CN108816241A - The preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst - Google Patents
The preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst Download PDFInfo
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- CN108816241A CN108816241A CN201810563006.8A CN201810563006A CN108816241A CN 108816241 A CN108816241 A CN 108816241A CN 201810563006 A CN201810563006 A CN 201810563006A CN 108816241 A CN108816241 A CN 108816241A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000003647 oxidation Effects 0.000 title claims abstract description 20
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000012065 filter cake Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001556 precipitation Methods 0.000 claims description 19
- 239000000314 lubricant Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 238000000748 compression moulding Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 12
- 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 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000012018 catalyst precursor Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910017116 Fe—Mo Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J23/881—Molybdenum and iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to formaldehyde catalyst manufacturing technology field, especially a kind of preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst.A kind of preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst, the method for preparing catalyst include the following steps：Step 1: slurry is made, Step 2: filter cake is made, Step 3: presoma is made, Step 4: crush, Step 5: compacting, Step 6: finished product.The preparation method of this iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst, this method passes through the hydrothermal synthesis reaction under higher temperature and pressure, uniform particle sizes, the relatively large presoma of crystallite dimension are obtained, there is high activity, highly selective for prepn. of formaldehyde by oxidation of methanol reaction using the catalyst of this precursor preparation.
Description
Technical field
The present invention relates to formaldehyde catalyst manufacturing technology field, especially a kind of iron molybdenum Division A League Matches of French Football alcohol aoxidizes making formaldehyde catalyst
Preparation method.
Background technique
Formaldehyde is a kind of important Organic Chemicals, is one of important derivatives of methanol, annual capacity is about so far
35000000 tons, it has also become the chemical products of large-scale production and consumption.The industrial mode of production of formaldehyde is according to catalyst type point
For Yin Fa and iron molybdenum method, advantage of the iron molybdenum method in production technology is received extensive attention.
Fe-Mo catalyst for preparing formaldehyde through methanol oxidation is that methanol reacts at a temperature of 300-350 DEG C with after excess air mixing
Formaldehyde is generated, methanol conversion is high, and formic acid content is low, the available highly concentrated formaldehyde solution after absorbing, and catalyst life
It can reach 12-18 months.
It is many that iron-molybdic catalyst patent is prepared disclosed in the country, in Publication No. CN1100667 patent, it is noted that a kind of
Iron, molybdenum, chromium, four component catalyst of cobalt, wherein method for preparing catalyst is common dripping method；Publication No. CN1546232's
In patent, a kind of iron, molybdenum, chromium, four component catalyst of vanadium are mentioned, catalyst calcination activation temperature is 380-450 DEG C, is equally
Common dripping method preparation；In the method for preparing catalyst of patent disclosure, all it is to carry out reacting under normal pressure then carrying out aging, obtains
The catalyst precursor particle diameter wider distribution arrived, grain size is relatively tiny, needs to obtain by the heat treatment of higher temperature
The lower specific surface that must be suitable for reaches the oxidation reaction degree of control methanol, improves the purpose of formaldehyde selectivity.Use such methods
The stability of catalyst obtained is relatively poor, and the selectivity of formaldehyde is not also high.
Summary of the invention
In order to overcome existing formaldehyde catalyst manufacture existing insufficient, it is logical by raw material of methanol that the present invention provides one kind
Cross the preparation method that gas phase oxidation produces the catalyst of formaldehyde.
The technical solution adopted by the present invention to solve the technical problems is：A kind of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst
Preparation method, which includes the following steps：
（1）Step 1：80 DEG C -150 DEG C of the temperature of reaction kettle, pressure are controlled in 0.1MPa -0.8MPa, mixing speed in 100r/
Min-250r/min configures 1.2-1.5Kg molybdenum salt and 20Kg 50-90 DEG C deionized water to the molybdenum salt of 0.22-0.28mol/L
After solution, 0.5-0.8Kg molysite and 5Kg 50-90 DEG C deionized water are configured to the iron salt solutions of 0.56-0.89mol/L, use tricks
Amount pump cocurrent, which is added in reaction kettle, carries out precipitation reaction, and the pH of control system is in 1.0-6.0, reaction time control in reaction process
After reaction in 1h-3h parallel-flow precipitation, the crystallization that above-mentioned reaction temperature, pressure and mixing speed are precipitated is continued to
It reacts, stops after 2h-4h, obtain slurry；
（2）Step 2：Slurry is washed with deionized water, is then filtered with filter press, and continues to use deionized water
Washing filter cake 2-7 times obtains the qualified filter cake of washing washing；
（3）Step 3：Dry 7h-14h obtains catalyst precursor to filter cake at 80 DEG C -200 DEG C in an oven；
（4）Step 4：It is mixed into the lubricant of the 2%-4% of total amount in active presoma, is pulverized and mixed uniformly；
（5）Step 5：The rotary tablet machine compression moulding of mixed material, is made having a size of 4.0-4.5mm × 4.0-
The hollow cylinder of 5.0mm × 1.5-2.5mm；
（6）Step 6：Hollow cylinder object activates 3h-10h at 300 DEG C -400 DEG C and obtains finished catalyst.
