CN113105379A - Method and device for preparing selenocysteine by using sodium formaldehyde sulfoxylate as reducing agent - Google Patents
Method and device for preparing selenocysteine by using sodium formaldehyde sulfoxylate as reducing agent Download PDFInfo
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- CN113105379A CN113105379A CN202110228475.6A CN202110228475A CN113105379A CN 113105379 A CN113105379 A CN 113105379A CN 202110228475 A CN202110228475 A CN 202110228475A CN 113105379 A CN113105379 A CN 113105379A
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 title claims abstract description 28
- ZKZBPNGNEQAJSX-UHFFFAOYSA-N selenocysteine Natural products [SeH]CC(N)C(O)=O ZKZBPNGNEQAJSX-UHFFFAOYSA-N 0.000 title claims abstract description 28
- FDKWRPBBCBCIGA-UWTATZPHSA-N D-Selenocysteine Natural products [Se]C[C@@H](N)C(O)=O FDKWRPBBCBCIGA-UWTATZPHSA-N 0.000 title claims abstract description 26
- 229940055619 selenocysteine Drugs 0.000 title claims abstract description 26
- 235000016491 selenocysteine Nutrition 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 17
- FDKWRPBBCBCIGA-REOHCLBHSA-N (2r)-2-azaniumyl-3-$l^{1}-selanylpropanoate Chemical compound [Se]C[C@H](N)C(O)=O FDKWRPBBCBCIGA-REOHCLBHSA-N 0.000 title claims abstract 5
- 239000000126 substance Substances 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 33
- 239000003513 alkali Substances 0.000 claims abstract description 31
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 239000002910 solid waste Substances 0.000 claims abstract description 12
- ASBJGPTTYPEMLP-REOHCLBHSA-N 3-chloro-L-alanine Chemical compound ClC[C@H]([NH3+])C([O-])=O ASBJGPTTYPEMLP-REOHCLBHSA-N 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 31
- 239000007788 liquid Substances 0.000 claims description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 238000003860 storage Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000011344 liquid material Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000011343 solid material Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- JULROCUWKLNBSN-UHFFFAOYSA-N selenocystine Chemical compound OC(=O)C(N)C[Se][Se]CC(N)C(O)=O JULROCUWKLNBSN-UHFFFAOYSA-N 0.000 claims description 4
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- ZKZBPNGNEQAJSX-REOHCLBHSA-N L-selenocysteine Chemical compound [SeH]C[C@H](N)C(O)=O ZKZBPNGNEQAJSX-REOHCLBHSA-N 0.000 description 23
- MQUNPMBEKMVOHA-UHFFFAOYSA-N (sodiodiselanyl)sodium Chemical compound [Na][Se][Se][Na] MQUNPMBEKMVOHA-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000002360 explosive Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- IENJPSDBNBGIEL-DKWTVANSSA-N (2r)-2-amino-3-chloropropanoic acid;hydrochloride Chemical compound Cl.ClC[C@H](N)C(O)=O IENJPSDBNBGIEL-DKWTVANSSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229930182853 L-selenocysteine Natural products 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- TYZYNGFWGHGRBZ-REOHCLBHSA-N (2s)-2-(chloroamino)propanoic acid Chemical compound ClN[C@@H](C)C(O)=O TYZYNGFWGHGRBZ-REOHCLBHSA-N 0.000 description 1
- JSJQXIKNYJDACT-UHFFFAOYSA-N (potassiodiselanyl)potassium Chemical compound [Se-][Se-].[K+].[K+] JSJQXIKNYJDACT-UHFFFAOYSA-N 0.000 description 1
- -1 (tert-butoxycarbonyl) amino Chemical group 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZDPYOECRAYBFTE-VKHMYHEASA-N methyl (2s)-2-(chloroamino)-3-hydroxypropanoate Chemical compound COC(=O)[C@H](CO)NCl ZDPYOECRAYBFTE-VKHMYHEASA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
Abstract
The invention discloses a method for mildly preparing selenocysteine by taking cheap sodium formaldehyde sulfoxylate as a reducing agent, which is characterized by comprising the following steps of: step one, loading selenium powder, strong alkaline substances and sodium formaldehyde sulfoxylate into a reactor, then adding a proper amount of distilled water, and stirring for a certain time at a certain temperature; step two, preparing 3-chloro-L-alanine into an aqueous solution with the pH value of 6-10, adding the aqueous solution into the reactor in the step one, continuously stirring and reacting for a certain time, adding acid, filtering, recovering excessive selenium powder for the next reaction, adding alkali until the pH value is 6-8, standing, filtering to obtain filter residue selenocysteine, evaporating the filtrate, and collecting solid waste. The method has simple and easy operation, mild and controllable reaction process, greatly reduces the synthesis cost of the selenocysteine, and has good market prospect.
