CN113683521A - Novel method for producing 2-amino-1, 3-propylene glycol by JIT method - Google Patents

Novel method for producing 2-amino-1, 3-propylene glycol by JIT method Download PDF

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CN113683521A
CN113683521A CN202110983269.6A CN202110983269A CN113683521A CN 113683521 A CN113683521 A CN 113683521A CN 202110983269 A CN202110983269 A CN 202110983269A CN 113683521 A CN113683521 A CN 113683521A
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propanediol
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chloro
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殷留文
陈东辉
杨沫
戴春江
樊才旺
殷贵
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Ningxia Youqi Pharmaceutical Co ltd
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    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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Abstract

The invention belongs to the field of fine chemical engineering, and relates to a novel method for producing 2-amino-1,3-propanediol by a JIT method, which consists of two steps of reactions of catalytic chlorination and catalytic amination, wherein glycerol is chlorinated and hydrochlorinated under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propanediol, and 2-chloro-1, 3-propanediol is aminated by ammonia under the catalysis of urotropine to obtain 2-amino-1, 3-propanediol.

Description

Novel method for producing 2-amino-1, 3-propylene glycol by JIT method
The technical field is as follows:
the invention belongs to the field of fine chemical engineering, relates to a novel method for producing 2-amino-1,3-propanediol, and particularly relates to a novel method for producing 2-amino-1,3-propanediol by a JIT method.
Background art:
radiology Department (Radiology Department) is a Department integrating examination, diagnosis and treatment in modern hospitals, and the related medical devices generally include an X-ray radiography machine, a direct digital radiography system (DR), a computed radiography system (CR), Computed Tomography (CT), Magnetic Resonance Imaging (MRI), a digital subtraction angiography system (DSA), etc., and when the medical devices are used for performing certain specific examinations on a patient, in order to increase the contrast of certain visceral tissues or lumens, i.e., to more clearly display the morphology, contour and lesion features of organs or lumens, a contrast Medium (Control Medium) is often used in combination, which is called as angiography. Contrast agents are commonly referred to as contrast agents, also known as enhancing agents in computed tomography and magnetic resonance imaging.
Iopamidol (Iopamidol), the chemical name is (S) -N, N' -bis (1, 3-dihydroxypropyl-2-yl) -5- [ [ (2S) -2-hydroxypropionyl ] amino ] -2,4, 6-triiodobenzene-1, 3-dicarboxamide, the CAS number is 60166-93-0, and the chemical structural formula is shown as formula 1. Iopamidol is widely used as a nonionic contrast agent for blood systems, lymphatic systems, urinary systems and nerve systems in developed countries at home and abroad. In recent years, many experts and scholars have found new uses of Iopamidol, such as Kaufman et al, who studied the cooperative mechanisms of their various organs by contrast enhanced Computed Tomography (CT) of Cyprinus Carpio by injecting Iopamidol (Kaufman, M., et al., Intravenous Iopamidol pharmaceuticals in Common Carp (cyminus Carpio [ J ]. J Zoo Wildl Med,2021,51(4):889-895.), Higashino et al, who performed angiography with Iopamidol to evaluate the effectiveness of embolization and the adhesion of embolization Material to balloon or microcatheter (Higashino, N., et al., Feasibility and Safety of n-Butyl Cyanophylate-Lipidol-Iopamidol as allophanate fatty tissue, 482-lymph node, J.: 482. interleuko fatty tissue, J.: 1, 2023, et al, who performed lymph node clearance by sampling with Iopamidol, Kaufman et al, Kaufman et al, who studied the cooperative mechanisms of various organs by contrast enhanced Computed Tomography (CT), y. a Diversity of a gravimetric flow in a capacity with a long compensated tomographics gravimetric map [ J ]. Interact cardio Thorac Surg.2021.); ahmad et al believe that the safety of enhanced CT imaging using iopamidol for measuring Glomerular Filtration Rate (GFR) is superior to the percutaneous renal function assessment method (Ahmad, A., et al., Noninivastic assessment of radiation-induced renal input in mice [ J ]. Int J radial Biol,2021,97(5): 664-.
