CN105642324B - A kind of base metal selective hydrocatalyst and its preparation method and application - Google Patents
A kind of base metal selective hydrocatalyst and its preparation method and application Download PDFInfo
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- CN105642324B CN105642324B CN201410723841.5A CN201410723841A CN105642324B CN 105642324 B CN105642324 B CN 105642324B CN 201410723841 A CN201410723841 A CN 201410723841A CN 105642324 B CN105642324 B CN 105642324B
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Abstract
The present invention discloses 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, the weight content of nickel is in terms of metallic nickel in the amorphous nickel phosphide of active component, account for the 10 15% of total catalyst weight, the mol ratio of phosphorus and nickel is 2.0 2.4:The mol ratio of 1, auxiliary agent X and nickel is 0.01 0.05:1, remaining is carrier, and described auxiliary agent X is the one or more in the rare earth elements such as lanthanum, cerium, praseodymium, samarium, ytterbium, preferably cerium.The non-precious metal catalyst has the catalytic activity suitable with noble metal catalyst, can substantially reduce catalyst cost in for the raw material selective hydrogenation and removing butadiene course of reaction of carbon four, while has relatively low 1 isomerization of butene 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
A kind of non-precious metal catalyst of the raw material selective hydrogenation and removing butadiene of carbon four and its preparation method and application.
Background technology
With the continuous expansion of China's refining capacity and ethene production capacity, the commercially available resource of by-product carbon four is also therewith
Increase, which also promotes the fast development of the intensive processing industry of carbon four in recent years.Fluid catalytic cracking（FCC）With cracking of ethylene pair
A certain amount of butadiene can more or less be contained in production carbon four, if being raw material directly with the carbon four containing butadiene, for producing height
Value-added product, it will catalyst performance and product quality are influenceed, such as aromatisation gasoline, gasoline alkylate, methyl tertiary butyl ether(MTBE)
（MTBE）With the product such as high-purity 1- butylene.Often it is required for carrying out selective hydrogenation processing to the raw material of carbon four, by the raw material of carbon four
In butadiene control in reduced levels（Ppm levels）.
Generally use noble metal catalyst, such as the Pd catalyst of support type, and using the removing of liquid phase fixed bed hydrogenation technique
Butadiene in the raw material of carbon four.Because in addition to butadiene is hydrogenated, butylene may also be hydrogenated into corresponding alkane, can lead in carbon four
Cause the loss of butylene.Because precious metals pd has a selective hydrogenation performance, but hydrogenation activity of Pd metals itself is also relatively strong, individually with
Pd can be such that a part of butylene is also hydrogenated as catalyst.Therefore, generally require that Pd catalyst is improved appropriately,
Its hydrogenation activity to butylene is reduced, improves the mainly exhibition in terms of second auxiliary agent of catalyst structure, support modification and introducing etc. three
Open.
USP 3531545 has been passivated part Pd hydrogenation activity, but cause catalyst by adding sulfide into raw material
Can only be used above at 160 DEG C.It is carrier that CN1238239, which employs δ, θ, α mixed phase aluminum oxide, is prepared for loading type Pd catalysis
Agent, to improve catalyst activity and selectivity.The aluminum oxide that USP 3485887 employs the lithium aluminate containing spinelle is carrier, system
For Supported Pd-Catalyst, but butadiene hydrogenation activity is relatively low, and butylene loss late is larger.In recent years, on using introducing
Second and third auxiliary agent is more and more to improve the patent of catalyst performance, as CN101850250, CN103418379,
CN1676214, CN1238239 etc., the auxiliary agent of introducing include Pb, WO3, K, Na, Li, Mg, Sr, Au etc..
The existing technical scheme using loaded noble metal catalyst, because noble metal is expensive, cause its catalyst into
This is higher.Moreover, existing loaded noble metal catalyst more or less also has certain 1- isomerization of butene activity, limit
Its application during 1- butylene precise distillation device pretreatments of raw material.
