CN114749191A - 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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- CN114749191A CN114749191A CN202210294740.5A CN202210294740A CN114749191A CN 114749191 A CN114749191 A CN 114749191A CN 202210294740 A CN202210294740 A CN 202210294740A CN 114749191 A CN114749191 A CN 114749191A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 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 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 238000011068 loading method Methods 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 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 21
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 11
- 125000003368 amide group Chemical group 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002196 fatty nitriles Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000000084 colloidal system Substances 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
- 239000006185 dispersion Substances 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
- 239000008187 granular material Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method 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 and a preparation method and application thereof, wherein a carrier of the catalyst is phosphate modified attapulgite clay, an active component is metal Ni, and the loading amount of the metal Ni is 30-60% of the total mass of the catalyst. According to the invention, attapulgite clay is used as a carrier, phosphate is used for regulating and controlling the surface property of the attapulgite clay through an impregnation method, and metal Ni is uniformly distributed on the modified attapulgite clay through a precipitation method to obtain the Ni/P-attapulgite clay catalyst.
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 reaction for preparing trimethylamine by hydrodeoxygenation of N, N-dimethylformamide.
Background
Fatty amine is used as an important chemical raw material and widely applied in the fields of pharmacy, daily chemical products, textile and the like, and the synthesis steps of the fatty amine in industry are generally that fatty acid is converted into amide, the amide is dehydrated to generate fatty nitrile, and the fatty nitrile is subjected to catalytic hydrogenation to obtain the fatty amine (ACS Catalysis, volume 5 in 2015, page 4814-4818). Researches find that amide groups can also be directly converted into fatty amines through catalytic hydrodeoxygenation, and the synthesis strategy can be effectively improvedEconomic efficiency of fatty amine synthesis (Journal of Separation Science, vol 37 2014, pp 558-565). Noble metals Ru, Pd, Pt and metal Ni catalysts have better catalytic activity in the reaction of directly converting amide groups into fatty amine through catalytic hydrodeoxygenation, wherein the metal Ni catalysts have better application prospects due to low price and rich resources (J. Catalysis, 292 vol.2012 and pages 130-137). Al (Al)2O3Due to good thermal stability and large specific surface area, the catalyst is often used as a carrier of a metallic Ni catalyst in industrial production. However, in the reaction process of catalytic hydrodeoxygenation of amide groups, a large amount of water is generated, so that the catalyst is in a hydrothermal environment, and Al can be generated in the hydrothermal environment for a long time2O3Surface-present unsaturated coordination A13+Hydration reactions (Langmuir, Vol. 18 2002, pp. 7530-7537) occur, which cause changes in the catalyst structure, leading to deactivation of the metallic Ni catalyst (Catalysis Today, Vol. 158 2010, pp. 475-480). Meanwhile, the amide group can form multiple adsorption bonds with metal Ni atoms in the catalyst, and the surface acidity of the catalyst can reduce the surface electron density of the metal Ni in the catalyst and greatly improve the adsorption strength of the amide group on the metal Ni atoms, so that the reaction activity of the catalyst on the amide group hydrodeoxygenation is improved (Angewandte chemical International Edition, volume 52 in 2013, pages 2231-2234).
In order to improve the hydrothermal stability of the metallic Ni catalyst, a small amount of auxiliary agent is added into the catalyst by the traditional method, such as a small amount of SiO added in the preparation process of the catalyst2Although the dispersion of metal Ni in the catalyst can be improved and the hydrothermal stability of the catalyst can be effectively improved, the service life of the catalyst still needs to be improved (Journal of Colloid and Interface Science, volume 2015 447, pages 68-76). In addition, the addition of the assistant metal La can also greatly improve the hydrothermal stability of the catalyst, but the catalyst can still be quickly deactivated under more severe reaction conditions, and more seriously, the metal La can enhance the surface alkalinity of the catalyst, weaken the surface acidity of the catalyst and inhibit the reaction activity of the catalyst on amide group catalytic hydrodeoxygenation (Journal of Catalysis, volume 338, pages 1 to 11 in 2016).