Figure 1
With the soaring market demand of iopamidol in the next half year of 2020, the market demand of the key raw material 2-amino-1,3-propanediol of iopamidol also rises, and the shortage of the market supply of 2-amino-1,3-propanediol is further increased due to the limitation of dangerous processes such as traditional kettle amination and hydrogenation in China. In addition, the market of Voglibose (chemical structural formula as formula 3) which is a medicine for improving the postprandial hyperglycemia of diabetes gradually becomes pretty in 2021, 3 months, and the market prospect of 2-amino-1,3-propanediol which is a key raw material is excellent. Therefore, the development of a new technology for producing 2-amino-1,3-propanediol which integrates automation, informatization and intellectualization into a whole is urgent. 2-amino-1,3-propanediol, CAS number 534-03-2, chemical structural formula as formula 2.
Figure 2
The production technology of 2-amino-1,3-propanediol is mainly divided into the following steps:
(1) catalytic decomposition method of dihydroxyacetone oxime
Figure BDA0003229890100000023
The production of 2-amino-1,3-propanediol by catalytic decomposition of dihydroxyacetone oxime was first reported by Pilot et al in 1897 with lower molar yields (Pilot O, Ruff O. Ueber eini Aminoakohol der Fettreihe [ J ]. Berichte der Deutschen Chemischen Gesellschaft,1897,30 (2): 2057-. In 1999, U.S. patent No. 5922917, improved on the basis of the study of pilot et al, uses rhodium and aluminum as catalysts, and at 70 ℃ and 70bar atmospheric pressure, dihydroxyacetone oxime can be decomposed into 2-amino-1,3-propanediol with 90% yield, but expensive catalyst and higher reaction pressure, and no manufacturer adopts the process at present.
(2) 2-nitro-1, 3-propylene glycol sodium salt reduction method
Figure BDA0003229890100000031
German patent DE2742981, US4448999, US6509504, US4221740 and Chinese patent CN1948272A all report that 2-nitro-1, 3-propanediol sodium salt can be reduced under certain conditions to prepare 2-amino-1, 3-propanediol. The method usually needs expensive catalyst which is easily covered and inactivated by 2-nitro-1, 3-propanediol sodium salt, the total cost is lower, and only a few foreign manufacturers adopt the process at present.
(3) 2-nitro-1, 3-propanediol reduction process
Figure BDA0003229890100000032
In order to solve the problem that 2-nitro-1, 3-propylene glycol sodium salt is easy to cover the surface of a catalyst to cause catalyst deactivation, Chinese patent CN103508905 changes 2-nitro-1, 3-propylene glycol sodium salt into 2-nitro-1, 3-propylene glycol, but uses extremely flammable and explosive dangerous chemical nitromethane, and has great potential safety hazard.
(4) Malonic acid diethyl ester process
Figure BDA0003229890100000033
Chinese patent CN101100439 reports that diethyl malonate can be nitrosated with sodium nitrite to obtain nitroso-diethyl malonate, and then reduced with sodium metal in absolute ethyl alcohol to obtain 2-amino-1, 3-propanediol. Because the water solubility of the 2-amino-1,3-propanediol is higher, the electrodialysis technology is needed for separating the 2-amino-1,3-propanediol from the water-soluble inorganic salt, the power consumption is extremely high, and the industrial production is not facilitated. Based on CN101100439, CN109535014 changes diethyl malonate into dimethyl malonate and changes reduction of sodium metal into catalytic hydrogenation, although the problem of separation of inorganic salts from products is solved, the selected catalyst is not sold in the market, and the actual service life of the catalyst needs to be examined.
(5) Biological method
Figure BDA0003229890100000034
Andree. beta. en et al reported that bradyrhizobium ehmitis USD94 can synthesize 2-amino-1,3-propanediol using glycerol, a production technique that has limited productivity despite mild reaction conditions (Andree. beta. en B, Steinbuchel A. Biotechnical conversion of glycerol to 2-amino-1,3-propanediol (serinol) in recombinant Escherichia coli [ J ] Applied Microbiology and Biotechnology,2012,93 (1): 357-365.). Chinese patent CN10476905 reports that Escherichia coli host cells without triose phosphate isomerase activity and with dihydroxyacetone phosphate aminotransferase activity can convert glycerol into serinol, but the whole process involves complicated bioengineering methods such as bacterial culture, DNA separation and modification, deletion cassette construction, rtx operon cloning, deletion cassette introduction and deletion vector, and the like, and has a certain distance from industrial preparation at present.
