CN108137464B - 制备丙烯酸的方法 - Google Patents
制备丙烯酸的方法 Download PDFInfo
- Publication number
- CN108137464B CN108137464B CN201780003368.5A CN201780003368A CN108137464B CN 108137464 B CN108137464 B CN 108137464B CN 201780003368 A CN201780003368 A CN 201780003368A CN 108137464 B CN108137464 B CN 108137464B
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- catalyst
- reaction
- mgo
- supported
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 90
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 167
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000002245 particle Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910002710 Au-Pd Inorganic materials 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 77
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- 230000007935 neutral effect Effects 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 230000020477 pH reduction Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000002585 base Substances 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 15
- 239000002243 precursor Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 229910052723 transition metal Inorganic materials 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- 229910052762 osmium Inorganic materials 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 229910052703 rhodium Inorganic materials 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- -1 i.e. Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000000366 colloid method Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 229920000729 poly(L-lysine) polymer Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229920000247 superabsorbent polymer Polymers 0.000 description 2
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- OEDQNDJKBBYAHI-UHFFFAOYSA-N 2-ethenyl-1-methyl-2h-pyridine Chemical compound CN1C=CC=CC1C=C OEDQNDJKBBYAHI-UHFFFAOYSA-N 0.000 description 1
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- 229920002491 Diethylaminoethyl-dextran Polymers 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000012696 Pd precursors Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229920001606 poly(lactic acid-co-glycolic acid) Polymers 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 108010055896 polyornithine Proteins 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/685—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J37/0072—Preparation of particles, e.g. dispersion of droplets in an oil bath
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
- C07C57/04—Acrylic acid; Methacrylic acid
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种制备丙烯酸的方法,并且,更具体而言,涉及一种制备丙烯酸的方法,其在通过烯丙醇的氧化生产丙烯酸时采用具有特定组成的负载型催化剂来生产丙烯酸的情况下,能够在短时间内以高的收率生产丙烯酸,并且与必需使用碱的常规技术不同而能够在中性条件下在无碱下进行反应。特别地,本发明的制备方法具有能够以丙烯酸而非丙烯酸盐的形式进行最终回收的优点,并由此可以排除常规技术中必需的工艺,如在将丙烯酸盐转化为丙烯酸所需的酸化过程之后的离子交换,因而降低了整体工艺的成本。
