CN1319927C - Method of microwave dehydrogenation for producing sodium oxalate - Google Patents
Method of microwave dehydrogenation for producing sodium oxalate Download PDFInfo
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- CN1319927C CN1319927C CNB2004100403032A CN200410040303A CN1319927C CN 1319927 C CN1319927 C CN 1319927C CN B2004100403032 A CNB2004100403032 A CN B2004100403032A CN 200410040303 A CN200410040303 A CN 200410040303A CN 1319927 C CN1319927 C CN 1319927C
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- microwave
- dehydrogenation
- sodium formate
- sodium
- temperature
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 66
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 229940039790 sodium oxalate Drugs 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 29
- 239000004280 Sodium formate Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 47
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 47
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000007086 side reaction Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开一种微波脱氢生产草酸钠的方法，它是利用先进的微波加热技术取代传统的外热源传导加热物料的一种方法。其特征是：将甲酸钠溶液或甲酸钠固体加入微波谐振腔内，利用微波能量快速将甲酸钠加热到350℃～450℃(典型的脱氢温度为380～420℃)，减少280～300℃温度段副反应的发生。使用本发明公开的微波脱氢生产草酸钠的方法，具有微波谐振腔内物料温度易于控制、加热快速、物料内外同时均匀加热、减少副反应的发生、提高收率、降低能耗、安全无明火、易于实现自动化等特点。
The invention discloses a method for producing sodium oxalate through microwave dehydrogenation, which uses advanced microwave heating technology to replace the traditional external heat source conduction heating material. Its characteristics are: add sodium formate solution or sodium formate solid into the microwave resonant cavity, and use microwave energy to quickly heat sodium formate to 350°C-450°C (typical dehydrogenation temperature is 380-420°C), reducing the temperature of 280-300°C. The reaction occurs. The method for producing sodium oxalate by using the microwave dehydrogenation disclosed by the present invention has the advantages of easy control of the temperature of the material in the microwave resonant cavity, rapid heating, uniform heating inside and outside the material at the same time, reducing the occurrence of side reactions, increasing the yield, reducing energy consumption, safety and no open flames , Easy to automate and so on.
Description
Technical Field
The present invention belongs to the field of organic chemical industry and carboxylate preparing technology, and is especially synthetic process of producing oxalic acid.
Background
Oxalic acid is an important chemical raw material, synthesis methods are mostly adopted to produce oxalic acid at present, and a dehydrogenation process is one of the important processes for producing oxalic acid by the synthesis methods.
The basic chemistry of dehydrogenation production is: concentrating 25% sodium formate solution produced in the synthesis process, heating in a dehydrogenation pot, dissolving the sodium formate in the dehydrogenation pot to 400 ℃ after water in the solution is evaporated, and decomposing the sodium formate in the dehydrogenation pot under normal pressure to generate sodium oxalate and hydrogen. The chemical reaction formula of the dehydrogenation process is
The existing dehydrogenation method adopts a pot-type dehydrogenating device for dehydrogenation, concentration, solidification, melting, temperature rise and dehydrogenation of sodium formate are all carried out in a dehydrogenation pot, the whole process is long in time, more materials are used, the heating area is small, the materials are heated unevenly, so that the reaction is incomplete, the side reaction is more, the dehydrogenation conversion rate cannot be improved, and the highest dehydrogenation conversion rate can only reach 80%; in addition, hydrogen is released in the dehydrogenation process, and the hydrogen can explode when meeting open fire or being mixed with air, so that the hydrogen often explodes in the dehydrogenation process, and potential safety hazards exist.
The main problems of the existing sodium formate dehydrogenation production process of the coal chafing dish type dehydrogenator are as follows:
(1) severe energy loss
The coal has low combustion heat efficiency in the hearth, the heat of the pot body is radiated, and the sodium formate exposed in the air is radiated.
(2) Low yield
The reasons for the low yield are:
① dehydrogenation of sodium formate is carried out at 380-420 ℃, because the temperature rise rate before dehydrogenation is slow, the following side reactions occur at 280-300 ℃:
it is clear that the slower the rate of temperature rise, the longer the time to go through this temperature period, the higher the conversion of this side reaction and the lower the yield of the positive reaction will be.
