CN109574893A - A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride - Google Patents
A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride Download PDFInfo
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- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 29
- XVIWVTWNQQUGQI-UHFFFAOYSA-L disodium;sulfanylidenemethanediolate Chemical compound [Na+].[Na+].[O-]C([O-])=S XVIWVTWNQQUGQI-UHFFFAOYSA-L 0.000 title claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 16
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 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 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical compound OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 238000009938 salting Methods 0.000 claims abstract description 7
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 238000010792 warming Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 7
- STAVCNDCTTVWEW-UHFFFAOYSA-N NCC[Na] Chemical compound NCC[Na] STAVCNDCTTVWEW-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 20
- 239000013078 crystal Substances 0.000 abstract description 12
- 239000011780 sodium chloride Substances 0.000 abstract description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 6
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 5
- 238000010189 synthetic method Methods 0.000 abstract description 3
- -1 2- amino-ethyl sodium sulfovinate Chemical compound 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000736199 Paeonia Species 0.000 description 2
- 235000006484 Paeonia officinalis Nutrition 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- UTTRXBOSBQFSQU-UHFFFAOYSA-N N1CC1.S Chemical compound N1CC1.S UTTRXBOSBQFSQU-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 235000019730 animal feed additive Nutrition 0.000 description 1
- 230000000767 anti-ulcer Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229960001380 cimetidine Drugs 0.000 description 1
- CCGSUNCLSOWKJO-UHFFFAOYSA-N cimetidine Chemical compound N#CNC(=N/C)\NCCSCC1=NC=N[C]1C CCGSUNCLSOWKJO-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- VMXUWOKSQNHOCA-LCYFTJDESA-N ranitidine Chemical compound [O-][N+](=O)/C=C(/NC)NCCSCC1=CC=C(CN(C)C)O1 VMXUWOKSQNHOCA-LCYFTJDESA-N 0.000 description 1
- 229960000620 ranitidine Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride, comprising the following steps: carbon disulfide and sodium sulfide solution are added in reaction kettle, are heated to reflux, reaction obtains thiocarbonic acid sodium solution；2- amino-ethyl sodium sulfovinate salting liquid or 2-chloroethyl amine HCI solution that concentration is 25%-30% are added in thiocarbonic acid sodium solution, controlled at 40-45 DEG C during dropwise addition, time for adding is 1.5h-2.5h, after half an hour is added dropwise, it is warming up to 58-62 DEG C the reaction was continued to the color of thiocarbonic acid sodium solution and thoroughly disappear；Hydrochloric acid is added to be reacted, reaction can be recycled after generating carbon disulfide condensation；Acquired solution vacuum distillation after fully reacting is concentrated, is filtered after crystallisation by cooling, gained crystal is sodium sulphate or sodium chloride, and gained filtrate is the aqueous solution of mercaptoethylamine hydrochloride；The aqueous solution of mercaptoethylamine hydrochloride is subjected to vacuum distillation until all moisture are removed, up to product mercaptoethylamine hydrochloride after cooling.The synthetic method not only simplifies step, has saved production cost, and the yield of products therefrom and purity are higher.
Description
Technical field
The present invention relates to technical field of organic synthesis, and in particular to synthesizes mercaptoethylamine hydrochloride to a kind of sodium thiocarbonate
Method.
Background technique
Mercaptoethylamine hydrochloride, also known as Mercaptamine are white crystalline powder under room temperature, and soluble easily in water.It
Also be important industrial chemicals and medicine intermediate, purposes is very extensive, cannot be only used for cosmetics, animal feed additive,
The production of complex agent also acts as the raw material for preparing anti-ulcer medicament such as ranitidine Cimetidine.
There are mainly three types of the existing methods for preparing sodium thiocarbonate conjunction mercaptoethylamine hydrochloride: 1, ethanol amine-sulfuric acid-thiophene
Oxazoline method, steps are as follows: ethanol amine and strong sulfuric acid response generate 2- amino-ethyl sulfuric ester, and 2- amino-ethyl sulfuric ester is again with two
Nitric sulfid reacts to obtain mercaptothiazoline, and last mercaptothiazoline hydrolyzes under the action of hydrochloric acid and obtains mercaptoethylamine hydrochloride.
The hydrolysis stage period of this method is longer, and usually more than 15 days, and a large amount of hydrogen sulfide gas can be released in hydrolytic process, vulcanize
Hydrogen has very strong toxicity, cannot directly be discharged, to recycle completely need to process Jing Guo multistep, improve into
This；2, ethanol amine-sulfuric acid-ethylenimine method, steps are as follows: ammonium acetate and sulfuric acid reaction obtain 2- amino-ethyl sulfuric ester, then
Ethylenimine is distilled to obtain with sodium hydroxide heat together, ethylenimine is passed through dry hydrogen sulfide gas under dehydrated alcohol environment, and occurs
Addition reaction generates mercaptoethylamine hydrochloride, and this method is complicated for operation, and the requirement in addition vulcanization hydrogen to reaction condition is extremely
Harshness, and yield is lower；3, hydrogen sulfide-aziridine method, steps are as follows: hydrogen sulfide and aziridine formula ethylene imine are stirred in methanol
Reaction is mixed, is cooled to 5 DEG C, crystallization obtains white crystal in nitrogen, is dissolved in isopropanol, sucks hydrogen chloride gas, finally again
It cools to 5 DEG C of crystallizations and obtains mercaptoethylamine hydrochloride.Although this method reaction progress time is short, raw materials used aziridine formula
The steam of ethylene imine easily causes combustion explosion after mixing with air, and reacts and need decrease temperature crystalline under nitrogen protection, right
Consersion unit it is more demanding, will correspondingly increase production cost.