Description
技术领域
本申请要求基于2016年04月12日提交的韩国专利申请第10-2016-0044700号的优先权的权益,其全部内容以引用的方式并入本文中。
本发明涉及一种制备丙烯酸的方法,所述丙烯酸可以在不使用碱的情况下于中性条件下制备。
背景技术
由于丙烯酸是一种兼具羧酸和双键的有机化合物,以及其结构非常简单且可以转化为各种物质,因此丙烯酸的固有价值非常大。其中,丙烯酸被用作超吸收性聚合物(SAP,Super Absorbent Polymer)、油漆、粘合剂等的原料,并被用作各种化学产品的原料。
丙烯酸通过各种方法来制备,并且工业上通过丙烯的氧化、丙烯腈的水解和乙炔的羰基化来制备。
然而,由于工艺采用源自原油的原料,故为了应对原油枯竭的问题,近来已提出采用生物质来源的资源作起始物质的方法。具体而言,采用甘油作为起始物质,通过“甘油-烯丙醇-丙烯酸”的反应路径来制备丙烯酸(韩国专利公开第2015-0006349号)。
在上述专利公开中,由烯丙醇来生产丙烯酸是通过加入如氢氧化钠的碱而在强碱条件下进行的。结果,最终物质是作为丙烯酸盐被制备的,而不是丙烯酸,因此额外的分离步骤是必不可少的。并且,由于强碱的使用,存在的问题是丙烯酸的制备中所用的工艺设备或装置会被腐蚀。因此,需要一种在中性条件而非强碱下制备丙烯酸的方法。
[现有技术文献]
[专利文献]
一种由甘油生产丙烯酸的方法(韩国专利公开第2015-0006349号)
发明内容
[技术问题]
因此,通过进行研究在中性条件下由烯丙醇制备丙烯酸,本发明人制备了一种在中性条件下展现出催化剂活性的催化剂,并且因而确定采用所制备的催化剂进行反应可以在不使用碱,特别是强碱的情况下在中性条件下以高的收率制备丙烯酸,从而完成了本发明。
因此,本发明的一个目的在于提供一种在不使用碱的情况下采用催化剂于中性条件下短时间内以高的收率制备丙烯酸的方法。
[技术方案]
为了实现上述目的,本发明提供了一种在催化剂的存在下通过烯丙醇的氧化反应来制备丙烯酸的方法,其特征在于,所述氧化反应在中性条件下进行。
此时,其特征在于,所述烯丙醇的氧化反应在pH 6-8下进行。
其特征在于,所述催化剂为负载型催化剂,其中选自Au-过渡金属合金催化剂、过渡金属催化剂以及它们的组合的金属催化剂被负载于载体上。
其特征在于,所述过渡金属为选自Ru、Rh、Pd、Os、Ir、Pt、Zn、Co、Ni、Cr、Fe、Mo、Nb、Mn以及它们的组合中的任意一种,优选Pd。
另外,其特征在于,所述载体为选自Mg、Al、Ca、Zn、Zr以及它们的组合中的任意一种的氧化物或水合物,并且优选地,所述载体为选自MgO、Mg(OH)2、Al2O3、cHT(煅烧水滑石)、羟基磷灰石(Ca5(OH)(PO4)3)、ZnO、Zr(OH)2以及它们的组合中的任意一种,最优选地,所述载体为MgO。
[有益效果]
根据本发明的制备丙烯酸的方法可以通过在中性条件下进行反应来生产丙烯酸而非丙烯酸盐作为最终产物。因此,本发明的方法具有的优点是,通过省略在将丙烯酸盐转化为丙烯酸所需的酸化过程之后的必需过程,如离子交换过程而可以降低整体工艺的成本。
另外,本发明的方法具有消除由于使用强碱而导致的设备腐蚀问题以及降低成本的效果。
附图说明
图1为图示了根据本发明一个实施方式制备负载型催化剂的步骤的流程图。
图2显示了由(a)制备实施例7(Pd/MgO)、(b)制备实施例8(Pd/Mg(OH)2)、(c)制备实施例10(Pd/HT)以及(d)制备实施例11(Pd/HAP)的负载型催化剂的透射电子显微镜而获得的图像。
图3显示了由采用实施例2中制备的催化剂的烯丙醇氧化反应产物的HPLC(高效液相色谱)而获得的谱图。
图4(a)显示了由采用实施例3中制备的催化剂的烯丙醇氧化反应产物的HPLC(高效液相色谱)而获得的谱图,以及图4(b)为12小时后的HPLC谱图。
具体实施方式
丙烯酸的制备可以以各种的方式进行,但在本发明中,丙烯酸的制备通过采用烯丙醇作为起始物质并且推进由烯丙醇至丙烯酸的反应路径来进行。具体而言,通过以下来制备丙烯酸:(S1)将原料(烯丙醇、催化剂、氧化气体)引入到反应器中,(S2)进行氧化反应,以及(S3)分离和纯化丙烯酸。
此时,其特征在于,所述氧化反应在中性条件下,即pH 6-8下进行,而不是在通过加入碱(如现有技术中采用的NaOH)的强碱环境中来进行,本发明提出了适用于此的最佳催化剂。
在应用于实际的化学反应中时,催化剂在酸性/中性/碱性条件下具有不同的活性。结果,催化剂也可以被分为酸性催化剂或碱性催化剂,并且所述碱性催化剂在酸性条件下具有很小的催化活性或没有催化活性。根据本发明的丙烯酸的制备在中性条件下而非常规的强碱条件下进行,因此有必要提供适合于该条件的催化剂。
(S1)原材料的输入
首先,将作为起始物质的烯丙醇、催化剂和氧化气体引入到反应器中。
引入烯丙醇、催化剂和氧化气体的方法和顺序没有特别的限制,但可以采用各种输入方法,如一次全部引入到反应器中的方法、连续引入的方法以及将一部分引入到反应器中且将剩余部分连续引入到反应器中的方法,并且可以采用这些方法中的任意一种。在本发明的一个实施方式中,首先将催化剂引入到反应器中,然后依序连续引入烯丙醇和氧化气体。
可以没有任何特别限制地使用用作起始物料的烯丙醇,只要其可用于丙烯酸的制备即可。作为实例,烯丙醇可以以浓缩的形式或以与水等混合的溶液形式使用,并且可以优选使用具有60至99.9%的纯度的烯丙醇。此外,需要时,可以通过韩国专利公开第2015-0006349号中描述的方法来制备和使用烯丙醇。
在这种情况下,所述反应器在本发明中没有特别的限制,并且可以为选自已知的间歇反应器、半间歇反应器、连续搅拌釜反应器、活塞流反应器、固定相反应器和流化床反应器中的任意一种反应器或者可以是这些反应器中两个以上的连接的混合反应器。
特别地,对于常规情况,在该原料输入步骤中加入碱,如NaOH以进行以下(S2)中的氧化反应,但对于本发明,由于排除了碱,因此该原料输入中碱的使用是不需要的。无需添加这些碱要归功于采用某种催化剂。
