CN1857770A - Solid catalyst for synthesizing propylene glycol ether and its preparing process - Google Patents

Solid catalyst for synthesizing propylene glycol ether and its preparing process Download PDF

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CN1857770A
CN1857770A CN 200610044391 CN200610044391A CN1857770A CN 1857770 A CN1857770 A CN 1857770A CN 200610044391 CN200610044391 CN 200610044391 CN 200610044391 A CN200610044391 A CN 200610044391A CN 1857770 A CN1857770 A CN 1857770A
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catalyst
propylene glycol
water
mgo
solid catalyst
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CN100386145C (en
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张文郁
班青
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Shandong Institute of Light Industry
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Shandong Institute of Light Industry
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Abstract

The catalyst for synthesizing propylene glycol ether is prepared with Zn(OH)2 or zinc citrate, pseudo boehmite and Mg(OH)2, and through mechanical kneading, extruding to form, stoving at 110 deg.c for 12 hr and roasting at 600 deg.c for 4 hr. It contains ZnO in 10-60 wt%, MgO in 6-15 wt% and Al2O3 in 30-80 wt%. The preparation process is simple, easy operation, less pollution caused by CO2 and water in the air and environment friendly, and the catalyst has high propylene oxide converting rate, high isomerization ratio and high propylene glycol ether selectivity.

