CN104959136A - Preparation method for resin hydrogenation eggshell type catalyst - Google Patents
Preparation method for resin hydrogenation eggshell type catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method for a resin hydrogenation eggshell type catalyst, and belongs to the technical field of industrial catalysis. The method comprises the following steps: adding a carrier into a noble metal salt solution, controlling noble metal nano particles to be deposited on the surface of the carrier through a rapid reducing reaction and the viscosity of the solution, performing filtering and washing, and heating and drying in inert atmosphere to form the stable eggshell type noble metal catalyst. The preparation method has the advantages of simple technology, controllable structure, low process energy consumption and the like; the noble metal particles in the prepared eggshell type noble metal catalyst are uniformly distributed on the surface of the carrier, so that the use amount of the noble metal is reduced, the catalyst cost is effectively reduced, and a good industrial application prospect is realized. The eggshell type noble metal catalyst can be used for resin hydrogenation reaction, is excellent in catalysis performance and long in service life and has high economical benefit and good industrial application prospect.
Description
Technical field
The invention belongs to Hydrogenation Technology of Petroleum Resin field, relate to a kind of preparation method for adding hydrogen into resin egg-shell catalyst.
Background technology
Loaded noble metal catalyst is widely used in the field such as petrochemical industry and fine chemistry industry.The use of carrier can increase the decentralization of noble metal, improves the utilization rate of noble metal thus the cost of reduction noble metal catalyst.In recent years, large quantifier elimination relates to the granularity of noble metal on carrier and distributed controll.Wherein the activity of the selection of metal Optimal Distribution mainly required by catalytic reaction in carrier, selective and other response parameter (as kinetics, quality transmission) decide.The distribution of typical active component on carrier can be divided into eggshell type, protein type, yolk type and evenly type.The main integrated distribution of active metal of egg-shell catalyst, at carrier surface, effectively can reduce the consumption of noble metal active component, improves the activity of catalyst; The catalyst of eggshell type distribution is conducive to product from catalyst surface desorption, avoids the further reaction of target product, can improve the selective of intermediate product in irreversible tandem reactor process.The preparation of egg-shell catalyst is based on infusion process, be controlled by the dipping of catalyst and drying mostly, comprise: change dip time, maceration extract the factor such as concentration, pH value, solvent kind and add competitive adsorbate and have material impact to preparing egg-shell catalyst.C5, C9 and C5C9 copolymerization is due to the difference of raw material and polymerizing condition, containing undersaturated double bond and phenyl ring in Petropols, under the effect of catalyst, it is made to be able to by hydrogenation saturated, and remove chlorine, element sulphur residual in polymerization process, and then improve colourity and the photo and thermal stability of resin, improve the quality of product.Therefore, research and development and the heavy industrialization application of carrying out hydrogenation of petroleum resin seem particularly important.As the catalyst in hydrogenation of petroleum resin process, most important to this technique, it determines production cost and subsequent product quality.Compared to C5 hydrogenation of petroleum resin, the difficulty of C9 hydrogenation of petroleum resin is larger, because C9 Petropols are main in the form of a ring, chain structure, molecular weight is between 200 ~ 4000, sterically hindered comparatively large, activation energy needed for hydrogenation reaction improves, so need research and development to have the hydrogenation catalyst of high catalytic activity.
For abundant Petropols recycling problem, we successfully develop eggshell type noble metal catalyst for the reaction of Petropols fixed bed continously hydrogen adding, due to the use of egg-shell catalyst, ensure that the service life of load type metal catalyst.Obtained hydrogenation resin, resin form and aspect are improved to water-white and have good heat endurance.Following known technology, all comes with some shortcomings:
Chinese patent, publication number: CN1736604 introduces a kind of egg shell type metal and Synthesis and applications thereof, this patent take hollow silicon dioxide as the eggshell type metal supported catalyst of carrier, described hollow silicon dioxide carrier is the mesoporous material with certain wall thickness and certain pore size, adopts infusion process or original position load method to be prepared into egg shell type metal catalyst.But have strict demand for carrier, reactions steps is loaded down with trivial details, and manufacturing cycle is longer.
Chinese patent, publication number: CN102451722A, introduce a kind of preparation method of egg-shell catalyst, the method adopts the active metal dipping solution containing thickener and active metal dispersant to soak conventional carrier, and flood under the condition passing into air bubbling, drying and roasting, obtain eggshell hydrogenation catalyst again.Its operation is more, more loaded down with trivial details, and noble metal waste is serious.
