CN107699277A - Method of the one kind using Pt MOF (La) RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation - Google Patents
Method of the one kind using Pt MOF (La) RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation Download PDFInfo
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- CN107699277A CN107699277A CN201711108492.6A CN201711108492A CN107699277A CN 107699277 A CN107699277 A CN 107699277A CN 201711108492 A CN201711108492 A CN 201711108492A CN 107699277 A CN107699277 A CN 107699277A
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- Prior art keywords
- mof
- phenolic compound
- oil base
- rgo catalyst
- biological oil
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- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 150000002989 phenols Chemical class 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 10
- 239000013049 sediment Substances 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000001896 cresols Chemical class 0.000 claims description 3
- 229960001867 guaiacol Drugs 0.000 claims description 3
- -1 dimethyl Formyl amine Chemical class 0.000 claims 2
- 238000006392 deoxygenation reaction Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000012621 metal-organic framework Substances 0.000 description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/396—
-
- B01J35/40—
-
- B01J35/60—
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/37—Lanthanum
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
One kind, to the method for biological oil base phenolic compound hydrogenation deoxidation, specifically includes following steps using Pt MOF (La) RGO catalyst：(1) Pt@MOF (La) RGO catalyst is synthesized：MOF (La) is first synthesized, then prepares MOF (La) GO, finally obtains Pt@MOF (La) RGO catalyst.(2) Pt MOF (La) RGO catalyst, biological oil base phenolic compound and deionized water are put into batch reactor, in solid-liquid ratio 0.01~0.1,0.5~2MPa of hydrogen dividing potential drop, hydrogenation deoxidation reaction is carried out under the conditions of 50~200 DEG C of temperature, finally gives hydrogenation deoxidation product.Specific surface area of catalyst is big made from this method, and feed stock conversion is high, good product selectivity, stable in catalytic performance.
Description
(1) technical field
The present invention provides one kind using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation
Method, belong to technical field of catalytic hydrogenation.
(2) background technology
Metal-organic framework materials (MOFs) have the chemical base of high-specific surface area, hole size adjustable, hole surface due to it
The advantages such as group and surface potential energy are controllable, very extensive work is played in gas separation, pharmaceutical carrier, heterogeneous catalysis etc.
With.Graphene oxide (GO) is the oxide of graphene, after graphene is oxidized, thereon oxygen-containing functional group increase and make property compared with
Graphene is more active.Wherein reduced form graphene oxide (RGO) has the characteristics of multilist planar defect, can be used as carried metal
The avtive spot of ion.
Composite is made as carrier in MOF (La) and GO by the present invention, supporting Pt metal, adds reducing agent microwave reaction
After obtain Pt MOF (La)-RGO catalyst, can be used for biological oil base phenolic compound (phenol, guaiacol, cresols etc.)
Carry out hydrogenation deoxidation.
(3) content of the invention
A kind of method using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation of the invention,
Specific steps include：Pt MOF (La)-RGO catalyst, biological oil base phenolic compound and deionized water are put into intermittent reaction
In device, in solid-liquid ratio 0.01~0.1,0.5~2MPa of hydrogen dividing potential drop, hydrogenation deoxidation reaction is carried out under the conditions of 50~200 DEG C of temperature, most
Hydrogenation deoxidation product is obtained eventually.
The preparation method of Pt@MOF (La)-RGO catalyst recited above, comprises the following steps：
Step 1：By mass concentration be 3%~7% lanthanum nitrate and mass concentration is that 3%~7% trimesic acid is put into two
NMF dissolves, and at 100~140 DEG C after 10~48h of hydro-thermal process, carries out centrifugal treating, then by sediment a diformazans
Base formamide and absolute ethyl alcohol are washed 3~5 times respectively, and 8~24h is then dried at 60~150 DEG C, that is, obtains MOF (La).
Step 2：GO is scattered in dimethylformamide, addition is 5~50%, then adds what step 1 obtained
MOF (La) material, produce MOF (La)-GO.
Step 3：Platinum nitrate is dissolved in ethanol, mass concentration is 5~50%, then adds the MOF that step 2 obtains
(La)-GO, load capacity are 1~50%, stir 1~3h；Then be rapidly added hydrazine hydrate, in microwave reactor react 1~
3min, 500~1200W of power；After being cooled to room temperature, centrifugal treating is carried out, then by sediment b deionized waters and absolute ethyl alcohol
Wash respectively 3~5 times, 8~24h is then dried at 60~150 DEG C, that is, obtains Pt MOF (La)-RGO catalyst.
Biological oil base phenolic compound recited above is one kind in phenol, guaiacol, cresols.
