CN108620122A - A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application - Google Patents
A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application Download PDFInfo
- Publication number
- CN108620122A CN108620122A CN201710164113.9A CN201710164113A CN108620122A CN 108620122 A CN108620122 A CN 108620122A CN 201710164113 A CN201710164113 A CN 201710164113A CN 108620122 A CN108620122 A CN 108620122A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- platinum
- cobalt
- biomass
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/898—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with vanadium, tantalum, niobium or polonium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The present invention relates to a kind of load type platinum Co catalysts and preparation method thereof, and the method for being used to prepare pentanediol by biomass and biomass derivatives using the loaded catalyst.Platinum/cobalt is carried on different contents on carrier in the load type platinum Co catalysts, two kinds of metal platinums:The weight ratio of cobalt is 1:20‑10:Between 1, the carrier can be acidic molecular sieve, activated carbon, ZrO2、Nb2O5Or Al2O3At least one of Deng.The catalyst preparation process of the present invention is simple, using the present invention catalyst the method that pentanediol alcohol is prepared by biomass and its derivative can be highly selective preparation 1,2 pentanediols or 1,5 pentanediols, compared with traditional route, this method has the remarkable advantages such as raw material is renewable, reaction process is green, has a good application prospect.
Description
Technical field
The present invention relates to a kind of catalysis biomass Hydrogenations for the catalyst and preparation method thereof of fine chemicals pentanediol
Method, more particularly to a kind of multiple active components catalyst, the catalyst can effective catalysis biomass and its derivatives selectivelies
Hydrogenation is for 1,2- pentanediols and 1,5- pentanediols.
Background technology
1,2- pentanediols and 1,5- pentanediols are important industrial chemicals.1,2- pentanediols are the key that bactericide propiconazoles
Intermediate, recently as the gradually popularization of fungicide application, the demand of 1,2- pentanediol improves year by year.Meanwhile 1,2-
Pentanediol is the cosmetic additive agent haveing excellent performance.1,2- pentanediols have moisturizing, lubrication, antibacterial, anti-as cosmetic additive agent
Rotten, many advantages, such as bio-compatibility is good.1,5-PD is a kind of widely used chemical products, both be can be used alone,
It may be used as production chemical intermediate.1,5- pentanediols can make directly as cutting pool, detergent, wetting agent and special solvent
With, it is also possible to make to produce the raw material of novel poly-vinegar, coating, adhesive, sealant, plasticizer etc., have in terms of synthesizing polyester
There is larger application prospect.
It is the C 5 fraction of PETROLEUM PROCESSING industry generally as combustion that 1, the 2- pentanediol country, which there is no large-scale production, main cause,
Material utilizes, can be as the 1- amylenes or its deep processing product 1 of raw material by rectifying separation, and the production of 2- epoxypentanes is almost sky
In vain.1, the 2- pentanediol raw materials used in production, are dependent on greatly import.The petroleum-based feedstock synthesis technology of existing document report
Mainly there is following method：(1) positive valeric acid method：Using positive valeric acid as raw material, 1,2- penta is made by bromo, hydrolysis and reduction reaction
Glycol.(2) n-amyl alcohol method：N-amyl alcohol dehydration → 1- amylenes → 1- epoxypentanes → 1,2- pentanediols.(3) 1,2- epoxypentanes
Method：It hydrolyzes to obtain 1,2- pentanediols by the formic acid solution of 1,2- epoxypentanes.Raw material 1,2- epoxypentanes are the oxidations of 1- amylenes
Process obtained product, it may also be said to be 1- amylene methods.United States Patent (USP) US4479021 is disclosed with n-pentene, formic acid and dioxygen
Water is raw material, to prepare 1,2- pentanediols, but will produce Peracetic acid in operating process, has certain security risk, in
State patent CN1552684A also utilizes similar method；United States Patent (USP) US4605795 is disclosed in benzene solvent, using amylene
Be made 1- pentylene oxides with perpropionic acid epoxidation, resaponifying obtains 1,2- pentanediol techniques, but the solvent environmental pollution compared with
Greatly.