Chinese patent, publication number: CN102451722B, introduce a kind of preparation method of egg-shell catalyst,, be aluminium oxide precursor mixed with Gemini surface active agent, adhesive, kneading makes catalyst carrier, then with the dipping solution impregnated carrier containing thickener, and flood under the condition passing into air bubbling, then drying and roasting, obtain eggshell hydrogenation catalyst.Its operation is more, more loaded down with trivial details, and noble metal waste is serious.
Chinese patent, publication number: CN1803871A, introduces the decolouring of a kind of C5 and C9 Petropols autoclave hydrogenation, except the method for look, although it has higher activity to adding hydrogen into resin, hydrogenation degraded is relatively more serious, and final resin yield is low, and softening point reduces serious.
Chinese patent, publication number: CN103386302A discloses a kind of hydrogenation of petroleum resin catalyst, namely with Al
2o
3for carrier, carried noble metal Pd and oxides additive, the Metal Palladium crystallite that particle diameter is less than 3nm accounts for more than 90%, and its weak point is that catalyst is for impurity S
2-tolerance difference and easy poisoning and deactivation, catalyst life receives impact.
Summary of the invention
The invention discloses a kind of preparation method for adding hydrogen into resin egg-shell catalyst, belong to Industrial Catalysis technical field.The method is joined by carrier in noble metal metal salt solution, reacted by fast restore, and solution viscosity, control noble metal nano particles and deposit at carrier surface, after filtration, wash, in inert atmosphere, namely heat drying forms stable eggshell type noble metal catalyst catalyst.Carry out under room temperature of the present invention, do not need to introduce heating source, technique is simple, the metal particle diameter of preparation is little, is evenly distributed, good stability, in the eggshell type noble metal catalyst of preparation, noble metal is evenly distributed on carrier surface, reduce the consumption of noble metal, effectively reduce catalyst cost, there is good prospects for commercial application.This eggshell type noble metal catalyst can be used for adding hydrogen into resin reaction, and this catalyst has excellent catalytic performance and good catalyst life, and has good economic benefit and prospects for commercial application.
Technical scheme of the present invention is as follows:
A kind of preparation method for adding hydrogen into resin egg-shell catalyst, noble metal precursor and inducing agent are dissolved in polyalcohol respectively, the concentration of precious metal salt is 0.001-2mol/L, to the polyhydric alcohol solutions of noble metal precursor aging a period of time, the concentration of inducing agent is 0.002-20mol/L, the mol ratio of inducing agent and noble metal precursor is 0.1-10, ball-type or column like catalyst carrier are added in noble metal precursor solution, by controlling dip time, reduction reaction speed and solution viscosity, prepare egg-shell catalyst.Dip time is 5-1000s, and solution viscosity is 5-100mPa.s; Add inducing agent solution again, atmospheric pressure at room is reacted, and by controlling reduction reaction rate and solution viscosity, controlling noble metal and depositing at carrier surface, after filtration, wash, namely inert atmosphere drying forms stable eggshell type noble metal catalyst.
In the present invention noble metal precursor be one or more in chloroplatinic acid, potassium chloroplatinate, platinum acetate, palladium nitrate, palladium bichloride, palladium, the acid of chlorine palladium; Inducing agent is one or more in sodium acetate, potassium acetate, ammonium acetate, sodium formate, potassium formate, ammonium formate, sodium propionate, potassium propionate, propionic acid ammonium, odium stearate, Sodium Polyacrylate; Solvent is one or more in ethylene glycol, glycerine, diethylene glycol (DEG), tetraethylene glycol, 1,2-PD, 1,3-PD; Carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3, Al
2o
3-TiO
2or porous carbon material.Described a kind of preparation method for adding hydrogen into resin egg-shell catalyst, is further characterized in that: can prepare polynary noble metal egg-shell catalyst.
The noble metal egg-shell catalyst of preparation is used for hydrogenation of petroleum resin reaction.With solvent, Petropols are dissolved, the ratio 20% shared by Petropols, then mix with hydrogen and carry out hydrogenation adsorption desulfurize and remove sulphur in resin, feeding temperature 240-280 DEG C, hydrogen partial pressure 0.5-2MPa, volume space velocity 4-8h
-1, hydrogen to oil volume ratio 200:1; Hydrogenation adsorption desulfurize catalyst is Ni/ZnO catalyst; After hydrogenation adsorption desulfurize, resin solution carries out hydrogenation decolouring, feeding temperature 220-260 DEG C, hydrogen partial pressure 6-18MPa, volume space velocity 0.6-0.96h
-1, hydrogen to oil volume ratio 200-600:1; The hydrogenation catalyst used that decolours is noble metal egg-shell catalyst, and the loading of noble metal is 0.8-2.0%; Resin form and aspect after hydrogenation decolouring are improved to water white, and softening point slightly reduces.