The content of the invention
The present invention provides a kind of base metal selective hydrocatalyst and preparation method thereof.The non-precious metal catalyst exists
For in the raw material selective hydrogenation and removing butadiene course of reaction of carbon four, to there is the catalytic activity suitable with noble metal catalyst,
Catalyst cost can be substantially reduced, while there is relatively low 1- isomerization of butene activity.
A kind of base metal selective hydrocatalyst, by the amorphous nickel phosphide of active component, alumina support and auxiliary agent X
Composition, in the final catalyst, the weight content of nickel accounts for total catalyst weight in terms of metallic nickel in the amorphous nickel phosphide of active component
The mol ratio of the 10-15% of amount, phosphorus and nickel is 2.0-2.4:The mol ratio of 1, auxiliary agent X and nickel is 0.01-0.05:1, remaining is load
Body, remaining is carrier, and described auxiliary agent X is at least one of rare earth element,
In catalyst of the present invention, described auxiliary agent X is the one or more in lanthanum, cerium, praseodymium, samarium, ytterbium, preferably 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 are as follows：
（1）Acid nickel salt aqueous solution is prepared, diammonium hydrogen phosphate, the salt and citric acid of the X containing auxiliary agent is then added, makes phosphorus/nickel
Mol ratio is 2.5-3.0, and X/ nickel mol ratio is 0.01-0.05:1, citric acid/nickel mol ratio is 1.0-2.0:1, solution A is obtained,
The aluminum oxide or aluminium hydroxide of metering are added into resulting solution A, forms slurries B, then slow evaporating water, forms dry glue C；
（2）By step（1）Middle gained dry glue C is placed under the atmosphere of inert gases continuously flowed, is warming up to 250-350 DEG C
Under, and in handling 5-10 hours at this temperature, make the citric acid in dry glue that pyrolysis occur, obtain catalyst precursor D；
（3）By step（2）In obtained catalyst precursor D be molded, after being molded rear catalyst drying, obtain into
Type catalyst precursor E；
（4）By step（3）In obtained preformed catalyst presoma E reduced in atmosphere of hydrogen, reduction temperature is
300-400 DEG C, the recovery time is 1-10 h, after catalyst reduction, room temperature is cooled to, using oxygen concentration as the blunt of 0.5-1.0%
Change gas and be passivated 0.5-1 h to catalyst at room temperature, obtain final catalyst.
The inventive method step（1）Described in nickel salt be selected from nickel nitrate, nickel chloride, nickelous bromide, nickel sulfate, nickel acetate,
One or more in nickel oxalate, preferably nickel nitrate.Described X salt is selected from the nitric acid containing rare earth elements such as lanthanum, cerium, praseodymium, samarium, ytterbiums
In one or more in salt, hydrochloride, sulfate, acetate, the preferably nitrate containing cerium, hydrochloride, sulfate, acetate
One or more, more preferably cerous nitrate.The acid for being used to adjust pH value is dust technology, and nitric acid molar concentration is 0.01-
0.05 mol/L。
The inventive method step（1）It is middle that nickel salt is dissolved in water at room temperature, acid for adjusting pH value is added in 2-3, obtains acidity
Nickel salt aqueous solution.
The inventive method step（2）Described inert gas is nitrogen, helium or argon gas, preferably nitrogen.
The inventive method step（3）In, catalyst can use extrusion, pressed disc method, drop ball or the shaping of spin comminution granulation,
Wherein preferred extrusion shaping.
The inventive method step（4）Described reduction temperature is 350-400 DEG C, and the recovery time is 5-10 h.Described is blunt
It is except for oxygen inert gas to change in gas, a kind of in nitrogen, helium or argon gas, preferably nitrogen.
The present invention also provides a kind of application of catalyst in the reaction of the selective hydrogenation and removing butadiene of carbon four, containing fourth two
Alkene raw material is 60~100 DEG C in reaction temperature, and stagnation pressure is 1.5~2.0 MPa, and air speed is 5~10 h-1, hydrogen/butadiene mole
Than to be reacted under conditions of 1.0~2.0.Described raw material containing butadiene comes from refinery FCC by-products carbon four or cracking of ethylene
Carbon-4.In above-mentioned application, charging procatalyst pre-processes 1~2 hour preferably in 100-200 DEG C of atmosphere of hydrogen.
