CN115624988B - Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof - Google Patents
Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN115624988B CN115624988B CN202211311915.5A CN202211311915A CN115624988B CN 115624988 B CN115624988 B CN 115624988B CN 202211311915 A CN202211311915 A CN 202211311915A CN 115624988 B CN115624988 B CN 115624988B
- Authority
- CN
- China
- Prior art keywords
- solution
- aerogel
- poly
- sodium
- trimellitate
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 229910004298 SiO 2 Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000004964 aerogel Substances 0.000 claims abstract description 50
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 45
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 22
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- PXEDJBXQKAGXNJ-UHFFFAOYSA-L disodium glutamate Chemical compound [Na+].[Na+].[O-]C(=O)C(N)CCC([O-])=O PXEDJBXQKAGXNJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000002791 soaking Methods 0.000 claims description 28
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 26
- 229910052742 iron Inorganic materials 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 125000005591 trimellitate group Chemical group 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 60
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000000536 complexating effect Effects 0.000 abstract 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 24
- 239000011148 porous material Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- SSGIGIHCHLJKIH-UHFFFAOYSA-M [Na+].NC(C(=O)[O-])CCC Chemical compound [Na+].NC(C(=O)[O-])CCC SSGIGIHCHLJKIH-UHFFFAOYSA-M 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011882 ultra-fine particle 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- 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]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/307—Monocyclic tricarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
An organic iron-SiO of the invention 2 The aerogel-like catalyst and the preparation method thereof comprise the following steps: preparing sodium silicate and sodium metatrimellitate into a double alkali solution according to a certain proportion; mixing phosphoric acid and ferric chloride according to a certain proportion, and adding a certain amount of sodium aminoglutarate solid to prepare a complex diacid solution; under a certain stirring speed, gradually dropwise adding the complexing diacid solution into the diacid solution to form organic iron-SiO 2 gel; standing and aging the gel at 25 ℃ under 1 atmosphere for 24 hours; sequentially placing the aged gel into methanol, acetone, ethyl acetate and dichloromethane with different concentrations for standing and purifying; and (3) gradually heating the purified gel to 300 ℃ in normal-pressure N2 to obtain the organic iron-SiO 2 aerogel catalyst. The aerogel and the catalyst are combined to form the aerogel-like catalyst with controllable temperature, excellent elasticity and ductility, high catalytic performance and three-dimensional high complexing network.
Description
Technical Field
The invention belongs to the technical field of iron-based catalysts, relates to aerogel-like preparation and catalyst preparation, and in particular relates to an organic iron-SiO 2 Aerogel-like catalysts and methods of making the same.
Background
The catalyst is a promoter for a plurality of chemical reactions, can shorten the chemical reaction time, improve the production efficiency, selectively promote the positive reaction, inhibit the side reaction, and has small dosage and great effect; the iron-based material has the advantages of rich resources, high activity, low toxicity, low cost and the like, and is widely researched in various electrocatalytic processes. It was found that iron-based materials also exhibit excellent catalytic properties as catalysts for electrocatalytic nitrate reduction. The specific surface structure of the aerogel ultrafine particles facilitates the dispersion of the active ingredient and can thus have a significant impact on many catalytic processes. Aerogel is a solid material composed of nano particles, and has the characteristics of small particle size, high specific surface area, low density and the like, so that the activity and the selectivity of the aerogel catalyst are far higher than those of the conventional catalyst, and the active components can be very uniformly dispersed in a carrier. Meanwhile, the aerogel has excellent thermal stability, and can effectively reduce side reactions. Therefore, the aerogel can be used as a catalyst, the activity and the selectivity of the aerogel can be greatly improved, and the aerogel has very good catalytic properties. In chemical experiments and chemical production activities, the aerogel catalyst has the advantages of remarkable effect, wide application range, convenient use and effective cost saving. Organic ironThe high-efficiency selectivity and the large contact area with reactants of the aerogel are combined with the characteristics of heat insulation and good space structure of the aerogel, which is favorable for preparing the catalyst with better catalytic effect, therefore, the organic iron-SiO is provided 2 Aerogel-like catalysts.
Disclosure of Invention
In order to solve the problems that the catalytic capability of the existing catalyst gradually weakens or deactivates along with the reaction proceeding process and the reaction efficiency is reduced, the invention improves the problems by preparing the aerogel catalyst, enlarges the specific surface area of the catalyst, improves the contact surface of reactants and the catalyst, thereby improving the catalytic effect, facilitating the improvement of the yield, and simultaneously greatly improving the problem of the catalyst that the catalytic capability is weakened at 300 ℃ by utilizing the characteristic of excellent heat insulation effect of the aerogel.