本发明中所用的催化剂在中性条件下具有催化剂活性。所述催化剂的活性直接影响烯丙醇的转化。本发明中所用的催化剂为其中金属催化剂负载于载体上的负载型催化剂,并且此时,催化活性受诸如用作催化剂的金属的组成、粒度、载体的种类以及负载量的因素的影响。优选地,存在所述催化剂的粒度越小且越均匀,以及所述负载量越高,则催化活性越高的趋势。
具体而言,可以采用选自由根据本发明的以下式1表示的Au-过渡金属合金催化剂、过渡金属催化剂以及它们的组合中的任一种:
[式1]
Aux-My
其中,M为过渡金属,并且0.01≤x/y≤100。
式1中的过渡金属M可以是可以用作催化剂的任何金属,并且在本发明中没有特别的限制。优选地,所述过渡金属可以是选自Ru、Rh、Pd、Os、Ir、Pt、Zn、Co、Ni、Cr、Fe、Mo、Nb、Mn以及它们的组合中的任意一种,更优选Ru、Rh、Pd、Os、Ir或Pt,最优选Pd。
由式1中x/y表示的Au与过渡金属M的摩尔比(x/y)为0.01至100,优选0.1至50。
另外,所述过渡金属催化剂可以是单独使用以上所述的过渡金属,即Ru、Rh、Pd、Os、Ir、Pt、Zn、Co、Ni、Cr、Fe、Mo、Nb或Mn,优选Ru、Rh、Pd、Os、Ir或Pt,更优选Pd的催化剂。
根据本发明的一个优选实验性实施例,可以看出,Au-Pd催化剂和Pd催化剂被用作金属催化剂,并且其全部可被用于丙烯酸的制备,但在活性方面,所述Pd催化剂具有最佳的催化活性,并由此可以在短时间内以高的收率制备丙烯酸。
除了这些金属催化剂的组成,粒度也是与催化活性有关的重要因素。
所述金属催化剂颗粒的尺寸越小,催化活性越高。此时,所述粒度越均匀,与反应材料的接触面积越大,因此提高了烯丙醇至丙烯酸的转化,并且提高了转化率,由此缩短了整体工艺的时间。
优选地,所述金属催化剂的粒度具有1至50nm,更优选2至10nm的平均粒径,并且具有单分散性和非常窄的分散范围。催化剂颗粒的尺寸在实际工艺中不能小于1nm,以及当催化剂颗粒的尺寸大于50nm时,不能保证以上所述的效果。
另外,根据本发明的负载型催化剂负载于载体(载体成分或载体)上,并且其上负载有所述金属催化剂的载体负载和分散所述金属催化剂,由此用于提高催化剂的表面积,通过防止烧结现象稳定催化剂,以及降低催化剂的价格。所述载体本身没有活性,但由于上述功能而影响催化活性,并且即使当催化剂的组成相同时,凭借负载有多少金属催化剂而在催化剂活性上展现出很大的差异,因此载体的选择也应当被认为是非常重要的。
可能的载体类型可以是选自Mg、Al、Ca、Zn、Zr以及它们的组合中的任意一种的氧化物或水合物,并且优选地,可以是选自MgO、Mg(OH)2、Al2O3、cHT(煅烧水滑石)、羟基磷灰石(Ca5(OH)(PO4)3)、ZnO、Zr(OH)2以及它们的组合中的任意一种,并且最优选地,可以是MgO。与传统的氧化硅、氧化铈等相比,这些载体可以有效地负载所述金属催化剂。
另外,所述载体的比表面积、孔隙体积和平均孔径是用于实现高的催化剂负载量的重要参数,并且优选所述载体具有1m2/g以上的比表面积。
当使用所述载体时,可以制备具有5重量%以下,优选0.0001至5重量%的负载量的催化剂。所述负载量越大越有利。然而,所述负载量应当与催化剂的应用于生产线时的重现性、物理稳定性、成本、活性和选择性一起考虑。如果所述负载量低于上述范围,则难以获得足够水平的催化剂活性。并且,高于上述范围的负载降低了催化剂的稳定性。因此,其适合在上述范围内使用。
制备根据本发明的催化剂的方法没有特别的限制,并且所述催化剂可以通过制备已知的金属催化剂,然后使其负载于载体上来制备。
用于生产所述金属催化剂的方法包括沉淀法、胶体法、多元醇法等。在本发明中,所述金属催化剂采用胶体法,具体为胶体沉积法来制备,所述胶体法没有复杂的条件且易于制备纳米级的颗粒。
在胶体沉积工艺中,前体至金属的还原反应发生在用分散剂稳定的胶束胶体中,而非在主体混合溶液中。结果,存在的优点是,参与还原反应的前体的量对每个胶束而言变得几乎均匀,并且由此最终还原之后获得的颗粒以纳米尺寸生成,且粒度的分布非常窄。
图1为图示了制备根据本发明的负载型催化剂的步骤的流程图。
参照图1,所述负载型催化剂通过以下步骤制备,其包括
步骤(a),通过将金属前体和酸溶于溶剂中来制备第一混合溶液;
步骤(b),通过向所述第一混合溶液中加入分散剂和水来制备第二混合溶液;
步骤(c),通过将所述第二混合溶液的pH调节至6至8,然后进行还原反应来制备金属催化剂;
步骤(d),向其中分散有所述金属催化剂的分散体中加入载体,然后混合,以制备具有负载于其上的所述金属催化剂的负载型催化剂;以及
步骤(e),分离和干燥。
以下将详细地描述各个步骤。
首先,通过制备所述金属催化剂的前体并将其溶于加了酸的溶剂中来制备所述第一混合溶液(步骤(a))。
所述金属前体可以是任何前体,只要其可以通过还原反应转化为所述金属催化剂即可,并且可以采用含金属的醇盐、乙酰乙酸盐、硝酸盐、草酸盐、卤化物、氰化物等,优选地,可以采用卤化物。
作为实例,当采用Au时,Au前体可以是HAuCl4、HAuCl4·3H2O、HAuCl4·4H2O、AuCl3、AuCl等,优选HAuCl4。另外,当采用Pd时,Pd前体可以是PdCl2、(NH4)2PdCl4、Pd(NO3)2、Pd(NH3)2Cl2、Pd(C2H3O2)2等,优选PdCl2。
此时,采用酸来使所述金属前体电离并使电离金属稳定地溶于溶剂中。所述酸在本发明中没有特别的限制,并且可以采用任何已知的强酸或弱酸。具体而言,所述酸可以是盐酸、硝酸、硫酸或乙酸,优选盐酸。
将这些前体和酸溶于溶剂中以制备所述第一混合溶液,并且所述溶剂可以是水、醇类、醚类、酮类和芳香族化合物,具体而言,水、醇类或水与醇类的混合物是优选的。
存在于所述第一混合溶液中的前体被电离并转化为金属离子,并且这些金属离子彼此配位以形成复合物。
接下来,通过向步骤(a)中制备的第一混合溶液中加入分散剂和水来制备所述第二混合溶液(步骤(b))。
本发明中所用的胶体沉积方法是一种以采用分散剂为特征的方法。
作为可被采用的分散剂,采用了聚合物分散剂,并且优选地,所述聚合物分散剂可为选自聚烯丙胺盐酸盐、聚乙烯亚胺、聚二烯丙基二甲基氯化铵、聚甲基丙烯酰氧基乙基三烷基卤化铵、氨基乙基化聚丙烯酰胺、霍夫曼灵敏度-聚丙烯酰胺(Hoffmann sensitivity-polyacrylamide)、聚乙烯胺、淀粉、阳离子化淀粉、壳聚糖、PLL(聚L-赖氨酸)、pAMEAMA树状大分子、PLGA(聚(L-谷氨酸))、PVP(聚(1-甲基-2-乙烯基吡啶))、聚L-鸟氨酸、聚精胺、DEAE葡聚糖(二乙基氨基乙基葡聚糖)以及它们的组合中的任意一种。更优选地,采用淀粉。
