CN105642324A - Non-noble metal selective hydrogenation catalyst, preparation method and application thereof - Google Patents
Non-noble metal selective hydrogenation catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a non-noble metal selective hydrogenation catalyst, which is composed of an active component amorphous nickel phosphide, an alumina carrier and an assistant X. In a final catalyst, in terms of metal nickel, the weight content of nickel in the active component amorphous nickel phosphide accounts for 10-15% of the total catalyst weight, the mole ratio of phosphorus to nickel is 2.0-2.4, the mole ratio of X to nickel is 0.01-0.05:1, and the balance is the carrier, the assistant X is one or more of lanthanum, cerium, praseodymium, samarium, ytterbium and other rare earth elements, preferably cerium. The non-noble metal catalyst has catalytic activity equivalent to that of noble metal catalysts when used in a reaction process for selective hydrogenation of a C4 raw material to remove butadiene, can greatly reduce the catalyst cost, and at the same time has low 1-butene isomerization activity.
Description
Technical field
The present invention relates to a kind of base metal selective hydrocatalyst and its preparation method and application, relate in particular to non-precious metal catalyst of a kind of carbon four material choice hydrogenation and removing butadiene and its preparation method and application.
Background technology
Along with the continuous expansion of China's refining capacity and ethylene production capacity, commercially available by-product carbon four resource is consequently increased, and which also promotes the fast development of carbon four intensive processing industry in recent years. Fluid catalytic cracking (FCC) and cracking of ethylene by-product carbon four more or less can contain a certain amount of butadiene, if directly with the carbon four containing butadiene for raw material, for producing high value added product, catalyst performance and product quality will be affected, such as products such as aromatisation gasoline, gasoline alkylate, methyl tertiary butyl ether(MTBE) (MTBE) and high-purity 1-butylene. Often it is required for carbon four raw material is carried out selective hydrogenation process, to control the butadiene in carbon four raw material in reduced levels (ppm level).
Generally adopt noble metal catalyst, such as the Pd catalyst of support type, and adopt the butadiene in liquid phase fixed bed hydrogenation technique elimination carbon four raw material. Except being hydrogenated except butadiene in carbon four, butylene is likely to and is hydrogenated into corresponding alkane, can cause the loss of butylene. Owing to precious metals pd has selective hydrogenation performance, but the hydrogenation activity of Pd metal own is also relatively strong, individually using Pd as catalyst, a part of butylene can be made also to be hydrogenated. Therefore, generally require and Pd catalyst be improved appropriately, reduced its hydrogenation activity to butylene, improve main from catalyst structure, support modification and introducing the second auxiliary agent etc. three aspect launch.
USP3531545, by adding sulfide in raw material, has been passivated the hydrogenation activity of part Pd, but has caused that catalyst can only be used above at 160 DEG C. It is carrier that CN1238239 have employed ��, ��, �� mixed phase aluminium oxide, is prepared for Supported Pd-Catalyst, to improve catalyst activity and selectivity. It is carrier that USP3485887 have employed the aluminium oxide containing spinelle lithium aluminate, is prepared for Supported Pd-Catalyst, but butadiene hydrogenation activity is relatively low, and butylene loss rate is bigger. In recent years, getting more and more about the patent adopting second and third auxiliary agent of introducing to improve catalyst performance, such as CN101850250, CN103418379, CN1676214, CN1238239 etc., the auxiliary agent of introducing includes Pb, WO3, K, Na, Li, Mg, Sr, Au etc.
The technical scheme of existing employing loaded noble metal catalyst, because noble metal is expensive, causes that its catalyst is relatively costly. And, existing loaded noble metal catalyst more or less also has certain 1-butylene isomerization activity, limits its application in 1-butylene precise distillation device pretreatment of raw material process.
Summary of the invention
The present invention provides a kind of base metal selective hydrocatalyst and preparation method thereof. This non-precious metal catalyst is for, in carbon four material choice hydrogenation and removing butadiene course of reaction, having the catalysis activity that same noble metal catalyst is suitable, can be substantially reduced catalyst cost, have relatively low 1-butylene isomerization activity simultaneously.
