CN101935288B - Process and device for synthesizing imino diacetate by using diethanol amine - Google Patents
Process and device for synthesizing imino diacetate by using diethanol amine Download PDFInfo
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Abstract
The invention discloses a process and a device for synthesizing imino diacetate by using diethanol amine. The process comprises the following steps of: dissolving the diethanol amine and uniformly mixing the dissolved diethanol amine, liquid alkali and deionized water to prepare 10 to 30 mass percent solution, and conveying the solution to a multistage shell and tube reactor filled with a solid catalyst through a metering pump to perform catalytic dehydrogenation reaction so as to obtain the imino diacetate. The device comprises the multistage shell and tube reactor designed based on an isothermal constant pressure reaction kinetics model, the reactor consists of 2 to 5 shell and tube reactors connected in series, each stage reactor consists of a plurality of shell and tubes, and equal catalyst is uniformly filled into the shell and tubes. The process and the device have the characteristics of simple process operation, more than 98 percent of product yield, capabilities of continuous production and improvement on work efficiency and the like.
Description
Technical field
The present invention relates to a kind of technique and device that utilizes continuously diethanolamine synthesis of iminodiacetic acid salt.
Background technology
Iminodiethanoic acid (iminodiacetic acid) is called for short IDA, molecular formula NH (CH
2cOOH)
2molecular weight 133.11, for white crystalline powder or white monoclinic crystal, 237 ℃ of fusing points, 247.5 ℃ of decomposition points, proportion 1.56, solubleness in 5 ℃ of water is 243g/100ml, is insoluble to ethanol, ether, acetone, tetracol phenixin, can generate salt with acid and alkali reaction, energy and many kinds of metal ions form chelate, and bivalent cupric ion can form blue chelate.
Iminodiethanoic acid (IDA) is the important source material of producing the amino pyrazine of herbicide glyphosate, new type amphoteric chromium complexing rosaniline dyes, pyrazine and 2-, fuel oil cleaning agent, cement setting retarder, articles for washing bleach-activating agent, suitable platinum-containing anticancer drug etc.IDA and terephthalic acid coordinate and can be used for producing the vibrin with good gas barrier.As a kind of sequestrant, IDA can be used for immobilizing biologically active molecule, preparation printed circuit board (PCB) precoating solder flux, chemical gilding etc., the various chelating ion exchange resins of producing with IDA, are widely used in process water and the wastewater treatment in the fields such as chemical industry, nuclear power, electronics, medical treatment, pharmacy.IDA China has now formed the market of about 10000t/a, and wherein content is greater than the have an appointment market of 3000t/a of 98% top grade product IDA, and it is substantially by About Monsanto Chemicals's import.
Iminodiethanoic acid (IDA), as a kind of important intermediate of synthesizing glyphosate, occupies sizable proportion in the application of agricultural chemicals industry.At present, IDA method glyphosate production technique is mainly divided into diethanolamine method (DEA process) and iminodiacetonitrile method (IDAN method) both at home and abroad, and two kinds of methods obtain identical intermediate iminodiacetic acid disodium salt (DSIDA) through dehydrogenation and alkaline hydrolysis reaction.Wherein, diethanolamine method process for synthesizing glyphosate route is representing the international most advanced level of glyphosate technical study, and this operational path is short, and device is easy to maximize, main raw material(s) source is more extensive, take the U.S. Meng Shan offshore company that all (Monsanto) is representative all to adopt this technique.But adopt at present this technique, the external form of many stills series connection that conventionally adopts realizes serialization, the domestic batch production that mostly is.
Have many pieces of patents all to relate to the preparation method who prepares iminodiethanoic acid and salt thereof both at home and abroad, but all have complex process, product yield is low, is not easy to the shortcomings such as industrialization.For example CN1563021A discloses a kind of diethanolamine Dehydrogenation Oxidation Method Synthesis Iminodiacetic Acid salt, and then the technique of synthesizing glyphosate.The method is to utilize intermittently dehydrogenation still to produce Iminodiacetate, operate comparatively loaded down with trivial detailsly, and many stills series connection back-mixings are more serious, in reaction, will carry out continuous emission control to the hydrogen producing, and existence must danger; Long reaction time in addition, dehydrogenation yield is not high.