The advantage of the invention is that：
1st, a kind of be hydrogenated with using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound proposed by the present invention is taken off
The method of oxygen, Pt@MOF (the La)-RGO catalyst prepared in this method have a size uniformity, regular appearance, stable performance, than
The advantages that surface area is big, and multiple aperture is distributed.
2nd, a kind of be hydrogenated with using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound proposed by the present invention is taken off
The method of oxygen, the catalytic activity of Pt@MOF (La)-RGO catalyst that this method obtains is good, and feed stock conversion is high, selectivity of product
Height, stable in catalytic performance.
(4) illustrate
Fig. 1：One kind proposed by the present invention is hydrogenated with using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound
The process chart of the method for deoxidation.
(5) embodiment
The technical characterstic of the present invention is described in detail below in conjunction with the drawings and specific embodiments, as shown in Figure 1.
Embodiment 1：
A kind of method using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation of the invention,
Specific steps include：Pt MOF (La)-RGO catalyst, biological oil base phenolic compound and deionized water are put into intermittent reaction
In device, in solid-liquid ratio 0.05, hydrogen dividing potential drop 1MPa, hydrogenation deoxidation reaction is carried out under the conditions of 100 DEG C of temperature, finally gives hydrogenation deoxidation
Product.
The preparation method of Pt@MOF (La)-RGO catalyst recited above, comprises the following steps：
Step 1：By mass concentration be 5% lanthanum nitrate and mass concentration is that 5% trimesic acid is put into dimethylformamide
Dissolving, at 110 DEG C after hydro-thermal process 20h, centrifugal treating is carried out, then by sediment a dimethylformamides and absolute ethyl alcohol
Wash 4 times respectively, 12h is then dried in vacuo at 100 DEG C, that is, obtains MOF (La).
Step 2：GO is scattered in dimethylformamide, addition 10%, then adds the MOF that step 1 obtains
(La) material, MOF (La)-GO is produced.
Step 3：Platinum nitrate is dissolved in ethanol, mass concentration 10%, the MOF (La) that then addition step 2 obtains-
GO, load capacity 20%, stir 2h；Then hydrazine hydrate is rapidly added, 2min, power 800W are reacted in microwave reactor；It is cold
But to after room temperature, centrifugal treating is carried out, then sediment b is washed 4 times respectively with deionized water and absolute ethyl alcohol, then 105
12h is dried at DEG C, that is, obtains Pt MOF (La)-RGO catalyst.
Biological oil base phenolic compound recited above is phenol.
As a result showing, the conversion ratio of Pt@MOF (La)-RGO catalyst Pyrogentisinic Acids is 98%, and the selectivity of product is 95%,
Catalytic effect is notable.
Embodiment 2：
A kind of method using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation of the invention,
Specific steps include：Pt MOF (La)-RGO catalyst, biological oil base phenolic compound and deionized water are put into intermittent reaction
In device, in solid-liquid ratio 0.01, hydrogen dividing potential drop 2MPa, hydrogenation deoxidation reaction is carried out under the conditions of 150 DEG C of temperature, finally gives hydrogenation deoxidation
Product.
The preparation method of Pt@MOF (La)-RGO catalyst recited above, comprises the following steps：
Step 1：By mass concentration be 4% lanthanum nitrate and mass concentration is that 6% trimesic acid is put into dimethylformamide
Dissolving, at 140 DEG C after hydro-thermal process 10h, centrifugal treating is carried out, then by sediment a dimethylformamides and absolute ethyl alcohol
Wash respectively 5 times, 8h is then dried at 150 DEG C, that is, obtains MOF (La).
Step 2：GO is scattered in dimethylformamide, addition 40%, then adds the MOF that step 1 obtains
(La) material, MOF (La)-GO is produced.
Step 3：Platinum nitrate is dissolved in ethanol, mass concentration 40%, the MOF (La) that then addition step 2 obtains-
GO, load capacity 40%, stir 1h；Then hydrazine hydrate is rapidly added, 1min, power 1200W are reacted in microwave reactor；It is cold
But to after room temperature, centrifugal treating is carried out, then sediment b is washed 5 times respectively with deionized water and absolute ethyl alcohol, then 150
8h is dried at DEG C, that is, obtains Pt MOF (La)-RGO catalyst.
Biological oil base phenolic compound recited above is phenol.
As a result showing, the conversion ratio of Pt@MOF (La)-RGO catalyst Pyrogentisinic Acids is 95%, and the selectivity of product is 93%,
Catalytic effect is notable.
Embodiment 3：
A kind of method using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation of the invention,
Specific steps include：Pt MOF (La)-RGO catalyst, biological oil base phenolic compound and deionized water are put into intermittent reaction
In device, in solid-liquid ratio 0.1, hydrogen dividing potential drop 0.5MPa, hydrogenation deoxidation reaction is carried out under the conditions of temperature 50 C, finally gives hydrogenation deoxidation
Product.
