CN106311243B - Nickel zirconium B catalyst, preparation method and its application of titanium dichloride load - Google Patents
Nickel zirconium B catalyst, preparation method and its application of titanium dichloride load Download PDFInfo
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- CN106311243B CN106311243B CN201610597316.2A CN201610597316A CN106311243B CN 106311243 B CN106311243 B CN 106311243B CN 201610597316 A CN201610597316 A CN 201610597316A CN 106311243 B CN106311243 B CN 106311243B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention belongs to γ valerolactone synthetic catalyst technical fields, and in particular to a kind of nickel zirconium B catalyst, preparation method and its application of titanium dichloride load.The preparation method, by the ratio of both modulations, has obtained the Ni Zr B/TiO of different loads amount using nickel zirconium boron and titanium dioxide as raw material2Catalyst.The catalyst of gained is applied in the hydrogenation reaction of LA, and at 110 DEG C, 3MPa hydrogen pressures, 2h, under conditions of water as solvent, the high conversion rate of LA is up to 98%, γ valerolactones (GVL) high selectivity up to 99%.Show the catalytic activity for being substantially better than ordinary oxide and carbon material supported nickel, nickel zirconium B catalyst.
Description
Technical field
The invention belongs to gamma-valerolactone synthetic catalyst technical fields, and in particular to a kind of nickel zirconium of titanium dichloride load
B catalyst, preparation method and its application.
Background technology
Biomass resource such as plant amylum (grain), cellulose, animal chitosan etc. are typical renewable resource, quantity
It is huge, it is cheap and easy to get.Such as biomass resource is utilized to replace non-renewable fossil energy, alleviating energy crisis can asked significantly
Topic.In recent years, the research of bulk chemical is converted by biomass catalyzing becomes the research hotspot that biomass resource efficiently uses.
For example, 5 hydroxymethyl furfural, sorbierite and GVL etc. can be obtained by biomass.Wherein, GVL is very extensive as purposes puts down
Platform compound can be used as the intermediate etc. of liquid fuel, food additives, organic solvent, medicine and chemicals synthesis.
GVL can be dehydrated by catalytic hydrogenation by the hydrolysate-LA of biomass and is made.Grinding for GVL is prepared by raw material of LA
In terms of studying carefully the selection for being concentrated mainly on catalyst.Ru composition catalyst catalysis LA hydrogenation conditions it is mild, GVL yields compared with
Height, but catalyst is difficult to detach with product.Manzer(Appl.Catal.A,2004,272:249-256.) compare Ir/C,
The catalytic performance of Rh/C, Pd/C, Ru/C, Pt/C, Re/C and Ni/C catalyst LA Hydrogenations GVL find Ru/C catalyst
Catalytic performance it is best, at 150 DEG C and under the conditions of 3448kPa, LA conversion ratios 100%, GVL is selectively more than 97%.Du
(Angew.Chem.Int.Ed.,2011,50(51)；7815-7819) etc. using formic acid as hydrogen donor, using Au/ZrO2Catalyst
LA Hydrogenation GVL are catalyzed, obtain higher yields in a mild condition.Yan(Energy&Fuels,2009,23(8):3853-
Etc. 3858.) using Ru/C as catalyst LA Hydrogenation GVL, under the conditions of 130 DEG C of hydrogen of reaction temperature press 1.2MPa, LA conversions
Rate 92%, GVL selectivity 99%.Bourne(Chem.Commun.,2007,(44):4632-4634.) etc. with Ru/SiO2Catalysis
Agent is catalyzed LA Hydrogenation GVL, with supercritical fluid CO2Make solvent, under the conditions of 200 DEG C and hydrogen press 10MPa, GVL yields are more than
99%.In addition, in order to reduce the cost of catalyst, Upare (ChemSusChem., 2011,4 (12):1749-1752.) etc. adopt
Non-precious metal catalyst Cu/SiO is prepared with deposition-precipitation2It is reacted for LA Hydrogenations GVL, 10MPa is pressed in 265 DEG C and hydrogen
Under the conditions of, GVL yields 99.9%.Hengne(Green Chem.,2012,14(4):1064-1072.) etc. use coprecipitation
Prepare Cu-ZrO2Catalyst, under the conditions of 200 DEG C and 3448kPa, with methanol as solvent, LA conversion ratios 100%, GVL selectivity
90%.Chinese invention patent CN104829559A discloses a kind of preparation method of catalyst by LA Hydrogenations for GVL and application.