Summary of the invention
The object of the invention is to overcome the deficiency that prior art exists, provide a kind of technique simple, production cost is low, utilizes serially technique and the device of diethanolamine synthesis of iminodiacetic acid salt.
The object of the invention is to complete by following technical solution, this technique is after diethanolamine is dissolved and liquid caustic soda, deionized water are evenly hybridly prepared into the feed liquid that mass concentration is 10-30%, this feed liquid is sent in the multistage shell and tube reactor that is filled with solid catalyst and is carried out catalytic dehydrogenating reaction through volume pump, obtains Iminodiacetate.
Described feed liquid is before entering multistage shell and tube reactor, first through preheater, heat up, the service temperature of each stage reactor is through the control of flow and pressure of heating medium at 100-200 ℃, and the pressure of each stage reactor respectively tail gas emptying by separately regulates and be controlled at 1.0-2.5Mpa.
Described feed liquid is the mixture of diethanolamine, liquid caustic soda and deionized water, and wherein the mol ratio of diethanolamine and liquid caustic soda is 1: 2.0-2.4, feed liquid is first mixed through mixing kettle, then enters in feed chute, utilizes N in feed chute
2protect, first displace the oxygen dissolving in feed liquid, feed liquid first heats up through a preheater before entering reactor, and the temperature of feed liquid before entering reactor is 100-200 ℃.
A kind of for the described device by diethanolamine synthesis of iminodiacetic acid salt technique, this device comprises a multistage shell and tube reactor designing based on isothermal level pressure reaction Kinetics Model, it is composed in series by 2-5 shell and tube reactor, every stage reactor is all comprised of a plurality of tubulations, is filled with equably equal catalyzer in every tubulation.
Described every stage reactor top is all provided with liquid distributor, and bottom is installed and supported, and the feed liquid feed-pipe of described each stage reactor adopts the form of upper entering and lower leaving or bottom in and top out to connect successively each stage reactor.
Described every stage reactor top or bottom are provided with the gas gas-liquid separator separated with out-feed liquid for dehydrogenation reaction is produced, after gas-liquid separator, be connected to by the scum dredger of tail gas after separation, and be connected in by variable valve the exhaust treatment system that carries out purifying treatment; The next stage reactor that also joins after gas-liquid separator liquid after separation is sent into.
The invention has the advantages that: designed a kind of residence time than existing autoclave or single fixed-bed reactor (thermal insulation) more even, more thorough, the continuable isothermal reactor system of material reaction, and a kind of application art is provided, make still can keep desirable product yield after its amplification; Technological operation is simple, product yield >=98%; And in the present invention, multistage tubular reaction system can be changed every grade respectively, do not affect production capacity performance, it is the continuous production method of the feasible Iminodiacetate of a kind of industrialization, simultaneously, every stage reactor is all provided with the separator of by-product hydrogen, in reaction process, remove at any time gas, be conducive to reflect efficiency, be also conducive to react safety.
Accompanying drawing explanation
Fig. 1 is that the structure of multistage shell and tube reactor of the present invention forms schematic diagram.
Embodiment
Below in conjunction with embodiment and accompanying drawing, invention is described in detail.The technique of utilizing diethanolamine synthesis of iminodiacetic acid salt of the present invention, it is after diethanolamine is dissolved and liquid caustic soda, deionized water are evenly hybridly prepared into the feed liquid that mass concentration is 10-30%, this feed liquid is sent in the multistage shell and tube reactor that is filled with solid catalyst and is carried out catalytic dehydrogenating reaction through volume pump, obtains Iminodiacetate.
Described feed liquid is before entering multistage shell and tube reactor, first through preheater, heat up, the service temperature of each stage reactor is through the control of flow and pressure of heating medium at 100-200 ℃, and the pressure of each stage reactor respectively tail gas emptying by separately regulates and be controlled at 1.0-2.5Mpa.