The synthetic method of 1,5- pentanediols includes mainly：(1) 1 is prepared using tetrahydrofurfuryl alcohol as raw material direct hydrogenation open loop,
5- pentanediols, pressure limit is in 8MPa-42MPa, and temperature is at 120 DEG C -330 DEG C, and this method reaction temperature is high, and equipment investment is big,
Operation difficulty is also high；(2) epoxypentene alcohol is produced with cyclopentadiene photooxidation, then added under 6MPa pressure at 70-100 DEG C and about
1,5-PD is made in hydrogen, but cyclopentadiene photooxidation preparation efficiency is low so that economy is not high；(3) glutaric acid is used first
1,5- glutaric acid first vinegar is prepared for raw material, then in 150-350 DEG C and Hydrogenation under 3-5MPa under CuZnAl catalyst effect
Standby 1,5-PD, conversion ratio are more than 95%, and 1,5-PD is selectively more than 95% (Chinese patent CN1565728), still
The technological process is long, and glutaric acid cost is relatively high；(4) anti-with substituted vinylacetaldehyde and substituted propenyl
It answers, generates substituted 3,4- dihydropyran, then produce glutaraldehyde by catalyzing hydrolysis, be hydrogenated to the pentanediol of substitution later
(Chinese patent CNI072168A, catalyst is using Raney's nickel, the aluminium oxide of modified Raney's nickel, Supported Pt Nanoparticles, palladium or nickel.It should
Method and technology route is long, and cost is higher.(5) use Ru for active component loaded catalyst, with 1,5- glutaraldehydes for raw material,
Under more mild reaction condition, 60-120 DEG C, 2MPa-8MPa, Hydrogenation for 1,5-PD, conversion ratio and high selectivity,
But the cost of material used in the technology is higher.
In the method for preparing pentanediol in summary, it is non-renewable that there are petroleum resources, and reaction condition is more harsh, the three wastes
The problems such as discharge.Biomass agriculture and forestry organic waste material contains abundant xylose, and the resources such as arabinose have and prepare the natural of pentanediol
Excellent carbon skeleton.Wherein, furfural contains as a kind of platform chemicals that output is larger there are two oxygen, need through efficient hydrogen
Solution means can be prepared by pentanediol.Therefore it develops and efficiently prepares pentanediol using biomass and biomass derivatives, not only
With the reproducible advantage of raw material, and the carbon skeleton advantage that owner is natural.Thus, with the increase of pentanediol demand,
New imperative as the biology base pentanediol production new technology of raw material using abundant inexpensive furfural of development.
Invention content
It is an object of the present invention to provide a kind of loaded catalyst, the catalyst can efficient catalytic be rich in five
Biomass and biomass derived chemicals (xylose, furfural, furfuryl alcohol, tetrahydrofurfuryl alcohol) direct hydrogenation of carbon sugar prepares pentanediol.Institute
It is the two of which gold by being selected from two kinds of metals of platinum and cobalt, being carried on carrier and obtained with different contents to state loaded catalyst
Belong to platinum:The weight ratio of cobalt is 1:20-10:Between 1, preferably 1:5-2:1, most preferably 1:1.Gross weight based on catalyst
Amount, the load capacity of the platinum is in 0.05%-10%, preferably 1%.
The carrier can be selected from acidic molecular sieve, activated carbon, ZrO2、Nb2O5Or Al2O3It is one or more in,
It is preferred that activated carbon is as carrier.The activated carbon can pass through a variety of pretreatments, such as be located in advance with formic acid, hypochlorous acid or nitric acid
Reason；In addition if desired, pretreated effect can be improved using modes such as microwave heatings in preprocessing process.
Not necessarily, the needs adjusted as catalyst acid basicity can contain one or more lists in catalyst simultaneously
One or metal composite oxide, such as ZrO2、Nb2O5And ZrO2-Nb2O5Metal composite oxide.
It is another object of the present invention to provide a kind of preparation methods of loaded catalyst, and the method includes following
Step：
Step 1: the preparation of carrier：
Molecular sieve, activated carbon, ZrO will be selected from2、Nb2O5Or Al2O3Deng at least one of carrier as starting material, in pipe
In formula stove, under nitrogen protection, 7 DEG C/min rises to 300-700 DEG C, high-temperature activation 1-8 hours, preferably 3 hours.Then it will obtain
Carrier material, be added in certain density acid solution, stir process 2-10 hours at a certain temperature, acid preferably nitric acid, secondary
Chloric acid or oxalic acid；Processed carrier is 2-10 hours vacuum dried.