It according to another embodiment of the invention, further comprise that temperature of reaction kettle described in step 1 is 80-150
DEG C, preferably 110-135 DEG C.
It according to another embodiment of the invention, further comprise that reactor pressure described in step 1 is 0.1
MPa-0.8MPa, preferably 0.15 MPa-0.5MPa.
According to another embodiment of the invention, further comprise, it is described in step 1 reaction at pH1.0-6.0 into
Row, preferably pH1.8-3.5.
According to another embodiment of the invention, further comprise, molybdenum salt described in step 1 can be ammonium dimolybdate,
Ammonium tetramolybdate, ammonium heptamolybdate, preferably ammonium tetramolybdate and ammonium heptamolybdate, the molysite are ferric nitrate, ferric oxalate, ferric sulfate, chlorination
Iron, preferably ferric nitrate and ferric sulfate.
It according to another embodiment of the invention, further comprise that drying temperature described in step 3 is 80-200 DEG C, excellent
Select 100-150 DEG C.
It according to another embodiment of the invention, further comprise that lubricant described in step 4 can be sesbania powder, stone
Ink, stearic acid, calcium stearate, preferably stearic acid and graphite.
It according to another embodiment of the invention, further comprise that activation temperature described in step 6 is 300-400 DEG C,
It is preferred that 320-380 DEG C, the activation time is 3h-10h, preferably 4h-8h.
The invention has the advantages that the preparation method of this iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst, this method are logical
The hydrothermal synthesis reaction under higher temperature and pressure is crossed, uniform particle sizes, the relatively large presoma of crystallite dimension are obtained, is used
The catalyst of this precursor preparation has high activity, highly selective for prepn. of formaldehyde by oxidation of methanol reaction.Simultaneously in higher temperature
Degree and the lower progress hydrothermal synthesis reaction of pressurization, the excellent catalyst precursor of processability：The raw material for preparing catalyst is prepared
It is added in the reaction kettle with certain temperature and pressure at cocurrent after aqueous solution and carries out precipitation reaction, continuing after reaction will be anti-
The precipitating that should be generated carries out crystallization under certain temperature and pressure.
Specific embodiment
A kind of preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst, the method for preparing catalyst include following step
Suddenly：
（1）Step 1：80 DEG C -150 DEG C of the temperature of reaction kettle, pressure are controlled in 0.1MPa -0.8MPa, mixing speed in 100r/
Min-250r/min configures 1.2-1.5Kg molybdenum salt and 20Kg 50-90 DEG C deionized water to the molybdenum salt of 0.22-0.28mol/L
After solution, 0.5-0.8Kg molysite and 5Kg 50-90 DEG C deionized water are configured to the iron salt solutions of 0.56-0.89mol/L, use tricks
Amount pump cocurrent, which is added in reaction kettle, carries out precipitation reaction, and the pH of control system is in 1.0-6.0, reaction time control in reaction process
After reaction in 1h-3h parallel-flow precipitation, the crystallization that above-mentioned reaction temperature, pressure and mixing speed are precipitated is continued to
It reacts, stops after 2h-4h, obtain slurry；
（2）Step 2：Slurry is washed with deionized water, is then filtered with filter press, and continues to use deionized water
Washing filter cake 2-7 times obtains the qualified filter cake of washing washing；
（3）Step 3：Dry 7h-14h obtains catalyst precursor to filter cake at 80 DEG C -200 DEG C in an oven；
（4）Step 4：It is mixed into the lubricant of the 2%-4% of total amount in active presoma, is pulverized and mixed uniformly；
（5）Step 5：The rotary tablet machine compression moulding of mixed material, is made having a size of 4.0-4.5mm × 4.0-
The hollow cylinder of 5.0mm × 1.5-2.5mm；
（6）Step 6：Hollow cylinder object activates 3h-10h at 300 DEG C -400 DEG C and obtains finished catalyst.