It can be seen that although Al in the industrial catalyst can be changed by adding an auxiliary agent2O3The surface structure of (2) to improve the hydrothermal stability of the catalyst, but the internal structure of the catalyst is not improved, and the hydrothermal stability of the catalyst cannot be improved fundamentally. In addition, the modification of the surface properties of the catalyst by the metal promoter also inhibits the reactivity of the catalyst towards the catalytic hydrogenation of the 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 amide group catalytic hydrodeoxygenation; the invention also aims to provide 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 a carrier is attapulgite clay with a phosphate modified surface, an active component is metal Ni, and the loading amount 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; dispersing the modified attapulgite clay in distilled water again, and respectively weighing Ni (NO)3)2·6H2O and anhydrous NaCO3Respectively dissolved in distilled water to contain Ni (NO)3)2·6H2O and anhydrous NaCO3Dropwise adding the solution into the aqueous solution dispersed with the modified attapulgite clay to form precipitate, washing the obtained precipitate with water to neutrality, drying to obtain solid powder, tabletting, sieving and reducing 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, said Ni (NO)3)2·6H2The mass of the O is calculated by the mass of the Ni, and the mass of the Ni accounts for 30-60% of the sum of the mass of the Ni and the mass of the phosphate modified attapulgite clay.
Further, Ni (NO) is added dropwise3)2·6H2O and anhydrous NaCO3During the solution process, the temperature of the reaction solution was controlled to 80 ℃.
Further, the drying temperature is 80-120 ℃, and the drying time is 6-12 hours.
Furthermore, the sieve is sieved by a sieve of 60-80 meshes.
Further, during reduction, the temperature is 400-550 ℃, and the reducing gas is H2The time is 2 h.
The invention has the further improved scheme that:
the Ni/P-attapulgite clay catalyst is applied to the reaction of preparing trimethylamine by hydrodeoxygenation of N, N-dimethylformamide.
The invention has the beneficial effects that:
the invention selects the water-containing attapulgite clay with rich magnesium aluminum silicate porous chain layers as a carrier, the attapulgite clay has the characteristics of porosity and large specific surface area, and the structure contains a large amount of water and has high hydrothermal stability. However, the attapulgite clay contained a large amount of Mg2+And thus has strong surface alkalinity. When the metal Ni carrier is used in the reaction of preparing trimethylamine by catalytic hydrodeoxygenation of N, N-dimethylformamide, the catalytic reaction activity of the metal Ni carrier can be inhibited, so that the surface property of the attapulgite clay needs to be modified. The phosphate has strong acidity, and the surface alkalinity can be inhibited and the surface acidity can be enhanced by modifying the phosphate by utilizing the phosphate. Not only can improve the hydrothermal stability of the metal Ni catalyst, but also can improve the catalytic reaction activity of the metal Ni catalyst.
In the preparation method, the surface property of the attapulgite clay is modified by methyl phosphate through an impregnation method, and the modified P-attapulgite clay is used as a carrier, and metal Ni is uniformly distributed in the modified P-attapulgite clay through a precipitation method to obtain the Ni/P-attapulgite clay catalyst, so that 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 the reaction of preparing trimethylamine by catalytic hydrodeoxygenation of N, N-dimethylformamide. The data show a temperature of 180 ℃, a pressure of 4 MPa and a space velocity of 2 h−1The Ni/P-attapulgite clay catalyst after being subjected to hydrothermal treatment at 180 ℃ for 12 hours still has very high activity, the conversion rate of N, N-dimethylformamide reaches 63%, the selectivity of trimethylamine is 91%, and the catalyst has good industrial application prospect.
Detailed Description
Reference ratio 1
2.5 g of commercial Al are weighed out2O3The powder was dispersed in 50 mL of distilled water; another 5.4 g of Na is taken2CO3Dissolving in distilled water to prepare 50 mL solution; further, 12.4 g of Ni (NO) was weighed3)2·6H2O was dissolved in distilled water to make 50 mL of solution. Under stirring, Na is added2CO3And Ni (NO)3)2Is simultaneously dropped into the Al-dispersed solution2O3Washing the precipitate with distilled water to neutrality, drying at 100 deg.C, tabletting, sieving to obtain 60-80 mesh granules, and drying in tubular furnace at 450 deg.C in H2Reducing for 2 h to obtain Ni/Al with 50 percent of load capacity2O3Catalyst, sample No. Ni/AlO.
