CN104248978B - A kind of preparation method of phosphomolybdate crystal catalyst - Google Patents

A kind of preparation method of phosphomolybdate crystal catalyst Download PDF

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Publication number
CN104248978B
CN104248978B CN201310255962.7A CN201310255962A CN104248978B CN 104248978 B CN104248978 B CN 104248978B CN 201310255962 A CN201310255962 A CN 201310255962A CN 104248978 B CN104248978 B CN 104248978B
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catalyst
phosphomolybdate
stainless steel
mixed liquor
steel cauldron
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CN104248978A (en
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张羽男
刘立新
张宇
沙靖全
黄展
张云杰
李达
张磊
杨铭
刘红
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Jiamusi University
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Jiamusi University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The present invention relates to a kind of preparation method of phosphomolybdate crystal catalyst, by (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in distilled water successively by mol ratio, through stirring, obtain mixed liquor, it is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) that the mixed liquor of gained is enclosed liner, stainless steel cauldron is put into baking oven heating crystallization, then after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black.The catalyst of this invention using phosphomolybdate crystalline compounds as synthesis aspirin, show higher catalytic activity in the esterification reaction, reaction condition is gentle, raw material can complete reaction, and productive rate is high, environmentally safe, corrosion-free to equipment, catalyst recycling capable of circulation, removal process is simple, has saved production cost.

Description

A kind of preparation method of phosphomolybdate crystal catalyst
Technical field: the preparation method that the present invention relates to a kind of phosphomolybdate crystal catalyst, particularly a kind of preparation method of the phosphomolybdate crystal catalyst for the synthesis of aspirin.
Background technology: aspirin and acetylsalicylic acid is time-honored analgesic-antipyretic, also can be used for preventing and treating artery sclerosis, Antiaggregating activity on platelet, has good effect for prevention breast cancer, lung cancer, cutaneum carcinoma.At present, catalyst used in suitability for industrialized production aspirin process is the concentrated sulfuric acid, it has strong oxidizing property and corrosivity, and strong oxidizing property causes raw material to reduce, and productive rate reduces, cause environmental pollution, corrosivity is higher to equipment requirement, and loss is comparatively large, and catalyst is difficult to recycle and reuse, waste raw material, improve production cost.
Summary of the invention: the object of the invention is to overcome above-mentioned shortcoming, a kind of preparation method of phosphomolybdate crystal catalyst is provided, it mainly solves catalyst used in current suitability for industrialized production aspirin process is the concentrated sulfuric acid, it has strong oxidizing property and corrosivity, productive rate is low, contaminated environment, catalyst is difficult to problems such as recycling and reusing.The object of the present invention is achieved like this, and a kind of preparation method of phosphomolybdate crystal catalyst, by (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1: 1: 8.6 successively, stir 1-12 hours, obtain mixed liquor; It is in the stainless steel cauldron of polytetrafluoroethylene (PTFE) that the mixed liquor of gained is enclosed liner, and in reactor, compactedness is 60%; Then stainless steel cauldron is put into the baking oven heating crystallization 100-200 hours of 100-200 DEG C, then after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black, its chemical formula is: (C 13h 14n 2) 2h 3pMo 12o 402H 2o.Elemental Analysis theory: C 26h 35o 42n 4pMo 12(2257.82): C (13.83%), N (2.48%), H (1.56%), O (29.76%), P (1.37%), Mo (50.99%).Measured value: C (14.25%), H (1.88%), N (2.03%), O (28.99%), P (1.54%), Mo (51.31%).
Phosphomolybdate crystal data is as follows:
Monoclinic system, space group α=103.941 (5) °, β=108.367 (5) °, γ=110.999 (5) °, z=1.R 1＝0.0437，wR 2＝0.1175，S＝1.000。
Phosphomolybdate crystal catalyst synthetic molecules structure is as follows:
Phosphomolybdate crystal catalyst ir data: at 3000cm -1~ 3650cm -1the strong broad peak at place can be attributed to the vibration peak of ν (-OH) and ν (-NH), 3077cm -1belong to the C-H stretching vibration peak on pyridine ring, 2850cm -1and 2924cm -1two spikes are attributed to ν (-CH 2), at 1629cm -1the absworption peak at place is attributed to the vibration peak of the β (-NH) on protonated pyridine ring.At 1502cm -1the absworption peak at place is attributed to the-CH of pyridine ring 2flexural vibrations peak, at 955cm -1the strong peak at place is attributed to ν as(Mo-O t), 1058cm -1the absworption peak at place can be attributed to ν as(P-O) vibration peak, 773cm -1the strong peak at place is attributed to ν as(Mo-O-Mo) vibration peak.
The catalyst of this invention using phosphomolybdate crystalline compounds as synthesis aspirin, show higher catalytic activity in the esterification reaction, reaction condition is gentle, raw material can complete reaction, and productive rate is high, environmentally safe, corrosion-free to equipment, catalyst recycling capable of circulation, removal process is simple, has saved production cost.
Detailed description of the invention
Embodiment 1
A. by raw material (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1: 1: 8.6 successively, stir 1 hour, obtain mixed liquor;
B. the mixed liquor of gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and in reactor, compactedness is 60%;
C. stainless steel cauldron is put into the baking oven heating crystallization 100 hours of 100 DEG C, after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black, catalyst production is 15.7%.
Catalytic effect test is as follows:
By above-mentioned 0.30g catalyst, 3g salicylic acid and 5mL acetic anhydride (0.05molL -1) load in the three-neck flask of 50mL drying, react 70 minutes under 90 DEG C of water-baths, salicylic acid conversion ratio is 94.3%, and aspirin productive rate is 80.7%, and catalyst choice is 85.6%.
Embodiment 2
A. by raw material (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1: 1: 8.6 successively, stir 6 hours, obtain mixed liquor;
B. the mixed liquor of gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and in reactor, compactedness is 60%;
C. stainless steel cauldron is put into the baking oven heating crystallization 180 hours of 170 DEG C, after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black, catalyst production is 23.6%.
Catalytic effect test is as follows:
By above-mentioned 0.30g catalyst, 3g salicylic acid and 5mL acetic anhydride (0.05molL -1) load in the three-neck flask of 50mL drying, react 70 minutes under 90 DEG C of water-baths, salicylic acid conversion ratio is 95.1%, and aspirin productive rate is 81.5%, and catalyst choice is 85.7%.
Embodiment 3
A. by raw material (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1: 1: 8.6 successively, stir 8 hours, obtain mixed liquor;
B. the mixed liquor of gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and in reactor, compactedness is 60%;
C. stainless steel cauldron is put into the baking oven heating crystallization 170 hours of 180 DEG C, after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black, catalyst production is 35.9%.
Catalytic effect test is as follows:
By above-mentioned 0.30g catalyst, 3g salicylic acid and 5mL acetic anhydride (0.05molL -1) load in the three-neck flask of 50mL drying, react 70 minutes under 90 DEG C of water-baths, salicylic acid conversion ratio is 95.3%, and aspirin productive rate is 82.2%, and catalyst choice is 86.3%.
Embodiment 4
A. by raw material (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1: 1: 8.6 successively, stir 12 hours, obtain mixed liquor;
B. the mixed liquor of gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and in reactor, compactedness is 60%;
C. stainless steel cauldron is put into the baking oven heating crystallization 200 hours of 200 DEG C, after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black, catalyst production is 27.3%.
Catalytic effect test is as follows:
By above-mentioned 0.30g catalyst, 3g salicylic acid and 5mL acetic anhydride (0.05molL -1) load in the three-neck flask of 50mL drying, react 70 minutes under 90 DEG C of water-baths, salicylic acid conversion ratio is 94.9%, and aspirin productive rate is 81.4%, and catalyst choice is 85.8%.

