Stirring uniformly, filtering the obtained product, washing and drying to obtain a component M3The precursor of (1).
Component M prepared as described above1Precursor and component M3The precursor is mixed evenly and then the mixture is put into a reactor,and preparing a solution from 12g of sodium nitrate and 3.1g of samarium nitrate, adding the solution into the mixture, adding sesbania powder and a nitric acid aqueous solution, extruding into strips, drying, and roasting to obtain the high fluorine-containing C9 resin hydrogenation catalyst.
Example 2:
adding 37.3g of nickel chloride, 6.7g of copper nitrate and 111.8g of aluminum nitrate into water to prepare a solution I, then dropwise adding 0.6mol/L ammonia water solution into the solution I, controlling the reaction temperature to be 50 ℃, keeping the pH of the system to be 10, and continuously stirring at constant temperature for 3 hours after the precipitation is finished to obtain slurry for later use. Dissolving 7.3g of ammonium heptamolybdate in water, adding 2.5g of hexadecyl trimethyl ammonium bromide to prepare a solution II, stirring and heating to 50 ℃, then adding the obtained slurry into the solution II, carrying out reflux reaction at 80 ℃ for 3 hours, filtering, washing and drying the obtained product to obtain a component M1The precursor of (1).
32.2g of sodium metaaluminate, 40g of sodium silicate (25% SiO)2Content), 67g of aluminum sulfate are respectively prepared into solutions, the solutions are added into a reaction vessel in a parallel flow mode, the reaction temperature is kept at 20 ℃, the pH value is 9.5, the reaction is carried out for 1.5h, then the solution is heated to 75 ℃, the aging is carried out for 0.5h to obtain amorphous silicon-aluminum slurry, and 12.7g of MgAl is added into the amorphous silicon-aluminum slurry2O4Stirring uniformly, filtering the obtained product, washing and drying to obtain a component M3The precursor of (1).
Component M prepared as described above1Precursor and component M3And uniformly mixing the precursors, adding a solution prepared from 5.9g of sodium sulfate and 4.6g of samarium nitrate into the mixture, adding sesbania powder and a nitric acid aqueous solution, extruding into strips, drying, and roasting to obtain the high fluorine-containing C9 resin hydrogenation catalyst.
Example 3:
adding 151g of nickel nitrate, 14.8g of copper nitrate and 31.6g of aluminum nitrate into water to prepare a solution I, then dropwise adding 0.5mol/L sodium hydroxide solution into the solution I, controlling the reaction temperature to be 80 ℃, keeping the pH of the system to be 9, and continuously stirring at constant temperature for 5 hours after the precipitation is finished to obtain slurry for later use. 6.8g of ammonium tetramolybdate is dissolved in water, 2g of sodium dodecyl sulfate is added to prepare a solution II, the solution II is stirred and heated to 65 ℃, and then the obtained slurry is added into the solution IIIn the solution II, refluxing and reacting for 5h at 100 ℃, filtering, washing and drying the obtained product to obtain a component M1The precursor of (1).
16g of sodium metaaluminate, 40g of sodium silicate (25% SiO)2Content), 47g of aluminum sulfate are respectively prepared into solutions, the solutions are added into a reaction container in parallel, the reaction temperature is kept at 50 ℃, the pH value is 8, the reaction is carried out for 2.5 hours, then the solution is heated to 90 ℃, the aging is carried out for 1.5 hours to obtain amorphous silicon-aluminum slurry, and 8g of MgAl is added into the slurry2O4Stirring uniformly, filtering the obtained product, washing and drying to obtain a component M3The precursor of (1).
Component M prepared as described above1Precursor and component M3The precursors are uniformly mixed, 6.8g of sodium nitrate and 2.9g of samarium nitrate are prepared into solution to be added into the mixture, sesbania powder and nitric acid aqueous solution are added to be extruded into strips, and the strips are dried and roasted to form the high fluorine-containing C9 resin hydrogenation catalyst.
The catalyst prepared in the above examples has the composition shown in table 1, in mass percent:
TABLE 1 analysis of catalyst composition
Figure DEST_PATH_IMAGE002AA
The prepared catalyst A1-A3 and a commercial 24% NiO content NiO/Al2O3The evaluation is carried out on a fixed bed hydrogenation reaction device, the catalyst is reduced by hydrogen for 5 hours at 430 ℃ before use, and the density of the C9 resin is 975kg/m3D40 solvent oil is used for dissolving C9 resin as a hydrogenation raw material, the weight ratio of the resin is 25%, the C9 resin is hydrogenated and then passes through a gas-liquid separator, a liquid phase product is subjected to reduced pressure distillation to remove the D40 solvent, hydrogenated C9 resin is obtained, and the fluorine and sulfur content in the hydrogenated resin is measured. The softening point of the raw material resin was 127 ℃, the sulfur content was 228mg/kg, the fluorine content was 309mg/kg, and the catalyst evaluation conditions and results are shown in tables 2 and 3.
