CN111659408A - Preparation method of catalyst for preparing acrylic acid by acrolein oxidation - Google Patents
Preparation method of catalyst for preparing acrylic acid by acrolein oxidation Download PDFInfo
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- CN111659408A CN111659408A CN202010327298.2A CN202010327298A CN111659408A CN 111659408 A CN111659408 A CN 111659408A CN 202010327298 A CN202010327298 A CN 202010327298A CN 111659408 A CN111659408 A CN 111659408A
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- catalyst
- salt
- acrylic acid
- preparing
- acrolein
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 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 32
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 239000001301 oxygen Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 14
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 12
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 12
- 239000011609 ammonium molybdate Substances 0.000 claims description 12
- 229940010552 ammonium molybdate Drugs 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 150000001868 cobalt Chemical class 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 150000002751 molybdenum Chemical class 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000008213 purified water Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 150000001879 copper Chemical class 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 230000003213 activating effect Effects 0.000 claims description 7
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 150000002505 iron Chemical class 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 claims 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001299 aldehydes Chemical class 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 229910052720 vanadium Inorganic materials 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 239000003570 air Substances 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- 238000005453 pelletization Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910020516 Co—V Inorganic materials 0.000 description 1
- 229910017816 Cu—Co Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas 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
- 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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/885—Molybdenum and copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
-
- 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a catalyst for preparing acrylic acid by acrolein oxidation, which is suitable for gas-phase oxidation of acrolein in the presence of air or molecular oxygen to generate acrylic acid. The raw material gas for reaction is composed of acrolein, air or oxygen and water vapor in a certain proportion, and is carried out in a tubular fixed bed reactor filled with catalyst. The reactor is heated by molten salt or heat conducting oil, aldehyde generated by olefin oxidation can be directly oxidized without separation to realize acrylic acid production, the catalyst is prepared by taking Mo element as a reference, adding V, Ni, Cu and other elements, and carrying out coprecipitation reaction or physical compounding by using salts or corresponding oxides of the elements, and the geometric shape of the catalyst is mostly spherical, cylindrical or special-shaped. Under a certain temperature condition, the catalyst is calcined to endow the catalyst with activity to form a catalyst product, and the catalyst obtained by the method has the advantages of high reaction speed, high selectivity, low impurity content of the obtained acrylic acid product and the like, and can be more suitable for use requirements.
Description
Technical Field
The invention relates to the field of catalyst preparation, in particular to a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof.
Background
The catalyst composition and preparation process for producing acrylic acid by acrolein gas-phase catalytic oxidation have been industrialized for 20 years, and many improvements and enhancements are made. However, for the production of acrylic acid by the catalytic gas phase oxidation of acrolein, the conventional catalyst systems for the production of acrylic acid, molybdenum-phosphorus or molybdenum-vanadium, have a high activity but a low selectivity and a short lifetime.
Most of the domestic and foreign catalysts for preparing acrylic acid by acrolein gas-phase catalytic oxidation are mainly composed of phosphorus, molybdenum or vanadium, and have the structure of heteropoly acid and/or its salt. The catalyst is usually in the shape of particles, hollow tablets, hollow rings and hollow cylinders, or the active ingredients of the catalyst are coated on an inert porous sphere carrier.
In the oxidation of acrolein to acrylic acid by gas phase catalytic oxidation using such catalysts, it is common to pack the catalyst at low relative humidity and start the catalytic reaction, run at a lower space velocity, and periodically reactivate the catalyst to maintain useful life. Therefore, continuing to improve catalyst activity, selectivity, and catalyst life remains a key to the current state of the art in acrylic acid production.
Disclosure of Invention
The invention provides a catalyst for preparing acrylic acid by acrolein oxidation, which has the advantages of high conversion rate, high selectivity, quick reaction and low impurity content of a generated product, and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that: a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing a certain amount of molybdenum salt, dissolving the certain amount of molybdenum salt in certain amount of purified water, uniformly shaking, adding certain amount of ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: weighing quantitative nickel salt, copper salt and iron salt, dissolving the quantitative nickel salt, copper salt, cobalt salt and iron salt in quantitative purified water, uniformly shaking, and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one, then slowly adding the solution B in the step two into the heated solution A under the condition of stirring, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick substance generated in the third step, crushing, adding a forming agent, and granulating to obtain coarse catalyst particles;
step five: and (4) activating the coarse catalyst particles in the fourth step at the temperature of 360-450 ℃ to obtain the catalyst product.