The present invention effect and have an advantage that, compared with traditional Pd systems noble metal catalyst, using the inventive method system
Catalyst be used in the reaction of the selective hydrogenation and removing butadiene of carbon four, have that catalyst cost is low, butylene hydrogenation loss late
The advantages of low.In addition, reacted using catalyst made from the inventive method for the selective hydrogenation and removing butadiene of carbon four
In, also with 1- isomerization of butene rates it is low the advantages of, the pretreatment particularly suitable for 1- butylene precise distillation device raw materials.
Brief description of the drawings
The XRD spectrums of Fig. 1 F2 and F0 catalyst.
Embodiment
The effect of the inventive method and effect, but following examples are further illustrated below by embodiment and comparative example
It is not construed as limiting the invention.
In the present invention, catalyst is represented using butadiene hydrogenation rate, butylene loss late and 1- isomerization of butene rate
Reactivity worth.The first two index is used for representing that the selective hydrogenation performance of catalyst, the 3rd index are used for representing catalyst
Isomerization performance.The computational methods of butadiene hydrogenation rate, butylene loss late and 1- butylene isomery rates are as follows：
Chemical reagent used such as indicates without special in following embodiments, is AR.Catalyst carrier is hydrogen-oxygen
Change aluminium powder, pore volume is 0.7-0.8 ml/g, is more than 220 m than table2/g。
Embodiment 1-4
Catalyst preparation step（1）
The weight as shown in table 1 weighs six water nickel nitrates and adds 500 ml deionized waters, then adds 0.05 mol/L nitric acid
PH value is adjusted to 2-3, then weight adds diammonium hydrogen phosphate, six water cerous nitrates, Citric Acid Mono, Ran Hou as shown in table 1 again
Stir 1 hour at room temperature, respectively obtain solution A 1-A4.
The catalyst preparation table of table 1
Aluminium hydrate powder 77g, 72g, 67g and 78g are added into solution A 1-A4 respectively, is allowed to disperse in the solution, respectively
Obtain slurries B1-B4, then by gained slurries move into Rotary Evaporators at 85 DEG C evaporating water, then dried at 120 DEG C
It is dry 24 hours, obtain dry glue C1-C4.
Catalyst preparation step（2）
Dry glue C1-C4 is placed in tubular heater, in the N continuously flowed2In atmosphere, 3- is handled at 250-300 DEG C
10 hours, make the citric acid in dry glue that pyrolysis occur, after required processing time to be achieved, temperature is reduced to room temperature
（25℃）Take out, respectively obtain catalyst precursor D1-D4.Treatment conditions are shown in Table 2.
The thermal decomposition steps treatment conditions of table 2
Catalyst preparation step（3）
By catalyst precursor D1-D4 and appropriate nitric acid, water, sesbania powder mixer kneader, extruded moulding.Extruded moulding
Afterwards, gained extrudate is first dried 24 hours at room temperature, is dried 24 hours then at 120 DEG C, is respectively obtained preformed catalyst forerunner
Body E1-E4.
Catalyst preparation step（4）
As the condition listed by table 3, preformed catalyst presoma E1-E4 is respectively placed in tubular heater, in continuous stream
Dynamic H2In atmosphere, 5-10 hours are reduced at 350-400 DEG C.After the required recovery time to be achieved, temperature is set to be reduced to room
Temperature（25℃）, then using oxygen volumetric concentration as 0.75% O2/N2Passivating gas is passivated processing 0.8 hour to catalyst, obtains
To the catalyst F1-F4 of final passivation state.
The reduction step treatment conditions of table 3
Using X-ray diffraction（XRD）Passivation state catalyst F1-F4 is characterized, the results showed that nickel phosphide on catalyst
In amorphous state.Fig. 1 shows the XRD spectra of F2 catalyst.
