CN104888844A - Preparation method of piperazine synthesis catalyst - Google Patents
Preparation method of piperazine synthesis catalyst Download PDFInfo
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- CN104888844A CN104888844A CN201510305517.6A CN201510305517A CN104888844A CN 104888844 A CN104888844 A CN 104888844A CN 201510305517 A CN201510305517 A CN 201510305517A CN 104888844 A CN104888844 A CN 104888844A
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- piperazine
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- molecular sieve
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Abstract
The invention discloses a preparation method of a piperazine synthesis catalyst and the method is used for solving the problem that in the prior art, piperazine is poor in selectivity and the yield ratio of piperazine and triethylene diamine is low. An impregnation method is adopted for the catalyst and the preparation method is as follows: with an HZSM-5 molecular screen as a carrier, adding the carrier into an impregnating liquid containing Na<+1> and Mg<2+>, standing, dehydrating, forming, drying and carrying out calcination to prepare the piperazine catalyst. When the catalyst is applied in a fixed bed continuous catalytic piperazine synthesis reaction with ethylenediamine, the selectivity is greater than 95% and the yield ratio of piperazine and triethylene diamine is greater than 15.
Description
Technical field
The invention belongs to field of catalyst preparation, be specifically related to a kind of method for preparing catalyst of catalysis ethylenediamine synthesizing piperazine.
Background technology
Piperazine, also known as hexahydropyrazine, piperazine, piperazidine, is a kind of important Organic Chemicals, is widely used in the synthesis of the medicines such as antibacterial, treating tuberculosis, step-down, hypoglycemic, sedation-analgesia; Also widely apply in the fields such as anticorrisive agent, antioxidant, stabilizing agent, surfactant, corrosion inhibiter, blowing agent, vulcanization accelerator, coating, agricultural chemicals, leather, fiber, wastewater treatment and solid carbon simultaneously.
CN201310351355.0 adopts nickeliferous, cobalt, molybdenum, iron, lanthanum solution impregnation γ-Al
2o
3with θ-Al
2o
3, then obtaining catalyst by steps such as dehydration, spray, drying, roasting and activation, piperazine is selective reaches 75.05%, and piperazine and triethylene diamine yield ratio are 4.6.CN201210065342.2 adopts ion-exchange, uses the HZSM-5 catalysis ethylenediamine synthesizing piperazine of potassium chloride, nickel nitrate and zinc nitrate solution modification, is selectively up to 81.39%, and piperazine and triethylene diamine yield ratio are 6.1.CN02112442.6 discloses the ZSM-5 synthetic method of a kind of hetero atom boron, iron, gallium, vanadium, zirconium or aluminium doping, and is applied in catalysis ethylenediamine synthesizing piperazine, and the most high selectivity of piperazine is 80%, and piperazine and triethylene diamine yield ratio are 4.7.
The problem of said method is, gained catalyst application is in catalyzing and synthesizing in piperazine reaction selective lower (being less than 82%), piperazine and triethylene diamine yield ratio little (being less than 6.5), product separation difficulty is large, can not meet the requirement of suitability for industrialized production to high selectivity.
Summary of the invention
The technical problem to be solved in the present invention is for shortcomings and deficiencies of the prior art, provides a kind of piperazine selective height, the method for preparing catalyst of piperazine and the large synthesizing piperazine of triethylene diamine yield ratio.