Description
Technical Field
The invention belongs to the field of chemical conversion, and particularly relates to a method and a device for preparing selenocysteine by using a sodium formaldehyde sulfoxylate as a reducing agent.
Background
Selenocysteine is a typical representative of organic selenium compounds, and has a wide range of biological activities. It can be used as an important raw material for synthesizing L-selenium-methyl selenocysteine, and has strong potential market demand. The current method for synthesizing selenocysteine comprises the following steps: 1) alpha-amino-beta-methyl chloropropionate hydrochloride is used as a raw material to react with potassium diselenide in an aqueous solution to produce selenocysteine, and the yield is 30%. 2) The racemic selenocysteine is obtained by taking beta-chloropropionic acid and sodium diselenide as raw materials to react, and the yield is about 62 percent. 3) (2S) -2- [ (tert-butoxycarbonyl) amino group]The raw materials of-3-hydroxy propionate and sodium diselenide are synthesized into L-selenocysteine with enantiomer purity in four steps, and the yield is 92%. 4) beta-chlorine-L-alanine and sodium diselenide are used as raw materials to synthesize selenocysteine, and the yield is 60%. 5) Sodium diselenide reacts with the chloro-serine methyl ester and then is hydrolyzed to generate selenocysteine, and the yield is 80.6 percent. 6) The hydrochloride of the chloroalanine and the sodium diselenide are used as raw materials to synthesize the L-selenocysteine, and the yield is 79 percent. These processes have the common disadvantage that the reaction uses sodium diselenide as it is now prepared, requiring the use of flammable and explosive reagents, such as NaBH4，KBH4Or metallic sodium, potassium, etc., which is extremely dangerous to handle and expensive in reagent cost.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims at providing a method for preparing selenocysteine by taking a rongalite as a reducing agent. The method is simple and easy to implement, has low cost and very obvious economic benefit.
The invention also aims to provide a reaction device for preparing selenocysteine by using the sodium formaldehyde sulfoxylate as a reducing agent.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing selenocysteine by using sodium formaldehyde sulfoxylate as a reducing agent comprises the following steps:
step one, selenium powder, strong alkaline substances, sodium formaldehyde sulfoxylate and water are mixed and stirred uniformly to obtain a mixed solution;
step two, preparing 3-chloro-L-alanine or salt thereof into an aqueous solution with the pH value of 6-10, then adding the aqueous solution into the mixed solution obtained in the step one, stirring and reacting at room temperature, adding acid and filtering after the reaction is finished, adding alkali into the filtrate until the pH value is 6-8, standing, and filtering again to obtain the filter residue which is selenocystine.
Preferably, in the first step, the molar equivalent ratio of the selenium powder, the strong alkaline substance and the sodium formaldehyde sulfoxylate is 1: (0.5-5): (0.2-2).
Preferably, the strongly basic material of step one comprises sodium hydroxide, potassium hydroxide solid or solution.
Preferably, the mass ratio of the selenium powder to the water in the first step is 1: (5-50).
Preferably, the stirring temperature in the step one is 20-90 ℃, the stirring time is 2-8 hours, and the stirring speed is 100-1000 r/min.