Using inductively coupled plasma atomic emission（ICP）Measure passivation state catalyst composition.Ni loadings are with Ni gold
Category weight accounts for total catalyst weight percentages, and P content and Ce contents are represented with P/Ni, Ce/Ni mol ratio respectively.F1 is catalyzed
Agent：Ni contents 10.12%, P/Ni=2.35, Ce/Ni=0.01；F2 catalyst：Ni contents 12.51%, P/Ni=2.24, Ce/Ni=
0.03；F3 catalyst：Ni contents 14.96%, P/Ni=2.06, Ce/Ni=0.05；F4 catalyst：Ni contents 10.23%, P/Ni=
2.14, Ce/Ni=0.02.
Comparative example 1
Using aluminum oxide as carrier, it is small to dry 24 at room temperature using the solution A 2 of the preparation of impregnation embodiment 2, after dipping
When, dry 24 hours, the presoma after drying is placed in tubular heater, in 50ml/min H then at 120 DEG C2In stream,
Reduced 8 hours at 370 DEG C.After the required recovery time to be achieved, temperature is set to be reduced to room temperature（25℃）, then with oxygen volume
Concentration is 0.75% O2/N2Passivating gas is passivated processing 0.8 hour to catalyst, and obtaining same embodiment 2 has same composition
Reference catalyst F0.Fig. 1 shows F0 XRD spectra, as illustrated, F0 contains Ni2P and Ni12P5Crystal phase structure.
Embodiment 5-10
Using the reactivity worth of selectively hydrogenating butadiene reaction evaluating catalyst.Before each evaluating catalyst, it will need to urge
Agent first pre-processes 2 hours in 200 DEG C of atmosphere of hydrogen, then is cooled to reaction temperature.It is raw material with one kind mixing carbon four, it is former
Material composition is shown in Table 4.Reaction product uses the type gas-chromatography on-line analyses of Agilent 7890.
The raw material of table 4 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 |
Be raw material with above-mentioned mixing carbon four using F0 as reference using F1-F4 as catalyst, 60-100 DEG C of reaction temperature,
Stagnation pressure is 1.5-2.0 MPa, air speed is 5-10 h-1, hydrogen/butadiene mol ratio be 1.0-2.0 under conditions of carry out selectivity
Hydrogenation reaction, reaction result are listed in table 5.
The process conditions of table 5 and reaction result
Claims (20)
- A kind of 1. base metal selective hydrocatalyst, it is characterised in that：The catalyst by the amorphous nickel phosphide of active component, Alumina support and auxiliary agent X compositions, in the final catalyst, the weight content of nickel is with metal in the amorphous nickel phosphide of active component Nickel meter, accounts for the 10-15% of total catalyst weight, and the mol ratio of phosphorus and nickel is 2.0-2.4:The mol ratio of 1, auxiliary agent X and nickel is 0.01-0.05:1, remaining is carrier, and described auxiliary agent X is at least one of rare earth element, in catalyst in XRD spectrograms Without Ni2P or Ni12P5Diffraction maximum.
- 2. catalyst according to claim 1, it is characterised in that：Described auxiliary agent X is one in lanthanum, cerium, praseodymium, samarium, ytterbium Kind is several.
- 3. catalyst according to claim 1, it is characterised in that：Described auxiliary agent X is cerium.
- 4. the preparation method of one of the claim 1-3 base metal selective hydrocatalysts, step are as follows：（1）Acid nickel salt aqueous solution is prepared, diammonium hydrogen phosphate, the salt and citric acid of the X containing auxiliary agent is then added, makes phosphorus/nickel mole Than being 0.01-0.05 for 2.5-3.0, X/ nickel mol ratio:1, citric acid/nickel mol ratio is 1.0-2.0:1, solution A is obtained, to institute The aluminum oxide or aluminium hydroxide that metering is added in solution A are obtained, forms slurries B, then slow evaporating water, forms dry glue C；（2）By step（1）Middle gained dry glue C is placed under the atmosphere of inert gases continuously flowed, is warming up at 250-350 DEG C, and In handling 5-10 hours at this temperature, make the citric acid in dry glue that pyrolysis occur, obtain catalyst precursor D；（3）By step（2）In obtained catalyst precursor D be molded, after being molded rear catalyst drying, obtain shaping and urge Agent presoma E；（4）By step（3）In obtained preformed catalyst presoma E reduced in atmosphere of hydrogen, reduction temperature 300- 400 DEG C, the recovery time is 1-10 h, after catalyst reduction, room temperature is cooled to, using oxygen volumetric concentration as the blunt of 0.5-1.0% Change gas and 0.5-1h is passivated to catalyst at room temperature, obtain final catalyst.