② the temperature of the materials at the bottom and the upper part is not consistent because the sodium formate is exposed in the atmosphere, when the bottom sodium formate reaches the dehydrogenation temperature, the middle and the upper part do not reach the same temperature, i.e. the lower part and the upper part do not react, which affects the yield.
③ when the temperature of sodium oxalate is higher than 700 ℃, the following side reactions occur:
(3) the operation environment is bad, the labor intensity of workers is high
The dehydrogenation section of a common scale is that a plurality of dehydrogenation pots are operated simultaneously, and because the time of dehydrogenation reaction can not be predicted and accurately controlled, the heating, water-adding cooling and charging time of each dehydrogenation pot can not be consistent or ordered, the automation of coal-adding and ash-removing can not be realized, operators need to add coal and remove ash by shovels, the operation environment is severe, and the labor intensity of the operators is high.
(4) Safety problem
The dehydrogenation pot is opened, the open fire is arranged below the pot for heating, the wall of the hearth pot is extremely easy to be burnt and cracked, the stove is not easy to be found and repaired after the burning crack, and the gas generated by the dehydrogenation reaction is particularly easy to ignite due to the leakage of the open fire, so that the detonation is caused, and the personal injury and the equipment damage are caused.
(5) Serious damage to equipment
The temperature of the pot bottom is very high due to open fire heating and twice solidification in the dehydrogenation process, the pot bottom is often burnt to be convex, the pot bottom, the wall, the stove opening and the like are also easily burnt out, the temperature of flue gas is high, and the service life of an induced draft fan is shortened.
The synthesis method is used for producing oxalic acid, and most of the dehydrogenators of the method adopt coal chafing dish type dehydrogenators; a fluidized bed continuous dehydrogenation unit (ZL 97110656.8, CN 87102067A); all the methods and devices are based on the traditional heat conduction heating method (coal heating, resistance wire heating or high-temperature gas and the like), the heat transfer is slow and uneven, and for the sodium formate dehydrogenation process, the more even the heat transfer is, the more beneficial the reaction is; the faster the heat transfer rate, the shorter the time for the entire dehydrogenation process, the shorter the time to undergo side reactions, and the higher the conversion of dehydrogenation. Therefore, changing the heat transfer mode of the dehydrogenation process and increasing the heat transfer rate become the key for realizing the continuous dehydrogenation.
Disclosure of Invention
The invention aims to provide a method for producing sodium oxalate through microwave dehydrogenation, which can reduce the occurrence of side reactions in a dehydrogenation process, improve the yield, reduce the energy consumption and increase the safety.
The invention provides a method for producing sodium oxalate by microwave dehydrogenation, which is characterized by comprising the following steps:
step 1, adding 25-100% of sodium formate solution or sodium formate solid into a microwave resonant cavity (microwave dehydrogenation furnace chamber);
step 2, starting microwave power of a microwave source, inputting microwaves into a microwave resonant cavity (a microwave dehydrogenation furnace) through a microwave transmission system to heat material sodium formate, quickly heating by full-power microwaves, after several minutes to dozens of minutes (when the input amount of the material sodium formate and the water content of a sodium formate solution are large, the time is long), when the temperature of the sodium formate reaches the dehydrogenation temperature of 350 ℃ -450 ℃ (the typical dehydrogenation temperature is 380 ℃ -420 ℃), enabling the sodium formate to be molten, carrying out hydrogen discharge reaction to generate sodium oxalate, properly adjusting microwave power, keeping the temperature of the material sodium formate at 380 ℃ -420 ℃ for proper time (the determination of the proper time is determined by the input amount of the material sodium formate, the microwave power and other parameters), and finishing dehydrogenation;
step 3, after the dehydrogenation is finished, closing the microwave power, expanding the generated sodium oxalate into a loose and porous state, and quickly pumping the sodium oxalate into a microwave resonant cavity (a microwave dehydrogenation furnace) to input sodium carbonate old alkali liquor for cooling and diluting so as to prevent the decomposition and carbonization of materials and facilitate the discharge of the product sodium oxalate;
and 4, discharging the dehydrogenated product sodium oxalate in time.