(6) Etherification method of 1, 3-dialkoxy isopropylamine
Figure BDA0003229890100000041
U.S. Pat. No. 4,4503252 reports that etherification of 1, 3-dialkoxyisopropylamine with hydrochloric acid can produce 2-amino-1,3-propanediol in yields of up to 99.8%. However, the preparation of the 1, 3-dialkoxyisopropylamine relates to 2A carcinogen epichlorohydrin and also relates to liquid ammonia with critical amount of only 10 tons for a major hazard source, which brings great inconvenience to the construction of chemical projects and the safety production after the construction of production devices.
The invention content is as follows:
in order to solve the defects and shortcomings in the invention, the invention provides a novel method for producing 2-amino-1,3-propanediol, which is economical, environment-friendly, safe, integrated, automatic and informationized.
In order to achieve the purpose, the invention is realized by the following technical scheme: the invention relates to a new method for producing 2-amino-1, 3-propylene glycol by JIT method, which mainly comprises two steps of reaction of catalytic chlorination and catalytic amination, wherein glycerol is chloridized and hydrochlorinated under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propylene glycol, and 2-chloro-1, 3-propylene glycol is aminated by ammonia under the catalysis of urotropine to obtain 2-amino-1, 3-propylene glycol.
The chlorination reaction device mainly comprises a glycerol head tank 1, a hydrochloric acid head tank 3, a mixer 2, a secondary mixing heating kettle 5, a feeding pump A6, a tubular reactor 4 and a receiving tank, wherein the parts of all equipment contacting materials are treated by lining with tetrafluoro or glass lining or an anticorrosive coating, so that the corrosion resistance is good; the glycerol head tank contains third glycerol; the hydrochloric acid elevated tank is filled with hydrochloric acid, the concentration of the hydrochloric acid is 36%, and the hydrochloric acid with other concentrations cannot achieve good chlorination effect; a three-way valve with an adjusting function is arranged before the glycerol head tank 1 and the hydrochloric acid head tank 3 enter the mixer 2, and the feeding proportion of glycerol and hydrochloric acid can be adjusted according to the process requirements; the secondary mixing and heating kettle is made of glass lining, the jacket adopts steam to adjust the reaction temperature, the temperature is set at 60-70 ℃, and other temperatures can not achieve good chlorination effect; the chloride A tank 7 and the chloride B tank 8 are used and prepared, the chloride B tank 8 receives materials when the chloride A tank 7 feeds materials, and the like is performed; the chlorination reaction pressure is normal pressure, the chlorination must be catalyzed by zinc chloride, the zinc chloride is filled in a tubular reactor in advance, and the usage amount of the zinc chloride is 1-20% of that of the glycerol, preferably 5%; the chlorination process chlorinates glycerol to a mixture of 1-chloro-2, 3-propanediol, 2-chloro-1, 3-propanediol, 1, 2-dichloropropanol, 1, 3-dichloropropanol, and 1,2, 3-trichloropropane.
The amination reaction device mainly comprises a feeding tank (a chloride A tank 7 and a chloride B tank 8 in the figure), a feeding pump B9, a rectifying device 11 and a receiving tank, wherein the receiving tank comprises a monochloride receiving tank 13 and a polychloride receiving tank 12, and all the parts of the equipment contacting materials are treated by lining with tetrafluoro or glass lining or anticorrosive coating, so that the equipment is good in corrosion resistance; materials in the feeding tanks (a chloride A tank 7 and a chloride B tank 8 in the figure) are transferred into a rectifying device 11 with a reboiler, the temperature of the reboiler 10 is set at 120-130 ℃, and the temperature of the rectifying device 11 is well preserved; the inner coil pipe heat conducting oil is arranged in the tower kettle of the rectifying device 11 for heating, when no fraction is extracted to the monochloride receiving tank 13, the materials in the tower kettle are heated until the materials are basically extracted to the monochloride receiving tank 12 by rectification, and the temperature at the final stage of rectification reaches 230 ℃; the rectification process is that water is evaporated out, then 2-chloro-1, 3-propanediol containing a small amount of 1-chloro-2, 3-propanediol is rectified and collected to a monochloride receiving tank, and finally 1, 3-dichloropropanol, 1, 2-dichloropropanol and 1,2, 3-trichloropropane are rectified and collected to a polychloride receiving tank; the rectification process is under negative pressure, and the vacuum degree is-0.095 MPa.