A kind of base metal selective hydrocatalyst, it is made up of the amorphous nickel phosphide of active component, alumina support and auxiliary agent X, in the final catalyst, in the amorphous nickel phosphide of active component, the weight content of nickel is in metallic nickel, accounts for the 10-15% of total catalyst weight, the mol ratio of phosphorus and nickel is 2.0-2.4:1, the mol ratio of auxiliary agent X and nickel is 0.01-0.05:1, and all the other are carrier, and all the other are carrier, described auxiliary agent X is at least one in rare earth element
In catalyst of the present invention, described auxiliary agent X is one or more in lanthanum, cerium, praseodymium, samarium, ytterbium, it is preferable that cerium.
In the catalyst of the present invention, without Ni in XRD spectra2P or Ni12P5Diffraction maximum.
The preparation method of base metal selective hydrocatalyst provided by the invention, step is as follows:
(1) the acid nickel salt aqueous solution of preparation, it is subsequently adding diammonium phosphate, salt containing auxiliary agent X and citric acid, making phosphorus/nickel mol ratio is 2.5-3.0, X/ nickel mol ratio is 0.01-0.05:1, and citric acid/nickel mol ratio is 1.0-2.0:1, obtains solution A, aluminium oxide or the aluminium hydroxide of metering is added in gained solution A, forming serosity B, then slow evaporating water, forms dry glue C;
(2) gained dry glue C in step (1) is placed under the atmosphere of inert gases of flowing continuously, at being warming up to 250-350 DEG C, and processes 5-10 hour at this temperature, make the citric acid generation pyrolysis in dry glue, obtain catalyst precursor D;
(3) the catalyst precursor D obtained in step (2) is shaped, after molding rear catalyst drying, obtains preformed catalyst presoma E;
(4) the preformed catalyst presoma E obtained in step (3) is reduced in atmosphere of hydrogen, reduction temperature is 300-400 DEG C, recovery time is 1-10h, after catalyst reduction, it is cooled to room temperature, at room temperature catalyst is passivated 0.5-1h with the passivating gas that oxygen concentration is 0.5-1.0%, obtains final catalyst.
Nickel salt described in the inventive method step (1) is selected from one or more in nickel nitrate, Nickel dichloride., nickelous bromide, nickel sulfate, nickel acetate, nickel oxalate, it is preferable that nickel nitrate. Described X salt is selected from containing one or more in the nitrate of rare earth element, hydrochlorate, sulfate, the acetates such as lanthanum, cerium, praseodymium, samarium, ytterbium, it is preferable that one or more in nitrate containing cerium, hydrochlorate, sulfate, acetate, more preferably cerous nitrate. The described acid for regulating pH value is dust technology, and nitric acid molar concentration is 0.01-0.05mol/L.
Nickel salt is at room temperature dissolved in water by the inventive method step (1), adds acid for adjusting pH value at 2-3, obtain acid nickel salt aqueous solution.
Noble gas described in the inventive method step (2) is nitrogen, helium or argon, it is preferable that nitrogen.
In the inventive method step (3), catalyst can adopt squeezing and pressing method, pressed disc method, drip ball or spin comminution granulation molding, wherein preferably squeezing and pressing method molding.
Reduction temperature described in the inventive method step (4) is 350-400 DEG C, and the recovery time is 5-10h. Described passivating gas is noble gas except for oxygen, a kind of in nitrogen, helium or argon, it is preferable that nitrogen.
The present invention also provides for this catalyst a kind of application in carbon four selective hydrogenation and removing butadiene reacts, and is 60��100 DEG C containing butadiene raw material in reaction temperature, and stagnation pressure is 1.5��2.0MPa, and air speed is 5��10h-1, hydrogen/butadiene mol ratio reacts when being 1.0��2.0. Described containing butadiene raw material from refinery FCC by-product carbon four or cracking of ethylene carbon-4. In above-mentioned application, charging procatalyst was preferably in pretreatment in the atmosphere of hydrogen of 100-200 DEG C 1��2 hour.
The effect of the present invention and haveing an advantage that, compares with traditional Pd system noble metal catalyst, adopts the catalyst that the inventive method prepares for, in the reaction of carbon four selective hydrogenation and removing butadiene, having the advantage that catalyst cost is low, butylene hydrogenation loss rate is low. In addition, adopt the catalyst that the inventive method prepares for, in the reaction of carbon four selective hydrogenation and removing butadiene, also having the advantage that 1-butylene isomerization rate is low, be particularly suitable for the pretreatment of 1-butylene precise distillation device raw material.
