CN106311243A - Titanium dioxide-laden nickel-zirconium-boron catalyst and the preparation method and application thereof - Google Patents
Titanium dioxide-laden nickel-zirconium-boron catalyst and the preparation method and application thereof Download PDFInfo
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- CN106311243A CN106311243A CN201610597316.2A CN201610597316A CN106311243A CN 106311243 A CN106311243 A CN 106311243A CN 201610597316 A CN201610597316 A CN 201610597316A CN 106311243 A CN106311243 A CN 106311243A
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- 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 the technical field of Upsilon-valerolactone synthetic catalyst, in particular to a titanium dioxide-laden nickel-zirconium-boron catalyst and the preparation method and application thereof. Ni-Zr-B/Tio2 catalyst with different lading amounts can be obtained with nickel-zirconium-boron and titanium dioxide as the raw material through modulating the proportion of nickel-zirconium-boron and titanium dioxide. When the catalyst obtained is used in the hydrogenation reaction of LA, under the condition that the temperature is 110oC, the hydrogen pressure is 3 MPa, the time is 2h, and the solvent is water, conversion rate of LA is as high as 98%, and selectivity of Upsilon-valerolactone (GVL) is as high as 99%, which shows the catalytic activity much better than that of nickel and nickel-zirconium-boron catalyst laden by oxide and carbon materials.
Description
Technical field
The invention belongs to gamma-valerolactone synthetic catalyst technical field, be specifically related to the nickel zirconium of a kind of titanium dichloride load
B catalyst, its preparation method and application thereof.
Background technology
Biomass resource such as plant amylum (grain), cellulose, animal chitosan etc. are typical Renewable resources, quantity
Huge, cheap and easy to get.As utilized biomass resource to replace non-renewable fossil energy, can significantly ask by alleviating energy crisis
Topic.In recent years, biomass catalyzing it is converted into the research of bulk chemical and becomes the study hotspot that biomass resource effectively utilizes.
Such as, biomass 5 hydroxymethyl furfural, sorbitol and GVL etc. can be obtained.Wherein, GVL is as purposes widely flat
Platform compound, can be used as liquid fuel, food additive, organic solvent, medicine and the intermediate etc. of chemicals synthesis.
GVL can be prepared by catalytic hydrogenation dehydration by the hydrolyzate-LA of biomass.Grinding of GVL is prepared for raw material with LA
Study carefully the selection aspect being concentrated mainly on catalyst.The composition catalyst catalysis LA hydrogenation conditions of Ru is gentle, and GVL yield is relatively
Height, but catalyst is difficult to separate 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 Hydrogenation GVL, finds Ru/C catalyst
Catalytic performance best, under the conditions of 150 DEG C and 3448kPa, LA conversion ratio 100%, GVL selectivity is more than 97%.Du
(Angew.Chem.Int.Ed.,2011,50(51)；7815-7819) etc. with formic acid as hydrogen donor, use Au/ZrO2Catalyst
Catalysis LA Hydrogenation GVL, obtains higher yields in a mild condition.Yan(Energy&Fuels,2009,23(8):3853-
3858.) etc. with Ru/C for catalyst LA Hydrogenation GVL, under the conditions of 130 DEG C of hydrogen pressure 1.2MPa of reaction temperature, LA converts
Rate 92%, GVL selectivity 99%.Bourne (Chem.Commun., 2007, (44): 4632-4634.) etc. are with Ru/SiO2Catalysis
Agent catalysis LA Hydrogenation GVL, with supercritical fluid CO2Making solvent, under the conditions of 200 DEG C and hydrogen pressure 10MPa, GVL yield is more than
99%.Additionally, for the cost reducing catalyst, Upare (ChemSusChem., 2011,4 (12): 1749-1752.) etc. adopts
Non-precious metal catalyst Cu/SiO is prepared with deposition-precipitation2React for LA Hydrogenation GVL, at 265 DEG C and hydrogen pressure 10MPa
Under the conditions of, GVL yield 99.9%.Hengne (Green Chem., 2012,14 (4): 1064-1072.) etc. use coprecipitation
Preparation Cu-ZrO2Catalyst, under the conditions of 200 DEG C and 3448kPa, with methanol as solvent, LA conversion ratio 100%, GVL selectivity
90%.Chinese invention patent CN104829559A disclose a kind of by LA Hydrogenation for the preparation method of catalyst of GVL and application.?
17.5 grams of methyl ester levulinates, 2% mass fraction Copper-Chromium Oxide Catalysts, 250 DEG C, react 6h, GVL under 30bar hydrogen pressure and produce
Rate is 90.8%.Chinese invention patent CN102617519A employing skeletal copper is as catalyst, for the selective hydrogenation of LA.?