The technical scheme of the invention is as follows:
raw material preparation:
step 1: adding trimellitic acid into deionized water, heating and stirring until the trimellitic acid is completely dissolved, and adding sodium hydroxide into the trimellitic acid solution to form a sodium trimellitate solution;
polymer formation:
step 2: adding FeCl into sodium trimellitate solution 3 The solution reacts with the sodium aminopentanedioate solution and is stirred uniformly to prepare a poly-m-benzene ferric trimellitate mixed solution, and a phosphoric acid solution is added into the poly-m-benzene ferric trimellitate mixed solution and is mixed uniformly;
crosslinking of the polymer:
step 3: preparing a sodium silicate solution with a certain concentration, uniformly stirring, then dripping a mixed solution of poly (m-trimellitate) and phosphoric acid into the sodium silicate solution, and rapidly stirring to uniformly mix the mixed solution, so as to obtain colloidal poly (m-trimellitate) aerogel after the reaction is completed; the molar concentration of the sodium silicate solution is 1-6mol/L;
aging of the product:
step 4: standing and aging the colloidal poly-m-benzene ferric trimellitate aerogel;
and (3) purifying and drying a product:
step 5: taking out the gelatiniform poly-m-trimellitic acid iron gel, and respectively soaking the gelatiniform poly-m-trimellitic acid iron gel in an ethanol solution with a certain concentration for a period of time according to a certain concentration gradient; in the step 5, the concentration of the ethanol solution is 10-98%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 6: respectively soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the ethanol solution for a period of time by using an acetone solution with a certain concentration and a certain concentration gradient; in the step 6, the concentration of the acetone solution is 10% -99.2%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 7: respectively soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the acetone in a mixed solution of ethyl acetate and acetone with a certain concentration for a period of time in a certain concentration gradient; in the step 7, the concentration of the mixed solution of ethyl acetate and acetone is 10% -99.9%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 8: respectively soaking the colloidal poly-m-benzene ferric trimellitate aerogel soaked by ethyl acetate in a mixed solution of dichloromethane and ethyl acetate with a certain concentration gradient for a period of time; in the step 8, the concentration of the mixed solution of dichloromethane and ethyl acetate is 10% -99.5%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 9: gradually heating the gel-like poly (m-trimellitic acid) iron aerogel soaked in dichloromethane from 25 ℃ to 300 ℃ in nitrogen atmosphere, and drying to obtain organic iron-SiO 2 Aerogel-like catalysts.
Further, in the step 1, the molar ratio of the m-trimellitic acid to the sodium hydroxide is 1:1 to 1:6.
further, in the step 2, feCl 3 The molar ratio of the sodium metabenzoate to sodium metabenzoate is 1:1 to 1:6, preparing a base material; feCl 3 The molar concentration of the solution is 0.1-6mol/L, and the volume ratio of the phosphoric acid to the poly (m-trimellitic acid) is 1:2 to 1:6, the phosphoric acid volume fraction is in the range of 40% -85%.
Further, in the step 3, heating and stirring are carried out to dissolve until all solids disappear during preparation; the dropping speed is 8-12 drops per minute, and after one drop of the mixed solution is added, the mixed solution is immediately and uniformly stirred.
Further, in the step 4, the standing aging time is 24-72 hours, and the standing environment is 25 ℃ and 1 atmosphere pressure.
The invention uses sodium metatrimellitate solution and FeCl 3 The solution reaction forms poly-m-benzene ferric trimellitate, the chemical substance can form a space three-dimensional net structure, the chemical substance has good stability through the connection of chemical bonds, a certain space and a certain channel are generated in the forming process, the structural stability of the chemical substance is reinforced by silicic acid, the space structure and the internal channel are not easy to collapse, a certain protection effect is achieved, the inflow and the discharge of reactants are facilitated, on the basis, the reactants are fully contacted with a catalyst to complete the catalytic reaction, the catalytic efficiency is greatly improved, the products can be timely discharged through holes and the internal channel, raw materials are input, and the reaction efficiency is greatly improved.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
Example 1:
step 1: adding 50ml of deionized water into 0.1mol of trimellitic acid, heating, stirring and dissolving, and adding 20ml of deionized water into 0.3mol of sodium hydroxide according to a proportion, stirring until the mixture is completely dissolved. Slowly adding the prepared sodium hydroxide solution into the trimellitic acid solution for reaction, and stirring (the stirring speed is 1000-3000 r/min) to obtain 1mol/L sodium trimellitate solution.