Accompanying drawing explanation
The XRD spectrum of Fig. 1 F2 and F0 catalyst.
Detailed description of the invention
By the examples below and comparative example further illustrate effect and the effect of the inventive method, but following example are not construed as limiting the invention.
In the present invention, butadiene hydrogenation rate, butylene loss rate and 1-butylene isomerization rate is adopted to represent the reactivity worth of catalyst. The first two index is used for representing that selectivity of catalyst Hydrogenation, the 3rd index are for representing the isomerization performance of catalyst. The computational methods of butadiene hydrogenation rate, butylene loss rate and 1-butylene isomery rate are as follows:
In following embodiment, chemical reagent used is as indicated without special, is analytical reagent. Catalyst carrier is aluminium hydrate powder, and pore volume is 0.7-0.8ml/g, than table more than 220m2/g��
Embodiment 1-4
Catalyst preparation step (1)
Weigh six water nickel nitrates by weight shown in table 1 and add 500ml deionized water, it is subsequently adding 0.05mol/L nitre acid for adjusting pH value to 2-3, then press weight shown in table 1 again and add diammonium phosphate, six water cerous nitrates, citric acid monohydrate, then at room temperature stir 1 hour, respectively obtain solution A 1-A4.
TableCatalyst preparing table
Aluminium hydrate powder 77g, 72g, 67g and 78g is added respectively in solution A 1-A4, so as to dispersion is in the solution, respectively obtain serosity B1-B4, then gained serosity is moved in Rotary Evaporators evaporating water at 85 DEG C, then dry 24 hours at 120 DEG C, obtain dry glue C1-C4.
Catalyst preparation step (2)
Dry glue C1-C4 is placed in tubular heater, at the N of flowing continuously2In atmosphere, process 3-10 hour at 250-300 DEG C, make the citric acid generation pyrolysis in dry glue, after the required process time to be achieved, make temperature be reduced to room temperature (25 DEG C) and take out, respectively obtain catalyst precursor D1-D4. Treatment conditions are in Table 2.
Table 2 thermal decomposition steps treatment conditions
Catalyst preparation step (3)
By catalyst precursor D1-D4 and appropriate nitric acid, water, sesbania powder mixer kneader, extruded moulding. After extruded moulding, gained extrudate, prior under room temperature dry 24 hours, is dried 24 hours then at 120 DEG C, is respectively obtained preformed catalyst presoma E1-E4.
Catalyst preparation step (4)
By the condition listed by table 3, preformed catalyst presoma E1-E4 is respectively placed in tubular heater, at the H of flowing continuously2In atmosphere, reduce 5-10 hour at 350-400 DEG C. After the required recovery time to be achieved, temperature is made to be reduced to room temperature (25 DEG C), the O being then 0.75% with carrier of oxygen volume concentrations2/N2Catalyst is passivated processing 0.8 hour by passivating gas, is finally passivated the catalyst F1-F4 of state.
Table 3 reduction step treatment conditions
Adopting X-ray diffraction (XRD) that passivation state catalyst F1-F4 is characterized, result shows that on catalyst, nickel phosphide is in amorphous state. Fig. 1 illustrates the XRD spectra of F2 catalyst.
Inductively coupled plasma atomic emission (ICP) is adopted to measure passivation state catalyst composition. Ni loading accounts for total catalyst weight percentages, P content and Ce content with Ni weight metal and represents with P/Ni, Ce/Ni mol ratio respectively. F1 catalyst: Ni content 10.12%, P/Ni=2.35, Ce/Ni=0.01; F2 catalyst: Ni content 12.51%, P/Ni=2.24, Ce/Ni=0.03; F3 catalyst: Ni content 14.96%, P/Ni=2.06, Ce/Ni=0.05; F4 catalyst: Ni content 10.23%, P/Ni=2.14, Ce/Ni=0.02.
Comparative example 1
With aluminium oxide for carrier, adopt the solution A 2 of impregnation embodiment 2 preparation, dry 24 hours under room temperature after dipping, dry 24 hours then at 120 DEG C, the presoma after drying is placed in tubular heater, at 50ml/minH2In stream, reduce 8 hours at 370 DEG C. After the required recovery time to be achieved, temperature is made to be reduced to room temperature (25 DEG C), the O being then 0.75% with carrier of oxygen volume concentrations2/N2Catalyst is passivated processing 0.8 hour by passivating gas, obtains same embodiment 2 and has the reference catalyst F0 of same composition. Fig. 1 illustrates the XRD spectra of F0, as it can be seen, F0 contains Ni2P and Ni12P5Crystal phase structure.