The amination reaction device mainly comprises a feeding tank (chlorine receiving tank 13), a feeding pump D15 and an amination kettle, wherein the amination kettle comprises an amination kettle A17 and an amination kettle B18, and is characterized in that: the materials contacted with all the equipment are treated by lining PTFE or glass lining or an anticorrosive coating, so that the corrosion resistance is good; urotropine is used as a catalyst in the amination process, and other catalysts cannot achieve a good amination effect; in the amination process, ammonia water is used as an amination reagent, the concentration of the ammonia water must be 20%, and ammonia water with other concentrations cannot achieve a good amination effect; the amination catalyst is used in an amount of 1 to 20%, preferably 3%, of the monochloride; the amination temperature is 50-60 ℃, and the other temperatures can not achieve good amination effect; the amination pressure is normal pressure; the amination time is 6-15h, preferably 8 h; amination Process 2-chloro-1, 3-propanediol is aminated to 2-amino-1, 3-propanediol.
The hydrolysis reaction device mainly comprises a feeding tank (polychlorid receiving tank 12), a feeding pump C14 and a hydrolysis kettle 16, and is characterized in that: the materials contacted with all the equipment are treated by lining with tetrafluoro or anticorrosive coatings, so that the corrosion resistance is good; the-Cl in the reaction molecules is hydrolyzed into-OH; the alkali used for hydrolysis is potassium hydroxide, potassium carbonate, sodium hydroxide and lithium hydroxide, preferably sodium hydroxide, and specifically, 32% sodium hydroxide solution is recommended alkali for hydrolysis, and the dosage of the alkali is 1-2 times, preferably 1.5 times of the mass of the polychlorinated substance; the hydrolysis temperature is 50-95 deg.C, preferably 80-90 deg.C; the hydrolysis pressure is normal pressure; the hydrolysis time is 8-15h, preferably 10 h; in the hydrolysis process, 1-chloro-2, 3-propanediol, 1, 3-dichloropropanol, 1, 2-dichloropropanol and 1,2, 3-trichloropropane are hydrolyzed into glycerol which is applied to the chlorination procedure.
The Just-In-Time production (Just In Time, JIT for short) related by the invention is specifically as follows: with the order quantity of 2-amino-1,3-propanediol as the guide, production is started when an order is made. Before production is started, 2-chloro-1, 3-propanediol stock is checked, if the stock is insufficient, a chlorination procedure is started, the stock of glycerol and hydrochloric acid is checked before the chlorination procedure is started, and the purchase amount of the glycerol and hydrochloric acid is determined according to the target 2-chloro-1, 3-propanediol production, so that the problem of fund occupation caused by unnecessary stock is reduced.
The invention integrates the JIT method into the production line design of the 2-amino-1, 3-propanediol. The JIT is also called Just In Time, Just-In-Time production, stockless production (stock less production), zero inventory (zero inventories), one-piece flow (one-piece flow) or supermarket production (supermarket production). The JIT method is a production mode which is implemented by Toyota automotive company in Japan in the 60 th century, is always used up to now, is considered to be one of the most ideal and most vital novel production systems in the manufacturing industry at present, and no report of applying the JIT method to a 2-amino-1,3-propanediol production line exists at present.
In order to realize the JIT method for producing the 2-amino-1,3-propanediol, the low stock of main raw materials, process products and products is realized through the reasonable control of production plans and the reasonable management of the stock, the unnecessary fund occupation of enterprises is reduced, the production equipment of the 2-amino-1,3-propanediol is reasonably configured, the material queuing time, the material transportation time and the production preparation time are reduced, and the logistics flow among operations, production lines, processes and factories in a balanced and balanced manner, so that the production efficiency is improved, the manufacturing cost is reduced, and the aim of improving the market competitiveness of the enterprises is finally fulfilled.
