CN121222495A - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereofInfo
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Abstract
本发明属于石油加工技术领域，具体涉及一种催化剂及其制备方法和应用。所述催化剂的原料包括金属活性组分、载体和助剂，所述金属活性组分为Mo和Ni元素的硫化物，所述载体为0.5～1mm的球型γ‑Al2O3，所述助剂为P；利用金属活性组分和助剂将载体改性作为催化剂。本发明通过采用改变焙烧温度、添加助剂掺杂改性、改变金属活性组分摩尔比、的策略合成了高活性的催化剂，助剂与表面铝原子结合，增强骨架强度，减少酸/水侵蚀导致的孔道塌陷，提高催化剂的耐水耐酸性，进一步提升催化反应活性。本发明的催化剂结构精确可控且可批量合成，能够应用于生物质热解油和/或其模型化合物与石油馏分油和/或VR共催化加氢过程中。
This invention belongs to the field of petroleum processing technology, specifically relating to a catalyst, its preparation method, and its application. The catalyst's raw materials include a metallic active component, a support, and an additive. The metallic active component is a sulfide of Mo and Ni elements, the support is 0.5–1 mm spherical γ- Al₂O₃ , and the additive is P. The support is modified using the metallic active component and the additive to serve as the catalyst. This invention synthesizes a highly active catalyst by employing strategies such as changing the calcination temperature, adding additives for doping modification, and changing the molar ratio of the metallic active component. The additive binds to surface aluminum atoms, enhancing the framework strength, reducing pore collapse caused by acid/water erosion, improving the catalyst's water and acid resistance, and further enhancing its catalytic activity. The catalyst structure of this invention is precisely controllable and can be synthesized in batches, enabling its application in the co-catalytic hydrogenation of biomass pyrolysis oil and/or its model compounds with petroleum distillate oil and/or VR.
Description
Technical Field
The invention belongs to the technical field of petroleum processing, and particularly relates to a catalyst and a preparation method and application thereof.
Background
The marine residue fuel oil is mainly prepared from inferior residue as a raw material, but the problem of carbon and sulfur emission is always closely concerned by various global economy, and how to realize green transformation becomes an important issue for the effort of the shipping industry.
Biomass is used as an important renewable carbon source, the resource amount is large, renewable biomass resources are used for preparing marine residue fuel oil, substitution of fossil fuel is completed, and dependence on fossil resources is eliminated, so that the biomass is a great demand for national development. Biomass is an important method for preparing bio-oil fuel through pyrolysis, but the bio-oil obtained through pyrolysis has high oxygen content, low heat value, poor chemical and thermal stability and other problems, so that the bio-oil fuel is directly prepared into marine residue fuel oil with great difficulty.
In recent years, a heavy oil and biomass pyrolysis oil co-hydrogenation process is a technology with application prospect. The method for preparing qualified marine residue fuel oil by co-hydrogenation with petrochemical raw materials is an effective way for realizing green transformation in the current shipping industry. However, the problems of serious degradation of catalyst performance, mutual inhibition in the deoxidation and desulfurization process in the reaction process and the like still exist in the current research due to the problems of high oxygen content, large acid value and the like of pyrolysis oil. Kilanowski and the like research a sulfided Co-Mo/gamma-Al 2O3 bimetallic catalyst, but in the catalytic conversion process, the catalytic activity is low, the production period is long, and only hydrodesulfurization is carried out. Chinese patent CN108940296a discloses an application of Co-Mo-Ni/TiO 2-Al2O3 catalyst in removing Co, chinese patent CN109894125A discloses a supported sulfided Co-Mo/γ -Al 2O3 bimetallic catalyst, and conventional cobalt salt and molybdenum salt are used, so that substances which are difficult to be completely sulfided are easily formed in the impregnation and calcination processes, resulting in a not very high hydrodesulfurization activity, and difficulty in simultaneous deoxidation, desulfurization and denitrification.