Carry out under room temperature of the present invention, to carrier not requirement, and do not need to introduce heating source, technique is simple, the metal particle diameter of preparation is little, be evenly distributed, good stability, in the eggshell type noble metal catalyst of preparation, noble metal is evenly distributed on carrier surface, reduce the consumption of noble metal, effective reduction catalyst cost, is beneficial to amplify and produces, have good prospects for commercial application.
Detailed description of the invention
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme.
Embodiment 1: chloroplatinic acid and sodium acetate are dissolved in ethylene glycol respectively, the concentration of chloroplatinic acid is 0.01mol/L, the aging 30d of polyhydric alcohol solutions of chloroplatinic acid, and the concentration of sodium acetate is 0.05mol/L, the molar ratio of sodium acetate and chloroplatinic acid is 5, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, and solution viscosity is 15mPa.s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading is 1.0%.Generating Pt thickness of the shell is 5 μm, and the particle diameter of Pt is 3.6nm.The egg-shell catalyst of preparation is used for hydrogenation of petroleum resin decoloring reaction, and reaction condition is: reaction temperature 260 DEG C, reaction pressure 18MPa, hydrogen-oil ratio 400, and air speed is 0.6h
-1, gained hydrogenated resin character is, color water-white, look number No. 0, softening point 105 DEG C, heat endurance <2.Softening point slightly reduces and has good thermostability compared with material resin.
Embodiment 2: chloroplatinic acid and sodium acetate are dissolved in respectively in glycerine, diethylene glycol (DEG) or tetraethylene glycol, compares different solvents to the impact preparing egg-shell catalyst.The concentration of chloroplatinic acid is 0.01mol/L, the aging 30d of polyhydric alcohol solutions of chloroplatinic acid, and the concentration of sodium acetate is 0.05mol/L, and the molar ratio of sodium acetate and chloroplatinic acid is 5, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading is 1.0%.Generating Pt thickness of the shell is 5 μm, and the particle diameter of Pt is respectively 3.2nm, 3.0nm and 2.9nm.According to result: the larger prepared metallic particle diameter of viscosity is less, shows catalytic activity better at adding hydrogen into resin.
Embodiment 3: chloroplatinic acid and sodium acetate are dissolved in respectively in ethylene glycol, compares the molar ratio of sodium acetate and chloroplatinic acid to the impact preparing egg-shell catalyst.The concentration of chloroplatinic acid is 0.01mol/L, the aging 30d of polyhydric alcohol solutions of chloroplatinic acid, and the concentration of sodium acetate is respectively 0.05,0.1,0.35 and 0.7mol/L, and the molar ratio of sodium acetate and chloroplatinic acid is respectively 5,10,35,70, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading is 1.0%.Generate Pt thickness of the shell and be 5 μm, the particle diameter of Pt is respectively 3.6nm, 3.5nm, 2.2nm and 2.0nm.According to adding hydrogen into resin result: the larger prepared metallic particle diameter of mol ratio of sodium acetate and chloroplatinic acid is less, and active better at adding hydrogen into resin, main because reaction is accelerated, metal nucleation is faster.
Embodiment 4: chloroplatinic acid and sodium acetate are dissolved in respectively in ethylene glycol, compares the polyhydric alcohol solutions ageing time of chloroplatinic acid to the impact preparing egg-shell catalyst.The concentration of chloroplatinic acid is 0.01mol/L, and the polyhydric alcohol solutions ageing time of chloroplatinic acid is respectively 15,30,45 and 60d, and the concentration of sodium acetate is 0.10mol/L, and the molar ratio of sodium acetate and chloroplatinic acid is respectively 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading is 1.0%.Generate Pt thickness of the shell and be 5 μm, the particle diameter of Pt is respectively 3.8nm, 3.6nm, 3.2nm and 3.1nm.According to adding hydrogen into resin result: the larger prepared metallic particle diameter of polyhydric alcohol solutions ageing time of chloroplatinic acid is less, and active better at adding hydrogen into resin, main because reaction is accelerated, metal nucleation is faster.