Further, in the first step, the molybdenum salt is ammonium molybdate.
Further, cobalt salt is added in the second step, and the cobalt salt is cobalt nitrate.
Further, the ferric salt in the second step is one of ferric nitrate, ferrous sulfate and ferroferric oxide.
Further, the nickel salt in the second step is one of nickel nitrate, nickel sulfate and nickel carbonate.
Further, the copper salt in the second step is one of copper nitrate, copper sulfate and basic copper carbonate.
Further, the heating temperature of the solution A in the third step is 50-100 ℃.
Furthermore, in the fourth step, the drying temperature is 80-160 ℃, and the drying time is 24-48 h.
Further, in the fourth step, the forming agent is a silicon tellurium oxide.
Further, the atomic number ratio of the molybdenum salt, the iron salt, the copper salt, the nickel salt and the vanadium powder is 12: 0.3:2:0.9:4.1, and the atomic number ratio of the cobalt salt to the molybdenum salt is 12: 1.1.
Compared with the prior art, the invention has the advantages and positive effects that:
the acrolein used as raw material in the invention can be heated by using the catalyst of Mo-Ni-Fe-Cu-Co system through molten salt, the catalyst is diluted by inert balls and filled in different concentrations in multiple sections, the distribution catalytic oxidation of the inlet material is controlled by the resistance drop of the catalyst bed layer to realize the reaction, the reaction product gas generated in the first step is directly subjected to continuous reaction without separation, and after the catalyst is filled and the reaction is started, the catalyst is operated at moderate temperature and high space velocity, and the calcination and activation treatment are carried out in the atmosphere of 8-12% of oxygen content in the tunnel kiln at the high temperature of 400-. Thereby improving the activity and selectivity of the catalyst and prolonging the service life of the catalyst, and being more capable of meeting the market demand.
Detailed Description
For a better understanding of the present invention, the present invention is further described below in conjunction with specific embodiments.
Example 1:
a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing 280g of analytically pure ammonium molybdate, dissolving 280g of analytically pure ammonium molybdate in 350ml of purified water at 40 ℃, uniformly stirring, adding 120g of analytically pure ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: accurately weighing 35.2g of analytically pure cobalt nitrate, 16.7g of analytically pure ferric nitrate, 55.3g of analytically pure nickel nitrate and 75.5g of analytically pure copper nitrate, sequentially dissolving in 185ml of water, uniformly stirring, and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one to 80 ℃, then slowly adding the solution B in the step two into the heated solution A under the stirring condition, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick matter produced in the third step at 120 deg.c for 24 hr, crushing to 150 mesh, kneading the crushed matter with 123g Si-Te oxide carrier, extruding and pelletizing to form 5 × 5mm diameter particle to obtain coarse catalyst particle;
step five: calcining the coarse catalyst particles in the fourth step for 7 hours at 440 ℃ by adopting a muffle furnace, and activating to obtain the catalyst product.
Example 2:
a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing 280g of analytically pure ammonium molybdate, dissolving 280g of analytically pure ammonium molybdate in 350ml of purified water at 40 ℃, uniformly shaking, adding 120g of analytically pure ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: accurately weighing 35.2g of analytically pure cobalt nitrate, 16.7g of analytically pure ferric nitrate, 55.3g of analytically pure nickel nitrate and 75.5g of analytically pure copper nitrate, sequentially dissolving in 185ml of water, uniformly shaking and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one to 80 ℃, then slowly adding the solution B in the step two into the heated solution A under the stirring condition, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick matter produced in the third step at 110 deg.c for 24 hr, crushing to 150 mesh, kneading the crushed matter with 123g Si-Te oxide carrier, extruding and pelletizing to form 5 × 5mm diameter particle to obtain coarse catalyst particle;
step five: calcining the coarse catalyst particles in the fourth step for 7 hours at 440 ℃ by adopting a muffle furnace, and activating to obtain the catalyst product.