Table 2 catalyst evaluation process conditions
A1 A2 A3 NiO/Al2O3
pressure/MPa 6.0 8.0 7.0 8.0
Temperature/. degree.C 330 210 270 270
Volume ratio of hydrogen to oil 300 600 450 450
Space velocity/h-1 0.5 1.5 1.0 1.0
Table 3 evaluation of catalyst test results
Figure DEST_PATH_IMAGE004AA
The experimental results in table 3 show that the catalyst provided by the invention has good hydrodefluorination and desulfurization functions when being applied to hydrogenation of high fluorine-containing C9 resin, has strong fluorine and sulfur poisoning resistance, has no obvious reduction in defluorination and desulfurization activities after 120 hours of operation, has stable hydrogenation activity, can effectively delay the deactivation of the subsequent hydrogenation catalyst caused by fluorine and sulfur poisoning, and ensures long-period operation of the device.

Claims (5)

1. A preparation method of a high fluorine-containing C9 resin hydrogenation catalyst is characterized by comprising the following steps: the catalyst consists of active component M1Auxiliary component M2And a carrier component M3The composition is used for removing fluorine and sulfur in the C9 resin by hydrogenation; m is calculated by the total weight of the catalyst being 100 percent1The content of the components is 37% -54%, M2The content of the components is 4 to 6 percent, and the balance is M3Preparing components; m1The component contains Ni, Mo, Cu, Al and M2The component contains Sm, Na and M3The component is amorphous silicon-aluminum-MgAl2O4A composite oxide; the preparation method of the catalyst comprises the following steps:
(1) adding soluble salts of Ni, Cu and Al into water to prepare a solution I, slowly adding a precipitator into the solution I, controlling the reaction temperature to be 50-80 ℃, controlling the pH value of the system to be 9-10, and continuously stirring at constant temperature for 3-5h after precipitation is finished to obtain slurry for later use;
(2) dissolving soluble salt of Mo in water, adding surfactant to prepare solution II, stirring and heating to 50-80 ℃, then adding the slurry obtained in the step (1) into the solution II, carrying out reflux reaction at 80-120 ℃ for 3-5h, filtering, washing and drying the obtained product to obtain a component M1A precursor of (a);
(3) adding sodium metaaluminate solution, sodium silicate solution and aluminum sulfate solution into a reaction container in parallel flow, and keeping the reaction temperatureReacting at 20-50 deg.C and pH 6.5-9.5 for 0.5-2.5 hr, heating to 60-90 deg.C, aging for 0.5-3 hr to obtain amorphous silicon-aluminum slurry, and adding MgAl into the slurry2O4Stirring uniformly, filtering the obtained product, washing and drying to obtain a component M3A precursor of (a);
(4) dissolving soluble salts of Na and Sm in water to obtain component M2And then adding M to the solution of1Precursor and component M of3The precursors are mixed evenly and then M is added2The solution of (A) is extruded into strips by sesbania powder and nitric acid aqueous solution, and the high fluorine-containing C9 resin hydrogenation catalyst is obtained after drying, roasting and forming.
2. The preparation method of the hydrogenation catalyst for the high fluorine-containing C9 resin according to claim 1, wherein the hydrogenation catalyst comprises: with M1Component (B) M, 100% of the total weight of the component1The NiO content in the components is 47 to 72 percent, and the MoO311-15 percent of CuO, 6-9 percent of CuO and the balance of Al2O3With M2Component (B) M, 100% of the total weight of the component2Sm in the component2O327% -48% of Na2The content of O is 52 to 73 percent, calculated as M3The total weight of the components is 100 percent, the content of amorphous silicon-aluminum is 74 to 88 percent, and MgAl is2O4The content is 12-26%.
3. The preparation method of the hydrogenation catalyst for the high fluorine-containing C9 resin according to claim 1, wherein the hydrogenation catalyst comprises: the Ni salt is selected from one of nickel nitrate and nickel chloride, the Mo salt is selected from one of ammonium heptamolybdate and ammonium tetramolybdate, the Cu salt is selected from one of copper nitrate and copper chloride, the aluminum salt is selected from one of aluminum nitrate and aluminum sulfate, the Sm salt is samarium nitrate, the sodium salt is selected from one of sodium nitrate and sodium sulfate, the precipitant is selected from one of sodium hydroxide and ammonia water, and the surfactant is selected from one of sodium dodecyl sulfonate and dodecyl trimethyl ammonium bromide.
4. The application of the catalyst prepared by the preparation method of the hydrogenation catalyst for the high fluorine-containing C9 resin according to claim 1, wherein the preparation method comprises the following steps: the application is used in the hydrodefluorination and desulfurization reaction of the high fluorine-containing C9 resin.
5. The use of claim 4, wherein: the catalyst is reduced by hydrogen at 430 ℃, and the reaction pressure is 6.0-8.0MPa, the reaction temperature is 210-330 ℃, the volume ratio of hydrogen to oil is 300-600 and the volume space velocity is 0.5-1.5h-1When the catalyst is used under the condition, the defluorination rate is more than 86 percent, and the desulfurization rate is more than 97 percent.
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CN106635139A (en) * 2017-01-13 2017-05-10 武汉科林精细化工有限公司 Application of catalyst in hydrogenation of crude benzene and coal-based naphtha mixture
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