Under conditions of adding KOH, controlling hydrogenation reaction temperature 130-140 DEG C, Hydrogen Vapor Pressure 4.0MPa, successive reaction 2.5 hours, LA turns
Rate is 99.7%, GVL selectivity 95.6%.
Owing to chemical reduction method is relatively costly, it is difficult to adapting to large-scale industrial production, the publication of catalytic hydrogenation method is then
Mostly use the noble metal catalysts such as Ru, Au, Pd, equally exist catalyst relatively costly, it is difficult to the problem of commercial Application.Use
The patented method of the non-precious metal catalyst such as nickel, copper, reaction temperature is generally more than 150 DEG C, and hydrogen pressure is at more than 4MPa.In addition.
Due to the acidity of raw material LA itself, cause catalyst activity reduction problem faster, as used Raney's nickel, for keeping catalyst to live
Property, needing LA is first converted into corresponding sodium salt, after hydrogenation, also want the acidified GVL that just can get, operating process is the most numerous
Trivial, and the yield of product GVL is the highest.
Summary of the invention
For solving the deficiencies in the prior art, the invention provides the nickel zirconium B catalyst of a kind of titanium dichloride load, its system
Preparation Method and the application in LA hydrogenation reaction thereof.The titanium dichloride load obtained by preparation method provided by the present invention
Non-precious metal catalyst and the nickel zirconium boron of other material load that nickel zirconium B catalyst is reported compared to existing patent and document are urged
Agent has higher catalysis activity and stability.In this preparation method, raw material is cheap and easy to get, preparation is simple, content is prone to adjust
Joint.Using potassium borohydride during load is reducing agent, mild condition, it is simple to washing and the exposure of avtive spot.The present invention
The catalyst provided is with titanium dioxide as carrier, with nickel zirconium boron as active center.Calculate on the basis of its weight, nickel zirconium boron
Load capacity is 5～30wt%.
The preparation method of the nickel zirconium B catalyst of a kind of titanium dichloride load, it is characterised in that comprise the steps:
1) by every 1.234～3.702g Nickel dichloride hexahydrate, 0～1.10g five nitric hydrate zirconium (without end points 0), 0.50
～the deionized water mixing of 2.5g PEG-8 00 and 1～50mL, after solid dissolves, in ultrasonic lower addition 0～13.5g bis-
Titanium oxide (without end points 0), continues ultrasonic 5～30min, take ultrasonic after the mixture that obtains be placed in baking oven, at 80～120 DEG C
It is dried 12～24h, obtains sample A；
2) 20～60g water, 0.2～0.6g sodium hydroxide and 1.08～3.24g potassium borohydrides are mixed, obtain solution B,
Solution B is slowly dropped in described sample A under condition of ice bath, then proceedes to stir 1～6h and obtain suspension, then by described outstanding
Turbid liquid sucking filtration, washing, and at 40～80 DEG C, it is vacuum dried 12～24h, obtain the nickel zirconium B catalyst of titanium dichloride load.
Preferably, step 2) in, the temperature of ice bath is 0 DEG C.
Present invention also offers what the preparation method of the nickel zirconium B catalyst according to above-mentioned titanium dichloride load prepared
The nickel zirconium B catalyst of titanium dichloride load, its chemical general formula is 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.
Present invention also offers the application of the nickel zirconium B catalyst of above-mentioned titanium dichloride load, select for LA (levulic acid)
Selecting property hydrogenation synthesis GVL (gamma-valerolactone) or the hydroconversion process of furfural.
Concrete, when being applied to LA selective hydrogenation synthesis GVL: temperature be 70～180 DEG C, Hydrogen Vapor Pressure be 1～
Under conditions of 4MPa, response time are 0.5～8h, with LA as raw material, it is molten with water, toluene, dioxane, hexamethylene, methanol
Agent, with hydrogen as reducing agent, under conditions of the nickel zirconium B catalyst of described titanium dichloride load exists, Hydrogenation is for GVL.
Preferably, the mass ratio of the nickel zirconium B catalyst of LA, solvent and described titanium dichloride load be 6～20:500～
2000:1～10.
Beneficial effect:
The present invention is with the cheap bimetallic of little consumption and the titanium dioxide of wide material sources as raw material, by simple both modulations
Ratio, obtained the titanium dioxide of different nickel zirconium Boron contents, use potassium borohydride as reducing agent, successfully by equal for nickel zirconium boron
Loaded on titanium dioxide evenly, and applied it to LA hydrogenation in the reaction of GVL, show be substantially better than existing specially
The catalysis activity of the nickel zirconium B catalyst of profit and the non-precious metal catalyst of document report and other material load.This low one-tenth
This, synthesis is simple, the preparation method of favorable reproducibility is conducive to nickel zirconium B catalyst large-scale application in LA selective hydrogenation.