Example 3:
a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing 280g of analytically pure ammonium molybdate, dissolving 280g of analytically pure ammonium molybdate in 350ml of purified water at 40 ℃, uniformly shaking, adding 120g of analytically pure ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: accurately weighing 35.2g of analytically pure cobalt nitrate, 16.7g of analytically pure ferric nitrate, 55.3g of analytically pure nickel nitrate and 75.5g of analytically pure copper nitrate, sequentially dissolving in 185ml of water, uniformly shaking and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one to 80 ℃, then slowly adding the solution B in the step two into the heated solution A under the stirring condition, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick matter produced in the third step at 130 deg.c for 24 hr, crushing to 150 mesh, kneading the crushed matter with 123g Si-Te oxide carrier, extruding and pelletizing to form 5 × 5mm diameter particle to obtain coarse catalyst particle;
step five: calcining the coarse catalyst particles in the fourth step for 7 hours at 450 ℃ by adopting a muffle furnace, and activating to obtain the catalyst product.
Example 4:
a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing 280g of analytically pure ammonium molybdate, dissolving 280g of analytically pure ammonium molybdate in 350ml of purified water at 40 ℃, uniformly shaking, adding 120g of analytically pure ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: accurately weighing 35.2g of analytically pure cobalt nitrate, 10.5g of analytically pure ferrous sulfate, 46.8g of analytically pure nickel sulfate and 64.3g of analytically pure copper sulfate, sequentially dissolving in 185ml of water, uniformly shaking and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one to 75 ℃, then slowly adding the solution B in the step two into the heated solution A under the stirring condition, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick matter produced in the third step at 120 deg.c for 24 hr, crushing to 150 mesh, kneading the crushed matter with 123g Si-Te oxide carrier, extruding and pelletizing to form 5 × 5mm diameter particle to obtain coarse catalyst particle;
step five: calcining the coarse catalyst particles in the fourth step for 7 hours at 440 ℃ by adopting a muffle furnace, and activating to obtain the catalyst product.
Example 5:
a catalyst for preparing acrylic acid by acrolein oxidation and a preparation method thereof comprise the following steps:
the method comprises the following steps: weighing 280g of analytically pure ammonium molybdate, dissolving 280g of analytically pure ammonium molybdate in 350ml of purified water at 40 ℃, uniformly shaking, adding 120g of analytically pure ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: accurately weighing 35.2g of analytically pure cobalt nitrate, 11.2g of analytically pure ferric chloride, 39g of analytically pure nickel chloride and 53.8g of analytically pure copper chloride, sequentially dissolving in 185ml of water, uniformly shaking and uniformly dissolving to form a solution B for later use;
step three: heating the solution A in the step one to 75 ℃, then slowly adding the solution B in the step two into the heated solution A under the stirring condition, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick matter produced in the third step at 120 deg.c for 24 hr, crushing to 150 mesh, kneading the crushed matter with 123g Si-Te oxide carrier, extruding and pelletizing to form 5 × 5mm diameter particle to obtain coarse catalyst particle;
step five: calcining the coarse catalyst particles in the fourth step for 7 hours at 440 ℃ by adopting a muffle furnace, and activating to obtain the catalyst product.
Example 6:
the catalysts provided in examples 1 to 5 were subjected to catalytic performance testing: the method is carried out on a tubular fixed bed reactor. The reactor tube is about 3.5m long and 25.4mm in diameter, and is heated by molten salt (heat conducting oil). The catalyst is diluted by inert balls and filled in different sections with different concentrations, and the distribution of the imported materials is controlled by the resistance drop of the catalyst bed. Space velocity: 1200-1600 h-1The raw material gas consists of propylene (acrolein), air and water (circulating waste gas), and the concentration of the reactant is generally controlled to be 6.5-9.0 (4.5-5.5) vol.%, and O2/C=1.8 to 2.5, H2O/ C=Is 1.7 to 2.0. If a cyclic process is used, H2O/C=Can be reduced to 1.0-1.5 percent, and the circulating gas amount is 25-30 percent. Or the aldehyde-containing product is directly oxidized to generate acid without separation, and the experimental result is shown in table 1.