The method for preparing catalyst of synthesizing piperazine provided by the present invention joins HZSM-5 molecular sieve containing Na
+and Mg
2+maceration extract in, more successively through leaving standstill, dehydration, prepared by process that is shaping, dry and roasting.Comprise the following steps:
(1) will containing Na
+and Mg
2+soluble-salt join successively in deionized water, be stirred under ultrasonic assistant and dissolve completely, then add HZSM-5 molecular sieve and continue ultrasonic and stir, then room temperature leaves standstill 8 ~ 48h.Wherein control Na content is 1% ~ 5%, Mg content of HZSM-5 molecular sieve quality is 2.5% ~ 12% of HZSM-5 molecular sieve quality, and the volume ratio of maceration extract and HZSM-5 molecular sieve is 1 ~ 10:1;
(2) the HZSM-5 molecular sieve decompression dehydration will flooded, then adds a certain amount of binding agent compression molding, puts into baking oven dry, then in Muffle furnace roasting 2 ~ 6h under 350 ~ 580 DEG C of conditions, namely obtain the catalyst of synthesizing piperazine.
Na in the present invention
+soluble-salt be one in sodium fluoride, sodium chloride, sodium bromide, sodium iodide; Mg
2+soluble-salt be one in magnesium nitrate, magnesium chloride or magnesium acetate.Catalyst adopts conventional aluminium oxide as binding agent, and compression molding, makes the cylinder of diameter 3 ~ 5mm, long 5mm.
The catalyst of the synthesizing piperazine that the present invention obtains, is mainly used in the reaction of gas and solid phase catalyzing ethylenediamine intermolecular condensation piperazine.
Advantage of the present invention: 1. catalyst piperazine of the present invention is selective is greater than 95%, and the ratio of piperazine and triethylene diamine yield is greater than 15, selectively compared with piperazine in prior art is less than 85%, and the ratio of piperazine and triethylene diamine yield is less than 6.5 and significantly improves; 2. the present invention uses sodium salt and magnesium salts to be catalytic component, has the low advantage of cost relative to the nickel used in prior art, zinc, vanadium, lanthanum etc.
Detailed description of the invention
The invention will be further described by the following examples, but the present invention is not by the restriction of the following example.
The evaluating apparatus of catalyst adopts fixed bed reactors, and reactor size is 700mm × Φ 40mm × 6mm.Reaction is carried out at ambient pressure, Catalyst packing 35mL, and the aqueous solution of ethylenediamine or ammonia spirit are reaction raw materials (mass concentration of ethylenediamine is 50%), first by constant-flux pump, then enters fixed bed reactors after preheater.Reactor adopts Electric heating heating, reaction temperature 300 DEG C, liquid hourly space velocity (LHSV) 1.0h
-1.Use Shimadzu GC-2010 gas-chromatography, hydrogen flame ionization detector, DB-35 chromatographic column is analyzed, and result adopts external standard method mole to correct.
Embodiment 1
70g deionized water, 13.21g magnesium nitrate hexahydrate, 1.40g sodium fluoride is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, 24h is left standstill, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 550 DEG C of roasting 4h, namely obtain piperazine catalyst A.
Embodiment 2
70g deionized water, 13.48g magnesium nitrate hexahydrate, 2.15g sodium iodide is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, lucifuge place leaves standstill 24h, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 500 DEG C of roasting 3h, namely obtain piperazine catalyst B.
Embodiment 3
100g deionized water, 28.50g magnesium acetate, 2.12g sodium bromide is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, 8h is left standstill, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 450 DEG C of roasting 2h, namely obtain piperazine catalyst C.
Embodiment 4
70g deionized water, 20.34g Magnesium dichloride hexahydrate, 3.97g sodium iodide is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, lucifuge place leaves standstill 12h, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 550 DEG C of roasting 4h, namely obtain piperazine catalyst D.
Embodiment 5
500g deionized water, 15.28g magnesium nitrate hexahydrate, 3.72g sodium fluoride is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, 48h is left standstill, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 350 DEG C of roasting 6h, namely obtain piperazine catalyst E.
Embodiment 6
100g deionized water, 18.45g Magnesium dichloride hexahydrate, 2.49g sodium chloride is added successively in container, 1h is stirred under ultrasonic assistant, completely to be dissolved, then add 50g HZSM-5 molecular sieve, continue ultrasonic agitation 1h, then with preservative film sealing, 8h is left standstill, by the HZSM-5 molecular sieve decompression dehydration flooded, then binding agent compression molding is added, put into baking oven dry, then put into Muffle furnace 400 DEG C of roasting 4h, namely obtain piperazine catalyst F.