在整个所述第二混合溶液中,以0.1至20重量%的浓度使用所述分散剂。如果所述含量小于上述范围,则不易控制催化剂颗粒的尺寸。相反,即使超过上述范围,也不存在与效果相关的优点,并且不经济。因此,其适合在上述范围内使用。
此时,以溶于溶剂中的形式使用所述分散剂,并且可以根据分散剂的类型而采用各种溶剂。例如,在本发明的实施方式中,当采用淀粉作为分散剂时,将淀粉溶于水中然后使用。
接下来,通过将步骤(b)中获得的第二混合溶液的pH调节至6至8,然后进行还原反应来制备所述金属催化剂(步骤(c))。
所述第二混合溶液的pH由于加入酸以解离金属离子而呈酸性,并且被调节至中性以进行所述还原反应。
可以用于pH控制的碱在本发明中没有特别的限制,并且可以采用本领域已知的碱。作为实例,所述碱可以是选自NaOH、KOH、NaHCO3、Na2CO3、KHCO3、K2CO3、CaCO3以及它们的组合中的任意一种。
所述还原反应包括在所述第二混合溶液中所述金属离子的合金化反应,此时,反应在30至200℃,优选80至140℃下进行5分钟至12小时,优选30分钟至3小时。温度和时间是所述还原反应可以充分进行的条件,并且反应在回流条件下进行,因此温度范围可以根据溶剂的类型而改变。并且,需要时,反应在减压下进行以改善反应速率。
通过该还原反应,制备了金属催化剂,并且如上所述,所述粒度具有1至50nm的纳米尺寸。
此时,进行从分散体中分离金属催化剂并使其承载在载体上的后续过程,或者进行使胶体状态原样承载于载体上的后续过程。
接下来,通过向其中分散有步骤c中制备的金属催化剂的分散体中加入载体,并由此发生所述载体与所述金属催化剂的浸渍来制备负载型催化剂(步骤(d))。
在用其中分散有所述金属催化剂的分散体浸渍之前,将所述载体在空气或惰性气体中在300至1500℃,优选350至1000℃,更优选400至600℃下煅烧3至20小时,优选5至15小时,以除去其中的杂质。
用所述金属催化剂浸渍所述载体的步骤可以通过湿式浸渍、干式浸渍、减压浸渍或以浆料形式的混合物的喷雾干燥或挤出干燥来进行,但并不限于此。在本发明的实施方式中,通过向所述催化剂分散体中加入所述载体,然后混合它们来进行浸渍。
该浸渍可以重复一次以上或若干次以具有所需的负载量,并且需要时,可以额外进行加热或搅拌。
接下来,通过分离和干燥步骤(d)中获得的负载型催化剂的步骤来制备根据本发明的丙烯酸催化剂(步骤(e))。
所述干燥可以通过常压干燥法或减压干燥法来进行。例如,所述常压干燥法是在大气压下在室温至200℃,优选室温至150℃下进行2至72小时,优选5至48小时。
所得的负载型催化剂具有中性状态的最终状态,并且因此可以适用于本发明中待进行的中性环境下的丙烯酸的制备。
就反应效率而言,在该阶段中,如上所述的负载型催化剂以10至2000的烯丙醇/金属催化剂的摩尔比来使用是有利的。
另外,本发明中用于氧化反应的氧化气体可以是氧气或含氧气体。考虑到反应物的浓度和反应温度,所述氧化气体的分压可以在燃烧范围与爆炸范围之间任意设定。以标准计,氧气分压为1至6巴,优选1至5巴。
另外,所述氧化气体中的含氧气体可以包含10体积%以上的氧,优选60体积%至100体积%,以及更优选90体积%至100体积%。如果氧的含量小于60体积%,则存在氧化反应速率非常慢的问题。
(S2)氧化反应
接下来,进行氧化反应以生产丙烯酸。
该氧化反应如以下反应式1所示进行,生成了作为主要产物的丙烯酸和作为副产物的丙酸和3-羟基丙酸:
[反应式1]
其中,当采用本发明的催化剂时,100%的烯丙醇参与了所述氧化反应并在短时间内转化为丙烯酸。根据本发明的实验实施例3,测定了在约3小时的反应时间内烯丙醇的转化率为100%,以及证实了丙烯酸的收率也较高。
所述反应温度没有特别的限制,只要反应在液相中进行即可,不过其为10至120℃,优选20至100℃,更优选30至90℃。如果反应器的内部温度低于10℃,则烯丙醇的转化率大大降低,因为氧化反应为丙烯酸的速率非常慢。相反,如果所述温度高于120℃,则存在的问题是归因于副反应的副产物(即丙酸、3-羟基丙酸)随温度的升高而显著增加,并且选择性大大降低。
此时,所述氧化反应进行1至10小时,优选2至5小时,并且可以在此时间范围内以100%的烯丙醇的转化率和高收率回收丙烯酸。可以看出,与现有技术中至少12小时,通常为30小时的反应时间相比,处理时间急剧缩短。
(S3)丙烯酸的分离和回收
接下来,由上述获得的产物中分离和回收丙烯酸。
在该步骤中制备的丙烯酸并不是如常规方法中那样以丙烯酸盐(即,丙烯酸的盐)的形式,而是以丙烯酸的形式获得。结果,存在的优点是,可以排除现有技术中的必需过程,如将丙烯酸盐转化为丙烯酸的额外过程,即酸化过程之后的离子交换过程,从而降低了整体工艺的成本。
所述丙烯酸的分离过程在本发明中没有特别的限制,以及可以采用本领域已知的方法。
作为实例,所述分离过程可以通过萃取、结晶或分馏来进行。
所述萃取方法中采用的溶剂可以包括但不限于选自醇类、醛类、酮类、醚类、酯类、芳香族化合物和其它有机溶剂中的至少一种。
所述结晶是利用混合物的溶解度差异的分离方法,并且可以包括悬浮结晶和层状结晶方法。
所述分馏是利用混合物的沸点差异的分离方法,并且可以在减压、常压和高压下进行。可以加入溶剂以改善分离效率。可采用反应蒸馏以同时影响反应和分离。
由此分离的丙烯酸可以在各种领域中用作有机合成材料的原料。
另外,上述步骤中制备的3-羟基丙酸可以在通过利用韩国早期公开专利申请第2015-6349号中所述的方法的催化剂的脱水反应而转化为丙烯酸之后被回收。
通过上述步骤生产的丙烯酸可以被应用为各种化学产品的原料。
下文中,将参照以下实施例更加详细地描述本发明。然而,以下实施例不应当被解读为限制本发明的范围,并且应当被解读为便于理解本发明。
制备实施例1:Au/MgO负载型催化剂的制备
向反应器中加入19.7mg的HAuCl4·3H2O(99.9%)和5ml的HCl水溶液(0.2摩尔浓度)并均匀混合10分钟。
向混合溶液中加入5g(4重量%)的预先制备的淀粉水溶液,并将混合物均匀混合30分钟。
通过向所得混合物中加入0.5ml的1M NaOH水溶液以将pH调节至7后,升高所述反应器的温度并在回流条件下进行还原反应2小时以制备Au催化剂。