The preparation method of Pt@MOF (La)-RGO catalyst recited above, comprises the following steps：
Step 1：By mass concentration be 7% lanthanum nitrate and mass concentration is that 7% trimesic acid is put into dimethylformamide
Dissolving, at 100 DEG C after hydro-thermal process 40h, centrifugal treating is carried out, then by sediment a dimethylformamides and absolute ethyl alcohol
Wash respectively 3 times, 24h is then dried at 60 DEG C, that is, obtains MOF (La).
Step 2：GO is scattered in dimethylformamide, addition 5%, then adds the MOF that step 1 obtains
(La) material, MOF (La)-GO is produced.
Step 3：Platinum nitrate is dissolved in ethanol, mass concentration 5%, the MOF (La) that then addition step 2 obtains-
GO, load capacity 1%, stir 3h；Then hydrazine hydrate is rapidly added, 3min, power 500W are reacted in microwave reactor；Cooling
To room temperature, centrifugal treating is carried out, then sediment b is washed 3 times respectively with deionized water and absolute ethyl alcohol, then at 60 DEG C
24h is dried, that is, obtains Pt MOF (La)-RGO catalyst.
Biological oil base phenolic compound recited above is phenol.
As a result showing, the conversion ratio of Pt@MOF (La)-RGO catalyst Pyrogentisinic Acids is 90%, and the selectivity of product is 91%,
Catalytic effect is notable.
Claims (3)
1. method of the one kind using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation, its feature exist
In the specific steps of this method include：Pt MOF (La)-RGO catalyst, biological oil base phenolic compound and deionized water are put
Enter in batch reactor, in solid-liquid ratio 0.01~0.1,0.5~2MPa of hydrogen dividing potential drop, be hydrogenated with the conditions of 50~200 DEG C of temperature
Deoxygenation, finally give hydrogenation deoxidation product.
2. the preparation method of Pt@MOF (La)-RGO catalyst described in a kind of claim 1, it is characterised in that including following step
Suddenly：
Step 1：By mass concentration be 3%~7% lanthanum nitrate and mass concentration is that 3%~7% trimesic acid is put into dimethyl
Formyl amine solvent, at 100~140 DEG C after 10~48h of hydro-thermal process, centrifugal treating is carried out, then by sediment a dimethyl methyls
Acid amides and absolute ethyl alcohol are washed 3~5 times respectively, and 8~24h is then dried at 60~150 DEG C, that is, obtains MOF (La)；
Step 2：GO is scattered in dimethylformamide, addition is 5~50%, then adds the MOF that step 1 obtains
(La) material, MOF (La)-GO is produced；
Step 3：Platinum nitrate is dissolved in ethanol, mass concentration is 5~50%, the MOF (La) that then addition step 2 obtains-
GO, load capacity are 1~50%, stir 1~3h；Then hydrazine hydrate is rapidly added, 1~3min, work(are reacted in microwave reactor
500~1200W of rate；After being cooled to room temperature, centrifugal treating is carried out, then sediment b is washed respectively with deionized water and absolute ethyl alcohol
Wash 3~5 times, 8~24h is then dried at 60~150 DEG C, that is, obtains Pt MOF (La)-RGO catalyst.
3. one kind according to claim 1 is hydrogenated with using Pt MOF (La)-RGO catalyst to biological oil base phenolic compound
The method of deoxidation, it is characterised in that：Described biological oil base phenolic compound is one kind in phenol, guaiacol, cresols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108492.6A CN107699277A (en) | 2017-11-09 | 2017-11-09 | Method of the one kind using Pt MOF (La) RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108492.6A CN107699277A (en) | 2017-11-09 | 2017-11-09 | Method of the one kind using Pt MOF (La) RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107699277A true CN107699277A (en) | 2018-02-16 |
Family
ID=61180039
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711108492.6A Pending CN107699277A (en) | 2017-11-09 | 2017-11-09 | Method of the one kind using Pt MOF (La) RGO catalyst to biological oil base phenolic compound hydrogenation deoxidation |
Country Status (1)
| Country | Link |
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| CN (1) | CN107699277A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280258A (en) * | 2019-08-02 | 2019-09-27 | 北京高新利华科技股份有限公司 | A kind of diesel oil hydrofining catalyst and preparation method thereof |
-
2017
- 2017-11-09 CN CN201711108492.6A patent/CN107699277A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110280258A (en) * | 2019-08-02 | 2019-09-27 | 北京高新利华科技股份有限公司 | A kind of diesel oil hydrofining catalyst and preparation method thereof |
| CN110280258B (en) * | 2019-08-02 | 2022-05-17 | 北京高新利华科技股份有限公司 | Diesel oil hydrofining catalyst and preparation method thereof |
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