Preferably, the molar equivalent ratio of the 3-chloro-L-alanine or the salt thereof in the second step to the selenium powder in the first step is 1: (1-10).
Preferably, the pH of the solution after the acid addition in step two is less than 2.
Preferably, the reaction time in the second step is 10 to 20 hours.
Preferably, the standing time in the second step is 1 to 4 days.
Preferably, after the reaction in the second step is finished, the excessive selenium powder can be recovered by adding acid and filtering for the next reaction;
preferably, the filtrate obtained by the second filtration in the step two is evaporated, and solid wastes such as inorganic salts and the like are collected.
A reaction device for realizing the method for preparing the selenocysteine by taking the rongalite as the reducing agent comprises a main reactor, an acid mixer, an alkali mixer, a filter, an evaporator, a condenser, a chemical pump, an acid liquid storage tank, an alkali liquid storage tank, a product tank, a solid waste tank and a water tank;
the main reactor comprises a stirring paddle, two solid sample inlets (one is used for feeding selenium powder, sodium formaldehyde sulfoxylate, solid alkali or acid, and the other is mainly used for recycling the selenium powder through a filter), two liquid sample inlets (used for feeding water and acid liquid) and a material outlet (discharging a mixture after reaction); the liquid sample inlet is respectively connected with the acid liquor storage tank and the chemical pump, and the material outlet is connected with the chemical pump; the acid mixer and the alkali mixer also comprise a stirring paddle, two liquid feed inlets (one is used for feeding acid liquid or alkali liquid, and the other is used for feeding the mixture after reaction) and a material outlet (the acid mixture after being adjusted by acid); the feeding port of the acid mixer is respectively connected with the acid liquid storage tank and the chemical pump, the material outlet is connected with the chemical pump, the feeding port of the alkali mixer is respectively connected with the alkali liquid storage tank and the filter, and the material outlet is connected with the chemical pump; the filter comprises a liquid sample inlet and a liquid outlet and a solid outlet; the inlet of one filter is connected with a chemical pump, the solid outlet is connected with a main reactor, and the liquid outlet is connected with an alkali mixer; the inlet of the other filter is connected with a chemical pump line, the solid outlet is connected with a product tank, and the liquid outlet is connected with an evaporator; the middle part of the evaporator is provided with a liquid sample inlet, the top part of the evaporator is provided with a gas material outlet which is connected with the condenser, and the bottom part of the evaporator is provided with a solid material outlet which is connected with the solid waste pipe; the top of the condenser is provided with a gas material inlet, and the bottom of the condenser is provided with a liquid material outlet which is connected with the water tank; the discharge hole of the water tank is connected with a chemical pump.
Aiming at the prior preparation of selenocysteine, the expensive NaBH is used4And the like are reducing agents, and the reaction is violent, so that the production danger is high. Therefore, the cost is high no matter production or management, and the tail gas contains a large amount of hydrogen and needs to be treated.
The invention utilizes the sodium formaldehyde sulfoxylate as a reducing agent to prepare the sodium diselenide solution, and has the important technical points that: fully dissolving selenium powder by using strong base, adding sodium formaldehyde sulfoxylate to reduce the selenium powder into a sodium diselenide solution, finally dropwise adding a 3-chloro-L-alanine solution, and stirring to complete the reaction. The reaction condition is mild, and the side reaction is less.
1) Cost advantage. The current preparation of selenocysteine requires the use of flammable and explosive NaBH4As reducing agent, the amount used is extremely large: 1 kg of selenocysteine, approximately 1 kg of NaBH is required4The unit price of the reagent is higher, and each kilogram of the reagent exceeds 400 yuan; in addition, flammable and explosive NaBH is used4And the cost is high in both production and management. The invention uses sodium formaldehyde sulfoxylate as a reducing agent, and the dosage is higher than that of NaBH41-2 times larger, but the price of the sodium formaldehyde sulfoxylate is only NaBH4One hundredth of the price, so the cost of using the invention may be only with NaBH4About ten percent reduction.