Catalyst performance evaluation
Example 1-6 prepared catalyst A, B, C, D, E, F load the reaction evaluating carrying out catalysis ethylenediamine synthesizing piperazine in fixed bed reactors respectively.Reaction result is in table 1.
Table 1 reaction result
Conclusion: catalyst piperazine of the present invention is selective is greater than 95%, and the ratio of piperazine and triethylene diamine yield is greater than 15.
Claims (2)
1. a method for preparing catalyst for synthesizing piperazine, is characterized in that HZSM-5 molecular sieve to join containing Na
+and Mg
2+maceration extract in, more successively through leaving standstill, dehydration, prepared by process that is shaping, dry and roasting.Comprise the following steps:
(1) will containing Na
+and Mg
2+soluble-salt join successively in deionized water, be stirred under ultrasonic assistant and dissolve completely, then add HZSM-5 molecular sieve and continue ultrasonic and stir, then at 25 DEG C, leave standstill 8 ~ 48h; Wherein control Na content is 1% ~ 5%, Mg content of HZSM-5 molecular sieve quality is 2.5% ~ 12% of HZSM-5 molecular sieve quality, and the volume ratio of maceration extract and HZSM-5 molecular sieve is 1 ~ 10:1;
(2) the HZSM-5 molecular sieve decompression dehydration will flooded, then adds a certain amount of binding agent compression molding, puts into baking oven dry, then in Muffle furnace roasting 2 ~ 6h under 350 ~ 580 DEG C of conditions, namely obtain the catalyst of synthesizing piperazine.
2. the method for preparing catalyst of synthesizing piperazine according to claim 1, is characterized in that step (1) described Na
+soluble-salt be one in sodium fluoride, sodium chloride, sodium bromide or sodium iodide; Described Mg
2+soluble-salt be one in magnesium nitrate, magnesium chloride or magnesium acetate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906116A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | It is a kind of for synthesizing the catalyst and preparation method and application of 2- methyl triethylene diamine |
| CN113443637A (en) * | 2021-06-02 | 2021-09-28 | 大连理工大学 | Double-acid-center zeolite molecular sieve and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432565A (en) * | 2011-11-10 | 2012-05-02 | 绍兴兴欣化工有限公司 | Method for preparing 2-hydroxyethylpiperazine |
| CN102600884A (en) * | 2012-03-13 | 2012-07-25 | 河北科技大学 | Preparation method for ethanediamine synthesis piperazine catalyst |
| CN104387340A (en) * | 2014-11-21 | 2015-03-04 | 江西科技师范大学 | Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine |
-
2015
- 2015-06-04 CN CN201510305517.6A patent/CN104888844B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432565A (en) * | 2011-11-10 | 2012-05-02 | 绍兴兴欣化工有限公司 | Method for preparing 2-hydroxyethylpiperazine |
| CN102600884A (en) * | 2012-03-13 | 2012-07-25 | 河北科技大学 | Preparation method for ethanediamine synthesis piperazine catalyst |
| CN104387340A (en) * | 2014-11-21 | 2015-03-04 | 江西科技师范大学 | Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108906116A (en) * | 2018-07-18 | 2018-11-30 | 西安近代化学研究所 | It is a kind of for synthesizing the catalyst and preparation method and application of 2- methyl triethylene diamine |
| CN108906116B (en) * | 2018-07-18 | 2021-01-29 | 西安近代化学研究所 | Catalyst for synthesizing 2-methyl triethylene diamine and preparation method and application thereof |
| CN113443637A (en) * | 2021-06-02 | 2021-09-28 | 大连理工大学 | Double-acid-center zeolite molecular sieve and preparation method and application thereof |
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