17.5 grams of methyl ester levulinates, 2% mass fraction Copper-Chromium Oxide Catalysts, 250 DEG C, 30bar hydrogen pressure reaction 6h, GVL production
Rate is 90.8%.Chinese invention patent CN102617519A, as catalyst, is used for the selective hydrogenation of LA using skeletal copper.
It is added under conditions of KOH, 130-140 DEG C, Hydrogen Vapor Pressure 4.0MPa of control hydrogenation reaction temperature, successive reaction 2.5 hours, LA turns
Rate is 99.7%, GVL selectivity 95.6%.
Since chemical reduction method cost is higher, it is difficult to adapt to large-scale industrial production, the publication of catalytic hydrogenation method is then
The noble metal catalysts such as Ru, Au, Pd are mostly used greatly, it is higher to equally exist catalyst cost, it is difficult to the problem of commercial Application.Using
The patented method of the non-precious metal catalysts such as nickel, copper, for reaction temperature usually at 150 DEG C or more, hydrogen is pressed in 4MPa or more.In addition.
Due to the acidity of raw material LA itself, the problem that catalyst activity reduction is very fast is caused, such as uses Raney's nickel, to keep catalyst to live
Property, it needs first to convert LA to corresponding sodium salt, adding hydrogen, also wanting acidified just can be obtained GVL later, and operating process is more numerous
It is trivial, and the yield of product GVL is not high.
Invention content
To solve the deficiencies in the prior art, the present invention provides a kind of nickel zirconium B catalyst of titanium dichloride load, its systems
Preparation Method and its application in LA hydrogenation reactions.The titanium dichloride load that the preparation method provided through the invention obtains
Nickel zirconium B catalyst is urged compared to the nickel zirconium boron of the non-precious metal catalyst and other material loads of existing patent and document report
Agent has higher catalytic activity and stability.Raw material is cheap and easy to get in the preparation method, prepares simple, content is easy to adjust
Section.Use potassium borohydride for reducing agent during load, mild condition, convenient for the exposure of washing and active site.The present invention
The catalyst provided is using titanium dioxide as carrier, using nickel zirconium boron as activated centre.It is calculated on the basis of its weight, nickel zirconium boron
Load capacity is 5~30wt%.
A kind of preparation method of the nickel zirconium B catalyst of titanium dichloride load, which is characterized in that include the following steps：
1) by every 1.234~3.702g Nickel dichloride hexahydrates, 0~1.10g, five nitric hydrate zirconiums (being free of endpoint 0), 0.50
0~13.5g bis- is added after solid dissolving in~2.5g polyethylene glycol-8 00 and the mixing of the deionized water of 1~50mL under ultrasound
Titanium oxide (is free of endpoint 0), continues 5~30min of ultrasound, takes the mixture obtained after ultrasound to be placed in baking oven, at 80~120 DEG C
Dry 12~for 24 hours, obtain sample A；
2) 20~60g water, 0.2~0.6g sodium hydroxides and 1.08~3.24g potassium borohydrides are mixed, obtains solution B,
Solution B is slowly dropped in the sample A under condition of ice bath, 1~6h of stirring is then proceeded to and obtains suspension, then will be described outstanding
Turbid filter, washing, and at 40~80 DEG C vacuum drying 12~for 24 hours, obtain the nickel zirconium B catalyst of titanium dichloride load.
Preferably, in step 2), the temperature of ice bath is 0 DEG C.