Step 2: the preparation of platinum, cobalt precursor：
By a certain amount of platinum salt, cobalt salt (required quality is determined according to the load capacity of catalyst) with deionized water dissolving, stirs
It mixes down, according to total metal salt:Ethylenediamine molar ratio is 1:Ethylenediamine is added drop-wise to above-mentioned containing platinum salt and cobalt salt by 6 amount
In solution, after being added dropwise, standing about 1 hour can be selected from respectively to get to ethylenediamine salt precursor, the platinum salt and cobalt salt
Chloroplatinic acid and cobalt nitrate.
Step 3: the preparation of platinum-cobalt catalyst：
The active component obtained in step 2 is loaded in catalyst carrier using infusion process or the precipitation method, after load
Material through 70-90 DEG C vacuum drying after in a nitrogen atmosphere in 300-500 DEG C roast 2-6 hours；Sample after roasting can be through
Cross NaBH4Or hydrogen reducing is spare, NaBH4Reducing condition is 0 DEG C, NaBH is added in the aqueous solution of pH=10-12 or so4It is molten
Liquid (10 times excessive), is sufficiently stirred 2-4 hours and obtains；Hydrogen reducing condition is 250-500 DEG C and is passed through hydrogen, heating rate 1-5
DEG C/min, recovery time 2-6 hour.
It is yet a further object of the present invention to provide above-mentioned load type platinum-Co catalysts to add for biomass and its derivative
The method that hydrogen prepares pentanediol, the described method comprises the following steps：
Reaction raw materials, polar solvent and support type platinum-cobalt according to the present invention is added in intermittent enclosed high pressure reaction kettle
Catalyst, stirs lower progress catalytic hydrogenation hydrogenation, and the catalyst amount is the 1/10000~1/ of reaction raw materials weight
10, initial hydrogen pressure 1-12Mpa, preferably 1.5-4Mpa, optimal is 3Mpa, and reaction temperature is 80-250 DEG C, preferably 120-
200 DEG C, most preferably 150 DEG C, reaction time 0.5-24h.Catalyst is isolated, volatile product 1,2- penta are isolated in rectifying
Glycol and 1,5- pentanediols.
The wherein described reaction raw materials are biomass or biomass derivatives furfural, furfuryl alcohol, and tetrahydrofurfuryl alcohol etc. is biological of fine quality
Biomass such as corncob of the choosing rich in pentose, rice husk etc..
The polar solvent is selected from water, methanol, ethyl alcohol, propyl alcohol, butanol, isopropanol, isobutanol, formic acid, acetic acid and acetone
In one or more, preferably water, isopropanol.
Advantageous effect
The advantage of the invention is that：It is described for catalysis biomass and its derivative furfural and furfural downstream product furfuryl alcohol,
The direct catalytic hydrogenation of tetrahydrofurfuryl alcohol prepares the catalyst of pentanediol, can high conversion, prepare pentanediol with high selectivity.This hair
Bright catalysis reaction process is simple, and mild condition can prepare 1,2- pentanediols and 1,5-PD simultaneously.Further, originally
Invention preferably compound platinum-cobalt catalyst has many advantages, such as that catalytic activity is high, easily prepared, of low cost, while being easy recycling；
Platinum-cobalt bimetallic and acid carrier concerted catalysis, in the preparation of biology base pentanediol using the upper potentiality with bigger.The present invention
Method compared to other technologies, raw material is and inexhaustible independent of petrochemical industry；Only one step of need, which is catalyzed, is
Product can be obtained.For technique compared to other technologies, reaction condition is mild, green.The method of the present invention has broad application prospects：
Technological process used in the present invention is simple, and small investment, low energy consumption, yield is high, pollution is small, and technology controlling and process is easy, and is suitble to industry
Metaplasia is produced
Specific implementation mode
It is according to the present invention to utilize load type platinum-Co catalysts for biomass and its derivative Hydrogenation for penta 2
In the method for alcohol, if initial hydrogen pressure is less than 1Mpa, the amount of dissolved hydrogen is few in polar solvent, cannot well with catalysis
The activated centre of agent contacts, hydrogenation products low yield unfavorable for hydrogenation process；If Hydrogen Vapor Pressure is more than 4Mpa, hold
Easily form relatively stable intermediate product tetrahydrofuran, it is difficult to which further efficiently hydrogenolysis prepares pentanediol.