反应完成后,在不降低温度的情况下加入0.5g的MgO(由西格玛奥德里奇公司(Sigma-Aldrich)制造)作为载体,并且将混合物原样保持1小时,然后终止反应并冷却至室温以制备Au/MgO催化剂。
将其中分散有所得的Au/MgO催化剂的分散体离心以回收催化剂,减压干燥4天,以制备题述催化剂。
制备实施例2:Au1Pd20.7/MgO负载型催化剂的制备
除了采用1mg的HAuCl4·3H2O(99.9%)和8mg的PdCl2(99%)作为前体之外,采用与上述制备实施例1相同的程序制备了题述催化剂。
制备实施例3:Au1Pd9.1/MgO负载型催化剂的制备
除了前体的摩尔比不同之外,采用与上述制备实施例2相同的程序制备了题述催化剂。
制备实施例4:Au1Pd3.7/MgO负载型催化剂的制备
除了前体的摩尔比不同之外,采用与上述制备实施例2相同的程序制备了题述催化剂。
制备实施例5:Au1Pd1.5/MgO负载型催化剂的制备
除了前体的摩尔比不同之外,采用与上述制备实施例2相同的程序制备了题述催化剂。
制备实施例6:Au1Pd0.4/MgO负载型催化剂的制备
除了前体的摩尔比不同之外,采用与上述制备实施例2相同的程序制备了题述催化剂。
制备实施例7:Pd/MgO负载型催化剂的制备
除了采用9mg的PdCl2(99%)作为前体之外,采用与上述制备实施例1相同的程序制备了题述催化剂。
制备实施例8:Pd/Mg(OH)2负载型催化剂的制备
除了采用Mg(OH)2代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
制备实施例9:Pd/Al2O3负载型催化剂的制备
除了采用Al2O3代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
制备实施例10:Pd/HT负载型催化剂的制备
除了采用HT(Mg4Al2(CO3)(OH)16·4H2O)代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
制备实施例11:Pd/HAP负载型催化剂的制备
除了采用HAP(Ca5(OH)(PO4)3)代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
制备实施例12:Pd/ZnO负载型催化剂的制备
除了采用ZnO代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
制备实施例13:Pd/Zr(OH)2负载型催化剂的制备
除了采用Zr(OH)2代替MgO作为载体之外,采用与上述制备实施例7相同的程序制备了题述催化剂。
实验实施例1:摩尔比和粒度的分析
制备实施例中制备的负载型催化剂颗粒的粒度显示于以下表1中。
所述催化剂的尺寸利用透射电子显微镜(TEM)来观察(参见图2)。
[表1]
负载型催化剂 | 负载型催化剂粒度 | |
制备实施例1 | Au/MgO | 2.2nm |
制备实施例2 | Au<sub>1</sub>Pd<sub>20.7</sub>/MgO | 2.6nm |
制备实施例3 | Au<sub>1</sub>Pd<sub>9.1</sub>/MgO | <2nm |
制备实施例4 | Au<sub>1</sub>Pd<sub>3.7</sub>/MgO | <2nm |
制备实施例5 | Au<sub>1</sub>Pd<sub>1.5</sub>/MgO | <2nm |
制备实施例6 | Au<sub>1</sub>Pd<sub>0.4</sub>/MgO | 2.0nm |
制备实施例7 | Pd/MgO | 2.2nm |
制备实施例8 | Pd/Mg(OH)<sub>2</sub> | 2.6nm |
制备实施例9 | Pd/Al<sub>2</sub>O<sub>3</sub> | 3.0nm |
制备实施例10 | Pd/HT | <2.0nm |
制备实施例11 | Pd/HAP | <2nm |
制备实施例12 | Pd/ZnO | 2.3nm |
制备实施例13 | Pd/Zr(OH)<sub>2</sub> | 2.3nm |
参见表1,可以看出,本发明中制备的负载型催化剂为具有约2nm的厚度的非常小的颗粒。
图2显示了由(a)制备实施例7(Pd/MgO)、(b)制备实施例8(Pd/Mg(OH)2)、(c)制备实施例10(Pd/HT)以及(d)制备实施例11(Pd/HAP)的负载型催化剂的透射电子显微镜而获得的图像。参照图2,可以看出,在所述负载型催化剂的情况下,几乎均匀地制备了粒度,由此可以稳定地展现出根据本发明的负载型催化剂的催化剂活性。
实施例1至12:丙烯酸的制备
采用制备实施例2至13中制备的负载型催化剂在中性条件下制备丙烯酸(参见表2)。
将所述负载型催化剂、0.2ml的烯丙醇和5ml的蒸馏水注入反应器中。此时,将烯丙醇/金属催化剂的摩尔比设定为287。
之后,降低所述反应器内部的压力,然后注入氧气至3巴,将所述反应器中的温度升高至50℃,并进行氧化反应。反应完成后,通过分馏纯化所得的丙烯酸。
[表2]
实施例 | 所用的负载型催化剂 | 实施例 | 所用的负载型催化剂 |
实施例1 | Au<sub>1</sub>Pd<sub>20.7</sub>/MgO(制备实施例2) | 实施例7 | Pd/Mg(OH)<sub>2</sub>(制备实施例8) |
实施例2 | Au<sub>1</sub>Pd<sub>9.1</sub>/MgO(制备实施例3) | 实施例8 | Pd/Al<sub>2</sub>O<sub>3</sub>(制备实施例9) |
实施例3 | Au<sub>1</sub>Pd<sub>3.7</sub>/MgO(制备实施例4) | 实施例9 | Pd/HT(制备实施例10) |
实施例4 | Au<sub>1</sub>Pd<sub>1.5</sub>/MgO(制备实施例5) | 实施例10 | Pd/HAP(制备实施例11) |
实施例5 | Au<sub>1</sub>Pd<sub>0.4</sub>/MgO(制备实施例6) | 实施例11 | Pd/ZnO(制备实施例12) |
实施例6 | Pd/MgO(制备实施例7) | 实施例12 | Pd/Zr(OH)<sub>2</sub>(制备实施例13) |