Embodiment 5-10
Adopt the reactivity worth of selectively hydrogenating butadiene reaction evaluating catalyst. Before each evaluating catalyst, by first for catalyst pretreatment 2 hours in the atmosphere of hydrogen of 200 DEG C, then reaction temperature need to be cooled to. Mixing carbon four for raw material with one, raw material forms in Table 4. Product adopts Agilent7890 type gas chromatogram on-line analysis.
Table 4 raw material forms
| Propane | Iso-butane | Normal butane | Trans-2-butene | 1-butylene | Isobutene. | Cis-2-butene | Butadiene | |
| Composition/weight % | 0.06 | 34.23 | 11.55 | 11.99 | 11.93 | 15.74 | 14.15 | 0.35 |
With F1-F4 for catalyst, using F0 as reference, with above-mentioned mixing carbon four for raw material, reaction temperature 60-100 DEG C, stagnation pressure be 1.5-2.0MPa, air speed be 5-10h-1, hydrogen/butadiene mol ratio carry out selective hydrogenation when being 1.0-2.0, reaction result is listed in table 5.
Table 5 process conditions and reaction result
Claims (21)
1. a base metal selective hydrocatalyst, it is characterized in that: this catalyst is made up of the amorphous nickel phosphide of active component, alumina support and auxiliary agent X, in the final catalyst, in the amorphous nickel phosphide of active component, the weight content of nickel is in metallic nickel, the mol ratio accounting for the 10-15% of total catalyst weight, phosphorus and nickel is 2.0-2.4:1, and the mol ratio of auxiliary agent X and nickel is 0.01-0.05:1, all the other are carrier, and described auxiliary agent X is at least one in rare earth element.
2. catalyst according to claim 1, it is characterised in that: described auxiliary agent X is one or more in lanthanum, cerium, praseodymium, samarium, ytterbium.
3. catalyst according to claim 1, it is characterised in that: described auxiliary agent X is cerium.
4. catalyst according to claim 1, it is characterised in that: without Ni in XRD spectra in described catalyst2P or Ni12P5Diffraction maximum.
5. the preparation method of the described base metal selective hydrocatalyst of one of claim 1-4, step is as follows:
(1) the acid nickel salt aqueous solution of preparation, it is subsequently adding diammonium phosphate, salt containing auxiliary agent X and citric acid, making phosphorus/nickel mol ratio is 2.5-3.0, X/ nickel mol ratio is 0.01-0.05:1, and citric acid/nickel mol ratio is 1.0-2.0:1, obtains solution A, aluminium oxide or the aluminium hydroxide of metering is added in gained solution A, forming serosity B, then slow evaporating water, forms dry glue C;
(2) gained dry glue C in step (1) is placed under the atmosphere of inert gases of flowing continuously, at being warming up to 250-350 DEG C, and processes 5-10 hour at this temperature, make the citric acid generation pyrolysis in dry glue, obtain catalyst precursor D;
(3) the catalyst precursor D obtained in step (2) is shaped, after molding rear catalyst drying, obtains preformed catalyst presoma E;
(4) the preformed catalyst presoma E obtained in step (3) is reduced in atmosphere of hydrogen, reduction temperature is 300-400 DEG C, recovery time is 1-10h, after catalyst reduction, it is cooled to room temperature, at room temperature catalyst is passivated 0.5-1h with the passivating gas that oxygen concentration is 0.5-1.0%, obtains final catalyst.
6. method according to claim 5, it is characterised in that: the nickel salt described in step (1) is selected from one or more in nickel nitrate, Nickel dichloride., nickelous bromide, nickel sulfate, nickel acetate, nickel oxalate.
7. method according to claim 6, it is characterised in that: described nickel salt is nickel nitrate.
8. method according to claim 5, it is characterised in that: the X salt described in step (1) is selected from one or more in the nitrate of rare earth element, hydrochlorate, sulfate, acetate.