The present invention also provides what is be prepared according to the preparation method of the nickel zirconium B catalyst of above-mentioned titanium dichloride load
The nickel zirconium B catalyst of titanium dichloride load, chemical general formula x%Ni-Zr-B/TiO2, wherein x% is equal to nickel and titanium dioxide
The value of the mass percent of titanium.
Preferably, the value of x is 5~30.
It is furthermore preferred that the value of x is 10.
The present invention also provides the applications of the nickel zirconium B catalyst of above-mentioned titanium dichloride load, are selected for LA (levulic acid)
The hydroconversion process of selecting property hydrogenation synthesis GVL (gamma-valerolactone) or furfural.
Specifically, when synthesizing GVL applied to LA selective hydrogenations：Temperature be 70~180 DEG C, Hydrogen Vapor Pressure be 1~
It is molten with water, toluene, dioxane, hexamethylene, methanol using LA as raw material under conditions of 4MPa, reaction time are 0.5~8h
Agent, using hydrogen as reducing agent, Hydrogenation is for GVL under the conditions of existing for the nickel zirconium B catalyst of the titanium dichloride load.
Preferably, the mass ratio of the nickel zirconium B catalyst of LA, solvent and the titanium dichloride load is 6~20:500~
2000:1~10.
Advantageous effect：
The present invention passes through both simple modulations using the cheap bimetallic of small dosage and the titanium dioxide derived from a wealth of sources as raw material
Ratio, obtained the titanium dioxide of different nickel zirconium boron contents, it is successfully that nickel zirconium boron is equal using potassium borohydride as reducing agent
Loaded on titanium dioxide evenly, and applied it to LA and add in hydrogen to the reaction of GVL, show be substantially better than it is existing specially
The catalytic activity of the nickel zirconium B catalyst of the non-precious metal catalyst and other material loads of profit and document report.It is this it is low at
Originally it, synthesizes simple, favorable reproducibility preparation method and is conducive to large-scale application of the nickel zirconium B catalyst in LA selective hydrogenations.
Specific implementation mode
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
(1) preparation of catalyst
1.234g Nickel dichloride hexahydrates, five nitric hydrate zirconiums of 0.055g, 00 and of 0.5g polyethylene glycol-8 are added in flask
5mL deionized waters.After to be dissolved, 2.7g titanium dioxide is added under ultrasound, continues ultrasound 20min.Substance after ultrasound is set
Dry 4h, obtains sample A in 120 DEG C of baking oven.20g water, 0.2g sodium hydroxides and 1.08g hydroborations are added in beaker
Potassium.Acquired solution is slowly dropped under condition of ice bath in sample A, stirring 1h is then proceeded to.Then gained suspension is taken out
Filter is washed, and 12h is dried in vacuo at 60 DEG C.The sample is labeled as 10%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL：
Accurately weighing catalyst 20mg and LA 114mg obtained, water 10g in above-mentioned steps (1) is warming up to 100 DEG C, leads to
Enter 3MPa hydrogen, carry out hydrogenation reaction, reacts 2h.Chromatography can obtain：LA conversion ratios are that 89.3%, GVL is selectively
100%, GVL yield are 89.3%.
Embodiment 2
(1) preparation of catalyst
2.468g Nickel dichloride hexahydrates, five nitric hydrate zirconiums of 0.11g, 00 and of 1.0g polyethylene glycol-8 are added in flask
5mL deionized waters.After to be dissolved, 2.7g titanium dioxide is added under ultrasound, continues ultrasound 20min.Substance after ultrasound is set
Dry 4h, obtains sample A in 120 DEG C of baking oven.40g water, 0.4g sodium hydroxides and 2.16g hydroborations are added in beaker
Potassium.Acquired solution is slowly dropped under condition of ice bath in sample A, stirring 1h is then proceeded to.Then gained suspension is taken out
Filter is washed, and 12h is dried in vacuo at 60 DEG C.The sample is labeled as 20%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL：
Accurately weighing catalyst 20mg and LA 114mg obtained, water 10g in above-mentioned steps (1) is warming up to 100 DEG C, leads to
Enter 3MPa hydrogen, carry out hydrogenation reaction, reacts 2h.Chromatography can obtain：LA conversion ratios are that 95.1%, GVL is selectively
100%, GVL yield are 95.1%.