Embodiment 5: compare dip time to the impact preparing egg-shell catalyst.Chloroplatinic acid and sodium acetate are dissolved in ethylene glycol respectively, the concentration of chloroplatinic acid is 0.01mol/L, the polyhydric alcohol solutions ageing time 30d of chloroplatinic acid, and the concentration of sodium acetate is 0.10mol/L, the molar ratio of sodium acetate and chloroplatinic acid is respectively 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time be respectively 60,120,300,600s, add inducing agent solution, atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pt catalyst, Pt loading is respectively 1.0%, 1.2%, 1.4% and 1.4%.It is 5,6,7 and 7 μm that generation Pt thickness of the shell is respectively, and the particle diameter of Pt is 3.6nm.According to characterization result: the longer prepared metal shell layer thickness of dip time is thicker, and metal particle diameter is substantially constant, in adding hydrogen into resin reaction, metal hydrogenation activity is basically identical, illustrates that metal shell layer thickness is little to hydrogenation reaction activity influence.Therefore, for egg-shell catalyst, egg-shell catalyst metal particle diameter should be controlled.
Embodiment 6: compare carboxylate carbon chain lengths to the impact preparing egg-shell catalyst.Chloroplatinic acid and sodium formate or sodium acetate odium stearate are dissolved in ethylene glycol respectively, the concentration of chloroplatinic acid is 0.01mol/L, the polyhydric alcohol solutions ageing time 30d of chloroplatinic acid, the concentration of sodium acetate is 0.10mol/L, the molar ratio of carboxylate and chloroplatinic acid is respectively 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time and be respectively 60s, add inducing agent solution, atmospheric pressure at room reaction 2h, after filtration, washing, namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading divides and is 1.0%.Generate Pt thickness of the shell and be 5 μm, the particle diameter of Pt is respectively 2.5,3.6,4.2nm.According to characterization result: the longer prepared metal particle diameter of carboxylate carbochain is less, in adding hydrogen into resin reaction, active better at adding hydrogen into resin.
Embodiment 7: different metal platinum precursor and sodium acetate are dissolved in ethylene glycol, the concentration of metal precursor is 0.01mol/L, metal precursor is respectively platinum acetate and potassium chloroplatinate, the polyhydric alcohol solutions ageing time 30d of platinum precursor, the concentration of sodium acetate is 0.10mol/L, the molar ratio of carboxylate and metal platinum precursor is 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time and be respectively 60s, add inducing agent solution, atmospheric pressure at room reaction 2h, after filtration, washing, namely inert atmosphere drying forms stable eggshell type Pt catalyst, and Pt loading divides and is 1.0%.Generate Pt thickness of the shell and be 5 μm, the particle diameter of Pt is respectively 2.5 and 3.8nm.Platinum ion concentration affects reduction degree degree, and reduction rate faster metal platinum particle diameter is less.
Embodiment 8: the acid of chlorine palladium and sodium acetate are dissolved in ethylene glycol respectively, the concentration of chlorine palladium acid is 0.01mol/L, the aging 30d of polyhydric alcohol solutions of chlorine palladium acid, and the concentration of sodium acetate is 0.10mol/L, the molar ratio of sodium acetate and the acid of chlorine palladium is 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, and solution viscosity is 15mPa.s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pd catalyst, and Pd loading is 0.8%.Generating Pd thickness of the shell is 4 μm, and the particle diameter of Pd is 4nm.The egg-shell catalyst of preparation is used for hydrogenation of petroleum resin decoloring reaction, and reaction condition is: reaction temperature 240 DEG C, reaction pressure 18MPa, hydrogen-oil ratio 400, and air speed is 0.6h
-1, gained hydrogenated resin character is, color water-white, look number No. 0, softening point 105 DEG C, heat endurance <1.Softening point slightly reduces and has good thermostability compared with material resin.
Embodiment 9: on the basis of embodiment 2-7, condition and the result of all applicable Pt metals are also applicable to metal Pd.
Embodiment 10: the acid of chlorine palladium and chloroplatinic acid are dissolved in ethylene glycol in proportion, sodium acetate is also dissolved in ethylene glycol, the concentration of chlorine palladium acid is 0.008mol/L, the concentration of chloroplatinic acid is 0.002mol/L, the aging 30d of polyhydric alcohol solutions of the acid of chlorine palladium and chloroplatinic acid, the concentration of sodium acetate is 0.10mol/L, and the molar ratio of sodium acetate and the acid of chlorine palladium and chloroplatinic acid summation is 10, by ball-type or column like catalyst carrier Al
2o
3add in platinum acid chloride solution, control dip time is 60s, and solution viscosity is 15mPa.s, adds inducing agent solution, and atmospheric pressure at room reaction 2h, after filtration, washs, and namely inert atmosphere drying forms stable eggshell type Pd
4pt catalyst, Pd loading is 0.6%.Generating Pd thickness of the shell is 6 μm, and the particle diameter of Pd is 4nm.The egg-shell catalyst of preparation is used for hydrogenation of petroleum resin decoloring reaction, and reaction condition is: reaction temperature 240 DEG C, reaction pressure 18MPa, hydrogen-oil ratio 400, and air speed is 0.6h
-1, gained hydrogenated resin character is, color water-white, look number No. 0, softening point 105 DEG C, heat endurance <1.Softening point slightly reduces and has good thermostability compared with material resin.