Reference ratio 2
Weighing 2.5 g of attapulgite clay, and dispersing in distilled water to prepare 50 mL of solution; another 5.4 g of Na is taken2CO3Dissolving in distilled water to prepare 50 mL solution; further, 12.4 g of Ni (NO) was weighed3)2·6H2O was dissolved in distilled water to make 50 mL of solution. Will contain Na under stirring2CO3And Ni (NO)3)2The aqueous solution is simultaneously dropped into distilled water dispersed with attapulgite clay to generate precipitate, and the precipitate is washed with distilled water to be inDrying at 100 ℃, tabletting and sieving to prepare particles of 60-80 meshes, and then carrying out H treatment in a tube furnace at 450 DEG C2Reducing for 2 h to obtain the Ni/attapulgite clay catalyst with the load of 50 percent, wherein the sample number is Ni/ATP.
Example 1
2.5 g of attapulgite clay was weighed and dispersed in distilled water to prepare 50 mL of a solution, which was heated to 60 ℃. Adding 20 mL of 0.1 mol/L methyl phosphate solution dropwise under the stirring state; filtering, drying at 100 deg.C, and calcining at 450 deg.C for 2 hr to obtain modified attapulgite clay with sample number of P-ATP.
Example 2
Weighing 2.5 g P-ATP, fully dispersing in distilled water, and preparing into 50 mL solution; another 5.4 g of Na is taken2CO3Dissolving in distilled water to prepare 50 mL solution; then, 12.4 g of Ni (NO) was weighed3)2·6H2O was dissolved in distilled water to make 50 mL of solution. Will contain Na under stirring2CO3And Ni (NO)3)2The aqueous solution is simultaneously dripped into distilled water dispersed with attapulgite clay to generate precipitate, the precipitate is washed to be neutral by distilled water, dried at 100 ℃, then tableted and sieved to prepare particles of 60-80 meshes, and then the particles are subjected to H treatment in a tubular furnace at 450 DEG C2Reducing for 2 h to obtain the Ni/attapulgite clay catalyst with the load of 50 percent, wherein the sample number is Ni/P-ATP.
Reference example 3
Transferring the Ni/AlO catalyst of the sample in the reference ratio 1 into a 100 mL hydrothermal reaction kettle filled with 20 mL of water, heating to 180 ℃ at the speed of 2 ℃/min and keeping for 12 h, cooling the sample after the hydrothermal treatment to room temperature, filtering and drying, wherein the obtained sample is numbered as Ni/AlO-HT.
Reference ratio 4
Transferring the Ni/ATP catalyst of the sample in the reference ratio 2 into a 100 mL hydrothermal reaction kettle filled with 20 mL of water, heating to 180 ℃ at the speed of 2 ℃/min, keeping for 12 hours, cooling the sample after the hydrothermal treatment to room temperature, filtering and drying, wherein the serial number of the obtained sample is Ni/ATP-HT.
Example 3
The Ni/P-ATP catalyst of the sample in the example 2 is transferred into a 100 mL hydrothermal reaction kettle filled with 20 mL water, the temperature is raised to 180 ℃ at the speed of 2 ℃/min and kept for 12 h, the sample after the hydrothermal treatment is cooled to the room temperature, filtered and dried, and the obtained sample is numbered as Ni/P-ATP-HT.
Reference ratio 5
0.4 g of the sample Ni/AlO in reference ratio 1 is weighed and filled into a reaction tube of a micro fixed bed reactor, the outer diameter of the reaction tube is 6 mm, and H is introduced2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 1.
Reference ratio 6
0.4 g of the sample Ni/ATP of reference example 2 was weighed and charged into a reaction tube of a mini fixed-bed reactor having an outer diameter of 6 mm, and H was introduced2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 1.