Embodiment 3
(1) preparation of catalyst
0.617g Nickel dichloride hexahydrates, five nitric hydrate zirconiums of 0.0275g, 0.25g polyethylene glycol-8 00 are added in flask
With 5mL deionized waters.After to be dissolved, 2.7g titanium dioxide is added under ultrasound, continues ultrasound 20min.By the substance after ultrasound
It is placed in 120 DEG C of baking oven dry 4h, obtains sample A.10g water, 0.1g sodium hydroxides and 0.54g hydroborations are added in beaker
Potassium.Acquired solution is slowly dropped under condition of ice bath in sample A, stirring 1h is then proceeded to.Then gained suspension is taken out
Filter is washed, and 12h is dried in vacuo at 60 DEG C.The sample is labeled as 5%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL：
Accurately weighing catalyst 20mg and LA 114mg obtained, water 10g in above-mentioned steps (1) is warming up to 100 DEG C, leads to
Enter 3MPa hydrogen, carry out hydrogenation reaction, reacts 2h.Chromatography can obtain：LA conversion ratios are that 31.9%, GVL is selectively
100%, GVL yield are 31.9%.
Embodiment 4
(1) preparation of catalyst
1.234g Nickel dichloride hexahydrates, 0.5g polyethylene glycol-8 00 and 5mL deionized waters are added in flask.It is to be dissolved
Afterwards, 2.7g titanium dioxide is added under ultrasound, continues ultrasound 20min.Substance after ultrasound is placed in 120 DEG C of baking oven dry
4h obtains sample A.20g water, 0.2g sodium hydroxides and 1.08g potassium borohydrides are added in beaker.By acquired solution in ice bath item
It is slowly dropped under part in sample A, then proceedes to stirring 1h.Then gained suspension is filtered, washing, is dried in vacuo at 60 DEG C
12h.The sample is labeled as 10%Ni-B/TiO2。
(2) LA hydrogenation synthesis GVL：
Accurately weighing catalyst 20mg and LA 114mg obtained, water 10g in above-mentioned steps (1) is warming up to 100 DEG C, leads to
Enter 3MPa hydrogen, carry out hydrogenation reaction, reacts 2h.Chromatography can obtain：LA conversion ratios are that 57.7%, GVL is selectively
100%, GVL yield are 57.7%.
Application examples 5
Accurately weigh catalyst 10%Ni-Zr-B/TiO obtained in above-described embodiment 1220mg and LA114mg, solvent
10mL is warming up to 100 DEG C, is passed through 3MPa hydrogen, reacts 2h, obtains GVL.As a result it shows：
Application examples 6
Accurately weigh catalyst 10%Ni-Zr-B/TiO obtained in above-described embodiment 1220mg and LA114mg, water
10mL is passed through 3MPa hydrogen, carries out hydrogenation reaction, reacts 2h, obtains GVL.As a result it shows：
Application examples 7
Accurately weigh catalyst 10%Ni-Zr-B/TiO obtained in above-described embodiment 1220mg and LA114mg, water
10mL is warming up to 100 DEG C, carries out hydrogenation reaction, reacts 2h, obtains GVL.As a result it shows：
Application examples 8
Accurately weigh catalyst 10%Ni-Zr-B/TiO obtained in above-described embodiment 1220mg and LA114mg, water
10mL is warming up to 100 DEG C, is passed through 3MPa hydrogen and carries out hydrogenation reaction, obtains GVL.As a result it shows：
Application examples 9
With reference to the preparation method and step of application examples 1, fixed catalyst 10%Ni-Zr-B/TiO2With reaction time 2h,
Catalyst is reused.As a result it shows：
In above-mentioned each application examples, GVL yields=LA conversion ratios × GVL selectivity.It is relevant disclosed in the prior art
In catalysis, usually single LA conversion values are higher or GVL selective values are higher.But catalyst provided by the present invention exists
LA selective hydrogenations synthesize in the application of GVL, and GVL yield values integrally significantly increase.