It should be noted that:
the 25% -100% sodium formate solution or solid in the step 1 is preferably more than 75% solid of sodium formate, and the sodium formate preferably contains 2% NaOH as catalyst;
when the material sodium formate is heated in the microwave resonant cavity (microwave dehydrogenation furnace) in the step 2, the material can be stirred by a stirrer, so that the uniformity of material heating is improved;
and (3) discharging the hydrogen generated in the dehydrogenation process in the step (2) through an exhaust port, and enabling the discharged hydrogen to enter a subsequent treatment and gas storage device.
The essence of the invention is as follows: by utilizing the characteristics of easy control of microwave power and temperature, quick heating, simultaneous heating inside and outside the material and uniform heating, the advanced microwave heating technology is used for replacing the traditional method for heating the material by conduction of an external heat source. Because the microwave heating is that electromagnetic energy permeates into the material sodium formate in the form of waves, the sodium formate absorbs microwaves and instantly generates heat by self dielectric loss, the temperature rises quickly, the microwave power is adjusted to enable the material to reach 350-450 ℃ (the typical dehydrogenation temperature is 380-420 ℃) in a few minutes, and the material simultaneously generates heat inside and outside without conduction, so the residence time of the material sodium formate at 280-300 ℃ is very short, the side reaction at 280-300 ℃ can be reduced, meanwhile, the microwave energy is almost free of inertia when being closed, the microwave power can be timely closed to prevent the temperature of the material from continuously rising, and the side reaction at 700 ℃ high temperature can be prevented. Because the material sodium formate absorbs the microwave and heats by medium loss, the microwave heating has no open fire, and is safe and reliable. Because the materials are heated uniformly inside and outside, the materials are heated uniformly, so the dehydrogenation is synchronous, the dehydrogenation conversion rate is high, and the product quality is excellent. Because microwave heating does not need heat conduction, and the container is not heated (the metal inner wall of the microwave heating chamber only reflects microwaves but does not absorb microwaves), the energy consumption can be reduced.
The invention has the innovation that: the method replaces the traditional method for heating the material by external heat source conduction by using the advanced microwave heating technology by utilizing the characteristics of rapid microwave heating, simultaneous heating inside and outside the material, uniform heating and easy control of microwave power and reaction temperature.
The invention has the advantages that:
① reducing the occurrence of side reactions
By adjusting the microwave power, the reaction temperature is easy to control, the material absorbs microwave to instantly generate heat, the temperature rises rapidly, the material can reach 350-450 ℃ (the typical dehydrogenation temperature is 380-420 ℃) in a few minutes under the action of high-power microwave, the material simultaneously generates heat inside and outside without heat conduction, so the stay time of the material at 280-300 ℃ is very short, the side reaction at 280-300 ℃ can be reduced, meanwhile, the microwave energy is almost closed without inertia, the microwave power is timely closed, the temperature of the material can be prevented from continuously rising, and the side reaction at 700 ℃ high temperature can be prevented.
② improving product quality
Because the materials are heated uniformly inside and outside, the materials are heated uniformly, so the dehydrogenation is synchronous, the dehydrogenation conversion rate is high, and the product quality is excellent.
③ high-efficiency energy-saving
The efficiency of converting microwave energy into heat energy is usually 80% -90% (while the heat efficiency of the coal-fire dehydrogenation stove is only about 12%), the microwave heating time is very short, and the sealing property of microwave power, the permeability to materials and the instantaneity of converting the microwave energy into heat form the basic characteristic of microwave heating energy saving, the microwave heating reduces the time of the heat conduction process of the traditional method, namely the time of uniformly distributing the temperature, thereby greatly reducing the heat loss to the environment, and simultaneously the microwave does not heat a container (the metal inner wall of the microwave heating cavity only reflects the microwave but does not absorb the microwave), thereby reducing the energy consumption, saving the energy by about 50%, and having considerable economic benefit.
④ the microwave heating is safe and reliable without open fire.
⑤ is easy to realize automatic continuous production.