2) The safety is good. The existing method uses flammable and explosive NaBH4As a reducing agent, the reaction is very violent, the reaction is difficult to control, and the treatment of a large amount of hydrogen in tail gas is very troublesome. The invention utilizes the sodium formaldehyde sulfoxylate as a reducing agent to prepare the sodium diselenide solution under the condition of strong basicity, and the reaction is very mild.
3) The process is more green and environment-friendly. The reaction post-treatment is simple, and the product can be obtained after simple filtration treatment. The selenium powder and water can be completely recycled.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The room temperature is 20-35 ℃.
As shown in figure 1, the reaction device for preparing selenocysteine by taking sodium formaldehyde sulfoxylate as a reducing agent comprises a main reactor 4, an acid mixer 10, an alkali mixer 19, two filters 6 and 23, an evaporator 20, a condenser 31, four chemical pumps 11, 15, 21 and 35, an acid liquid storage tank 16, an alkali liquid storage tank 17, a product tank 25, a solid waste tank 30 and a water tank 33.
The top of the main reactor 4 is provided with feed pipes 1 and 2 (wherein, the pipe 1 is used for feeding selenium powder, sodium formaldehyde sulfoxylate, solid alkali and 3-chloro-L-alanine solution, the pipe 2 is used for feeding recovered selenium powder and is connected with the outlet of the solid material of the filter 6), 3 and 14 are liquid material inlets which are respectively connected with the acid liquor storage tank 16 and the discharge hole of the chemical pump 35, and the bottom is provided with a material outlet 5 which is connected with the chemical pump 11; the top of the acid mixer 10 is provided with two feeding pipes 8 and 9 which are respectively connected with an acid liquor storage tank 16 and a chemical pump 11, while the bottom is provided with a discharge hole which is connected with a chemical pump 15 through a pipe 12; the filter 6 is provided with a feeding hole which is connected with a chemical pump 15 through a pipeline 13, and also comprises two discharging holes, wherein the solid material discharging hole is connected with the main reactor 4 through a pipeline 2, and the liquid material discharging hole is connected with one inlet of an alkali mixer 19 through a pipeline 7; the other inlet of the alkali mixer 19 is connected with an alkali liquor storage tank 17 through a pipeline 18, the bottom of the alkali mixer is provided with a material outlet, and the alkali mixer is connected with an inlet of a chemical pump 21 through a pipe 20; the filter 23 is provided with a material inlet which is connected with the chemical pump 21 through a pipeline 22, and is provided with two outlets, the solid material outlet is connected with the product tank 25 through a pipeline 24, and the liquid material outlet is connected with the evaporator 20 through a pipeline 26; the two outlets of the evaporator 20 are respectively steam outlets which are connected with a condenser 31 through a pipeline 27 and a solid outlet which is connected with a solid waste tank 30 through a pipeline 29; the inlet of the water tank 33 is connected to the condenser 31 through a pipe 32, and the outlet is connected to the chemical pump 35 through a pipe 34.
A method for preparing selenocysteine with rongalite as a reducing agent comprises the steps of putting selenium powder, rongalite and solid alkali into a main reactor 4 from a material pipe 1, starting a chemical pump 35, injecting certain moisture through a pipeline 14, starting a stirrer of the main reactor 4, fully dissolving the selenium powder, the rongalite and the solid alkali, reacting for a period of time, adding an aqueous solution of 3-chloro-L-alanine from the material pipe 1, and still stirring and reacting for a period of time at normal temperature. After the stirring reaction is finished, a chemical pump 11 is started, materials in the main reactor 4 are transferred to an acid mixer 10, certain acidic materials are injected through a pipeline 8, the materials in the acid mixer 10 are made to be strong acidic, then a pump 15 is started, the materials enter a filter 6 through a pipeline 13, and filter residues are excessive selenium powder and can be recycled. The filtrate enters an alkali mixer 19 through a pipeline 7, a certain amount of alkaline substances are injected through a pipeline 18, the pH of the solution is finally about 6.5, after the solution is kept stand for a certain time, a chemical pump 21 is started to convey the materials to a filter 23, the obtained filter residue is the target product selenocysteine, the filtrate enters an evaporator 28 through a pipeline 26 and is concentrated to obtain solid waste, and the steam is condensed by a condenser 31 and then collected to be used for producing the next cycle product.