The foregoing is merely the better embodiments of the present invention, are not intended to limit the invention, all spirit in the present invention
Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of preparation method of the nickel zirconium B catalyst of titanium dichloride load, which is characterized in that include the following steps：
1) by every 1.234~3.702g Nickel dichloride hexahydrates, more than 0 and less than or equal to 1.10g five nitric hydrate zirconiums, 0.50~
2.5g polyethylene glycol-8 00 and the mixing of the deionized water of 1~50mL are added more than 0 and are less than under ultrasound after solid dissolving
Titanium dioxide equal to 13.5g continues 5~30min of ultrasound, the mixture obtained after ultrasound is taken to be placed in baking oven, 80~120 DEG C
Lower drying 12~for 24 hours, obtain sample A；
2) 20~60g water, 0.2~0.6g sodium hydroxides and 1.08~3.24g potassium borohydrides are mixed, solution B is obtained, in ice bath
Under the conditions of solution B is slowly dropped in the sample A, then proceed to 1~6h of stirring and obtain suspension, then by the suspension
Filter, washing, and at 40~80 DEG C vacuum drying 12~for 24 hours, obtain the nickel zirconium B catalyst of titanium dichloride load.
2. the preparation method of the nickel zirconium B catalyst of titanium dichloride load according to claim 1, it is characterised in that：Step
2) in, the temperature of ice bath is 0 DEG C.
3. a kind of preparation method of the nickel zirconium B catalyst of titanium dichloride load according to claim 1 or 2 is prepared
Titanium dichloride load nickel zirconium B catalyst, it is characterised in that：Chemical general formula is x%Ni-Zr-B/TiO2, wherein x% etc.
In the value of the mass percent of nickel and titanium dioxide.
4. the nickel zirconium B catalyst of titanium dichloride load according to claim 3, it is characterised in that：The value of x is 5~30.
5. a kind of application of the nickel zirconium B catalyst of titanium dichloride load according to claim 3 or 4, it is characterised in that：
The hydroconversion process of GVL or furfural is synthesized applied to LA selective hydrogenations.
6. the application of the nickel zirconium B catalyst of titanium dichloride load according to claim 5, which is characterized in that when applied to
When LA selective hydrogenations synthesize GVL：In the item that temperature is 70~180 DEG C, Hydrogen Vapor Pressure 1-4MPa, reaction time are 0.5-8h
Under part, using LA as raw material, using water, toluene, dioxane, hexamethylene, methanol as solvent, using hydrogen as reducing agent, described two
Hydrogenation is for GVL under the conditions of titania oxide supported nickel zirconium B catalyst is existing.
7. the application of the nickel zirconium B catalyst of titanium dichloride load according to claim 6, it is characterised in that：LA, solvent
Mass ratio with the nickel zirconium B catalyst of the titanium dichloride load is 6~20:500~2000:1~10.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246076A (en) * | 1996-12-19 | 2000-03-01 | 巴特勒记忆研究所 | Nickel-based catalyst and method for aqueous phase reactions |
| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
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2016
- 2016-07-26 CN CN201610597316.2A patent/CN106311243B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1246076A (en) * | 1996-12-19 | 2000-03-01 | 巴特勒记忆研究所 | Nickel-based catalyst and method for aqueous phase reactions |
| CN103193736A (en) * | 2013-03-30 | 2013-07-10 | 浙江工业大学 | Method for synthesizing gamma-valerolactone based on catalytic hydrogenation |
Non-Patent Citations (2)
| Title |
|---|
| Ni/ZrO2催化乙酰丙酸加氢制备γ-戊内酯;盛栋等;《化学反应工程与工艺》;20160430;第32卷(第2期);188-192 * |
| Vapour phase hydrocyclisation of levulinic acid to γ -valerolactone over supported Ni catalysts;Varkolu Mohan; et al.;《catalysis science & technology》;20140130;第4卷;1253-1260 * |
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