Detailed description of the invention
Principle and feature to the present invention are described below, and example is served only for explaining 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 hexahydrate, 0.055g five nitric hydrate zirconium, 0.5g PEG-8 00 and is added in flask
5mL deionized water.After to be dissolved, at ultrasonic lower addition 2.7g titanium dioxide, continue ultrasonic 20min.Material after ultrasonic is put
In the baking oven of 120 DEG C, it is dried 4h, obtains sample A.20g water, 0.2g sodium hydroxide and 1.08g hydroboration is added in beaker
Potassium.Gained solution is slowly dropped in sample A under condition of ice bath, then proceedes to stir 1h.Then gained suspension is taken out
Filter, washing, be vacuum dried 12h at 60 DEG C.This sample is labeled as 10%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL:
Accurately weigh the catalyst 20mg and LA 114mg, water 10g prepared in above-mentioned steps (1), be warming up to 100 DEG C, logical
Enter 3MPa hydrogen, carry out hydrogenation reaction, react 2h.Chromatography can obtain: LA conversion ratio is 89.3%, and GVL selectivity is
100%, GVL yield is 89.3%.
Embodiment 2
(1) preparation of catalyst
2.468g Nickel dichloride hexahydrate, 0.11g five nitric hydrate zirconium, 1.0g PEG-8 00 and is added in flask
5mL deionized water.After to be dissolved, at ultrasonic lower addition 2.7g titanium dioxide, continue ultrasonic 20min.Material after ultrasonic is put
In the baking oven of 120 DEG C, it is dried 4h, obtains sample A.40g water, 0.4g sodium hydroxide and 2.16g hydroboration is added in beaker
Potassium.Gained solution is slowly dropped in sample A under condition of ice bath, then proceedes to stir 1h.Then gained suspension is taken out
Filter, washing, be vacuum dried 12h at 60 DEG C.This sample is labeled as 20%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL:
Accurately weigh the catalyst 20mg and LA 114mg, water 10g prepared in above-mentioned steps (1), be warming up to 100 DEG C, logical
Enter 3MPa hydrogen, carry out hydrogenation reaction, react 2h.Chromatography can obtain: LA conversion ratio is 95.1%, and GVL selectivity is
100%, GVL yield is 95.1%.
Embodiment 3
(1) preparation of catalyst
0.617g Nickel dichloride hexahydrate, 0.0275g five nitric hydrate zirconium, 0.25g PEG-8 00 is added in flask
With 5mL deionized water.After to be dissolved, at ultrasonic lower addition 2.7g titanium dioxide, continue ultrasonic 20min.By the material after ultrasonic
It is placed in the baking oven of 120 DEG C and is dried 4h, obtain sample A.10g water, 0.1g sodium hydroxide and 0.54g hydroboration is added in beaker
Potassium.Gained solution is slowly dropped in sample A under condition of ice bath, then proceedes to stir 1h.Then gained suspension is taken out
Filter, washing, be vacuum dried 12h at 60 DEG C.This sample is labeled as 5%Ni-Zr-B/TiO2。
(2) LA hydrogenation synthesis GVL:
Accurately weigh the catalyst 20mg and LA 114mg, water 10g prepared in above-mentioned steps (1), be warming up to 100 DEG C, logical
Enter 3MPa hydrogen, carry out hydrogenation reaction, react 2h.Chromatography can obtain: LA conversion ratio is 31.9%, and GVL selectivity is
100%, GVL yield is 31.9%.
Embodiment 4
(1) preparation of catalyst
1.234g Nickel dichloride hexahydrate, 0.5g PEG-8 00 and 5mL deionized water is added in flask.To be dissolved
After, at ultrasonic lower addition 2.7g titanium dioxide, continue ultrasonic 20min.Material after ultrasonic is placed in the baking oven of 120 DEG C dry
4h, obtains sample A.20g water, 0.2g sodium hydroxide and 1.08g potassium borohydride is added in beaker.By gained solution in ice bath bar
It is slowly dropped under part in sample A, then proceedes to stir 1h.Then by gained suspension sucking filtration, washing, it is vacuum dried at 60 DEG C
12h.This sample is labeled as 10%Ni-B/TiO2。
(2) LA hydrogenation synthesis GVL:
Accurately weigh the catalyst 20mg and LA 114mg, water 10g prepared in above-mentioned steps (1), be warming up to 100 DEG C, logical
Enter 3MPa hydrogen, carry out hydrogenation reaction, react 2h.Chromatography can obtain: LA conversion ratio is 57.7%, and GVL selectivity is
100%, GVL yield is 57.7%.