Example 4
0.4 g of the sample Ni/P-ATP of example 2 was weighed and charged into a reaction tube of a mini fixed-bed reactor having an outer diameter of 6 mm, and H was introduced2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 1.
Reference ratio 7
0.4 g of the sample Ni/AlO-HT of reference example 3 was weighed out and loadedIn a reaction tube of the miniature fixed bed reactor, the outer diameter of the reaction tube is 6 mm, and H is introduced2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 2.
Reference ratio 8
0.4 g of the sample Ni/ATP-HT obtained in reference example 4 was weighed and charged into a reaction tube of a mini fixed-bed reactor having an outer diameter of 6 mm, and H was introduced thereinto2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 2.
Example 5
0.4 g of the sample Ni/P-ATP-HT obtained in example 3 was weighed and loaded into a reaction tube of a mini-fixed-bed reactor, the outer diameter of the reaction tube was 6 mm, and H was introduced2And heating to 450 ℃ at the speed of 2 ℃/min and reducing for 2 h. When the temperature of the catalyst bed layer is cooled to the set reaction temperature, namely 180 ℃, a liquid sample injection pump is utilized to introduce 20 percent by mass of N, N-dimethylformamide aqueous solution, N (H)2) N (N, N-dimethylformamide) = 8/1, WHSV = 2 h−1The pressure was 4 MPa, and the results of the conversion and selectivity analyses of the reaction are shown in Table 2.
TABLE 1 catalytic activity of the catalyst in the preparation of trimethylamine by hydrodeoxygenation of N, N-dimethylformamide
| Examples of catalyst preparation | Catalyst and process for producing the same | Conversion rate | Selectivity is |
| Reference ratio 5 | Ni/AlO | 56% | 89% |
| Reference ratio 6 | Ni/ATP | 51% | 97% |
| Example 4 | Ni/P-ATP | 71% | 93% |
TABLE 2 hydrothermal stability of catalyst in preparation of trimethylamine by hydrodeoxygenation with N, N-dimethylformamide
| Examples of catalyst preparation | Catalyst and process for preparing same | Conversion rate | Selectivity is |
| Reference ratio7 | Ni/AlO-HT | 36% | 90% |
| Reference ratio 8 | Ni/ATP-HT | 48% | 95% |
| Example 5 | Ni/P-ATP-HT | 63% | 91% |
As shown in tables 1 and 2, the Ni/P-attapulgite clay catalyst prepared by the invention has higher catalytic activity and hydrothermal stability when used for preparing trimethylamine by catalytic hydrodeoxygenation of N, N-dimethylformamide.
Claims (10)
1. The Ni/P-attapulgite clay catalyst is characterized in that a carrier of the catalyst is attapulgite clay with a phosphate modified surface, an active component is metal Ni, and the loading amount is 30-60%.
2. A process for the preparation of the Ni/P-attapulgite clay catalyst according to claim 1, wherein the process comprises 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; dispersing the modified attapulgite clay in distilled water again, and respectively weighing Ni (NO)3)2·6H2O and anhydrous NaCO3Respectively dissolved in distilled water to contain Ni (NO)3)2·6H2O and anhydrous NaCO3The solution is dropwise added into the modified attapulgite clay dispersed in the solution simultaneouslyForming a precipitate in an aqueous solution of soil, washing the obtained precipitate with water to be neutral, and tabletting, sieving and reducing 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)2·6H2The mass of the O is calculated by the mass of the Ni, and the mass of the Ni accounts for 30-60% of the sum of the mass of the 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: in the dropwise addition of Ni (NO)3)2·6H2O and anhydrous NaCO3During 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 drying temperature is 80-120 ℃, and the drying 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: and sieving by a sieve of 60-80 meshes.
9. The Ni/P-attapulgite clay catalyst of claim 2The preparation method of the reagent is characterized in that: during reduction, the temperature is 400-550 ℃, and the reducing gas is H2The time is 2 h.
10. The use of the Ni/P-attapulgite clay catalyst of claim 1 in the hydrodeoxygenation of N, N-dimethylformamide to produce trimethylamine.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
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