Described feed liquid is the mixture of diethanolamine, liquid caustic soda and deionized water; wherein the mol ratio of diethanolamine and liquid caustic soda is 1: 2.0-2.4; feed liquid is first mixed through mixing kettle; then enter in feed chute; in feed chute, utilize N2 to protect; first displace the oxygen dissolving in feed liquid, feed liquid first heats up through a preheater before entering reactor, and the temperature of feed liquid before entering reactor is 100-200 ℃.
A kind of for the described device by diethanolamine synthesis of iminodiacetic acid salt technique, this device comprises a multistage shell and tube reactor designing based on isothermal level pressure reaction Kinetics Model, it is composed in series by 2-5 shell and tube reactor, every stage reactor is all comprised of a plurality of tubulations, in every tubulation, be filled with equably equal catalyzer, guarantee the residence time of flowing through each tubulation catalyst surface of uniform liquid, thereby guarantee the uniform and stable of level of response; Adopt diameter tubulation within the scope of 38-150mm, thus make each reactor radially, axial temperature distributes compared with homogeneous, makes Response calculation model simplification; Use the multistage calandria type fixed bed timely discharge that is conducive to reaction product hydrogen, assurance reaction impellent is compared stable with single fixed bed, and is more conducive to reflect efficiency; Use multistage shell and tube system to be conducive to each bed catalyst and regularly replace in the situation that not affecting production, guarantee the continuous of production.
Described every stage reactor top is all provided with liquid distributor, and bottom is installed and supported, and the feed liquid feed-pipe of described each stage reactor adopts the form of upper entering and lower leaving or bottom in and top out to connect successively each stage reactor.
Every stage reactor top or bottom are provided with the gas gas-liquid separator separated with out-feed liquid for dehydrogenation reaction is produced, tail gas after separation is by after scum dredger, and after variable valve enters exhaust treatment system to carry out purifying treatment, compression makes hydrogen for hydrogen burning boiler or producing hydrogen peroxide.Liquid after separation enters next stage reactor, the like, the isolated Iminodiacetate feed liquid of last level enters scale tank through pipeline.Every stage reactor pressure is automatically adjusted by tail gas variable valve, guarantees that liquid enters next stage smoothly.
Liquid in reactor, solid two-phase fully contact and carry out dehydrogenation reaction mutually, obtain Iminodiacetate feed liquid, and reaction has a large amount of hydrogen to produce simultaneously, and liquid carries out separation in tower reactor at different levels, considers the easy crystallization of feed liquid, and tower reactor must heat with chuck, be incubated.
The present invention evenly mixes diethanolamine, liquid caustic soda, deionized water in proportion, is mixed with the feed liquid that mass concentration is 10-30%; Solid catalyst is filled in by staged reactor multistage shell and tube reactor in series, and DEA feed liquid contacts with catalyzer is full and uniform, and under the reaction conditions through selecting, diethanolamine obtains Iminodiacetate through continuous dehydrogenation;
Reaction principle following (equation):
Described mass concentration is that the feed liquid of 10-30% is the mixture of diethanolamine, liquid caustic soda, deionized water, and diethanolamine and liquid caustic soda mol ratio are 1: 2.0-2.4; Feeding liquid first mixes through mixing kettle, after mixing, enters in feed chute, utilizes N in feed chute
2protect, displace the oxygen dissolving in feed liquid; Feeding liquid sends into through volume pump the multistage shell and tube reactor that fills solid catalyst again, and feed rate is adjusted according to reactor capacity is different; Feed liquid will heat up through preheater before entering reactor, and material inlet temperature of stabilizer is 100-200 ℃;
This multistage tubular reaction system is based on isothermal level pressure reaction Kinetics Model design, and the flow of the service temperature of each stage reactor by heating medium or pressure-controlling are at 100-200 ℃; The pressure of each stage reactor respectively tail gas emptying by separately regulates and is controlled at 1.0-2.5Mpa.