- 5. according to the method for claim 4, it is characterised in that：Step（1）Described in nickel salt be selected from nickel nitrate, chlorination One or more in nickel, nickelous bromide, nickel sulfate, nickel acetate, nickel oxalate.
- 6. the method according to claim 5, it is characterised in that：Described nickel salt is nickel nitrate.
- 7. the method according to claim 4, it is characterised in that：Step（1）Described in X salt be selected from rare earth element nitre One or more in hydrochlorate, hydrochloride, sulfate, acetate.
- 8. the method according to claim 7, it is characterised in that：Rare earth element in lanthanum, cerium, praseodymium, samarium, ytterbium at least It is a kind of.
- 9. the method according to claim 4, it is characterised in that：The salt of the X containing auxiliary agent is cerous nitrate.
- 10. the method according to claim 4, it is characterised in that：Step（1）It is middle that nickel salt is dissolved in water at room temperature, add Acid for adjusting pH value obtains acid nickel salt aqueous solution in 2-3.
- 11. according to the method for claim 10, it is characterised in that：Acid for adjusting pH value is dust technology, nitric acid mole Concentration is 0.01-0.05 mol/L.
- 12. the method according to claim 4, it is characterised in that：Step（2）Described inert gas be nitrogen, helium or Argon gas.
- 13. according to the method for claim 12, it is characterised in that：Step（2）Described inert gas is nitrogen.
- 14. according to the method for claim 4, it is characterised in that：Step（3）Middle catalyst is using extrusion, pressed disc method, drop Ball or the shaping of spin comminution granulation.
- 15. according to the method for claim 14, it is characterised in that：Catalyst is molded using extrusion.
- 16. according to the method for claim 4, it is characterised in that：Step（4）Described reduction temperature is 350-400 DEG C, also The former time is 5-10h.
- 17. according to the method for claim 4, it is characterised in that：Step（4）It is inertia except for oxygen in described passivating gas Gas, the one kind of inert gas in nitrogen, helium or argon gas.
- 18. one of the claim 1-3 base metal selective hydrocatalysts are in the selective hydrogenation and removing fourth two of carbon four Application in alkene reaction, it is characterised in that：Raw material containing butadiene is 60~100 DEG C in reaction temperature, and stagnation pressure is 1.5~2.0 MPa, air speed are 5~10h-1, hydrogen/butadiene mol ratio be 1.0~2.0 under conditions of reacted.
- 19. application according to claim 18, it is characterised in that：Described raw material containing butadiene comes from refinery's FCC pairs Produce carbon four or cracking of ethylene carbon-4.
- 20. application according to claim 18, it is characterised in that：Feed atmosphere of hydrogen of the procatalyst at 100-200 DEG C Middle pretreatment 1~2 hour.
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| CN107930661B (en) * | 2016-10-13 | 2020-02-18 | 中国石油化工股份有限公司 | Nickel-based catalyst for synthesizing acetone downstream condensation product by one-step method |
| CN108855090B (en) * | 2017-05-08 | 2021-02-05 | 中国石油化工股份有限公司 | Ethylene glycol hydrogenation catalyst and preparation method thereof |
| CN106975502B (en) * | 2017-05-11 | 2019-08-02 | 大连理工大学 | Rare earth modified Ni3P catalyst and its application |
| 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 |
| CN107051430B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of catalyst and preparation method of hydrogenation of petroleum resin |
| 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 |
| 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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