Claims (1)

1. a preparation method for phosphomolybdate crystal catalyst, is characterized in that:
A. by raw material (NH 4) 6mo 7o 244H 2o, 1,3-bis-(4-pyridine radicals) propane and phosphoric acid join in 15mL distilled water by mol ratio 1:1:8.6 successively, stir 1-12 hours, obtain mixed liquor;
B. the mixed liquor of gained being enclosed liner is in the stainless steel cauldron of polytetrafluoroethylene (PTFE), and in reactor, compactedness is 60%;
C. stainless steel cauldron is put into the baking oven heating crystallization 100-200 hours of 100-200 DEG C, then after room temperature cooling, obtain the pain phosphorus molybdate crystal catalyst of black.
CN201310255962.7A 2013-06-25 2013-06-25 A kind of preparation method of phosphomolybdate crystal catalyst Expired - Fee Related CN104248978B (en)

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CN107597156A (en) * 2017-09-19 2018-01-19 常州大学 A kind of preparation method of phosphomolybdic acid Mn catalyst
CN110284190B (en) * 2019-07-29 2021-04-16 合肥学院 Dodecaphosphomolybdic acid H3PMo12O40·21H2Preparation method of O crystal material
CN110624579B (en) * 2019-09-27 2022-05-10 河北师范大学 Electrochemical method for quantitatively detecting Cr (VI) in water body

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407529A (en) * 2007-10-11 2009-04-15 北京化工大学 Method for synthesizing organophosphorus molybdate complexes
CN102218348A (en) * 2011-04-27 2011-10-19 哈尔滨师范大学 Preparation method for substituted molybdophosphate crystal catalyst

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US6664408B2 (en) * 2001-03-29 2003-12-16 The Curators Of The University Of Missouri Process for preparing organically-substituted polyoxometalates

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101407529A (en) * 2007-10-11 2009-04-15 北京化工大学 Method for synthesizing organophosphorus molybdate complexes
CN102218348A (en) * 2011-04-27 2011-10-19 哈尔滨师范大学 Preparation method for substituted molybdophosphate crystal catalyst

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