Multistage tubular reaction system is composed in series by 2-5 shell and tube reactor, and every stage reactor is all comprised of a plurality of tubulations, loads equably equal catalyzer in every tubulation.Adopt diameter tubulation within the scope of 38-150mm, thus make each reactor radially, axial temperature distributes compared with homogeneous, makes Response calculation model simplification; The respond timely discharge of product hydrogen of every grade of shell and tube reactor, guarantees that reaction impellent compares stable with single fixed bed;
Every stage reactor top or bottom are provided with the gas gas-liquid separator separated with out-feed liquid for dehydrogenation reaction is produced, tail gas after separation is by after scum dredger, and after variable valve enters exhaust treatment system to carry out purifying treatment, compression makes hydrogen for hydrogen burning boiler or producing hydrogen peroxide.Liquid after separation enters next stage reactor, the like, the isolated Iminodiacetate feed liquid of last level enters scale tank through pipeline.Every stage reactor pressure is automatically adjusted by tail gas variable valve, in the time of the stability of keeping system pressure, guarantees that liquid enters next stage smoothly.
Described gas-liquid separator reply gas-liquid two-phase material has good separating effect.During discharging, gas-liquid separator planted agent utilizes regulated valve to control certain liquid level, guarantees the stability of system; DSIDA feed liquid drop temperature is 100-150 ℃, can not be lower than 100 ℃, in order to avoid discharging pipeline is stopped up in the crystallization of DSIDA feed liquid;
Embodiment 1
Diethanolamine, liquid caustic soda, deionized water are evenly mixed in proportion, be mixed with mass concentration and be 20% feed liquid; Utilize volume pump by feed liquid squeeze into fill solid catalyst by staged reactor multistage shell and tube reactor in series, it is front through three grades of heater heats that feed liquid enters reactor, feeding temperature is controlled at 145 ℃, reactor pressure maintains 1.6Mpa, 140～150 ℃ of reactor temperatures, feed rate is 150Kg/h.Stable each reaction parameter of controlling in process of the test, reaction result is in Table 1:
| Sampling | DEA content | Feed rate Kg/h | Temperature of reaction ℃ | Reaction pressure Mpa | DSIDA yield |
| 1 | 20.0％ | 150.1 | 145.0 | 1.60 | 98.26％ |
| 2 | 20.0％ | 150.5 | 147.6 | 1.64 | 98.13％ |
| 3 | 20.0％ | 151.0 | 148.2 | 1.67 | 98.57％ |
| 4 | 20.0％ | 149.8 | 145.9 | 1.70 | 98.15％ |
| 5 | 20.0％ | 149.6 | 146.3 | 1.71 | 98.09％ |
| 6 | 20.0％ | 149.2 | 144.8 | 1.65 | 98.30％ |
| 7 | 20.0％ | 149.6 | 142.1 | 1.63 | 98.02％ |
| 8 | 20.0％ | 148.8 | 145.5 | 1.61 | 98.13％ |
Embodiment 2 (temperature change)
Diethanolamine, liquid caustic soda, deionized water are evenly mixed in proportion, be mixed with mass concentration and be 20% feed liquid; Utilize volume pump by feed liquid squeeze into fill solid catalyst by staged reactor multistage shell and tube reactor in series, it is front through three grades of heater heats that feed liquid enters reactor, feeding temperature is controlled at 120 ℃, reactor pressure maintains 1.6Mpa, 120～130 ℃ of reactor temperatures, feed rate is 150Kg/h.Stable each reaction parameter of controlling in process of the test, reaction result is in Table 2:
| Sampling | DEA content | Feed rate Kg/h | Temperature of reaction ℃ | Reaction pressure Mpa | DSIDA yield |