Step 2: 0.1mol FeCl is taken 3 Adding 100ml deionized water, stirring and dissolving to obtain 1mol/L FeCl 3 Adding 1mol/L of sodium aminoglutarate solution into the solution, and adding 85% phosphoric acid into deionized water to dilute to 65%. 0.2mol of sodium silicate is added into 100ml of deionized water, heated and stirred until the sodium silicate is completely dissolved, and 2mol/L of sodium silicate solution is obtained.
Step 3: taking 10ml of prepared sodium metatrimellitate solution and FeCl 3 Mixing with sodium aminoglutarate 10ml and 65% phosphoric acid solution 20ml according to 1:1:2, after being evenly mixed, the mixture is poured into an acid buretteIs a kind of medium. Pouring 30ml of the sodium silicate solution into a beaker, and slowly dripping sodium trimellitate and FeCl into the sodium silicate solution 3 Mixing with sodium aminoglutarate and phosphoric acid, stirring continuously and uniformly (stirring speed is 1200-3000 r/min), and dripping into the mixed solution to obtain colloidal poly-m-benzene ferric trimellitate aerogel;
step 4: the gel-like poly (m-trimellitate) iron gel is placed at 25 ℃ and kept stand and aged for 24 hours under 1 atmosphere.
Step 5: taking out the gelatinous poly-m-trimellitic acid iron gel, and respectively soaking the gelatinous poly-m-trimellitic acid iron gel in 10-98% ethanol solution for 24 hours with a concentration gradient of 20%;
step 6: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the ethanol solution in a concentration gradient of 20% for 24 hours by using 10% -99.2% of acetone solution respectively;
step 7: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the acetone in a mixed solution of 10% -99.9% of ethyl acetate and acetone (ethyl acetate: acetone) for 24 hours respectively in a concentration gradient of 20%;
step 8: soaking the colloidal poly-m-benzene tricarboxylic acid iron aerogel soaked by ethyl acetate in 10% -99.5% mixed solution of dichloromethane and ethyl acetate (dichloromethane: ethyl acetate) for 24h respectively with a concentration gradient of 20%;
step 9: gradually heating the gel-like poly (m-trimellitic acid) iron aerogel soaked in methylene dichloride from 25 ℃ to 300 ℃ in a nitrogen atmosphere, and drying to obtain the organic iron-SiO 2 Aerogel-like catalysts;
the organic iron-SiO obtained by the above embodiment 2 The microstructure analysis of the aerogel catalyst surface is carried out on a Hitachis-4700 type field emission scanning electron microscope; the specific surface, pore size distribution and pore volume of the aerogel were characterized using a NOVA4200e specific surface and porosity analyzer and the density of the aerogel was calculated using a drainage method. The characterization obtained is: specific surface area 453m 2 Per g, pore diameter of 14nm and density of 0.083g/cm 3 . And is used in the reaction of preparing dimethyl ether by dehydrating methanol. Under one atmosphere of pressure at 300℃methanol (ω (CH) 3 OH) greater than 99.9 percent of feed through a 2PB-00C advection pumpAnd (3) metering and then feeding the methanol into a reactor, and carrying out dehydration reaction on the gasified methanol in a catalytic bed by adopting an isothermal integral reactor. The reacted gas enters a condenser through a back pressure valve, and water and methanol are condensed. The condensate is sampled and weighed at regular time, and the flow of tail gas after the condenser is measured by a soap film flowmeter. The water and organic matter were analyzed by Agi-length GC6820 type thermal conductivity detector, the organic matter was mainly methanol and dimethyl ether, and the Agilent GC6890N type hydrogen flame ion detector was used for analyzing methanol and dimethyl ether. The result shows that the conversion rate of methanol is 85.32%, and the highest yield of dimethyl ether can reach 14.63 g/(g.h).
Example 2:
step 1: adding 50ml of deionized water into 0.1mol of trimellitic acid, heating, stirring and dissolving, and adding 20ml of deionized water into 0.3mol of sodium hydroxide according to a proportion, stirring until the mixture is completely dissolved. Slowly adding the prepared sodium hydroxide solution into the trimellitic acid solution for reaction, and stirring (the stirring speed is 1000-3000 r/min) to obtain 1mol/L sodium trimellitate solution.