In the prior art, few catalysts with activities such as deoxidation and desulfurization are adopted, and the key technical bottleneck of improving the reaction efficiency has not been substantially broken through so far. Therefore, how to prepare a catalyst with good water resistance and acid resistance and high deoxidation and desulfurization efficiency is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a catalyst and a preparation method and application thereof, the adopted raw materials comprise a metal active component, gamma-Al 2O3 and an auxiliary agent, the high-activity catalyst is synthesized by adopting strategies of changing the roasting temperature, adding the auxiliary agent for doping modification and changing the mole ratio of the metal active component, the auxiliary agent is combined with surface aluminum atoms, the skeleton strength is enhanced, the pore channel collapse caused by acid/water erosion is reduced, the water resistance and the acid resistance of the catalyst are improved, the deoxidization rate can be changed, and the catalytic reaction activity is further improved.
The technical scheme adopted is as follows:
The catalyst comprises a metal active component, a carrier and an auxiliary agent, wherein the metal active component is sulfide of Mo and Ni elements, the carrier is spherical gamma-Al 2O3 with the concentration of 0.5-1 mm, the auxiliary agent is P, the carrier is modified by the metal active component and the auxiliary agent to be used as the catalyst, the metal simple substance accounts for 5-25 wt% of the prepared modified catalyst, the P accounts for 0.1-3 wt% of the prepared modified catalyst, and the balance is the carrier.
A method for preparing a catalyst comprising the steps of:
(1) Roasting gamma-Al 2O3;
(2) Adding (NH 4)2HPO4 into deionized water, stirring to obtain a uniform solution, and obtaining an auxiliary agent precursor solution (NH 4)2HPO4 solution;
(3) Uniformly dripping the (NH 4)2HPO4 solution on gamma-Al 2O3, standing, aging, drying and roasting to obtain a phosphorus modified carrier;
(4) Uniformly dripping soluble molybdenum salt and soluble nickel salt solution on a phosphorus modified carrier, and obtaining a modified catalyst after standing, dipping, aging, drying and roasting;
(5) And adding the modified catalyst into a fixed bed reactor, vulcanizing, and obtaining the vulcanized catalyst after vulcanization.
Preferably, in the step (1), the roasting temperature is 500-800 ℃ and the roasting time is 2-8 hours.
Preferably, in the step (2), the auxiliary agent precursor solution is prepared at normal temperature for 20-30 minutes, and the prepared (NH 4)2HPO4 solution concentration is 0.3-0.9 mol/L.) phosphorus source can be phosphoric acid, and the phosphoric acid can be used for replacing (NH 4)2HPO4).
Preferably, in the step (3), the dropping speed of the (NH 4) 2HPO4 solution is 0.1-1 ml/min, the standing aging time is 5-12 hours, the drying time at 90-120 ℃ is 2-12 hours, the roasting temperature is 500-800 ℃ and the roasting time is 2-8 hours.
Preferably, in the step (4), the soluble molybdenum salt is any one of ammonium paramolybdate, sodium molybdate and ammonium molybdate, the soluble nickel salt is any one of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate, the concentration of the soluble molybdenum salt is 0.2-0.8 mol/L, and the concentration of the soluble nickel salt is 0.2-0.8 mol/L.
Preferably, the molar ratio of Ni to Mo is 0.1-1:1.
Preferably, in the step (4), the baking temperature is 400-700 ℃ and the baking time is 4-12 hours.
Preferably, in the step (5), the vulcanizing agent is a mixed solution of carbon disulfide and n-hexane, wherein the carbon disulfide accounts for 2% of the mass fraction of the mixed solution, the vulcanizing temperature is 270-360 ℃, the vulcanizing time is 8-12 hours, the gas-agent ratio is 200-300, and the operating pressure is 2-4 MPa.
The catalyst provided by the invention is applied to improving water resistance and acid resistance and deoxidizing desulfurization in the process of co-refining biomass pyrolysis oil and vacuum residuum, and the reaction temperature of the catalyst is 330-440 ℃;
the catalyst is used for operating at a pressure of 6-10 MPa;
the reaction raw material is biomass pyrolysis oil and vacuum residue.
Compared with the prior art, the invention has the beneficial effects that:
The method synthesizes the catalyst with high activity by adopting a strategy of changing the roasting temperature and adding the doping modification of the auxiliary agent, removes water molecules on the surface of the catalyst carrier by changing the roasting temperature, simultaneously maintains the strength of the carrier, enhances the strength of a framework by combining the auxiliary agent with aluminum atoms on the surface, reduces pore canal collapse caused by acid/water erosion, improves the water resistance and the acid resistance of the catalyst, and further improves the catalytic reaction activity.