Table 1: the catalysts provided in examples 1 to 5 were subjected to the catalytic performance test
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Conversion of propylene | 98.8% | 97.9% | 98.3% | 97.8% | 98.1% |
| Conversion of acrolein | 99.5% | 98.2% | 99.1% | 99.7% | 99.2% |
| Yield of acrylic acid | 90.5%mol | 89.9%mol | 90.8%mol | 90.1%mol | 90.1%mol |
| Acetic acid yield | 1.6%mol | 1.5%mol | 1.4%mol | 1.5%mol | 1.6%mol |
| Carbon oxide yield | 5.9%mol | 6.1%mol | 5.6%mol | 5.7%mol | 5.8%mol |
As can be seen from Table 1, examples 1 to 5 all have excellent catalytic properties, acrolein can be heated by molten salt using a catalyst of Mo-Ni-Fe-Cu-Co-V system, the catalyst is diluted by inert balls and loaded in multiple stages at different concentrations, the distribution of the inlet materials is controlled by the catalyst bed resistance drop to realize catalytic oxidation reaction, and the reaction product gas generated in the first step into acrolein is directly reacted continuously without separation, and after the catalyst is filled and the reactor is started, the catalyst is operated at moderate temperature and space velocity, and is calcined and activated by a muffle furnace (or tunnel kiln) under high temperature conditions to give the catalyst long service life, thereby improving the activity, selectivity, catalyst and service life of the catalyst, and further meeting the needs of users.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention should be covered by the present patent.
Claims (11)
1. A preparation method of a catalyst for preparing acrylic acid by acrolein oxidation is characterized by comprising the following steps: the method comprises the following specific steps:
the method comprises the following steps: weighing a certain amount of molybdenum salt, dissolving the certain amount of molybdenum salt in certain amount of purified water, uniformly stirring, adding certain amount of ammonium metavanadate, and uniformly dissolving to form solution A for later use;
step two: weighing quantitative nickel salt, copper salt, cobalt salt and iron salt, dissolving the quantitative nickel salt, copper salt, cobalt salt and iron salt in quantitative purified water, uniformly stirring, and dissolving to form a solution B for later use;
step three: heating the solution A in the step one, then slowly adding the solution B in the step two into the heated solution A under the condition of stirring, and carrying out precipitation reaction to obtain a thick substance;
step four: drying the thick substance generated in the third step, crushing, adding a forming agent, and granulating to obtain coarse catalyst particles;
step five: and (4) activating the coarse catalyst particles in the fourth step at 380-450 ℃ to obtain the catalyst product.
2. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: in the first step, the molybdenum salt is ammonium molybdate.
3. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: and adding cobalt salt in the second step, wherein the cobalt salt is cobalt nitrate or cobalt oxalate.
4. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: and the ferric salt in the second step is one of ferric nitrate, ferrous sulfate and ferroferric oxide.
5. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: the nickel salt in the second step is one of nickel nitrate, nickel sulfate and nickel carbonate.
6. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: and the copper salt in the second step is one of copper nitrate, copper sulfate and basic copper carbonate.
7. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: the heating temperature of the solution A in the third step is 50-100 ℃.
8. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: in the fourth step, the drying temperature is 80-160 ℃, and the drying time is 12-48 h.
9. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 1, wherein: in the fourth step, the forming agent is silicon tellurium oxide.
10. The method for preparing a catalyst for preparing acrylic acid by acrolein oxidation according to claim 2, wherein: the atomic number ratio of the molybdenum salt, the iron salt, the copper salt, the nickel salt, the cobalt salt and the vanadium powder is 12: 0.3:2:0.9:4.1, and the atomic number ratio of the cobalt salt to the molybdenum salt is 12: 1.1.
11. The product of claim 1 is suitable for the production of acrylic acid or methacrylic acid products from acrolein in the presence of air or oxygen, and the obtained products have low by-product content and high purity.
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| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
| CN102989480A (en) * | 2011-09-08 | 2013-03-27 | 中国石油天然气股份有限公司 | Composite multi-metal oxide catalyst and preparation method thereof |
| CN103894204A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | Catalyst for catalyzing acrolein oxidation reaction to prepare acrylic acid, and preparation method thereof |
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| CN1445020A (en) * | 2003-04-17 | 2003-10-01 | 中国石油天然气股份有限公司 | Compound catalyst for many metals oxide and preparation method |
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| JP2008229627A (en) * | 2008-06-16 | 2008-10-02 | Lg Chem Ltd | Method for producing catalyst for oxidizing acrolein |
| CN102114427A (en) * | 2010-12-13 | 2011-07-06 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein |
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