Embodiment 11: with PtPd loaded catalyst for hydrogenation decolours catalyst, Al
2o
3for carrier.On the basis of embodiment 10, reaction condition is: feeding temperature 240 DEG C, hydrogen partial pressure 18MPa, volume space velocity 0.6h
-1, hydrogen to oil volume ratio 400:1, resin concentration is 20%.Following table 1 is shown in the rear hydrogenated resin character of 500h hydrogenation decolouring.
The experimental result of this process operation 500h as shown in Table 1, take Ni/ZnO as reactive adsorption desulphurization catalyst, PtPd loaded catalyst is hydrogenation decolouring catalyst, two sections of fixed bed hydrogenation modes are adopted to carry out hydrogenation reaction to resin, obtained hydrogenated resin, resin form and aspect are improved to water-white, and softening point slightly reduces and has good thermostability.The above results shows that technology of the present invention has good stability, catalyst long service life.
Claims (3)
1., for a preparation method for adding hydrogen into resin egg-shell catalyst, it is characterized in that:
Noble metal precursor and inducing agent are dissolved in polyalcohol respectively, the concentration of precious metal salt is 0.001-2mol/L, to the polyhydric alcohol solutions of noble metal precursor aging a period of time, the concentration of inducing agent is 0.002-20mol/L, the mol ratio of inducing agent and noble metal precursor is 0.1-10, ball-type or column like catalyst carrier being added in noble metal precursor solution, by controlling dip time, reduction reaction speed and solution viscosity, preparing egg-shell catalyst; Dip time is 5-1000s, and solution viscosity is 5-100mPa
.s; Add inducing agent again, atmospheric pressure at room is reacted, and by controlling reduction reaction rate and solution viscosity, controlling noble metal and depositing at carrier surface, after filtration, wash, namely inert atmosphere drying forms stable eggshell type noble metal catalyst catalyst;
Described noble metal precursor is one or more mixing in chloroplatinic acid, potassium chloroplatinate, platinum acetate, palladium nitrate, palladium bichloride, palladium, the acid of chlorine palladium;
Described inducing agent is one or more mixing in sodium acetate, potassium acetate, ammonium acetate, sodium formate, potassium formate, ammonium formate, sodium propionate, potassium propionate, propionic acid ammonium, odium stearate, Sodium Polyacrylate;
Described polyalcohol is one or more mixing in ethylene glycol, glycerine, diethylene glycol (DEG), tetraethylene glycol, 1,2-PD, 1,3-PD.
2. preparation method according to claim 1, is characterized in that: described carrier is SiO
2, Al
2o
3, TiO
2, SiO
2-Al
2o
3, Al
2o
3-TiO
2or porous carbon material.
3. preparation method according to claim 1 and 2, is characterized in that: prepare polynary noble metal egg-shell catalyst.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105367714A (en) * | 2015-12-03 | 2016-03-02 | 大连理工大学 | Method for preparing hydrogenated DCPD resin |
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| CN105903468B (en) * | 2016-04-22 | 2018-10-16 | 大连理工大学 | A kind of preparation method and applications for the eggshell type noble metal catalyst for adding hydrogen to clean for glymes lube base oil |
| CN105879862B (en) * | 2016-04-22 | 2019-03-29 | 大连理工大学 | A kind of preparation method of eggshell type noble metal catalyst and its method for adding hydrogen open loop to prepare o-phenyl phenol for dibenzofuran |
| CN110078847A (en) * | 2019-04-28 | 2019-08-02 | 恒河材料科技股份有限公司 | A kind of preparation method of high softening-point hydrogenated petroleum resin |
| CN110078847B (en) * | 2019-04-28 | 2021-08-20 | 恒河材料科技股份有限公司 | Preparation method of high-softening-point hydrogenated petroleum resin |
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| CN104959136B (en) | 2017-08-01 |
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