Below in conjunction with specific embodiment, the invention will be further described.The embodiment provided is given for example only this hair
It is bright, the protection domain of but do not limit the invention in any way.
Prepare embodiment 1
Catalyst preparation：By chloroplatinic acid, cobalt nitrate according to molar ratio 1:20 be made into molar concentration be respectively 0.05mol/L,
The mixed solution of 1mol/L is spare；100g is taken to pass through dust technology impregnation, the ZSM-5 of 90 DEG C of vacuum drying, 450 DEG C of roastings divides
Son sieve (silica alumina ratio 80) is in steeper；The mixed solution is impregnated on carrier under stiring, the mixed solution
Dosage, which is subject to, just forms slurry；Material after dip loading after 70 DEG C of vacuum drying 10 hours in a nitrogen atmosphere in
450 DEG C roast 5 hours；Repeatedly until platinum theoretical negative carrying capacity reaches 1%；Sample after roasting can through hydrogen reducing,
Hydrogen reducing condition is to be warming up to 300 DEG C with 5 DEG C/min, and 3 hours recovery times, nitrogen protection is spare.
Prepare embodiment 2
By chloroplatinic acid, cobalt nitrate according to molar ratio 1:5 to be made into molar concentration be respectively the mixed of 0.01mol/L, 0.05mol/L
Close solution for standby；Take 100g by 90 DEG C of vacuum drying of dust technology impregnation, the ZSM-5 molecular sieve (silica alumina ratio of 450 DEG C of roastings
For 80) in steeper；The mixed solution is impregnated on carrier under stiring, mixed solution dosage is just to form slurry
Subject to material；Material after dip loading roasts 5 hours in 500 DEG C in a nitrogen atmosphere after 70 DEG C are dried in vacuo 10 hours；Such as
This is repeatedly until platinum theoretical negative carrying capacity reaches 1%；Sample after roasting can be with 5 through hydrogen reducing, hydrogen reducing condition
DEG C/min is warming up to 300 DEG C, 3 hours recovery times, nitrogen protection is spare.
Prepare embodiment 3
By chloroplatinic acid, cobalt nitrate according to molar ratio 1:5 to be made into molar concentration be respectively the mixed of 0.01mol/L, 0.05mol/L
Close solution for standby；100g is taken to pass through the Nb of 450 DEG C of roastings2O5In steeper；The mixed solution is impregnated under stiring
On carrier, mixed solution dosage, which is subject to, just forms slurry；Material after dip loading is after 70 DEG C are dried in vacuo 10 hours
It is roasted 5 hours in 500 DEG C in a nitrogen atmosphere；Repeatedly until platinum theoretical negative carrying capacity reaches 1%；Sample after roasting
Can be to be warming up to 300 DEG C with 5 DEG C/min through hydrogen reducing, hydrogen reducing condition, 3 hours recovery times, nitrogen protection is spare.
Testing example 1
50g furfurals are added in batch type high pressure reactor, 200mL isopropanols are added, will be prepared according to embodiment 1 is prepared
Catalyst 0.5g reaction kettle is added, it is multiple with the air in hydrogen displacement autoclave, later at Hydrogen Vapor Pressure 5MPa,
The reaction time is 12h at 150 DEG C of temperature, and reaction is completed to be cooled to room temperature, and takes the supernatant fluid after centrifugation, crosses 0.22 μm of filter
Film carries out qualitative analysis by the control of the reference substance GC retention times of gas chromatography mass spectrometry (GC-MS) and product to low-boiling products.Chaff
For aldehyde conversion ratio close to 100%, 1,5-PD selectivity is selective up to 7.8% up to 56.2%, 1,2- pentanediol.