9. method according to claim 8, it is characterised in that: rare earth element at least one in lanthanum, cerium, praseodymium, samarium, ytterbium.
10. method according to claim 5, it is characterised in that: the salt containing auxiliary agent X is cerous nitrate.
11. method according to claim 5, it is characterised in that: nickel salt is at room temperature dissolved in water by step (1), adds acid for adjusting pH value at 2-3, obtain acid nickel salt aqueous solution.
12. method according to claim 11, it is characterised in that: the acid being used for regulating pH value is dust technology, and nitric acid molar concentration is 0.01-0.05mol/L.
13. method according to claim 5, it is characterised in that: the noble gas described in step (2) is nitrogen, helium or argon.
14. method according to claim 13, it is characterised in that: the noble gas described in step (2) is nitrogen.
15. method according to claim 5, it is characterised in that: in step (3), catalyst adopts squeezing and pressing method, pressed disc method, drips ball or spin comminution granulation molding.
16. method according to claim 15, it is characterised in that: catalyst adopts squeezing and pressing method molding.
17. method according to claim 5, it is characterised in that: the reduction temperature described in step (4) is 350-400 DEG C, and the recovery time is 5-10h.
18. method according to claim 5, it is characterised in that: the passivating gas described in step (4) is except for oxygen noble gas, noble gas one in nitrogen, helium or argon.
19. the application that the described base metal selective hydrocatalyst of one of claim 1-4 is in carbon four selective hydrogenation and removing butadiene reacts, it is characterized in that: be 60��100 DEG C containing butadiene raw material in reaction temperature, stagnation pressure is 1.5��2.0MPa, and air speed is 5��10h-1, hydrogen/butadiene mol ratio reacts when being 1.0��2.0.
20. application according to claim 19, it is characterised in that: described containing butadiene raw material from refinery FCC by-product carbon four or cracking of ethylene carbon-4.
21. application according to claim 19, it is characterised in that: charging procatalyst is pretreatment 1��2 hour in the atmosphere of hydrogen of 100-200 DEG C.
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| CN107051430A (en) * | 2017-06-02 | 2017-08-18 | 钦州学院 | The catalyst and preparation method of a kind of hydrogenation of petroleum resin |
| CN107930661A (en) * | 2016-10-13 | 2018-04-20 | 中国石油化工股份有限公司 | The nickel-base catalyst of one-step synthesis method acetone downstream condensed products |
| CN108855090A (en) * | 2017-05-08 | 2018-11-23 | 中国石油化工股份有限公司 | A kind of ethylene glycol hydrogenation catalyst and preparation method thereof |
| CN108855129A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | A kind of nickel-silver series hydrocatalyst and preparation method thereof |
| CN110054542A (en) * | 2019-05-16 | 2019-07-26 | 中煤陕西榆林能源化工有限公司 | The method for adding the C4 component hydrogenation and removing butadiene of regulator |
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| CN114471550A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Noble metal hydrogenation catalyst, and preparation method and application thereof |
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| CN106975502A (en) * | 2017-05-11 | 2017-07-25 | 大连理工大学 | Rare earth modified Ni3P catalyst and its application |
| CN108855129A (en) * | 2017-05-15 | 2018-11-23 | 中国石油天然气股份有限公司 | A kind of nickel-silver series hydrocatalyst and preparation method thereof |
| CN108855129B (en) * | 2017-05-15 | 2021-04-30 | 中国石油天然气股份有限公司 | Nickel-silver hydrogenation catalyst and preparation method thereof |
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| CN110054542A (en) * | 2019-05-16 | 2019-07-26 | 中煤陕西榆林能源化工有限公司 | The method for adding the C4 component hydrogenation and removing butadiene of regulator |
| CN110054542B (en) * | 2019-05-16 | 2022-03-29 | 中煤陕西榆林能源化工有限公司 | Method for removing butadiene by hydrogenation of C4 component added with regulator |
| CN114471550A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Noble metal hydrogenation catalyst, and preparation method and application thereof |
| CN114471550B (en) * | 2020-10-26 | 2024-04-12 | 中国石油化工股份有限公司 | Noble metal hydrogenation catalyst and preparation method and application thereof |
| CN112717960A (en) * | 2021-01-05 | 2021-04-30 | 南昌大学 | Preparation method of Pr-P-Ni catalyst for cellulose platform molecular transformation |
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