In summary, the present invention adopts the microwave heating process, because the microwave heating is the heating caused by the electromagnetic energy penetrating into the medium in the form of wave to cause the medium loss, and does not need to be conducted, it has instantaneity, it means fast heating, and it is the heating inside and outside simultaneously, and it has the characteristic of even heating for even medium. The microwave heating mode can overcome the defect of slow heating in the traditional method, thereby reducing the occurrence of side reactions, improving the yield and reducing the energy consumption. The microwave rapid heating is heated by the medium loss of the material, no open fire exists, and the safety can be ensured.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention
The specific implementation mode is as follows:
a microwave power source of 915MHz/20kW is adopted for a single unit, a microwave transmission system and a microwave resonant cavity are connected, 150kg of 75% sodium formate solution or sodium formate solid containing 2% NaOH as a catalyst is added into the microwave resonant cavity from a feeding port, the microwave power of the microwave source is started, microwaves are input into the microwave resonant cavity through the microwave transmission system to heat the material sodium formate, full-power microwaves are used for rapid heating, a stirrer in the microwave resonant cavity is started to stir the material while the microwave power of the microwave source is started, the material is heated for about 60 minutes, when the temperature of the material sodium formate reaches the dehydrogenation temperature of 380-420 ℃, the sodium formate is molten, the dehydrogenation reaction is carried out to generate sodium oxalate, the microwave power is properly adjusted to keep the temperature of the material sodium formate at 380-420 ℃ for several minutes, and the microwave power is timely turned off after the dehydrogenation is finished; the generated sodium oxalate swells to be in a loose and porous state, and at the moment, a pump is quickly started to input sodium carbonate old alkali liquor from a water injection port into microwave resonance for cooling and diluting so as to prevent the decomposition and carbonization of the material sodium oxalate. And discharging the dehydrogenated product sodium oxalate in time. And hydrogen generated in the dehydrogenation process is discharged from an exhaust port, the discharged hydrogen enters a subsequent treatment and gas storage device, and the dehydrogenated product sodium oxalate is discharged from a feed opening of the microwave resonant cavity.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100403032A CN1319927C (en) | 2004-07-26 | 2004-07-26 | Method of microwave dehydrogenation for producing sodium oxalate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100403032A CN1319927C (en) | 2004-07-26 | 2004-07-26 | Method of microwave dehydrogenation for producing sodium oxalate |
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| Publication Number | Publication Date |
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| CN1727322A CN1727322A (en) | 2006-02-01 |
| CN1319927C true CN1319927C (en) | 2007-06-06 |
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| CNB2004100403032A Expired - Fee Related CN1319927C (en) | 2004-07-26 | 2004-07-26 | Method of microwave dehydrogenation for producing sodium oxalate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9085827B2 (en) | 2012-07-26 | 2015-07-21 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
| US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103377A (en) * | 1985-05-01 | 1986-10-29 | 线步正 | The method for making of sodium oxalate |
| CN1502599A (en) * | 2002-11-22 | 2004-06-09 | 于学平 | Technological process for producing sodium oxalate by liquid-spraying type sodium formate dehydrogenation and use equipment |
-
2004
- 2004-07-26 CN CNB2004100403032A patent/CN1319927C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103377A (en) * | 1985-05-01 | 1986-10-29 | 线步正 | The method for making of sodium oxalate |
| CN1502599A (en) * | 2002-11-22 | 2004-06-09 | 于学平 | Technological process for producing sodium oxalate by liquid-spraying type sodium formate dehydrogenation and use equipment |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9085827B2 (en) | 2012-07-26 | 2015-07-21 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
| US9175407B2 (en) | 2012-07-26 | 2015-11-03 | Liquid Light, Inc. | Integrated process for producing carboxylic acids from carbon dioxide |
| US10329676B2 (en) | 2012-07-26 | 2019-06-25 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
| US11131028B2 (en) | 2012-07-26 | 2021-09-28 | Avantium Knowledge Centre B.V. | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion electrode |
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| Publication number | Publication date |
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| CN1727322A (en) | 2006-02-01 |
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Assignee: Zhongshan Casanova Chemical Co., Ltd. Assignor: University of Electronic Science and Technology of China Contract fulfillment period: 2007.6.6 to 2012.6.5 contract change Contract record no.: 2008440000524 Denomination of invention: Method of microwave dehydrogenation for producing sodium oxalate Granted publication date: 20070606 License type: Exclusive license Record date: 20081211 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.6.6 TO 2012.6.5; CHANGE OF CONTRACT Name of requester: ZHONGSHAN CITY BASIJI CHEMICALS CO., LTD. Effective date: 20081211 |
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