Step 2: 0.1mol FeCl is taken 3 Adding 100ml deionized water, stirring and dissolving to obtain 1mol/L FeCl 3 Adding 1mol/L of sodium aminoglutarate solution into the solution, and adding 85% phosphoric acid into deionized water to dilute to 65%. 0.2mol of sodium silicate is added into 100ml of deionized water, heated and stirred until the sodium silicate is completely dissolved, and 2mol/L of sodium silicate solution is obtained.
Step 3: taking 10ml of prepared sodium metatrimellitate solution and FeCl 3 Mixing 20ml with sodium aminopentanoate and 20ml of 65% phosphoric acid solution according to the weight ratio of 1:2:2, after being evenly mixed, the mixture is poured into an acid burette. Pouring 30ml of the sodium silicate solution into a beaker, and slowly dripping sodium trimellitate and FeCl into the sodium silicate solution 3 Mixing with sodium aminoglutarate and phosphoric acid, stirring continuously and uniformly (stirring speed is 1200-3000 r/min), and dripping into the mixed solution to obtain colloidal poly-m-benzene ferric trimellitate aerogel;
step 4: the gel-like poly (m-trimellitate) iron gel is placed at 25 ℃ and kept stand and aged for 24 hours under 1 atmosphere.
Step 5: taking out the gelatinous poly-m-trimellitic acid iron gel, and respectively soaking the gelatinous poly-m-trimellitic acid iron gel in 10-98% ethanol solution for 24 hours with a concentration gradient of 20%;
step 6: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the ethanol solution in a concentration gradient of 20% for 24 hours by using 10% -99.2% of acetone solution respectively;
step 7: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the acetone in a mixed solution of 10% -99.9% of ethyl acetate and acetone (ethyl acetate: acetone) for 24 hours respectively in a concentration gradient of 20%;
step 8: soaking the colloidal poly-m-benzene tricarboxylic acid iron aerogel soaked by ethyl acetate in 10% -99.5% mixed solution of dichloromethane and ethyl acetate (dichloromethane: ethyl acetate) for 24h respectively with a concentration gradient of 20%;
step 9: gradually heating the gel-like poly (m-trimellitic acid) iron aerogel soaked in methylene dichloride from 25 ℃ to 300 ℃ in a nitrogen atmosphere, and drying to obtain the organic iron-SiO 2 Aerogel-like catalysts.
The organic iron-SiO obtained by the above embodiment 2 The microstructure analysis of the aerogel catalyst surface is carried out on a Hitachis-4700 type field emission scanning electron microscope; the specific surface, pore size distribution and pore volume of the aerogel were characterized using a NOVA4200e specific surface and porosity analyzer and the density of the aerogel was calculated using a drainage method. The characterization obtained is: specific surface area of 527m 2 Per g, pore diameter of 18nm, density of 0.074g/cm 3 . And is used in the reaction of preparing dimethyl ether by dehydrating methanol. Under one atmosphere of pressure at 300℃methanol (ω (CH) 3 OH) is greater than 99.9 percent, the mixture is metered by a 2PB-00C advection pump and then enters a reactor, an isothermal integral reactor is adopted, and the gasified methanol is subjected to dehydration reaction in a catalytic bed. The reacted gas enters a condenser through a back pressure valve, and water and methanol are condensed. The condensate is sampled and weighed at regular time, and the flow of tail gas after the condenser is measured by a soap film flowmeter. The water and organic matter were analyzed by Agi-length GC6820 type thermal conductivity detector, the organic matter was mainly methanol and dimethyl ether, and the Agilent GC6890N type hydrogen flame ion detector was used for analyzing methanol and dimethyl ether. The result shows that the conversion rate of methanol is 87.45%, and the highest yield of dimethyl ether can reach 17.68 g/(g.h).
Example 3:
step 1: adding 50ml of deionized water into 0.2mol of trimellitic acid, heating, stirring and dissolving, and adding 20ml of deionized water into 0.6mol of sodium hydroxide according to a proportion, stirring until the mixture is completely dissolved. Slowly adding the prepared sodium hydroxide solution into the trimellitic acid solution for reaction, and stirring (the stirring speed is 1000-3000 r/min) to obtain 1mol/L sodium trimellitate solution.