Example 1
Step one, 3.0 g of selenium powder, 2.0 g of sodium hydroxide and 3.0 g of sodium formaldehyde sulfoxylate are put into a reactor, then 20mL of distilled water is added, and the mixture is stirred for 3 hours at room temperature and 180 minutes (the stirring speed is 800 r/min);
step two, preparing 3.0 g of 3-chloro-L-alanine hydrochloride into an aqueous solution with the pH value of 8-9, adding the aqueous solution into the reactor in the step one, continuously stirring for reaction for 12 hours, transferring the material to an acid mixer, adjusting the pH value of the solution to 1 by using concentrated hydrochloric acid, filtering out excessive selenium powder (the selenium powder can be recycled) by using a filter, transferring the filtrate to an alkali mixer, adjusting the pH value to about 6.5 by adding sodium hydroxide, standing for 2 days, transferring the material to the filter, evaporating the filtrate, and collecting solid waste. The residue was selenocysteine, and after drying, 1.78 g was weighed, giving a yield of 51%.
Example 2:
step one, 3.0 g of selenium powder, 2.5 g of potassium hydroxide and 3.5 g of sodium formaldehyde sulfoxylate are put into a reactor, then 30mL of distilled water is added, and the mixture is stirred for 5 hours at the temperature of 60 ℃ (the stirring speed is 600 r/min);
step two, preparing 3.0 g of 3-chloro-L-alanine hydrochloride into an aqueous solution with the pH value of 8-9, adding the aqueous solution into the reactor in the step one, continuously stirring and reacting for 20 hours, transferring the material to an acid mixer, adjusting the pH value of the solution to 1 by using dilute hydrochloric acid, precipitating a large amount of selenium powder, filtering out excessive selenium powder by using a filter, transferring the filtrate to an alkali mixer, adjusting the pH value to about 6.5 by adding potassium hydroxide, standing for 3 days, transferring the material to the filter, evaporating the filtrate, and collecting solid waste. The residue was selenocysteine, and after drying, 1.94 g was weighed, giving a yield of 58%.
Example 3:
step one, 3.0 g of selenium powder, 2.5 g of sodium hydroxide and 4.5 g of sodium formaldehyde sulfoxylate are put into a reactor, then 20mL of distilled water is added, and the mixture is stirred for 3 hours at 90 ℃ (the stirring speed is 500 r/min);
step two, preparing 3.0 g of 3-chloro-L-alanine hydrochloride into an aqueous solution with the pH value of 8-9, adding the aqueous solution into the reactor in the step one, continuously stirring for reacting for 18 hours, transferring the material to an acid mixer, adjusting the pH value of the solution to 1 by using hydrochloric acid, filtering out excessive selenium powder by using a filter, transferring the filtrate to an alkali mixer, adding potassium hydroxide to adjust the pH value to about 6.5, standing for 1 day, transferring the material to the filter, evaporating the filtrate, and collecting solid waste. The residue was selenocysteine, and after drying, 1.95 g was weighed, giving a yield of 58%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for preparing selenocysteine by taking sodium formaldehyde sulfoxylate as a reducing agent is characterized by comprising the following steps:
step one, selenium powder, strong alkaline substances, sodium formaldehyde sulfoxylate and water are mixed and stirred uniformly to obtain a mixed solution;
step two, preparing 3-chloro-L-alanine or salt thereof into an aqueous solution with the pH value of 6-10, then adding the aqueous solution into the mixed solution obtained in the step one, stirring and reacting at room temperature, adding acid and filtering after the reaction is finished, adding alkali into the filtrate until the pH value is 6-8, standing, and filtering again to obtain the filter residue which is selenocystine.