Testing example 2
50g furfurals are added in batch type high pressure reactor, 200mL isopropanols are added, will be prepared according to embodiment 2 is prepared
Catalyst 0.5g reaction kettle is added, it is multiple with the air in hydrogen displacement batch type high pressure reactor, later in Hydrogen Vapor Pressure
Under 1.5MPa, the reaction time is 12h at 150 DEG C of temperature, and reaction is completed to be cooled to room temperature, and takes the supernatant fluid after centrifugation, mistake
0.22 μm of filter membrane determines low-boiling products by the control of the reference substance GC retention times of gas chromatography mass spectrometry (GC-MS) and product
Property analysis.For furfural conversion ratio close to 100%, 1,5-PD selectivity is selective up to 57.8% up to 12.7%, 1,2- pentanediol.
Testing example 3
5g corncobs are added in batch type high pressure reactor, 20mL isopropanols and 180mL water are added, by 0.5g according to system
Reaction kettle is added in catalyst prepared by standby embodiment 2, multiple with the air in hydrogen displacement batch type high pressure reactor, Zhi Hou
Under Hydrogen Vapor Pressure 5MPa, the reaction time is 24 hours at 180 DEG C of temperature, and hemicellulose is totally converted completely in corncob, 1,
5- pentanediols selectivity is up to 22.1% (based on the xylose meter in corncob), and 1,2- pentanediol selectivity is up to 30.5% (based on jade
Xylose meter in meter Xin), contain the products such as propylene glycol, butanediol in product simultaneously.
Testing example 4
5g xyloses are added in batch type high pressure reactor, 20mL isopropanols and 180mL water are added, by 0.5g according to preparation
Reaction kettle is added in catalyst prepared by embodiment 2, multiple with the air in hydrogen displacement batch type high pressure reactor, later in hydrogen
Under atmospheric pressure 5MPa, the reaction time is 24 hours at 180 DEG C of temperature, and beautiful xylose rate 100% converts completely, 1,5- penta 2
Alcohol selectivity contains propylene glycol and ethylene glycol simultaneously up to 2.3%, 1,2- pentanediol selectivity up to 41.2% in product.
Testing example 5
50g furfurals are added in batch type high pressure reactor, 200mL isopropanols are added, will be prepared according to embodiment 3 is prepared
Catalyst 1.0g reaction kettle is added, it is multiple with the air in hydrogen displacement batch type high pressure reactor, later in Hydrogen Vapor Pressure
Under 1.5MPa, the reaction time is 12h at 150 DEG C of temperature, and close to 100%, 1,5-PD selectively reaches furfural conversion ratio
0.9%, 1,2- pentanediol is selective up to 48.6%.
Claims (10)
1. a kind of loaded catalyst, the loaded catalyst is to be born with different contents by being selected from two kinds of metals of platinum and cobalt
It is loaded on carrier and obtains, two of which metal platinum:The weight ratio of cobalt is 1:20-10:Between 1；Total weight based on catalyst,
The load capacity of the platinum is in 0.05%-10%.
2. loaded catalyst according to claim 1, which is characterized in that two kinds of metal platinums in the catalyst:The weight of cobalt
Amount ratio is 1:5-2:Between 1；The load capacity of total weight based on catalyst, the platinum is 1%.
3. loaded catalyst according to claim 1, which is characterized in that two kinds of metal platinums in the catalyst:The weight of cobalt
Amount ratio is 1:1.
4. loaded catalyst according to claim 1, which is characterized in that the carrier is selected from acidic molecular sieve, activity
Charcoal, ZrO2、Nb2O5Or Al2O3It is one or more in.
5. loaded catalyst according to claim 4, which is characterized in that the carrier is activated carbon.
6. loaded catalyst according to claim 1, which is characterized in that containing one or more single in the catalyst
Or metal composite oxide, such as ZrO2、Nb2O5And ZrO2-Nb2O5Metal composite oxide.