Specifically, glycerol is hydrochlorinated by chloride in hydrochloric acid under the catalysis of zinc chloride to obtain a mixture of 1-chloro-2, 3-propanediol, 2-chloro-1, 3-propanediol, 1, 2-dichloropropanol, 1, 3-dichloropropanol and 1,2, 3-trichloropropane, wherein the 2-chloropropanol is rectified and separated to be reacted with ammonia in water under the catalysis of urotropine to obtain 2-amino-1,3-propanediol, 1-chloro-2, 3-propanediol, 1, 3-dichloropropanol and 1, 2-dichloropropanol, and the reaction process comprises the following steps:
Figure BDA0003229890100000061
correspondingly, preparing glycerol and hydrochloric acid in respective overhead tanks for standby, filling a catalytic amount of zinc chloride in the tubular reactor 4, preliminarily mixing a set amount of glycerol and hydrochloric acid by a mixer, then discharging the mixture to the secondary heating mixing kettle 5 by gravity, pumping the mixed glycerol hydrochloric acid solution to the tubular reactor 4 filled with the zinc chloride by a feed pump A6 to obtain chloride, and storing the chloride in a chloride A tank 7 or a chloride B tank 8 (one for one). The chloride is transferred to a rectifying device 11 with a reboiler 10 (the rectifying device consists of a tower bottom, a rectifying tower and a tower top condenser, and is called as a rectifying device collectively) through a feed pump B9 to obtain 2-chloro-1, 3-propanediol, the obtained 2-chloro-1, 3-propanediol is placed in a monochloride receiving tank 13, and the obtained 1-chloro-2, 3-propanediol, 1, 3-dichloropropanol and 1, 2-dichloropropanol are placed in a polychloride receiving tank 12. Wherein, the material in the monochloride receiving tank 13 is pumped to the amination kettle A17 or the amination kettle B18 through a feed pump D15 to carry out catalytic amination to obtain 2-amino-1, 3-propylene glycol, the material in the polychloride receiving tank 12 is pumped to the hydrolysis kettle 16 through a feed pump C14 to be hydrolyzed into glycerol by 32 percent of sodium hydroxide for a chlorination process, and the flow chart of the device refers to the attached drawing 1:
drawings
The invention is further illustrated below with reference to the accompanying drawings:
FIG. 1 is a diagram of an apparatus for carrying out the process of the invention:
FIG. 2 is a gas chromatogram of 2-amino-1,3-propanediol produced according to the invention;
in the figure: 1. glycerol elevated tank, 2 mixer, 3 hydrochloric acid elevated tank, 4 tubular reactor, 5 secondary mixing heating kettle, 6 feeding pump A, 7, chloride A tank, 8, chloride B tank, 9, feeding pump B, 10, reboiler, 11, rectifying device, 12, polychloride receiving tank, 13, monochloride receiving tank, 14, feeding pump C, 15, feeding pump D, 16, hydrolysis kettle, 17, amination kettle A, 18 and amination kettle B.
Example (b):
the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example (b):
chlorination process
Figure BDA0003229890100000071
Glycerol (1000.00kg, 10.86kmol) and 36% hydrochloric acid (1800.00kg, 17.77kmol) were added to the glycerol head tank 1 and hydrochloric acid head tank 3, respectively; particulate zinc chloride (75.00kg, 0.55kmol) was charged in the tubular reactor 4 with screen.
Glycerin and 36% hydrochloric acid were fed into the second mixing and heating tank 5 through the mixer 2 at a rate that controlled the hydrochloric acid and glycerin to be fed substantially simultaneously. After the addition, the secondary mixing and heating kettle 5 is stirred and heated to 60-70 ℃. After the temperature rise is finished, the materials in the secondary mixing and heating kettle 5 are pumped into the tubular reactor at a certain speed, most of the glycerol is chlorinated after passing through the tubular reactor 4, the chlorinated products are temporarily stored in the chloride A tank 7 or the chloride B tank 8, and the weight of the chlorinated products is 2765.38 kg.