对比实施例1:丙烯酸的制备
除了采用制备实施例1的Au/MgO催化剂之外,采用与上述实施例1至12相同的程序制备了丙烯酸。
实验实施例2:根据催化剂的类型的烯丙醇转化率和丙烯酸产率的分析
计算实施例1至6和对比实施例1中制备的烯丙醇的转化率和丙烯酸的产率,其结果总结于以下表3中。
通过HPLC(高效液相色谱)分析来确定烯丙醇的转化率和丙烯酸的产率。烯丙醇的转化率为反应期间消耗的烯丙醇与反应前加入的烯丙醇的摩尔比,100%的转化率表示所有的烯丙醇参与了反应。另外,丙酸和3-HPA作为氧化反应的副反应产物产生(参见图3中的HPLC分析)。
[表3]
参照表3,当将对比实施例1的Au/MgO用作负载型催化剂时,在中性条件下烯丙醇的转化率非常低,并且不能实现向丙烯酸的转化。
相比于实施例1至6,可以看出,当采用Au-过渡金属和过渡金属催化剂时,100%的烯丙醇参与反应中,并且丙烯酸的收率也很高。
特别地,当采用实施例6的Pd/MgO时,丙烯酸的收率高达24.2%。
此外,参照实施例1至5,收率随着Au-Pd的摩尔比而变化,并且存在Pd比Au的摩尔比越高,丙烯酸的收率越高的趋势。
实验实施例3:根据催化剂反应时间的烯丙醇氧化反应的分析
为了证实根据本发明的负载型催化剂的反应性,根据反应时间收集产物以测定烯丙醇的转化率和丙烯酸的收率,其结果显示于表4和图4中。图4(a)显示了由实施例3中氧化反应1小时之后制备的产物的HPLC而获得的谱图,以及图4(b)为12小时后的HPLC谱图。
[表4]
参照表4和图4,可以看出,对于实施例3的催化剂,3小时内100%的烯丙醇参与了反应,并且丙烯酸的收率随时间增加。
相比之下,其展现出当采用实施例6的Pd/MgO催化剂时,1小时反应期间的转化率为90%以上。
特别地,考虑到相同的反应时间,可以看出,由于丙烯酸12小时后的产率对于实施例3为18.1%以及对于实施例6为24.2%,因此当采用所述Pd/MgO负载型催化剂时,获得了更高的收率。
实验实施例4:根据载体的类型的对丙烯酸产率和负载型催化剂耐久性的测试
为了证实根据载体的类型的负载型催化剂的耐久性,通过如下改变载体的类型而制备了催化剂,并用于丙烯酸的生产中。
在完成丙烯酸的生产之后,将催化剂回收并利用ICP-OES(电感耦合等离子体原子发射光谱法)测定这些催化剂的金属含量的损失。其结果显示于以下表5中。此时,金属含量的损失越低,所述催化剂越耐用。
[表5]
实施例 | 负载型催化剂 | 反应时间(h) | 丙烯酸的产率(%) | 元素 | 损失(%) |
实施例3 | Au<sub>1</sub>Pd<sub>3.7</sub>/MgO | 12 | 18.0 | Mg | 22.3 |
实施例7 | Pd/Mg(OH)<sub>2</sub> | 6 | 20.0 | Mg | 31.4 |
实施例8 | Pd/Al<sub>2</sub>O<sub>3</sub> | 6 | 6.4 | Al | 2.8 |
实施例9 | Pd/HAP | 6 | 5.6 | Ca | 8.7 |
实施例10 | Pd/ZnO | 12 | 17.8 | Zn | 39 |
实施例11 | Pd/Zr(OH)<sub>2</sub> | 12 | 2.4 | Zr | - |
如表5所示,发现丙烯酸的收率根据载体的类型而不同。
具体而言,当Pd催化剂负载于Mg(OH)2和ZnO上时,丙烯酸的产率同时较高,但Mg和Zn的损失以高水平发生。并且,在比较对比实施例3和7时,存在当以MgO的氧化物形式使用Mg时,Mg损失率略低的趋势。
并且,由实施例8和11可以看出,存在当采用Al2O3和Zr(OH)2作为载体时,12小时反应之后损失很小或者没有损失的趋势,不过丙烯酸的生产产率低于其它载体。
根据本发明的催化剂适用于作为有机合成材料的原料的丙烯酸的制备工业。
Claims (8)
1.一种在催化剂的存在下通过烯丙醇的氧化反应来制备丙烯酸的方法,其特征在于,所述氧化反应在pH 6-8下进行,其中,所述催化剂为其中金属催化剂负载于载体上的负载型催化剂,
其中,所述负载型催化剂选自Au-Pd合金/MgO催化剂、Pd/MgO催化剂、Pd/Mg(OH)2催化剂和Pd/ZnO催化剂以及它们的组合中的任意一种,其中所述Au-Pd合金/MgO催化剂中Au和Pd的摩尔比为1:20.7至1:1.5。
2.根据权利要求1所述的制备丙烯酸的方法,其特征在于,使用所述负载型催化剂以使得烯丙醇与金属催化剂的摩尔比为10至2000。
3.根据权利要求1所述的制备丙烯酸的方法,其特征在于,所述金属催化剂具有1至50nm的粒度。
4.根据权利要求1所述的制备丙烯酸的方法,其特征在于,基于所述载体的总干重,所述负载型催化剂具有以0.0001至5重量%的量负载的所述金属催化剂。
5.根据权利要求1所述的制备丙烯酸的方法,其特征在于,所述氧化反应通过注入氧化气体来进行。
6.根据权利要求5所述的制备丙烯酸的方法,其特征在于,所述氧化气体为氧气或含氧气体。
7.根据权利要求5所述的制备丙烯酸的方法,其特征在于,将所述氧化气体注入至1至6巴的表压。
8.根据权利要求1所述的制备丙烯酸的方法,其特征在于,所述氧化反应在10至120℃下进行。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2016-0044700 | 2016-04-12 | ||
KR1020160044700A KR102069833B1 (ko) | 2016-04-12 | 2016-04-12 | 아크릴산의 제조방법 |
PCT/KR2017/001008 WO2017179805A1 (ko) | 2016-04-12 | 2017-01-31 | 아크릴산의 제조방법 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108137464A CN108137464A (zh) | 2018-06-08 |
CN108137464B true CN108137464B (zh) | 2022-03-18 |
Family
ID=60041804