Step 2: 0.1mol FeCl is taken 3 Adding 100ml deionized water, stirring and dissolving to obtain 1mol/L FeCl 3 Adding 1mol/L of sodium aminoglutarate solution into the solution, and adding 85% phosphoric acid into deionized water to dilute to 65%. 0.2mol of sodium silicate is added into 100ml of deionized water, heated and stirred until the sodium silicate is completely dissolved, and 2mol/L of sodium silicate solution is obtained.
Step 3: taking 10ml of prepared sodium metatrimellitate solution and FeCl 3 Mixing with sodium aminoglutarate 10ml and 65% phosphoric acid solution 20ml according to 1:1:2, after being evenly mixed, the mixture is poured into an acid burette. Pouring 30ml of the sodium silicate solution into a beaker, and slowly dripping sodium trimellitate and FeCl into the sodium silicate solution 3 Mixing with sodium aminoglutarate and phosphoric acid, stirring continuously and uniformly (stirring speed is 1200-3000 r/min), and dripping into the mixed solution to obtain colloidal poly-m-benzene ferric trimellitate aerogel;
step 4: the gel-like poly (m-trimellitate) iron gel is placed at 25 ℃ and kept stand and aged for 24 hours under 1 atmosphere.
Step 5: taking out the gelatinous poly-m-trimellitic acid iron gel, and respectively soaking the gelatinous poly-m-trimellitic acid iron gel in 10-98% ethanol solution for 24 hours with a concentration gradient of 20%;
step 6: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the ethanol solution in 20% -99.2% acetone solution for 24 hours respectively with a concentration gradient of 20%;
step 7: soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the acetone in a mixed solution of 10% -99.9% of ethyl acetate and acetone (ethyl acetate: acetone) for 24 hours respectively in a concentration gradient of 20%;
step 8: soaking the colloidal poly-m-benzene tricarboxylic acid iron aerogel soaked by ethyl acetate in 10% -99.5% mixed solution of dichloromethane and ethyl acetate (dichloromethane: ethyl acetate) for 24h respectively with a concentration gradient of 20%;
step 9: gradually heating the gel-like poly (m-trimellitic acid) iron aerogel soaked in methylene dichloride from 25 ℃ to 300 ℃ in a nitrogen atmosphere, and drying to obtain the organic iron-SiO 2 Aerogel-like catalysts;
the organic iron-SiO obtained by the above embodiment 2 The microstructure analysis of the aerogel catalyst surface is carried out on a Hitachis-4700 type field emission scanning electron microscope; the specific surface, pore size distribution and pore volume of the aerogel were characterized using a NOVA4200e specific surface and porosity analyzer and the density of the aerogel was calculated using a drainage method. The characterization obtained is: specific surface area of 583m 2 Per g, pore diameter of 20nm, density of 0.103g/cm 3 . And is used in the reaction of preparing dimethyl ether by dehydrating methanol. Under one atmosphere of pressure at 300℃methanol (ω (CH) 3 OH) is greater than 99.9 percent, the mixture is metered by a 2PB-00C advection pump and then enters a reactor, an isothermal integral reactor is adopted, and the gasified methanol is subjected to dehydration reaction in a catalytic bed. The reacted gas enters a condenser through a back pressure valve, and water and methanol are condensed. The condensate is sampled and weighed at regular time, and the flow of tail gas after the condenser is measured by a soap film flowmeter. The water and organic matter were analyzed by Agi-length GC6820 type thermal conductivity detector, the organic matter was mainly methanol and dimethyl ether, and the Agilent GC6890N type hydrogen flame ion detector was used for analyzing methanol and dimethyl ether. The result shows that the conversion rate of methanol is 91.24%, and the highest yield of dimethyl ether can reach 19.31 g/(g.h).