Description

A kind of novel solid Catalysts and its preparation method of synthesis of propylene glycol
Technical field:
The invention belongs to field of fine chemical, relate to solid catalyst and preparation method thereof, relate in particular to the novel solid Catalysts and its preparation method that is used for the propylene oxide method synthesis of propylene glycol.
Background technology
Propylene glycol is widely used in industries such as printing ink, paint, printing, dyestuff, electronic chemical product and weaving as a kind of hypotoxic senior solvent product, is progressively replacing highly toxic glycol ether, and swift and violent development was arranged in the more than ten years in the past.The industrial propylene oxide method synthesis of propylene glycol of using, promptly synthetic under the effect of catalyst by expoxy propane and lower aliphatic alcohols.Because there is open loop orientation problem in expoxy propane, has two kinds of isomers in the product, 1-alkoxyl-2-propyl alcohol (uncle's ether) and 2-alkoxyl-1-propyl alcohol (secondary ether) are lower according to result of study uncle ether toxicity.
Industrial synthesis of propylene glycol has homogeneous phase method and heterogeneous method, is catalyst with the soda acid generally, and homogeneous acid or base catalyst mainly comprise BF 3, mineral acid and NaOH, sodium alkoxide, potassium alcoholate and tertiary amine, homogeneous catalysis soda acid uniform intensity, catalytic efficiency height, but have problems such as separate complex, equipment corrosion and liquid waste processing, and gradually being eliminated.Solid acid catalyst mainly comprises: cation or hydrogen ion exchange clay, cationic ion-exchange resin and acidic molecular sieve.Be characterized in that catalyst need not separate with product, active and stable high, can the applied catalysis rectification process as the acid molecular sieve catalyst of patent CN1033742C report, product need not to separate with catalyst, but the product isomer proportion is low (generally at 75-80: 25-20).Solid base catalyst mainly contains: alkaline water talcum, anion hydrogen oxide clay, anion exchange resin, magnalium complex hydroxide Mg aAl b(OH) 2a+3bAnd alkali metal exchange molecular sieve.Be characterized in that catalyst need not separate with product, (uncle's ether: secondary ether) the ratio height is (generally at 95-97: 5-3) for the product isomers, but solid base catalyst is easy to by airborne water and carbon dioxide pollution, has the inconvenience that stores and transport, and activity stability awaits further to improve simultaneously.
Summary of the invention:
The purpose of this invention is to provide and a kind ofly can improve propylene glycol product uncle ether and secondary ether isomery ratio, possess high catalytic activity catalyst and preparation method thereof simultaneously.
Catalyst of the present invention is:
With ZnO is active material, is carrier with the alundum (Al, and MgO is a co-catalyst; The weight percentage of ZnO is 10-60%, and the weight percentage of alundum (Al is 80-30%, and the content of co-catalyst MgO is 6-15%.
Preferred above-mentioned ZnO predecessor is a zinc hydroxide, zinc citrate; The predecessor of alundum (Al is a boehmite; The predecessor of MgO is a magnesium hydroxide.
The method for making of catalyst of the present invention comprises the steps
(1) with Zn (OH) 2Powder, boehmite powder and Mg (OH) 2Powder mixes in ball mill
(2) material that mixes in the step (1) is added 20～40% water and mix and pinch, till the water material is evenly, agent bar shaping in agent bar machine then.
(3) with 110 ℃ of oven dry of the stripe shape catalyst 12h that obtains in the step (2), the heating rate with 15 ℃/Min rises to 500-700 ℃ with temperature then, and constant temperature 2-6h reduces to room temperature and promptly gets catalyst.
Catalyst of the present invention is used for synthesis of propylene glycol, and method is to be 3-7 with the mol ratio with methyl alcohol and expoxy propane: 1 ratio, and through 5ml Solid Bed, 80～140 ℃ of reaction temperatures, reaction pressure 8atm, liquid hourly space velocity (LHSV) 2.5～5h -1
Product analysis: product is analyzed with the GC-920 that sea, Shanghai glad chromatogram Co., Ltd produces.Chromatographic condition is as follows: chromatographic column: external diameter 3mm, the stainless steel column of long 2m; Carrier: GDX-203 (60-80 order); Detector: hydrogen flame; Injector temperature: 220 ℃; The column temperature temperature programming: 100 ℃ of initial temperature, 4 minutes time, 8 ℃/min of heating rate, temperature is 230 ℃ eventually, eventually the 10 minutes time of temperature; Sample size: 0.1ul.
The present invention compared with prior art has following advantage:
(1) preparation method is simple, and is easy to operate, and no waste liquid and waste gas are (as NO 2Deng pollutant) produce.
(2) in the propylene glycol synthetic reaction, expoxy propane conversion ratio height, reaction condition gentleness, uncle's ether: secondary ether isomery ratio height.
(3) propylene glycol selectivity height
(4) cost is low, and catalyst is difficult for by airborne CO 2, H 2O pollutes.
The specific embodiment:
Embodiment 1:
With 10g Zn (OH) 2, 15g boehmite and 2gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 100 ℃ of bed temperatures, reaction pressure 8atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 2:
With 15g Zn (OH) 2, 15g boehmite and 3.1gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is dried 12h at 110C, is that 10C/min rises to 600C with the heating rate, constant temperature 4 hours gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, bed temperature 100C, reaction pressure 8atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 3:
With 6g Zn (OH) 2, 15g boehmite and 2.5gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 100 ℃ of bed temperatures, reaction pressure 8atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 4:
With 10g Zn (OH) 2, 15g boehmite and 2gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 5:
With 15g Zn (OH) 2, 15g boehmite and 3.1gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 6:
With 6g Zn (OH) 2, 15g boehmite and 2.5gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 7:
With 30g zinc citrate, 15g boehmite and 3gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Embodiment 8:
With 18g zinc citrate, 15g boehmite and 2gMg (OH) 2Powder fully mixes, add the 6ml deionized water then, mix and pinch, mix up to the water material, mixed uniformly material is carried out the agent bar be shaped on agent bar machine, the sample after the shaping is that 10 ℃/min rises to 600 ℃ at 110 ℃ of oven dry 12h with heating rate, constant temperature 4h gets this catalysts.With the 5ml catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Comparative Examples 1:
With the commercial active γ-Al of 5ml 2O 3The catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Comparative Examples 2:
With 93.78gAl (NO 3) 39H 2O and 192.3g Mg (NO 3) 26H 2O is made into the 670ml water solution A; Again with 90g NaOH and 70.70g Na 2CO 3Be made into the 670ml solution B.With A solution, B solution and drip are added to together with the flow velocity of 10ml/min, stirring at room, and 60 ℃ of ageing 12h filter, and wash to filtrate PH=7, and 60 ℃ of dry 24h make hydrotalcite.With the 5ml hydrotalcite catalyst fixed bed reactors of packing into, material benzenemethanol and expoxy propane mol ratio were advanced 5: 1 by institute, and liquid hourly space velocity (LHSV) is 3.5h -1, 120 ℃ of bed temperatures, reaction pressure 10atm, product cools off through mixture of ice and water, uses gas chromatographic analysis.The results are shown in Table 1.
Table 1
Embodiment PO conversion ratio (%) Propylene glycol monomethyl ether selectivity (%) Isomery ratio uncle ether: secondary ether
Embodiment 1 91.37 97.23 96.11∶3.89
Embodiment 2 94.73 98.47 97.47∶2.53
Embodiment 3 86.17 97.14 97.10∶2.90
Embodiment 4 97.59 98.32 97.97∶2.03
Embodiment 5 98.37 98.49 98.79∶1.21
Embodiment 6 95.16 98.21 97.89∶2.11
Embodiment 7 98.48 98.67 98.66∶1.34
Embodiment 8 97.58 98.69 98.34∶1.66
Comparative Examples 1 99.10 90.03 73.41∶26.59
Comparative Examples 2 69.22 96.28 87.91∶12.09