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201780003368.5A Active CN108137464B (zh) | 2016-04-12 | 2017-01-31 | 制备丙烯酸的方法 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10266475B2 (zh) |
EP (1) | EP3321249B1 (zh) |
KR (1) | KR102069833B1 (zh) |
CN (1) | CN108137464B (zh) |
WO (1) | WO2017179805A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020173909A1 (en) * | 2019-02-26 | 2020-09-03 | Umicore Ag & Co. Kg | Catalyst materials comprising nanoparticles on a carrier and methods for their production |
WO2023234688A1 (ko) * | 2022-05-31 | 2023-12-07 | 주식회사 엘지화학 | 아크릴산 제조 방법 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4051181A (en) * | 1975-08-11 | 1977-09-27 | National Distillers And Chemical Corporation | Oxidation of allyl alcohol to acrylic acid |
CN104193615A (zh) * | 2014-05-16 | 2014-12-10 | 江苏大学 | 一种1,2-丙二醇催化氧化的方法 |
CN104350032A (zh) * | 2012-02-03 | 2015-02-11 | 英威达技术有限公司 | 在负载型双金属金-钯催化剂存在下环烷烃的氧化 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3739020A (en) * | 1969-05-13 | 1973-06-12 | Nat Distillers Chem Corp | Preparation of carboxylic acids |
US4552860A (en) | 1982-05-14 | 1985-11-12 | National Distillers And Chemical Corporation | Catalyst for the preparation of unsaturated aldehydes and carboxylic acids |
US4792620A (en) * | 1983-10-14 | 1988-12-20 | Bp Chemicals Limited | Carbonylation catalysts |
KR100247524B1 (ko) | 1994-05-31 | 2000-03-15 | 겐지 아이다 | 아크릴산 제조용 촉매 및 이 촉매를 이용한 아크릴산의 제조방법 |
KR100264966B1 (ko) | 1998-02-25 | 2000-09-01 | 김충섭 | 다원금속 복합산화물 촉매 및 이를 사용한 아크릴산의 제조방법 |
JP3887511B2 (ja) | 1999-05-19 | 2007-02-28 | 三菱レイヨン株式会社 | 触媒の製造方法 |
KR101002761B1 (ko) | 2007-12-03 | 2010-12-21 | 주식회사 엘지화학 | 아크릴산의 제조방법 |
BRPI1004306B1 (pt) * | 2010-08-18 | 2018-04-17 | Int - Instituto Nacional De Tecnologia | Processo catalítico oxidativo para síntese de ácido lático |
CN103007929B (zh) | 2012-12-07 | 2018-01-12 | 上海华谊(集团)公司 | 胶体沉积法制备的Pd基催化剂、制备方法及应用 |
KR101504673B1 (ko) | 2013-03-27 | 2015-03-23 | 서울대학교산학협력단 | 3차원의 열린 기공 구조를 갖는 산성 산화물 나노 입자, 그 제조방법 및 상기 나노 입자를 이용하여 글리세롤로부터 아크롤레인 또는 아크릴산을 제조하는 방법 |
KR101634221B1 (ko) | 2013-07-08 | 2016-06-28 | 주식회사 엘지화학 | 글리세롤로부터 아크릴산을 제조하는 방법 |
EP3015448B1 (en) | 2013-06-27 | 2017-10-25 | LG Chem, Ltd. | Method for producing acrylic acid from glycerol |
KR101622236B1 (ko) | 2014-06-16 | 2016-05-18 | 주식회사 엘지화학 | 알릴 알콜로부터 아크릴산 제조용 불균일계 촉매, 이를 이용한 알릴 알콜로부터 아크릴산을 제조하는 방법 |
KR101643859B1 (ko) | 2014-10-07 | 2016-07-29 | 주식회사 엘지화학 | 알릴 알콜로부터 3-하이드록시프로피오닉산 제조용 불균일계 촉매, 이를 이용한 알릴 알콜로부터 3-하이드록시프로피오닉산을 제조하는 방법 |
KR101964275B1 (ko) | 2015-09-01 | 2019-04-01 | 주식회사 엘지화학 | 아크릴산 제조용 촉매 제조방법 및 이로부터 제조되는 촉매 |
-
2016
- 2016-04-12 KR KR1020160044700A patent/KR102069833B1/ko active IP Right Grant
-
2017
- 2017-01-31 EP EP17782562.7A patent/EP3321249B1/en active Active