It according to another embodiment of the invention, further comprise that temperature of reaction kettle described in step 1 is 80-150
DEG C, preferably 110-135 DEG C.
It according to another embodiment of the invention, further comprise that reactor pressure described in step 1 is 0.1
MPa-0.8MPa, preferably 0.15 MPa-0.5MPa.
According to another embodiment of the invention, further comprise, it is described in step 1 reaction at pH1.0-6.0 into
Row, preferably pH1.8-3.5.
According to another embodiment of the invention, further comprise, molybdenum salt described in step 1 can be ammonium dimolybdate,
Ammonium tetramolybdate, ammonium heptamolybdate, preferably ammonium tetramolybdate and ammonium heptamolybdate, the molysite are ferric nitrate, ferric oxalate, ferric sulfate, chlorination
Iron, preferably ferric nitrate and ferric sulfate.
It according to another embodiment of the invention, further comprise that drying temperature described in step 3 is 80-200 DEG C, excellent
Select 100-150 DEG C.
It according to another embodiment of the invention, further comprise that lubricant described in step 4 can be sesbania powder, stone
Ink, stearic acid, calcium stearate, preferably stearic acid and graphite.
It according to another embodiment of the invention, further comprise that activation temperature described in step 6 is 300-400 DEG C,
It is preferred that 320-380 DEG C, the activation time is 3h-10h, preferably 4h-8h.
The embodiment of the present invention one：
110 DEG C -135 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 1.8-3.5, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 3 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.
Embodiment 1-1
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
4h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-1-1.
Embodiment 1-2
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
4h is activated at 330 DEG C -360 DEG C obtains finished catalyst FMAL-1-2.
Embodiment 1-3
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
6h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-1-3.
Embodiment 1-4
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
8h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-1-4.
The embodiment of the present invention two：
115 DEG C -125 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 1.8-3.5, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 3 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.The 2-4% of total amount is mixed into active presoma
Lubricant, be pulverized and mixed uniformly, the rotary tablet machine compression moulding of mixed material, be made having a size of（4.0-
4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object activates 8h at 350 DEG C -380 DEG C and obtains
Finished catalyst FMAL-2-1.
The embodiment of the present invention three：
110 DEG C -135 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 2.2-3.0, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 3 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.The 2-4% of total amount is mixed into active presoma
Lubricant, be pulverized and mixed uniformly, the rotary tablet machine compression moulding of mixed material, be made having a size of（4.0-
4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object activates 8h at 350 DEG C -380 DEG C and obtains
Finished catalyst FMAL-3-1.
The embodiment of the present invention four：
110 DEG C -135 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 2.2-3.0, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 5 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.The 2-4% of total amount is mixed into active presoma
Lubricant, be pulverized and mixed uniformly, the rotary tablet machine compression moulding of mixed material, be made having a size of（4.0-
4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object activates 8h at 350 DEG C -380 DEG C and obtains
Finished catalyst FMAL-4-1.
The embodiment of the present invention five：
110 DEG C -135 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 2.2-3.0, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 7 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.The 2-4% of total amount is mixed into active presoma
Lubricant, be pulverized and mixed uniformly, the rotary tablet machine compression moulding of mixed material, be made having a size of（4.0-
4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object activates 8h at 350 DEG C -380 DEG C and obtains
Finished catalyst FMAL-5-1.
The embodiment of the present invention six：
110 DEG C -135 DEG C of the temperature of reaction kettle, pressure are controlled in 0.15MPa-0.5MPa, mixing speed in 100r/min-250r/
Min prepared molybdenum saline solution and molysite aqueous solution is added in reaction kettle with metering pump cocurrent and carries out precipitation reaction, reacts
For the pH of control system in 2.2-3.0, the reaction time is controlled in 1h-3h parallel-flow precipitation after reaction in the process, continues to
The crystallization that reaction temperature, pressure and mixing speed are precipitated is stated, stops after 2h-4h, obtains slurry.It is filtered with stainless steel
Machine filter slurry, obtains filter cake and filtrate, the filter cake after being washed is washed with deionized 5 times in filter cake, the filter after washing
Cake obtains catalyst activity presoma with the dry 8h of drying box at 100-150 DEG C.
Embodiment 6-1
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
4h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-6-1.