The catalyst has the advantages of accurate and controllable structure, batch synthesis, simple and controllable loading and size of the active components of the catalyst, and excellent catalytic performance, and can be applied to the co-catalytic hydrogenation process of biomass pyrolysis oil and/or model compounds thereof and petroleum distillate oil and/or VR, so that on one hand, the catalyst is not easy to collapse in pore channels under the erosion of biomass pyrolysis oleic acid/water, and further, the stability of the catalyst is maintained, and on the other hand, the active metal promotes the adsorption and activation of C-O and C-S, and further, the catalytic reaction activity is improved.
Drawings
FIG. 1 is a flow chart of the preparation method of the invention.
FIG. 2 is an XRD pattern of the catalysts synthesized in examples 1-4 and comparative example 4 of the present invention.
FIG. 3 shows N 2 adsorption-desorption isotherms for the catalysts synthesized in examples 1-4 and comparative example 4 of the present invention.
FIG. 4 is an XPS plot of the catalysts synthesized in examples 1-4 and comparative example 4 of the present invention.
Detailed Description
The drawings are only for purposes of illustrating the invention and are to be construed as limiting the scope of the invention. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. All percentages, ratios, proportions, or parts are by weight unless otherwise indicated.
The catalysts of the present invention and their water and acid resistance effects are further described below in conjunction with the specific examples. The raw materials, chemical reagents, etc. used in the present invention are all available through a normal commercial route, and the standard of the chemical reagents is a laboratory standard, unless otherwise specified.
Reference example 1, a method for preparing a catalyst.
6G of gamma-Al 2O3 was taken and calcined at 800℃for 6 hours, designated CAR-1. The water resistance and acid resistance experiments are respectively carried out, wherein the water resistance experiments comprise the steps of loading 1g of carrier into a crystal bloom kettle according to the proportion of 50ml of deionized water, then sealing the crystal bloom kettle, reacting for 24 hours at 180 ℃, and finally measuring the specific surface area, pore volume and pore diameter of the carrier before and after the reaction. The acid resistance test comprises the steps of putting 1g of carrier into a beaker according to the proportion of 50ml of nitric acid solution, starting stirring, wherein ph=0 of the nitric acid solution, and reacting for 24 hours. After the water resistance test, the test piece was named as CAR-1H. The acid resistance test was followed by the designation CAR-1S.
Reference example 2, a method for preparing a catalyst.
0.26G (NH 4)2HPO4 is dissolved in 6ml deionized water, the solution is evenly dripped on 6gCAR-1 according to the dripping speed of 0.5ml/min, the mixture is stood and aged for 8 hours, dried for 6 hours at 110 ℃ and roasted for 6 hours at 500 ℃ to obtain the phosphorus modified carrier, which is named as CAR-4. The phosphorus modified carrier is named as CAR-4H after the water resistance experiment, and the phosphorus modified carrier is named as CAR-4S.P after the acid resistance experiment, and the load is about 1wt%.
Reference example 3 was conducted in the same manner as in reference example 2 except that (mass of NH 4)2HPO4 was 0.52g, which was designated as CAR-5. After the water resistance test, which was designated as CAR-5H. After the acid resistance test, the amount of CAR-5S.P supported was about 2% by weight.
Reference example 4 was conducted in the same manner as in reference example 3 except that (mass of NH 4)2HPO4 was 0.78g, which was designated as CAR-6. After the water resistance test, which was designated as CAR-6H. After the acid resistance test, the amount of the supported portion, which was designated as CAR-6S.P, was about 3% by weight.
Example 1, a process for preparing a catalyst.
0.26GNi (NO 3)2·6H2 O and 1.56g (NH 4)6Mo7O24·4H2 O dissolved in 5ml deionized water), the solution was uniformly dropped on 6gCAR-4, left to stand for 8 hours, dried at 110 ℃ for 6 hours, baked at 550 ℃ for 6 hours, then added to a fixed bed for vulcanization, vulcanized at 330 ℃ for 8 hours, gas-to-catalyst ratio 300, operating pressure 3MPa, and after vulcanization is finished, named CAT-1.
Calculated by metal simple substance, the total metal load is 15%, the mole ratio of Ni to Mo is 0.1 (namely 0.1:1), the vulcanizing agent is a mixed solution of carbon disulfide and n-hexane, wherein the carbon disulfide accounts for 2% of the mass fraction of the mixed solution.