Claims (4)

1. a solid catalyst is characterized in that with ZnO being active material, is carrier with the alundum (Al, and MgO is a co-catalyst; The weight percentage of ZnO is 10～60%, and the weight percentage of alundum (Al is 80～30%, and the weight percentage of co-catalyst MgO is 6～15%.
2. catalyst as claimed in claim 1, the predecessor that it is characterized in that described ZnO is Zn (OH) 2Or zinc citrate; The carrier alundum predecessor is a boehmite; Co-catalyst MgO predecessor is Mg (OH) 2
3. the preparation method of a solid catalyst as claimed in claim 1 is characterized in that the method for making of catalyst comprises:
(1) with Zn (OH) 2Powder, boehmite powder and Mg (OH) 2Powder mixes in ball mill;
(2) material that mixes in the step (1) is added 20～40% water and mix and pinch, till the water material is evenly, agent bar shaping in agent bar machine then;
(3) with 110 ℃ of oven dry of the stripe shape catalyst 12h that obtains in the step (2), the heating rate with 15 ℃/Min rises to 500-700 ℃ with temperature then, and constant temperature 2-6h reduces to room temperature and promptly gets catalyst.
4. the application of a solid catalyst as claimed in claim 1 is characterized in that, is used for synthesis of propylene glycol.
CNB2006100443912A 2006-06-07 2006-06-07 Solid catalyst for synthesizing propylene glycol ether and its preparing process Expired - Fee Related CN100386145C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110408018A (en) * 2019-08-07 2019-11-05 南京师范大学 A kind of ternary composite metal oxide solid caustic soda catalyst and the preparation method and application thereof

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* Cited by examiner, † Cited by third party
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DE3264572D1 (en) * 1981-10-29 1985-08-08 Texaco Development Corp Process for preparing glycol ethers
JPH062716B2 (en) * 1985-06-20 1994-01-12 日本農薬株式会社 Method for producing aromatic secondary amino compound
CN1063099C (en) * 1996-10-22 2001-03-14 中国石油化工总公司上海石油化工研究院 Catalyzer for preparing propylene-glycol ether
DE10351697A1 (en) * 2003-11-05 2005-06-09 Basf Ag Process for the preparation of butanediol from γ-butyrolactone in the presence of water
CN1597649A (en) * 2004-08-04 2005-03-23 河北工业大学 Method of synthesizing 2-hydroxyproply method ether using loading type aldaline catalyst
CN1762578A (en) * 2005-09-28 2006-04-26 茂名学院 Supported solid alkali catalyst for synthesis of propylene glycol

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110408018A (en) * 2019-08-07 2019-11-05 南京师范大学 A kind of ternary composite metal oxide solid caustic soda catalyst and the preparation method and application thereof
CN110408018B (en) * 2019-08-07 2024-07-02 南京师范大学 Ternary composite metal oxide solid base catalyst and preparation method and application thereof

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