The material (2765.38kg) in the chloride A tank 7 or the chloride B tank 8 in the previous step is heated to 120 ℃ and 130 ℃ by a reboiler 10, and is firstly extracted as dilute hydrochloric acid (1108.27kg) by a rectifying device 11 and is received by a chlorine storage tank 12. After the water is distilled, the water in the polychloride storage tank 12 is discharged, a vacuum system is started, and 2-chloro-1, 3-propanediol containing a small amount of 1-chloro-2, 3-propanediol is rectified to a monochloride receiving tank 13 (weight: 420.12 kg; temperature: 105-. After the monochloro is distilled, a valve of a discharge pipe is switched, the temperature is continuously increased, the mixture of the 1-chloro-2, 3-propanediol, the 1, 3-dichloropropanol, the 1, 2-dichloropropanol and the 1,2, 3-trichloropropane in the tower kettle is rectified under negative pressure until no fraction is discharged, the end temperature is about 230 ℃, the mixture (1053.02kg) of the fraction main components of the 1-chloro-2, 3-propanediol, the 1, 3-dichloropropanol, the 1,2, 3-trichloropropane and the glycerol which does not participate in the reaction is stored in a polychlorinated product storage tank 12, and the remaining in the tower kettle is brown tar-like impurities (155.28kg), which are delivered to qualified environmental protection companies for treatment.
Amination Process
Figure BDA0003229890100000081
Transferring the 2-chloro-1, 3-propanediol (420.12kg, 3.80kmol) obtained in the previous step to an amination kettle A17 or an amination kettle B18, adding 20% ammonia (800.00kg, 9.41kmol) and urotropine (15.00kg, 0.11kmol), stirring and heating to 50-60 ℃ for reacting for 8 hours. After the reaction is finished, the 2-amino-1,3-propanediol (346.27kg) is obtained by pressure filtration after deamination and dehydration, and the analysis results are shown in the following table after gas chromatography analysis:
Figure BDA0003229890100000082
hydrolysis step
Figure BDA0003229890100000091
Adding a mixture (1053.02kg) of 1-chloro-2, 3-propanediol, 1, 3-dichloropropanol, 1,2, 3-trichloropropane and unreacted glycerol obtained in the chlorination step into a hydrolysis kettle, then adding 32% NaOH (1580.00kg), stirring and heating to 80-90 ℃ for reaction for 10 hours. After the reaction is finished, the mixture is concentrated into slurry, filter pressing is carried out, the filtrate is continuously concentrated until no fraction is obtained, the filter pressing is carried out again, the filtrate is glycerol (563.22kg) and can be applied to a chlorination procedure, and the filter residue is a mixture of sodium hydroxide and sodium chloride and is delivered to qualified environment-friendly companies for treatment.
While the basic teachings of the present invention have been described, numerous extensions and variations will be apparent to those of ordinary skill in the art. As the present invention disclosed in the specification may be embodied in other specific forms without departing from the spirit or general characteristics thereof, and it is noted that some of these specific forms have been set forth, the embodiments disclosed in the specification should be considered as illustrative and not restrictive. The scope of the invention is indicated by the appended claims, rather than the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are intended to be embraced therein.

Claims (6)

1. A new method for producing 2-amino-1,3-propanediol by JIT method, which consists of two steps of reaction of catalytic chlorination and catalytic amination, and is characterized in that: glycerol is chloridized and hydrochlorinated under the catalysis of zinc chloride to obtain 2-chloro-1, 3-propanediol, and 2-chloro-1, 3-propanediol is aminated by ammonia under the catalysis of urotropine to obtain 2-amino-1, 3-propanediol.
2. The novel process for producing 2-amino-1,3-propanediol according to claim 1, characterized in that: the device for chlorination reaction of the invention mainly comprises a glycerin head tank, a hydrochloric acid head tank, a mixer, a secondary mixing heating kettle, a feeding pump A, a tubular reactor and a receiving tank, and is characterized in that: all the parts of the equipment contacting materials are treated by lining with tetrafluoro or glass lining or anticorrosive coating; the glycerol elevated tank is used for containing glycerol; the hydrochloric acid head tank is filled with hydrochloric acid, and the concentration of the hydrochloric acid is 36%; a three-way valve with a regulating function is arranged before the glycerol head tank and the hydrochloric acid head tank enter the mixer, the secondary mixing and heating kettle is made of glass lining, a jacket adopts steam to regulate the reaction temperature, and the temperature is set to be 60-70 ℃; the chlorination reaction pressure is normal pressure, the chlorination must be catalyzed by zinc chloride, the zinc chloride is filled in a tubular reactor in advance, and the usage amount of the zinc chloride is 1-20% of that of the glycerol, preferably 5%; the chlorination process chlorinates glycerol to a mixture of 1-chloro-2, 3-propanediol, 2-chloro-1, 3-propanediol, 1, 2-dichloropropanol, 1, 3-dichloropropanol, and 1,2, 3-trichloropropane.