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (4)
1. Organic iron-SiO 2 The aerogel-like catalyst is characterized in that: comprises porous silicic acid and poly-m-benzene trimellitic acidThe three-dimensional high-complexation reticular structure formed by the structure comprises the following manufacturing steps:
raw material preparation:
step 1: adding trimellitic acid into deionized water, heating and stirring until the trimellitic acid is completely dissolved, and adding sodium hydroxide solution into the trimellitic acid solution to form sodium trimellitate solution;
polymer formation:
step 2: adding FeCl into sodium trimellitate solution 3 Reacting with the sodium aminopentanedioate mixed solution and stirring uniformly to prepare a poly-m-benzene ferric trimellitate mixed solution, and adding a phosphoric acid solution into the poly-m-benzene ferric trimellitate mixed solution and mixing uniformly;
crosslinking of the polymer:
step 3: preparing a sodium silicate solution with a certain concentration, uniformly stirring, then dripping a mixed solution of poly (m-trimellitate) and phosphoric acid into the sodium silicate solution, and rapidly stirring to uniformly mix the mixed solution, so as to obtain colloidal poly (m-trimellitate) aerogel after the reaction is completed; the molar concentration of the sodium silicate solution is 1-6mol/L;
aging of the product:
step 4: standing and aging the colloidal poly-m-benzene ferric trimellitate aerogel;
and (3) purifying and drying a product:
step 5: taking out the gelatiniform poly-m-trimellitic acid iron gel, and respectively soaking the gelatiniform poly-m-trimellitic acid iron gel in an ethanol solution with a certain concentration for a period of time according to a certain concentration gradient; in the step 5, the concentration of the ethanol solution is 10-98%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 6: respectively soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the ethanol solution for a period of time by using an acetone solution with a certain concentration and a certain concentration gradient; in the step 6, the concentration of the acetone solution is 10% -99.2%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 7: respectively soaking the colloidal poly-m-ferric trimellitate aerogel soaked by the acetone solution for a period of time by using a mixed solution of ethyl acetate and acetone with a certain concentration in a certain concentration gradient; in the step 7, the concentration of the mixed solution of ethyl acetate and acetone is 10% -99.9%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 8: respectively soaking the colloidal poly-m-benzene trimellitic acid iron aerogel soaked by the mixed solution of ethyl acetate and acetone for a period of time by using the mixed solution of dichloromethane and ethyl acetate with a certain concentration in a certain concentration gradient; in the step 8, the concentration of the mixed solution of dichloromethane and ethyl acetate is 10% -99.5%, the concentration gradient is 20%, and the soaking time is 6-24 hours;
step 9: gradually heating the gel-like poly (m-trimellitic acid) iron aerogel soaked by a mixed solution of dichloromethane and ethyl acetate from 25 ℃ to 300 ℃ in a nitrogen atmosphere, and drying to obtain the organic iron-SiO 2 Aerogel-like catalysts;
in the step 2, feCl 3 The molar ratio of the sodium metabenzoate to sodium metabenzoate is 1:1 to 1:6, preparing a base material; feCl 3 The molar concentration of the solution is 0.1-6mol/L.
2. An organic iron-SiO according to claim 1 2 The aerogel-like catalyst is characterized in that: in the step 1, the molar ratio of the m-trimellitic acid to the sodium hydroxide is 1:1 to 1:6.
3. an organic iron-SiO according to claim 1 2 The aerogel-like catalyst is characterized in that: in the step 3, heating and stirring are carried out during preparation until all solids disappear; the dropping speed is 8-12 drops per minute, and after one drop of the mixed solution is added, the mixed solution is immediately and uniformly stirred.
4. An organic iron-SiO according to claim 1 2 The aerogel-like catalyst is characterized in that: in the step 4, the standing aging time is 24-72 h, and the standing environment is 25 ℃ and 1 atmosphere pressure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211311915.5A CN115624988B (en) | 2022-10-25 | 2022-10-25 | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211311915.5A CN115624988B (en) | 2022-10-25 | 2022-10-25 | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN115624988A CN115624988A (en) | 2023-01-20 |
CN115624988B true CN115624988B (en) | 2024-03-26 |
Family
ID=84906608
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202211311915.5A Active CN115624988B (en) | 2022-10-25 | 2022-10-25 | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN115624988B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103435055A (en) * | 2013-06-29 | 2013-12-11 | 浙江工业大学 | Method for preparing low density silica aerogel under normal pressure |