2. The preparation method according to claim 1, wherein the molar equivalent ratio of the selenium powder, the strong alkaline substance and the rongalite in the first step is 1: (0.5-5): (0.2-2).
3. The method of claim 1 wherein the strongly basic material in step one comprises sodium hydroxide, potassium hydroxide solid or solution.
4. The preparation method according to claim 1, wherein the mass ratio of the selenium powder to water in the first step is 1: (5-50).
5. The preparation method according to claim 1, wherein the stirring temperature in the first step is 20-90 ℃, the stirring time is 2-8 hours, and the stirring speed is 100-1000 r/min.
6. The method according to claim 1, wherein the molar equivalent ratio of the 3-chloro-L-alanine or the salt thereof added in step two to the selenium powder added in step one is 1: (1-10).
7. The method according to claim 1, wherein the pH of the solution after the addition of the acid in the second step is less than 2.
8. The method according to claim 1, wherein the reaction time in the second step is 10 to 20 hours; and the standing time in the step two is 1-4 days.
9. A reaction device for realizing the preparation method of any one of claims 1 to 8, which is characterized by comprising a main reactor, an acid mixer, an alkali mixer, a filter, an evaporator, a condenser, a chemical pump, an acid liquor storage tank, an alkali liquor storage tank, a product tank, a solid waste tank and a water tank;
the main reactor comprises a stirring paddle, two solid sample inlets and two liquid sample inlets; the liquid sample inlet is respectively connected with the acid liquor storage tank and the chemical pump, and the material outlet is connected with the chemical pump; the acid mixer and the alkali mixer also comprise a stirring paddle, two liquid feeding holes and a material outlet; the feeding port of the acid mixer is respectively connected with the acid liquid storage tank and the chemical pump, the material outlet is connected with the chemical pump, the feeding port of the alkali mixer is respectively connected with the alkali liquid storage tank and the filter, and the material outlet is connected with the chemical pump; the filter comprises a liquid sample inlet and a liquid outlet and a solid outlet; the inlet of one filter is connected with a chemical pump, the solid outlet is connected with a main reactor, and the liquid outlet is connected with an alkali mixer; the inlet of the other filter is connected with a chemical pump line, the solid outlet is connected with a product tank, and the liquid outlet is connected with an evaporator; the middle part of the evaporator is provided with a liquid sample inlet, the top part of the evaporator is provided with a gas material outlet which is connected with the condenser, and the bottom part of the evaporator is provided with a solid material outlet which is connected with the solid waste pipe; the top of the condenser is provided with a gas material inlet, and the bottom of the condenser is provided with a liquid material outlet which is connected with the water tank; the discharge hole of the water tank is connected with a chemical pump.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113603622A (en) * | 2021-08-13 | 2021-11-05 | 暨南大学 | Method and device for preparing L-selenium-methyl selenocysteine by reducing zinc and iron |
| CN113603623A (en) * | 2021-08-13 | 2021-11-05 | 暨南大学 | Synthetic method and device of selenomethionine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2508185A1 (en) * | 1975-02-26 | 1976-09-09 | Univ California | Selenium deficiency treatment in plants and animals - lowers pH of skin |
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| DE2508185A1 (en) * | 1975-02-26 | 1976-09-09 | Univ California | Selenium deficiency treatment in plants and animals - lowers pH of skin |
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| CN105294528A (en) * | 2015-11-26 | 2016-02-03 | 成都百事兴科技实业有限公司 | Preparation method for L-selenocysteine |
| CN111004162A (en) * | 2019-12-27 | 2020-04-14 | 暨南大学 | Method and device for preparing L-selenocysteine by using sodium triacetoxyborohydride as reducing agent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113603622A (en) * | 2021-08-13 | 2021-11-05 | 暨南大学 | Method and device for preparing L-selenium-methyl selenocysteine by reducing zinc and iron |
| CN113603623A (en) * | 2021-08-13 | 2021-11-05 | 暨南大学 | Synthetic method and device of selenomethionine |
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