3. The novel process for producing 2-amino-1,3-propanediol according to claim 2, characterized in that: the device for amination reaction of the invention mainly comprises a chloride A tank, a chloride B tank, a feeding pump B, a rectifying device and a receiving tank, wherein the receiving tank comprises a chlorine receiving tank and a polychloride receiving tank, and is characterized in that: all the parts of the equipment contacting materials are treated by lining with tetrafluoro or glass lining or anticorrosive coating; the chloride A tank and the chloride B tank are used and prepared, the chloride B tank receives materials when the chloride A tank feeds materials, and the like is performed; materials in the chloride A tank and the chloride B tank are transferred into a rectifying device with a reboiler, and the temperature of the reboiler is set at 120-130 ℃; the inner coil pipe heat conducting oil is arranged in the tower kettle of the rectifying device for heating, when no fraction is extracted to the monochloride receiving tank, the materials in the tower kettle are heated until the materials are basically rectified and extracted to the monochloride receiving tank, and the temperature at the final stage of rectification reaches 230 ℃; the rectification process is that water is evaporated out, then 2-chloro-1, 3-propanediol containing a small amount of 1-chloro-2, 3-propanediol is rectified and collected to a monochloride receiving tank, and finally 1, 3-dichloropropanol, 1, 2-dichloropropanol and 1,2, 3-trichloropropane are rectified and collected to a polychloride receiving tank; the rectification process is under negative pressure, and the vacuum degree is-0.095 MPa.
4. The novel process for producing 2-amino-1,3-propanediol according to claim 3, characterized in that: the device for amination reaction of the invention mainly comprises a chlorine receiving tank, a feeding pump D and an amination kettle, and is characterized in that: all the parts of the equipment contacting materials are treated by lining with tetrafluoro or glass lining or anticorrosive coating; urotropine is used as a catalyst in the amination process; in the amination process, ammonia water is used as an amination reagent, and the concentration of the ammonia water must be 20%; the amination catalyst is used in an amount of 1 to 20%, preferably 3%, of the monochloride; the amination temperature is 50-60 ℃; the amination pressure is normal pressure; the amination time is 6-15h, preferably 8 h; amination Process 2-chloro-1, 3-propanediol is aminated to 2-amino-1, 3-propanediol.
5. The novel process for producing 2-amino-1,3-propanediol according to claim 4, wherein: the hydrolysis reaction device mainly comprises a polychlorid receiving tank, a feeding pump C and a hydrolysis kettle, and is characterized in that: all the parts of the equipment contacting materials are treated by lining with tetrafluoro or anticorrosive coatings; the-Cl in the reaction molecules is hydrolyzed into-OH; the alkali used for hydrolysis is potassium hydroxide, potassium carbonate, sodium hydroxide and lithium hydroxide, preferably sodium hydroxide, and specifically, 32% sodium hydroxide solution is recommended alkali for hydrolysis, and the dosage of the alkali is 1-2 times, preferably 1.5 times of the mass of the polychlorinated substance; the hydrolysis temperature is 50-95 deg.C, preferably 80-90 deg.C; the hydrolysis pressure is normal pressure; the hydrolysis time is 8-15h, preferably 10 h; in the hydrolysis process, 1-chloro-2, 3-propanediol, 1, 3-dichloropropanol, 1, 2-dichloropropanol and 1,2, 3-trichloropropane are hydrolyzed into glycerol which is applied to the chlorination procedure.
6. The novel process for producing 2-amino-1,3-propanediol according to claim 5, characterized in that: the Just-In-Time production (Just In Time, JIT for short) related by the invention is specifically as follows: taking 2-amino-1,3-propanediol as the order quantity as the guide, and starting production when an order is available; before production is started, 2-chloro-1, 3-propanediol stock is checked, if the stock is insufficient, a chlorination procedure is started, the stock of glycerol and hydrochloric acid is checked before the chlorination procedure is started, and the purchase amount of the glycerol and hydrochloric acid is determined according to the target 2-chloro-1, 3-propanediol production, so that the problem of fund occupation caused by unnecessary stock is reduced.
CN202110983269.6A 2021-08-25 2021-08-25 Novel method for producing 2-amino-1, 3-propylene glycol by JIT method Pending CN113683521A (en)

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