Application examples 5
Accurately weigh the catalyst 10%Ni-Zr-B/TiO prepared 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.Result shows:
Application examples 6
Accurately weigh the catalyst 10%Ni-Zr-B/TiO prepared in above-described embodiment 1220mg and LA114mg, water
10mL, is passed through 3MPa hydrogen, carries out hydrogenation reaction, reacts 2h, obtains GVL.Result shows:
Application examples 7
Accurately weigh the catalyst 10%Ni-Zr-B/TiO prepared in above-described embodiment 1220mg and LA114mg, water
10mL, is warming up to 100 DEG C, carries out hydrogenation reaction, reacts 2h, obtains GVL.Result shows:
Application examples 8
Accurately weigh the catalyst 10%Ni-Zr-B/TiO prepared 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.Result shows:
Application examples 9
With reference to preparation method and the step of application examples 1, fixed catalyst is 10%Ni-Zr-B/TiO2With response time 2h,
Catalyst is reused.Result shows:
In above-mentioned each application examples, GVL yield=LA conversion ratio × GVL selectivity.Relevant disclosed in prior art
In catalysis, the most single LA conversion value is higher or GVL selective value is higher.But catalyst provided by the present invention exists
In the application of LA selective hydrogenation synthesis GVL, GVL yield value entirety significantly increases.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all spirit in the present invention
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (7)
1. the preparation method of the nickel zirconium B catalyst of a titanium dichloride load, it is characterised in that comprise the steps:
1) by every 1.234～3.702g Nickel dichloride hexahydrate, 0～1.10g five nitric hydrate zirconium, 0.50～2.5g Polyethylene Glycol-
The deionized water mixing of 800 and 1～50mL, after solid dissolves, at ultrasonic lower addition 0～13.5g titanium dioxide, continues ultrasonic
5～30min, take ultrasonic after the mixture that obtains be placed in baking oven, be dried 12～24h at 80～120 DEG C, obtain sample A；
2) 20～60g water, 0.2～0.6g sodium hydroxide and 1.08～3.24g potassium borohydrides are mixed, obtain solution B, at ice bath
Under the conditions of solution B is slowly dropped in described sample A, then proceed to stir 1～6h and obtain suspension, then by described suspension
Sucking filtration, washing, and at 40～80 DEG C, it is vacuum dried 12～24h, obtain the nickel zirconium B catalyst of titanium dichloride load.
The preparation method of the nickel zirconium B catalyst of titanium dichloride load the most according to claim 1, it is characterised in that: step
2), in, the temperature of ice bath is 0 DEG C.
3. the preparation method of the nickel zirconium B catalyst of a titanium dichloride load according to claim 1 and 2 prepares
The nickel zirconium B catalyst of titanium dichloride load, it is characterised in that: chemical general formula is x%Ni-Zr-B/TiO2, wherein, x% etc.
Value in nickel Yu the mass percent of titanium dioxide.
The nickel zirconium B catalyst of titanium dichloride load the most according to claim 3, it is characterised in that: the value of x is 5～30.
5. the application according to the nickel zirconium B catalyst of the titanium dichloride load described in claim 3 or 4, it is characterised in that:
It is applied to LA selective hydrogenation synthesis GVL or the hydroconversion process of furfural.
The application of the nickel zirconium B catalyst of titanium dichloride load the most according to claim 5, it is characterised in that when being applied to
During LA selective hydrogenation synthesis GVL: temperature be 70～180 DEG C, Hydrogen Vapor Pressure be 1-4MPa, the response time be the bar of 0.5-8h
Under part, with LA as raw material, with water, toluene, dioxane, hexamethylene, methanol as solvent, with hydrogen as reducing agent, described two
Under conditions of titania oxide supported nickel zirconium B catalyst existence, Hydrogenation is for GVL.
The application of the nickel zirconium B catalyst of titanium dichloride load the most according to claim 6, it is characterised in that: LA, solvent
It is 6～20:500～2000:1～10 with the mass ratio of the nickel zirconium B catalyst of described titanium dichloride load.
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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 |
-
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 |
|---|
| VARKOLU MOHAN; ET AL.: "Vapour phase hydrocyclisation of levulinic acid to γ -valerolactone over supported Ni catalysts", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| 盛栋等: "Ni/ZrO2催化乙酰丙酸加氢制备γ-戊内酯", 《化学反应工程与工艺》 * |
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