Other places not mentioned are the same as in reference example 2.
Example 2, the procedure of example 1 was followed except that 0.69gNi (NO 3)2·6H2 O and 1.39g (NH 4)6Mo7O24·4H2 O, designated CAT-2.Ni: mo molar ratio 0.3 (i.e., 0.3: 1)) were weighed out.
Other points not described are the same as in example 1.
Example 3 the procedure of example 1 was followed except that 1.04gNi (NO 3)2·6H2 O and 1.27g (NH 4)6Mo7O24·4H2 O, denominated CAT-3.Ni: mo molar ratio 0.5 (i.e. 0.5: 1) were weighed out.
Other points not described are the same as in example 1.
Example 4 the procedure of example 1 was followed except that 1.34gNi (NO 3)2·6H2 O and 1.16g (NH 4)6Mo7O24·4H2 O, denominated CAT-4.Ni: mo molar ratio of 0.7 (i.e. 0.7: 1) were weighed out.
Other points not described are the same as in example 1.
Comparative example 1 was conducted in the same manner as in reference example 1 except that the 500 ℃ calcination was conducted for 6 hours. Designated CAR-2. After the water resistance test, the test piece was named as CAR-2H. The acid resistance test was followed by the designation CAR-2S.
Comparative example 2 was conducted in the same manner as in reference example 1 except that it was baked at 650℃for 6 hours. Designated CAR-3. After the water resistance test, the test piece was named as CAR-3H. The acid resistance test was followed by the designation CAR-3S.
Comparative example 3 the method of reference example 3 was followed except that 0.45g (C 2H5O)4 Si instead of 0.26g (NH 4)2HPO4, designated CAR-7. After the water resistance test, designated CAR-7H. After the acid resistance test, the load of CAR-7S. Si was about 1% by weight) was weighed.
Comparative example 4 the procedure of example 1 was followed except that 1.66g (NH 4)6Mo7O24·4H2 O instead of 0.26gNi (NO 3)2·6H2 O and 1.56g (NH 4)6Mo7O24·4H2 O, designated CAT-5.Ni: mo molar ratio 0) were weighed out.
Comparative example 5 the procedure of example 1 was followed except that 0.69gNi (NO 3)2·6H2 O and 1.39g (NH 4)6Mo7O24·4H2 O, CAR-1 instead of CAR-4, designated CAT-6) was weighed.
Test example 1.
The water resistance test was carried out using the carriers prepared in referential example 1 and comparative examples 1-2, respectively, comprising the steps of charging 1g of the carrier into a sublimation kettle in a proportion of 50ml of deionized water, then sealing the sublimation kettle, reacting for 24 hours at 180 ℃, and finally measuring the specific surface area, pore volume and pore diameter of the carrier before and after the reaction.
Table 1 water resistance effect of carriers at different firing temperatures:
Experimental results show that with the increase of the roasting temperature, the water resistance of the carrier is gradually enhanced, and the CAR-1 has the optimal water resistance. The specific surface and pore volume loss rate are the lowest. But further increases in firing temperature can result in phase changes in the support.
Test example 2.
The acid resistance test was carried out using the carriers prepared in referential example 1 and comparative examples 1-2, respectively, and included the steps of putting a 50ml nitric acid solution of 1g of the carrier into a beaker and stirring the mixture for 24 hours.
Table 2 acid resistance effect of carriers at different firing temperatures:
Experimental results show that with the increase of the roasting temperature, the acid resistance of the carrier is gradually increased, the specific surface, pore volume and mass loss rate are reduced, and the aluminum dissolution rate is also reduced. CAR-1 has the best acid resistance properties, so that subsequent studies based on CAR-1 were performed.
Test example 3.
The water resistance test was carried out using the carriers prepared in reference examples 2 to 4 and comparative example 3, respectively, and the same procedure as in experimental example 1 was adopted.
Table 3 comparison of water resistance of the carriers prepared in reference examples 2-4 and comparative example 3:
Comparing the different P loadings and 1% Si loadings, it can be seen that adding Si to dope the modification is less water resistant than P. The water resistance of the carrier can be greatly improved by adding 1% of P for modification, and the carrier is favorable for stability because the P-OH is dehydroxylated on the surface to form P=O bond and then becomes P-OH again due to the existence of water.