CN106669554A (en) * | 2016-11-18 | 2017-05-17 | 江苏大学 | Atmospheric pressure preparation method of iron-containing organic framework silicon-based composite aerogel |
CN112058235A (en) * | 2020-08-29 | 2020-12-11 | 曲阜师范大学 | Copper organic framework-silicon oxide porous composite material and preparation method and application thereof |
CN113289598A (en) * | 2021-04-27 | 2021-08-24 | 南京工业大学 | FePO4-SiO2Preparation method of aerogel catalyst material |
CN114249637A (en) * | 2021-12-31 | 2022-03-29 | 南京工业大学 | Method for preparing dimethyl ether by dehydrating methanol |
-
2022
- 2022-10-25 CN CN202211311915.5A patent/CN115624988B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103435055A (en) * | 2013-06-29 | 2013-12-11 | 浙江工业大学 | Method for preparing low density silica aerogel under normal pressure |
CN106669554A (en) * | 2016-11-18 | 2017-05-17 | 江苏大学 | Atmospheric pressure preparation method of iron-containing organic framework silicon-based composite aerogel |
CN112058235A (en) * | 2020-08-29 | 2020-12-11 | 曲阜师范大学 | Copper organic framework-silicon oxide porous composite material and preparation method and application thereof |
CN113289598A (en) * | 2021-04-27 | 2021-08-24 | 南京工业大学 | FePO4-SiO2Preparation method of aerogel catalyst material |
CN114249637A (en) * | 2021-12-31 | 2022-03-29 | 南京工业大学 | Method for preparing dimethyl ether by dehydrating methanol |
Non-Patent Citations (1)
Title |
---|
Preparation of FeBTC/silica aerogels by a co-sol-gel process for organic pollutant adsorption;Hongli Liu et al.;《Materials Research Express》;第6卷;摘要和实验部分 * |
Also Published As
Publication number | Publication date |
---|---|
CN115624988A (en) | 2023-01-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN112038648B (en) | Hollow-structure transition metal cobalt and nitrogen co-doped carbon oxygen reduction catalyst and preparation method and application thereof | |
CN102527377B (en) | High-efficiency nano Pd catalyst used in the process of preparing oxalate through CO carbonylation and prepared by dipping-controllable reduction method | |
CN101940958B (en) | Method for preparing low-carbon olefin catalyst by loading iron-based synthetic gas | |
CN107694603B (en) | Immobilized ionic liquid catalyst and preparation method and application thereof | |
CN101269331B (en) | Process for producing high-stability central-hole material Cu-Zn-Al2O3, and application of the same in producing mellow wine dehydrogenating catalyst | |
CN102698761A (en) | Preparation method of catalyst for hexone synthesis by acetone hydrogenation and application | |
CN110862548A (en) | Preparation method and new application of metal organogel catalyst based on MIL-53 | |
CN109453762A (en) | A kind of preparation method and application of modified clay mine loaded palladium catalyst | |
CN104437474A (en) | Ordered mesoporous carbon material loaded platinum catalyst and application thereof to catalytic hydrogenation of aromatic nitro compound | |
CN115624988B (en) | Organic iron-SiO 2 Aerogel-like catalyst and preparation method thereof | |
CN108479798B (en) | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation and preparation method thereof | |
CN103657653B (en) | A kind of solid acid catalyst C/Fe3O4The method of MWCNTs and catalyzing cellulose hydrolysis thereof | |
CN102389832B (en) | Catalyst for preparing C5 and C6 alkanes by hydrogenating high-activity sorbierite water phase, and preparation method of catalyst | |
CN110961136B (en) | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof | |
CN113996324A (en) | For CO2Preparation method of SiC-C composite aerogel through photocatalytic reduction | |
CN106784879B (en) | A kind of preparation method of the palladium ruthenium catalyst of titanium plate load | |
CN107570157B (en) | Preparation method of ordered mesoporous carbon catalyst for preparing p-aminophenol | |
CN105413670A (en) | Solid acid catalyst for preparing butane through normal butanol dehydration and preparation method thereof | |
CN115591585B (en) | Organic aluminum-SiO 2 Aerogel-like catalyst and preparation method thereof | |
CN108993598A (en) | The preparation method of ruthenium-based catalyst for producing cyclohexene with benzene selective hydrogenation | |
CN106816605B (en) | A kind of preparation method of the palladium nanocatalyst of titanium plate load | |
CN117504917B (en) | Palladium-based alloy formic acid hydrogen production catalyst and preparation method and application thereof | |
CN115094470B (en) | Hierarchical pore carbon loaded cobalt-ruthenium nano alloy material and preparation method thereof | |
CN115475626B (en) | Preparation method of catalyst for preparing long-chain hydrocarbon and co-producing low-carbon olefin through carbon dioxide hydrogenation | |
CN102350343B (en) | Pd-Pt alloy structural catalyst, and preparation method and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |