CN114749191B - Ni/P-attapulgite clay catalyst and preparation method and application thereof - Google Patents
Ni/P-attapulgite clay catalyst and preparation method and application thereof Download PDFInfo
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- CN114749191B CN114749191B CN202210294740.5A CN202210294740A CN114749191B CN 114749191 B CN114749191 B CN 114749191B CN 202210294740 A CN202210294740 A CN 202210294740A CN 114749191 B CN114749191 B CN 114749191B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 56
- 239000004927 clay Substances 0.000 title claims abstract description 56
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 17
- 239000010452 phosphate Substances 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000012153 distilled water Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 150000002196 fatty nitriles Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a Ni/P-attapulgite clay catalyst, a preparation method and application thereof, wherein the carrier of the catalyst is phosphate modified attapulgite clay, the active component is metal Ni, and the load amount of the catalyst is 30-60% of the total mass of the catalyst. According to the invention, the attapulgite clay is used as a carrier, the surface property of the attapulgite clay is regulated and controlled by a phosphate through an impregnation method, and the metal Ni is uniformly distributed on the modified attapulgite clay through a precipitation method, so that the Ni/P-attapulgite clay catalyst is obtained, the hydrothermal stability of the catalyst is improved, the surface acidity of the catalyst is enhanced, and the catalytic reaction activity of the amide group hydrodeoxygenation is improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a Ni/P-attapulgite clay catalyst, a preparation method thereof and application thereof in a trimethylamine preparation reaction by hydrodeoxygenation of N, N-dimethylformamide.
Background
Fatty amine is used as an important chemical raw material and is widely applied to the fields of pharmacy, daily chemicals, textile and the like, and the industrial fatty amine is generally synthesized by the steps of firstly converting fatty acid into amide, dehydrating the amide to generate fatty nitrile, and then carrying out catalytic hydrogenation on the fatty nitrile to obtain the fatty amine (ACS Catalysis, volume 2015, pages 4814-4818). The research shows that the amide group can be directly converted into the fatty amine through catalytic hydrodeoxygenation, and the synthetic strategy can effectively improve the economic efficiency of fatty amine synthesis (Journal of Separation Science, 37 volumes in 2014, and pages 558-565). Catalytic hydrodeoxygenation of noble metals Ru, pd, pt and metal Ni catalysts on amide groupsThe metal Ni catalyst has better catalytic activity in the reaction of converting into fatty amine, wherein the metal Ni catalyst has lower price and rich resources, and has better application prospect (J. Catalysis,2012, 292, 130-137 pages). Al (Al) 2 O 3 It is used as a carrier of metal Ni catalyst in industrial production due to its good thermal stability and large specific surface area. However, during the reaction of amide groups by catalytic hydrodeoxygenation, a large amount of water is generated, the catalyst is in a hydrothermal environment, and Al is caused by the long-term hydrothermal environment 2 O 3 Unsaturated coordination A1 present on the surface 3+ Hydration reactions (Langmuir, 18, pages 7530-7537 in 2002) occur, causing a change in the catalyst structure, resulting in deactivation of the metallic Ni catalyst (catalytic Today, 158, pages 475-480 in 2010). Meanwhile, the amide group can form multiple adsorption bonds with metal Ni atoms in the catalyst, the surface acidity of the catalyst can reduce the surface electron density of the metal Ni in the catalyst, and the adsorption strength of the amide group on the metal Ni atoms is greatly improved, so that the reaction activity of the catalyst on hydrodeoxygenation of the amide group is improved (Angewandte Chemie International Edition, 52 volumes in 2013, 2231-2234).
In order to improve the hydrothermal stability of the metal Ni catalyst, the conventional method adds a small amount of auxiliary agents to the catalyst, such as adding a small amount of SiO during the preparation of the catalyst 2 Not only can the dispersity of the metal Ni in the catalyst be improved, but also the hydrothermal stability of the catalyst can be effectively improved, but the service life of the catalyst still needs to be improved (Journal of Colloid and Interface Science, volume 447 of 2015, pages 68-76). In addition, the hydrothermal stability of the catalyst can be greatly improved by adding the auxiliary metal La, but the catalyst can still be deactivated rapidly under worse reaction conditions, and more serious, the metal La can strengthen the surface alkalinity of the catalyst, weaken the surface acidity of the catalyst and inhibit the reactivity of the catalyst to the catalytic hydrodeoxygenation of amide groups (Journal of Catalysis, volume 338 of 2016, pages 1-11).
It can be seen that although Al in the industrial catalyst can be changed by adding auxiliaries 2 O 3 To improve the hydrothermal stability of the catalystQualitative, but its internal structure is not improved and the hydrothermal stability of the catalyst cannot be fundamentally improved. In addition, the modification of the surface properties of the catalyst by the metal promoters also inhibits the reactivity of the catalyst for the catalytic hydrogenation of amide groups.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a Ni/P-attapulgite clay catalyst which has high hydrothermal stability and higher conversion rate and selectivity when being used in the reaction of preparing amino by catalytic hydrodeoxygenation of amide groups; the invention also aims at providing a preparation method of the Ni/P-attapulgite clay catalyst.
The invention is realized by the following technical scheme:
a Ni/P-attapulgite clay catalyst is characterized in that the carrier is phosphate modified attapulgite clay, the active component is metal Ni, and the load is 30-60%.
The invention further improves the scheme as follows:
a preparation method of a Ni/P-attapulgite clay catalyst comprises the following preparation steps: dispersing attapulgite clay in distilled water, adding phosphate solution under heating and stirring, drying, and calcining to obtain phosphate modified attapulgite clay; re-dispersing the modified attapulgite clay in distilled water, and weighing Ni (NO) 3 ) 2 ·6H 2 O and anhydrous NaCO 3 Respectively dissolving in distilled water, and adding Ni (NO 3 ) 2 ·6H 2 O and anhydrous NaCO 3 The solution of (2) is dropwise added into an aqueous solution dispersed with modified attapulgite clay at the same time to form a precipitate, the obtained precipitate is washed with water to be neutral, and solid powder obtained by drying is subjected to tabletting, sieving and reduction to obtain the Ni/P-attapulgite clay catalyst.
Further, the phosphate solution is a methyl phosphate aqueous solution, and the heating temperature is 60 ℃.
Further, the drying temperature is 80-120 ℃, the calcining temperature is 400-550 ℃, and the calcining time is 2-4 hours.
Further, the Ni (NO 3 ) 2 ·6H 2 The mass of O is calculated by the mass of Ni, so that the mass of Ni accounts for 30-60% of the sum of the mass of Ni and the mass of the phosphate modified attapulgite clay.
Further, ni (NO 3 ) 2 ·6H 2 O and anhydrous NaCO 3 In the solution process, the temperature of the reaction solution was controlled to 80 ℃.
Further, the temperature of the drying is 80-120 ℃ and the time is 6-12 hours.
Further, the sieving process is performed by sieving with a 60-80 mesh sieve.
Further, during the reduction, the temperature is 400-550 ℃, and the reducing gas is H 2 Time was 2h.
The invention further improves the scheme as follows:
the Ni/P-attapulgite clay catalyst is applied to the reaction of preparing trimethylamine by hydrodeoxygenation of N, N-dimethylformamide.
The beneficial effects of the invention are as follows:
the invention selects the water-containing magnesium-rich aluminosilicate porous chain layered attapulgite clay as a carrier, and the attapulgite clay has the characteristics of porous and large specific surface area, contains a large amount of water in the structure, and has high hydrothermal stability. However, attapulgite clay contains a large amount of Mg 2+ Thus having strong surface alkalinity. As a carrier of metal Ni, when used in the reaction of preparing trimethylamine by catalytic hydrodeoxygenation of N, N-dimethylformamide, the catalyst activity of the catalyst is inhibited, so that the surface property of the attapulgite clay is required to be modified. The phosphate has stronger acidity, and the phosphate is utilized to modify the phosphate, so that the surface alkalinity of the phosphate can be inhibited, and the surface acidity of the phosphate can be enhanced. Not only can the hydrothermal stability of the metal Ni catalyst be improved, but also the catalytic reaction activity of the metal Ni catalyst can be improved.
In the preparation method, the surface property of the attapulgite clay is modified by utilizing methyl phosphate through an impregnation method, and the modified P-attapulgite clay is used as a carrier, so that metal Ni is uniformly distributed in the modified P-attapulgite clay through a precipitation method to obtain the Ni/P-attapulgite clay catalyst, the activity of the catalyst is improved, and the hydrothermal stability of the catalyst is improved.
The Ni/P-attapulgite clay catalyst is used for preparing trimethylamine by N, N-dimethylformamide catalytic hydrodeoxygenation. The data shows that at 180℃temperature, 4 MPa pressure and space velocity of 2h −1 Under the condition, the Ni/P-attapulgite clay catalyst after being subjected to the hydrothermal treatment at 180 ℃ of 12h still has very high activity, the conversion rate of N, N-dimethylformamide reaches 63%, the trimethylamine selectivity is 91%, and the catalyst has good industrial application prospect.
Detailed Description
Reference example 1
Weigh 2.5. 2.5 g commercial Al 2 O 3 Dispersing the powder in 50 mL distilled water; another 5.4 g Na 2 CO 3 Dissolving in distilled water to obtain 50 mL solution; then, 12.4 g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in distilled water to prepare 50 mL solution. Will contain Na under stirring 2 CO 3 And Ni (NO) 3 ) 2 Is added dropwise to the Al-dispersed aqueous solution at the same time 2 O 3 Generating precipitate, washing the precipitate with distilled water to neutrality, drying at 100deg.C, tabletting, sieving to obtain 60-80 mesh granule, and H at 450deg.C in a tube furnace 2 Reducing 2h to obtain Ni/Al with load of 50% 2 O 3 The catalyst, sample number is Ni/AlO.
Reference example 2
2.5, g attapulgite clay is weighed and dispersed in distilled water to prepare 50 mL solution; another 5.4 g Na 2 CO 3 Dissolving in distilled water to obtain 50 mL solution; then, 12.4 g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in distilled water to prepare 50 mL solution. Will contain Na under stirring 2 CO 3 And Ni (NO) 3 ) 2 Dripping the aqueous solution of the above into distilled water dispersed with attapulgite clay to generate precipitate, washing the precipitate with distilled water to neutrality, drying at 100deg.C, tabletting, sieving to obtain 60-80 mesh granule, and standing in a tube furnace at 450deg.C for H 2 Reducing 2h to obtain Ni with load capacity of 50%Attapulgite clay catalyst, sample number Ni/ATP.
Example 1
2.5 percent g attapulgite clay is weighed and dispersed in distilled water to prepare 50 percent mL solution, and the solution is heated to 60 ℃. Dropwise adding 20 mL of 0.1 mol/L methyl phosphate solution under stirring; filtering, drying at 100deg.C, and calcining at 450deg.C for 2h to obtain modified attapulgite clay with sample number of P-ATP.
Example 2
Weighing 2.5 g of P-ATP and fully dispersing in distilled water to prepare 50 mL solution; another 5.4 g Na 2 CO 3 Dissolving in distilled water to obtain 50 mL solution; then, 12.4 g of Ni (NO) 3 ) 2 ·6H 2 O was dissolved in distilled water to prepare 50 mL solution. Will contain Na under stirring 2 CO 3 And Ni (NO) 3 ) 2 Dripping the aqueous solution of the above into distilled water dispersed with attapulgite clay to generate precipitate, washing the precipitate with distilled water to neutrality, drying at 100deg.C, tabletting, sieving to obtain 60-80 mesh granule, and standing in a tube furnace at 450deg.C for H 2 And (3) reducing 2h to obtain the Ni/attapulgite clay catalyst with the loading capacity of 50%, wherein the sample number is Ni/P-ATP.
Reference example 3
The sample Ni/AlO catalyst of reference example 1 was transferred to a 100 mL hydrothermal reaction vessel containing 20 mL water, heated to 180℃at a rate of 2℃per minute and held at 12h, and the sample after hydrothermal treatment was cooled to room temperature, filtered and dried, and the obtained sample was designated Ni/AlO-HT.
Reference example 4
The sample Ni/ATP catalyst of reference example 2 was transferred to a 100 mL hydrothermal reaction vessel containing 20 mL water, heated to 180deg.C at a rate of 2deg.C/min and held at 12h, the sample after hydrothermal treatment was cooled to room temperature, filtered and dried, and the sample number was Ni/ATP-HT.
Example 3
The sample Ni/P-ATP catalyst from example 2 was transferred to a 100 mL hydrothermal reaction vessel containing 20 mL water, heated to 180deg.C at a rate of 2deg.C/min and held at 12h, the sample after hydrothermal treatment was cooled to room temperature, filtered and dried to give sample number Ni/P-ATP-HT.
Reference example 5
Weighing 0.4 and g of the sample Ni/AlO in reference example 1, filling the sample Ni/AlO into a reaction tube of a miniature fixed bed reactor, wherein the outer diameter of the reaction tube is 6 mm, and introducing H 2 And reduced by 2h at a rate of 2 ℃/min to 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 1.
Reference example 6
Weighing 0.4 and g of sample Ni/ATP in reference example 2, filling the sample Ni/ATP into a reaction tube of a miniature fixed bed reactor, wherein the outer diameter of the reaction tube is 6 mm, and introducing H 2 And reduced by 2h at a rate of 2 ℃/min to 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 1.
Example 4
Weighing 0.4. 0.4 g sample Ni/P-ATP in example 2, filling into reaction tube of miniature fixed bed reactor, whose outer diameter is 6 mm, and introducing H 2 And reduced by 2h at a rate of 2 ℃/min to 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 1.
Reference example 7
Weighing 0.4 and g of the sample Ni/AlO-HT in reference example 3, filling the sample into a reaction tube of a miniature fixed bed reactor, wherein the outer diameter of the reaction tube is 6 mm, and introducing H 2 And rise at a rate of 2 ℃/minThe reaction mixture was reduced to 2h at 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 2.
Reference example 8
Weighing 0.4 and g of the sample Ni/ATP-HT in reference example 4, filling the sample Ni/ATP-HT into a reaction tube of a miniature fixed bed reactor, wherein the outer diameter of the reaction tube is 6 mm, and introducing H 2 And reduced by 2h at a rate of 2 ℃/min to 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 2.
Example 5
Weighing 0.4. 0.4 g sample Ni/P-ATP-HT in example 3, filling into reaction tube of miniature fixed bed reactor, with outer diameter of 6 mm, and introducing H 2 And reduced by 2h at a rate of 2 ℃/min to 450 ℃. After the catalyst bed temperature is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is used for introducing an N, N-dimethylformamide aqueous solution with the mass fraction of 20 percent, N (H) 2 ) N (N, N-dimethylformamide) =8/1, whsv=2 h −1 The pressure was 4 MPa, and the conversion and selectivity of the reaction were as shown in Table 2.
TABLE 1 catalytic Activity of catalyst in the preparation of trimethylamine by hydrodeoxygenation of N, N-dimethylformamide
| Catalyst preparation examples | Catalyst | Conversion rate | Selectivity of |
| Reference example 5 | Ni/AlO | 56% | 89% |
| Reference example 6 | Ni/ATP | 51% | 97% |
| Example 4 | Ni/P-ATP | 71% | 93% |
TABLE 2 hydrothermal stability of catalyst in the hydrodeoxygenation of N, N-dimethylformamide to trimethylamine
| Catalyst preparation examples | Catalyst | Conversion rate | Selectivity of |
| Reference example 7 | Ni/AlO-HT | 36% | 90% |
| Reference example 8 | Ni/ATP-HT | 48% | 95% |
| Example 5 | Ni/P-ATP-HT | 63% | 91% |
As can be seen from tables 1 and 2, the Ni/P-attapulgite clay catalyst prepared by the invention is used for preparing trimethylamine by catalytic hydrodeoxygenation of N, N-dimethylformamide, and has higher catalytic activity and hydrothermal stability.
Claims (10)
1. The Ni/P-attapulgite clay catalyst is characterized in that the carrier of the catalyst is phosphate modified attapulgite clay, the active component is metal Ni, and the mass loading is 30-60%.
2. A method for preparing the Ni/P-attapulgite clay catalyst according to claim 1, comprising the steps of: dispersing attapulgite clay in distilled water, adding phosphate solution under heating and stirring, drying, and calcining to obtain phosphate modified attapulgite clay; re-dispersing the modified attapulgite clay in distilled water, and weighing Ni (NO) 3 ) 2 ·6H 2 O and anhydrous Na 2 CO 3 Respectively dissolving in distilled water, and adding Ni (NO 3 ) 2 ·6H 2 O and anhydrous Na 2 CO 3 Is added dropwise into the aqueous solution dispersed with the modified attapulgite clay at the same time to form a precipitate, and the obtained precipitateWashing the mixture with water to be neutral, and tabletting, sieving and reducing the solid powder obtained by drying to obtain the Ni/P-attapulgite clay catalyst.
3. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: the phosphate solution is methyl phosphate aqueous solution, and the heating temperature is 60 ℃.
4. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: the drying temperature is 80-120 ℃, the calcining temperature is 400-550 ℃, and the calcining time is 2-4 h.
5. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: the Ni (NO) 3 ) 2 ·6H 2 The mass of O is calculated by the mass of Ni, so that the mass of Ni accounts for 30-60% of the sum of the mass of Ni and the mass of the phosphate modified attapulgite clay.
6. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: adding Ni (NO) in drop by drop 3 ) 2 ·6H 2 O and anhydrous Na 2 CO 3 In the solution process, the temperature of the reaction solution was controlled to 80 ℃.
7. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: the temperature of the drying is 80-120 ℃ and the time is 6-12 h.
8. The method for preparing the Ni/P-attapulgite clay catalyst according to claim 2, wherein the method comprises the following steps: the sieving process is to pass through a 60-80 mesh sieve.
9. The method for preparing a Ni/P-attapulgite clay catalyst according to claim 2, whereinThe method comprises the following steps: the temperature is 400-550 ℃ during the reduction, and the reducing gas is H 2 The time was 2h.
10. The use of a Ni/P-attapulgite clay catalyst according to claim 1 in a process for preparing trimethylamine by hydrodeoxygenation of N, N-dimethylformamide.
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Citations (17)
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