Test example 4.
The acid resistance test was carried out using the carriers prepared in reference example 2 and comparative example 3, respectively, and the same procedure as in test example 2 was adopted.
Table 4 acid resistance comparison of the carriers prepared in reference example 2 and comparative example 3:
Comparing the 1% P loading with the 1% Si loading, it can be seen that doping modification with Si is less acid resistant than P. The acid resistance of the carrier can be greatly improved by adding 1% of P for modification, and the phosphate radical can form a compact passivation layer on the surface of the carrier to prevent H + from directly contacting with an aluminum oxide framework, so that acid corrosion is reduced.
Test example 5.
The catalysts prepared in examples 1-4 and comparative examples 4-5 were used in the catalytic hydrogenation process of biomass pyrolysis oil, respectively, and the method comprises the steps of loading the catalyst and biomass pyrolysis oil into a reaction kettle according to a ratio of 4g of the catalyst to 40g of biomass pyrolysis oil by using a high-pressure reaction kettle, sealing the reaction kettle, introducing 8MPa H 2, heating to 360 ℃ and starting timing, wherein the reaction time is 2 hours. After the reaction was completed, the reaction vessel was cooled to room temperature, and the liquid-phase product was collected and its deoxidization rate and physical properties were measured, and the results are shown in Table 5.
Table 5 comparison of catalytic effect of catalysts prepared in examples 1-4 and comparative examples 4-5:
the catalysts prepared in examples 1 to 4 and comparative example 4 were subjected to X-ray diffraction analysis, X-ray photoelectron spectroscopy and N 2 adsorption and desorption experiments to test the structure of the catalyst and the metal Mo valence peak area, and the results are shown in table 6, which are the XRD patterns, N 2 adsorption and desorption isotherms and XPS patterns in fig. 2, 3 and 4.
Table 6 comparison of physical adsorption of catalyst N 2 and valence results of metallic Mo prepared in examples 1-4 and comparative example 4:
The XRD curves of the catalysts with different molar ratios of Ni to Mo can observe obvious characteristic peaks of gamma-Al 2O3, and no obvious metal characteristic peaks are observed, so that the metal dispersion is uniform. Meanwhile, as the mole ratio of Ni to Mo is increased, the specific surface area and the pore volume are increased and reduced, the mole ratio is maximized when the mole ratio is 0.3, and the mole ratio is further increased, and excessive nickel species are deposited to cover active sites to block pore channels, so that the specific surface area and the pore volume are reduced.
Mo having hydrogenation activity has a valence of 4, and Mo 5+ and Mo 6+ are present due to partial ammonium molybdate being not completely sulfided. At a Ni to Mo molar ratio of 0.3, the catalyst had the most Mo 4+. CAT-2 thus exposes more active sites, resulting in a more excellent catalytic effect.
Test example 6.
The catalyst prepared in the experiment is applied to a biomass pyrolysis oil and vacuum residue co-catalytic hydrogenation process, and the influence of the reaction temperature of the reaction on the catalytic performance is explored, wherein a high-pressure reaction kettle is utilized, the catalyst and the mixed oil are filled into the reaction kettle according to the proportion of 4g of the catalyst, namely 4g of biomass pyrolysis oil and 36g of vacuum residue, then the reaction kettle is sealed, 8MPa H 2 is introduced, and the reaction temperatures are respectively 360 ℃, 380 ℃, 400 ℃, 420 ℃ and 440 ℃ and the reaction time is 2 hours. After the reaction was completed, the reaction vessel was cooled to room temperature, and the liquid-phase product was collected, and the deoxidization rate and desulfurization rate were measured, and the results are shown in Table 7.
Table 7 effect of reaction temperature on the co-hydrogenation reaction performance of biomass pyrolysis oil and vacuum residuum:
As the reaction temperature increases, the deoxidation rate and the desulfurization rate are gradually increased, and both the deoxidation rate and the desulfurization rate are maintained at a higher level. The catalyst has great potential in the co-catalytic hydrogenation process of biomass pyrolysis oil and/or model compounds thereof, petroleum distillate oil and/or VR.
In the specification, unless the context requires otherwise, the terms "comprise", "comprising" and "include" are to be construed as open-ended, meaning "including, but not limited to.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (10)
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