| 1 | 20.0％ | 150.1 | 125.0 | 1.69 | 97.28％ |
| 2 | 20.0％ | 150.3 | 124.6 | 1.68 | 96.72％ |
| 3 | 20.0％ | 149.9 | 126.3 | 1.67 | 96.11％ |
| 4 | 20.0％ | 149.8 | 123.8 | 1.63 | 96.98％ |
| 5 | 20.0％ | 150.0 | 121.7 | 1.60 | 96.63％ |
| 6 | 20.0％ | 149.2 | 120.2 | 1.61 | 96.98％ |
| 7 | 20.0％ | 149.6 | 123.5 | 1.62 | 96.84％ |
| 8 | 20.0％ | 148.8 | 124.7 | 1.59 | 97.27％ |
embodiment 3 (temperature change)
Diethanolamine, liquid caustic soda, deionized water are evenly mixed in proportion, be mixed with mass concentration and be 20% feed liquid; Utilize volume pump by feed liquid squeeze into fill solid catalyst by staged reactor multistage shell and tube reactor in series, it is front through three grades of heater heats that feed liquid enters reactor, feeding temperature is controlled at 180 ℃, reactor pressure maintains 1.6Mpa, 175～185 ℃ of reactor temperatures, feed rate is 150Kg/h.Stable each reaction parameter of controlling in process of the test, reaction result is in Table 3:
| Sampling | DEA content | Feed rate Kg/h | Temperature of reaction ℃ | Reaction pressure Mpa | DSIDA yield |
| 1 | 20.0％ | 149.7 | 178.9 | 1.60 | 94.92％ |
| 2 | 20.0％ | 150.1 | 177.8 | 1.67 | 94.41％ |
| 3 | 20.0％ | 151.2 | 178.5 | 1.68 | 93.94％ |
| 4 | 20.0％ | 149.8 | 183.6 | 1.66 | 94.30％ |
| 5 | 20.0％ | 149.6 | 180.0 | 1.63 | 94.65％ |
| 6 | 20.0％ | 150.0 | 180.2 | 1.61 | 93.61％ |
| 7 | 20.0％ | 149.6 | 179.3 | 1.63 | 95.56％ |
| 8 | 20.0％ | 148.4 | 179.0 | 1.65 | 94.99％ |
Embodiment 4 (flow change)
Diethanolamine, liquid caustic soda, deionized water are evenly mixed in proportion, be mixed with mass concentration and be 20% feed liquid; Utilize volume pump by feed liquid squeeze into fill solid catalyst by staged reactor multistage shell and tube reactor in series, it is front through three grades of heater heats that feed liquid enters reactor, feeding temperature is controlled at 145 ℃, reactor pressure maintains 1.6Mpa, 140～150 ℃ of reactor temperatures, feed rate is 150Kg/h.Stable each reaction parameter of controlling in process of the test, reaction result is in Table 4:
| Sampling | DEA content | Feed rate Kg/h | Temperature of reaction ℃ | Reaction pressure Mpa | DSIDA yield |
| 1 | 20.0％ | 130.2 | 145.2 | 1.67 | 94.56％ |
| 2 | 20.0％ | 130.8 | 144.3 | 1.66 | 94.94％ |
| 3 | 20.0％ | 131.3 | 141.2 | 1.65 | 95.86％ |
| 4 | 20.0％ | 130.6 | 143.9 | 1.60 | 95.23％ |
| 5 | 20.0％ | 129.8 | 144.5 | 1.58 | 94.28％ |
| 6 | 20.0％ | 129.2 | 144.5 | 1.60 | 94.83％ |
| 7 | 20.0％ | 128.5 | 147.1 | 1.65 | 95.21％ |
| 8 | 20.0％ | 129.0 | 145.8 | 1.70 | 95.86％ |
Embodiment 5 (concentration change)
Diethanolamine, liquid caustic soda, deionized water are evenly mixed in proportion, be mixed with mass concentration and be 15% feed liquid; Utilize volume pump by feed liquid squeeze into fill solid catalyst by staged reactor multistage shell and tube reactor in series, it is front through three grades of heater heats that feed liquid enters reactor, feeding temperature is controlled at 145 ℃, reactor pressure maintains 1.6Mpa, 140～150 ℃ of reactor temperatures, feed rate is 150Kg/h.Stable each reaction parameter of controlling in process of the test, reaction result is in Table 4:
| Sampling | DEA content | Feed rate Kg/h | Temperature of reaction ℃ | Reaction pressure Mpa | DSIDA yield |
| 1 | 15.0％ | 150.2 | 144.2 | 1.60 | 90.24％ |
| 2 | 15.0％ | 150.8 | 145.3 | 1.63 | 90.73％ |
| 3 | 15.0％ | 151.3 | 143.2 | 1.65 | 90.72％ |
| 4 | 15.0％ | 150.6 | 144.9 | 1.62 | 90.59％ |
| 5 | 15.0％ | 149.8 | 146.5 | 1.58 | 90.10％ |