Embodiment 6-2
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
6h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-6-2.
Embodiment 6-3
It is mixed into the lubricant of the 2-4% of total amount in active presoma, is pulverized and mixed the uniformly rotary tabletting of mixed material
Machine compression moulding, be made having a size of（4.0-4.5mm*4.0-5.0mm*1.5-2.5mm）Hollow cylinder, hollow cylinder object
8h is activated at 350 DEG C -380 DEG C obtains finished catalyst FMAL-6-3.
Active testing：It takes the advanced industrial catalyst of certain external company to do reference, distinguishes together with above-described embodiment sample
It is reacted on fixed bed single tube analogue reactor device, active comparative evaluation's result such as following table：
Table one：
As shown in Table 1, Catalyst Conversion and yield are all higher than under equivalent responses condition and equivalent parameters in the present invention
The advanced industrial catalyst of certain external company.
Described above to be merely exemplary for the purpose of the present invention, and not restrictive, those of ordinary skill in the art understand,
In the case where not departing from spirit and scope as defined in the appended claims, many modifications, variation or equivalent can be made, but all
It will fall within the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst, characterized in that the method for preparing catalyst includes
Following steps：
（1）Step 1：80 DEG C -150 DEG C of the temperature of reaction kettle, pressure are controlled in 0.1MPa -0.8MPa, mixing speed in 100r/
Min-250r/min configures 1.2-1.5Kg molybdenum salt and 20Kg 50-90 DEG C deionized water to the molybdenum salt of 0.22-0.28mol/L
After solution, 0.5-0.8Kg molysite and 5Kg 50-90 DEG C deionized water are configured to the iron salt solutions of 0.56-0.89mol/L, use tricks
Amount pump cocurrent, which is added in reaction kettle, carries out precipitation reaction, and the pH of control system is in 1.0-6.0, reaction time control in reaction process
After reaction in 1h-3h parallel-flow precipitation, the crystallization that above-mentioned reaction temperature, pressure and mixing speed are precipitated is continued to
It reacts, stops after 2h-4h, obtain slurry；
（2）Step 2：Slurry is washed with deionized water, is then filtered with filter press, and continues to use deionized water
Washing filter cake 2-7 times obtains the qualified filter cake of washing washing；
（3）Step 3：Dry 7h-14h obtains catalyst precursor to filter cake at 80 DEG C -200 DEG C in an oven；
（4）Step 4：It is mixed into the lubricant of the 2%-4% of total amount in active presoma, is pulverized and mixed uniformly；
（5）Step 5：The rotary tablet machine compression moulding of mixed material, is made having a size of 4.0-4.5mm × 4.0-
The hollow cylinder of 5.0mm × 1.5-2.5mm；
（6）Step 6：Hollow cylinder object activates 3h-10h at 300 DEG C -400 DEG C and obtains finished catalyst.
2. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 1
Described in temperature of reaction kettle be 80-150 DEG C, preferably 110-135 DEG C.
3. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 1
Described in reactor pressure be 0.1 MPa-0.8MPa, preferably 0.15 MPa-0.5MPa.
4. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 1
Described in reaction carried out at pH1.0-6.0, preferably pH1.8-3.5.
5. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 1
Described in molybdenum salt can be ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, preferably ammonium tetramolybdate and ammonium heptamolybdate, the molysite
For ferric nitrate, ferric oxalate, ferric sulfate, iron chloride, preferably ferric nitrate and ferric sulfate.
6. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 3
Described in drying temperature be 80-200 DEG C, preferably 100-150 DEG C.
7. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 4
Described in lubricant can be sesbania powder, graphite, stearic acid, calcium stearate, preferably stearic acid and graphite.
8. the preparation method of iron molybdenum Division A League Matches of French Football alcohol oxidation making formaldehyde catalyst according to claim 1, characterized in that step 6
Described in activation temperature be 300-400 DEG C, preferably 320-380 DEG C, the activation time be 3h-10h, preferably 4h-8h.
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Address after: 213000 No.78, gangang Avenue, Binjiang chemical industry park, Xinbei Industrial Park, Changzhou City, Jiangsu Province Applicant after: Changzhou Xinri catalyst Co.,Ltd. Address before: 213000 No.78, gangang Middle Road, Binjiang Industrial Park, Xinbei District, Changzhou City, Jiangsu Province Applicant before: CHANGZHOU NEW SOLAR CATALYSTS Co.,Ltd. |
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Application publication date: 20181116 |