7. a kind of preparation method of loaded catalyst, the described method comprises the following steps：
Step 1: the preparation of carrier：
Molecular sieve, activated carbon, ZrO will be selected from2、Nb2O5Or Al2O3Deng at least one of carrier as starting material, in tube furnace
In, under nitrogen protection, 7 DEG C/min rises to 300-700 DEG C, high-temperature activation 1-8 hours, preferably 3 hours.Then the load that will be obtained
Body material is added in certain density acid solution, stir process 2-10 hours at a certain temperature, acid preferably nitric acid, hypochlorous acid
Or oxalic acid；Processed carrier is 2-10 hours vacuum dried；
Step 2: the preparation of platinum, cobalt precursor：
By a certain amount of platinum salt, cobalt salt (required quality is determined according to the load capacity of catalyst), with deionized water dissolving, stirring
Under, according to total metal salt:Ethylenediamine molar ratio is 1:Ethylenediamine is added drop-wise to above-mentioned molten containing platinum salt and cobalt salt by 6 amount
In liquid, after being added dropwise, chlorine can be selected from respectively by standing about 1 hour to get to ethylenediamine salt precursor, the platinum salt and cobalt salt
Platinic acid and cobalt nitrate；
Step 3: the preparation of platinum-cobalt catalyst：
The active component obtained in step 2 is loaded in catalyst carrier using infusion process or the precipitation method, the material after load
Material roasts 2-6 hours in 300-500 DEG C in a nitrogen atmosphere after 70-90 DEG C of vacuum drying；Sample after roasting can pass through
NaBH4Or hydrogen reducing is spare, NaBH4Reducing condition is 0 DEG C, NaBH is added in the aqueous solution of pH=10-12 or so4Solution,
It is sufficiently stirred 2-4 hours and obtains；Hydrogen reducing condition is 250-500 DEG C and is passed through hydrogen, 1-5 DEG C of heating rate/min, when reduction
Between 2-6 hours.
8. it is a kind of by biomass and its derivative Hydrogenation for the method for pentanediol, the described method comprises the following steps：
Reaction raw materials, polar solvent is added in intermittent enclosed high pressure reaction kettle and according to any one of claim 1 to 6 institute
Load type platinum-Co catalysts are stated, lower progress catalytic hydrogenation hydrogenation is stirred, the catalyst amount is reaction raw materials weight
1/10000~1/10, initial hydrogen pressure 1-12Mpa, preferably 1.5-4Mpa, optimal is 3Mpa, reaction temperature 80-250
DEG C, preferably 120-200 DEG C, most preferably 150 DEG C, reaction time 0.5-24h；Catalyst is isolated, volatility is isolated in rectifying
Product 1,2- pentanediols and 1,5- pentanediols.
9. it is according to claim 8 by biomass and its derivative Hydrogenation for the method for pentanediol, which is characterized in that institute
Reaction raw materials are stated as biomass or biomass derivatives furfural, furfuryl alcohol, tetrahydrofurfuryl alcohol etc., biomass is preferably rich in pentose
Biomass such as corncob, rice husk etc..
10. it is according to claim 8 by biomass and its derivative Hydrogenation for the method for pentanediol, which is characterized in that
The polar solvent is selected from water, methanol, ethyl alcohol, propyl alcohol, butanol, isopropanol, isobutanol, formic acid, one kind in acetic acid and acetone
Or a variety of, preferably water, isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710164113.9A CN108620122A (en) | 2017-03-20 | 2017-03-20 | A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710164113.9A CN108620122A (en) | 2017-03-20 | 2017-03-20 | A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108620122A true CN108620122A (en) | 2018-10-09 |
Family
ID=63687819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710164113.9A Pending CN108620122A (en) | 2017-03-20 | 2017-03-20 | A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108620122A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
| WO2020258408A1 (en) * | 2019-06-26 | 2020-12-30 | 北京化工大学 | Method for efficient hydro-conversion of furfuryl alcohol, and high-dispersion supported pt catalyst |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
| CN113398879A (en) * | 2021-05-18 | 2021-09-17 | 济南大学 | Method for preparing cobalt-based composite material by using biomass and diatomite |
| CN113877583A (en) * | 2021-11-11 | 2022-01-04 | 中国石油大学(华东) | Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application |