| 6 | 15.0％ | 149.2 | 147.5 | 1.57 | 90.46％ |
| 7 | 15.0％ | 148.5 | 149.1 | 1.55 | 91.58％ |
| 8 | 15.0％ | 149.0 | 146.8 | 1.60 | 91.27％ |
Claims (1)
1. the technique with diethanolamine synthesis of iminodiacetic acid salt, this technique is after diethanolamine is dissolved and liquid caustic soda, deionized water are evenly hybridly prepared into the feed liquid that mass concentration is 10-30%, this feed liquid is sent in the multistage shell and tube reactor that is filled with solid catalyst and is carried out catalytic dehydrogenating reaction through volume pump, obtains Iminodiacetate;
Described multistage shell and tube reactor is a reactor designing based on isothermal level pressure reaction Kinetics Model, and it is composed in series by 2-5 shell and tube reactor, and every stage reactor is all comprised of a plurality of tubulations, is filled with equably equal catalyzer in every tubulation;
Described feed liquid is before entering multistage shell and tube reactor, first through preheater, heat up, the service temperature of each stage reactor is through the control of flow and pressure of heating medium at 100-200 ℃, and the pressure of each stage reactor respectively tail gas emptying by separately regulates and be controlled at 1.0-2.5Mpa.
2.according to the technique with diethanolamine synthesis of iminodiacetic acid salt described in claim 1, it is characterized in that described feed liquid is the mixture of diethanolamine, liquid caustic soda and deionized water, wherein the mol ratio of diethanolamine and liquid caustic soda is 1: 2.0-2.4, feed liquid is first mixed through mixing kettle, then enter in feed chute, in feed chute, utilize N
2protect, first displace the oxygen dissolving in feed liquid, feed liquid first heats up through a preheater before entering reactor, and the temperature of feed liquid before entering reactor is 100-200 ℃.
3.technique with diethanolamine synthesis of iminodiacetic acid salt according to claim 1, it is characterized in that described every stage reactor top is all provided with liquid distributor, bottom is installed and is supported, and the feed liquid feed-pipe of described each stage reactor adopts the form of upper entering and lower leaving or bottom in and top out to connect successively each stage reactor.
4.technique with diethanolamine synthesis of iminodiacetic acid salt according to claim 3, it is characterized in that described every stage reactor top or bottom are provided with the gas gas-liquid separator separated with out-feed liquid for dehydrogenation reaction is produced, after gas-liquid separator, be connected to by the scum dredger of tail gas after separation, and be connected in by variable valve the exhaust treatment system that carries out purifying treatment; The next stage reactor that also joins after gas-liquid separator liquid after separation is sent into.
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| CN102827013A (en) * | 2011-06-13 | 2012-12-19 | 浙江新安化工集团股份有限公司 | Method for continuously producing iminodiacetic acid salt |
| CN107185476B (en) * | 2017-05-19 | 2020-01-14 | 南京大学 | Multi-stage, multi-functional injection reactor system and method of operating the same |
| CN112371075B (en) * | 2020-11-09 | 2022-07-12 | 杭州燕麟科技有限公司 | Continuous tubular reaction equipment for preparing cyclic phosphonate |
| CN113578244A (en) * | 2021-08-09 | 2021-11-02 | 聊城鲁西甲胺化工有限公司 | Tube array type reaction device and application thereof |
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