- 2017-01-31 WO PCT/KR2017/001008 patent/WO2017179805A1/ko active Application Filing
- 2017-01-31 CN CN201780003368.5A patent/CN108137464B/zh active Active
- 2017-01-31 US US15/752,181 patent/US10266475B2/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4051181A (en) * | 1975-08-11 | 1977-09-27 | National Distillers And Chemical Corporation | Oxidation of allyl alcohol to acrylic acid |
CN104350032A (zh) * | 2012-02-03 | 2015-02-11 | 英威达技术有限公司 | 在负载型双金属金-钯催化剂存在下环烷烃的氧化 |
CN104193615A (zh) * | 2014-05-16 | 2014-12-10 | 江苏大学 | 一种1,2-丙二醇催化氧化的方法 |
Non-Patent Citations (1)
Title |
---|
"Au-Pd supported nanocrystals prepared by a sol immobilisation technique as catalysts for selective chemical synthesis";Jose Antonio Lopez-Sanchez等;《Physical Chemistry Chemical Physics》;20080218;第10卷(第14期);第1922页左栏最后一段-右栏第一、三段,第1923页右栏倒数第二段,第1928页table 4b * |
Also Published As
Publication number | Publication date |
---|---|
CN108137464A (zh) | 2018-06-08 |
US20180237372A1 (en) | 2018-08-23 |
WO2017179805A1 (ko) | 2017-10-19 |
KR20170116745A (ko) | 2017-10-20 |
US10266475B2 (en) | 2019-04-23 |
EP3321249B1 (en) | 2023-03-01 |
EP3321249A4 (en) | 2019-01-16 |
EP3321249A1 (en) | 2018-05-16 |
KR102069833B1 (ko) | 2020-01-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2021505365A (ja) | アセトフェノンの水素化によってα−フェニルエタノールを製造するための触媒、その製造方法および応用 | |
US9433932B2 (en) | Hydrogenation catalyst and method of manufacturing the same | |
EP3647310B1 (en) | Method for preparing 2,5-furandimethylcarboxylate from hydroxymethylfurfural | |
CN113797947B (zh) | C改性铂基催化剂在催化卤代硝基苯加氢反应的应用 | |
CN108993497B (zh) | 一种纳米钌炭催化剂及其制备方法与应用 | |
US20210322958A1 (en) | Copper-based catalysts | |
Gandarias et al. | The selective oxidation of n-butanol to butyraldehyde by oxygen using stable Pt-based nanoparticulate catalysts: an efficient route for upgrading aqueous biobutanol | |
CN108137464B (zh) | 制备丙烯酸的方法 | |
CN110075835B (zh) | 一种一步氧化酯化法制甲基丙烯酸甲酯的催化剂及其制备方法和应用 | |
CN1094791C (zh) | 用于马来酸氢化成1,4-丁二醇的改善的催化剂 | |
CN114054061A (zh) | 一种氮掺杂碳负载钯催化剂及其制备方法和应用 | |
CN111013585A (zh) | 一种乙烯环氧化反应用银催化剂及其制备方法和应用 | |
WO2006006277A1 (ja) | シクロオレフィン製造用触媒及び製造方法 | |
WO2016133213A1 (ja) | アンモニア合成触媒とその製造方法 | |
CN107921429B (zh) | 用于制备丙烯酸的非均相催化剂和使用其制备丙烯酸的方法 | |
JP2012188390A (ja) | 1,2−プロパンジオールの製造方法 | |
CN114849694B (zh) | 一种基于金属负载氧化钨氢化硝基芳烃的催化剂及其制备方法和应用 | |
CN115770600A (zh) | 一种氮掺杂碳包覆镍纳米催化剂及其制备方法和应用 | |
CN112717941B (zh) | 一种酯加氢催化剂及其制备方法和应用 | |
CN115228471B (zh) | 乙醇偶联制丁醇和/或高碳醇的催化剂及其制法和应用 | |
CN114870847B (zh) | 铜锌铝系气相加氢催化剂的制备方法及制得催化剂与应用 | |
CN114471580B (zh) | 一种负载型镍镓催化剂的合成及其应用方法 | |
CN115254188B (zh) | 一种一锅法制备两亲性复合催化剂Pd@IL/CNT-COOH的方法 | |
CN117225439A (zh) | 抗CO中毒的Pd单原子催化剂及其制备方法与应用 | |
CN107335441B (zh) | 一种Ni-Zn-Co金属复合催化剂及其制备方法 |
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 |