| CN114302904A (en) * | 2019-08-30 | 2022-04-08 | 可隆工业株式会社 | Polymer compound containing cyclic monomer derived from biomass and method for producing same |
| CN116351414A (en) * | 2023-04-06 | 2023-06-30 | 中国科学院广州能源研究所 | Method for preparing pentanediol by catalyzing furfural hydro-conversion through mesoporous silica bimetallic catalyst |
-
2017
- 2017-03-20 CN CN201710164113.9A patent/CN108620122A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109908957A (en) * | 2019-03-18 | 2019-06-21 | 江南大学 | A kind of corrdination type phosphotungstic acid Zr catalyst and its application in catalytic hydrogenation furfural |
| WO2020258408A1 (en) * | 2019-06-26 | 2020-12-30 | 北京化工大学 | Method for efficient hydro-conversion of furfuryl alcohol, and high-dispersion supported pt catalyst |
| CN114302904A (en) * | 2019-08-30 | 2022-04-08 | 可隆工业株式会社 | Polymer compound containing cyclic monomer derived from biomass and method for producing same |
| CN113024350A (en) * | 2021-03-19 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
| CN113024350B (en) * | 2021-03-19 | 2022-06-14 | 中国科学院兰州化学物理研究所 | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound |
| CN113398879A (en) * | 2021-05-18 | 2021-09-17 | 济南大学 | Method for preparing cobalt-based composite material by using biomass and diatomite |
| CN113877583A (en) * | 2021-11-11 | 2022-01-04 | 中国石油大学(华东) | Catalyst in process for producing 1, 5-pentanediol by biological furfuryl alcohol hydrogen ring-opening, preparation and application |
| CN113877583B (en) * | 2021-11-11 | 2023-08-08 | 中国石油大学(华东) | Catalyst in process for producing 1, 5-pentanediol by hydrofuran alcohol hydro-ring opening, preparation and application |
| CN116351414A (en) * | 2023-04-06 | 2023-06-30 | 中国科学院广州能源研究所 | Method for preparing pentanediol by catalyzing furfural hydro-conversion through mesoporous silica bimetallic catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108620122A (en) | A kind of biomass prepares the catalyst of pentanediol, and its preparation method and application | |
| CN105289592B (en) | It is catalyzed method of the levulic acid Hydrogenation for γ valerolactones | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN104744204A (en) | Method for preparing aromatic hydrocarbon by carrying out catalytic hydrodeoxygenation on lignin | |
| CN100467432C (en) | Synthesis method of substituted cyclohexanone and/or substituted cyclohexanol | |
| CN101575295B (en) | Method for preparing diaminonaphthalene by catalytic hydrogenation of dinitronaphthalene | |
| CN101875016A (en) | Catalyst for preparing methane by low-temperature oxidization of methane and preparation method and application thereof | |
| CN113024350B (en) | Method for preparing 1, 5-pentanediol or 1, 6-hexanediol by utilizing bio-based furan compound | |
| CN106279075B (en) | A method of catalysis 5 hydroxymethyl furfural prepares 2,5- dimethyl furans | |
| CN102085479A (en) | Catalyst for hydro-conversion of mixed aqueous solution containing alcohol, aldehyde, acid and ester into alcohols | |
| CN110694618B (en) | Method for hydrodeoxygenation of lignin by ruthenium-based catalyst under deep eutectic solvent condition | |
| CN111218308B (en) | Method for preparing high-density fuel from biomass raw material | |
| CN103691429B (en) | Catalyst for rapid pyrolysis and liquefaction of biomass as well as preparation method and application thereof | |
| CN108187730A (en) | A kind of support type composition metal-acid bifunctional catalyst | |
| CN104098439A (en) | Biomass glycol refining method | |
| CN106866364A (en) | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol | |
| CN102786424A (en) | Method for preparing 3-chloro-4-methylaniline through catalytic hydrogenation | |
| CN103055851A (en) | Catalyst for synthesizing oxalic ester through oxidative coupling of CO gas phase as well as preparation and application method thereof | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| CN113877583B (en) | Catalyst in process for producing 1, 5-pentanediol by hydrofuran alcohol hydro-ring opening, preparation and application | |
| CN103071512A (en) | Catalyst and application of catalyst in technology for preparing 1,5-pentanediol through hydrogenolysis of tetrahydrofurfuryl alcohol | |
| Lou et al. | Agricultural waste valorization towards (nano) catalysts for the production of chemicals and materials | |
| CN112778250B (en) | Preparation method of 5-hydroxymethyl furoic acid | |
| CN101412661A (en) | Solid-state cardanol and preparation thereof | |
| CN109851473B (en) | Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181009 |