Summary of the invention
The technical problem to be solved in the present invention is that it is higher and can effectively save cost to provide a kind of easy to operate, yield
The method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride.
To solve the above-mentioned problems, using following technical scheme: a kind of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride
Method, comprising the following steps:
Step 1: carbon disulfide and sodium sulfide solution are added in reaction kettle, stir and be heated to reflux, reaction obtains thio
Sodium carbonate liquor；
Step 2: the 2- amino-ethyl sodium sulfovinate salting liquid or 2-chloroethyl amine hydrochloride that concentration is 25%-30% is molten
Drop is added in the thiocarbonic acid sodium solution that step 1 is prepared, controlled at 40-45 DEG C during dropwise addition, time for adding
For 1.5h-2.5h, after half an hour is added dropwise, be warming up to 58-62 DEG C, the reaction was continued to thiocarbonic acid sodium solution color it is thorough
It disappears；
It is reacted Step 3: hydrochloric acid is added in step 2 acquired solution, temperature control is 70-85 in reaction process
DEG C, and by reaction generate carbon disulfide re-used in return step one after condenser pipe recycles, when carbon disulfide no longer
Generating is fully reacting；
Step 4: acquired solution vacuum distillation concentration after step 3 fully reacting is filtered, gained filtrate after crystallisation by cooling
For the aqueous solution of mercaptoethylamine hydrochloride；
Step 5: the aqueous solution for the mercaptoethylamine hydrochloride that step 4 obtains is evaporated under reduced pressure, all moisture are removed
Product mercaptoethylamine hydrochloride can be obtained in cooling afterwards.
The chemical equation to be reacted in step 1 is as follows:
CS2+Na2S → S=C (- SNa)2。
When step 2 be added be 2- amino-ethyl sodium sulfovinate salting liquid when, the chemical equation to be reacted is such as
Under:
S=C (- SNa)2+H2NCH2CH2OSO3Na → S=C (- SNa) (- SCH2CH2NH2)+Na2SO4, corresponding step
The solid being precipitated after crystallisation by cooling in four is sodium sulfate crystal and sodium chloride crystal.
When step 2 be added be 2-chloroethyl amine HCI solution when, the chemical equation to be reacted is as follows:
S=C (- SNa)2+ClCH2CH2NH2HCl → S=C (- SNa) (- SCH2CH2NH2)+NaCl, corresponding step
The solid being precipitated after crystallisation by cooling in four is sodium chloride crystal.
The chemical equation to be reacted in step 3 is as follows:
S=C (- SNa) (- SCH2CH2NH2)+2HCl→H2SCH2CH2NH2·HCl+NaCl+CS2↑。
Wherein, the molar ratio of carbon disulfide and vulcanized sodium is 1:1.05-1:1 in step 1, and reaction temperature is 40-45 DEG C,
Reaction time is 2-3h.
Wherein, mixing speed is 60r/min in step 1.
Wherein, the concentration of gained thiocarbonic acid sodium solution is 45%-50% in step 1.
Wherein, the temperature after heating up in step 2 is 60 DEG C.
Wherein, it is 70 DEG C that reaction, which starts to control temperature in rear 2h, in step 3, and reaction temperature is promoted to 85 DEG C after 2h
And the reaction was continued completely.
Wherein, the concentration of hydrochloric acid is 25-35% in step 3.
Further, the concentration of hydrochloric acid is 30% in step 3.
Compared to the prior art, the invention has the following advantages:
1, the method for synthesis mercaptoethylamine hydrochloride does not pollute the environment, and reacts in step 3 in the present invention two
Nitric sulfid gas is not needed by specially treated, but is made by being condensed into return in step 1 after liquid as raw material
With not only simplifying process flow, and meet environmentally protective and double requirements that are recycling.
2, the method for synthesizing mercaptoethylamine hydrochloride in the present invention not only has that easy to operate, the production cycle is shorter, to life
Produce lower, the safe and reliable advantage of requirement of equipment, and the yield of products therefrom, purity are higher, by experiments have shown that, make
It can reach 93% or more with the synthetic method total recovery in the present invention, purity can reach 95% or more.From all angles,
The synthetic method can replace existing mercaptoethylamine hydrochloride production technology completely in actual production, and obtain considerably better
Economic benefit.
Specific embodiment
Embodiment is given below so that the present invention to be specifically described, it is necessary to which indicated herein is following embodiment
It is used to further illustrate the present invention, should not be understood as limiting the scope of the invention, the ordinary skill in the field
Personnel still fall within protection scope of the present invention to some nonessential improvement of the invention made or adjustment according to this embodiment.
Embodiment 1
A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride, comprising the following steps:
It is reacted Step 1: 3000ml enamel is added with the sodium sulfide solution that 600kg concentration is 35% in 200kg carbon disulfide
In kettle, stirring is opened, slow heating reflux, control reaction temperature is 40-45 DEG C, mixing speed 60r/min, after reacting 2.5h
Obtain thiocarbonic acid sodium solution；
It is warded off Step 2: the 2- amino-ethyl sodium sulfovinate salting liquid that 860kg concentration is 25% is added drop-wise to above-mentioned 3000ml
In porcelain reaction kettle, controlled at 40-45 DEG C during dropwise addition, then time for adding 2h delays to warm 0.5h after being added dropwise
Slowly 60 DEG C are warming up to, and keep the temperature the reaction was continued, until the color (peony or isabelline) of thiocarbonic acid sodium solution
It thoroughly disappears and reaches reaction end；
Step 3: the hydrochloric acid that 660kg concentration is 30% is slowly added in reaction kettle, the carbon disulfide for reacting generation passes through
The reaction raw materials that can be used as in step 1 after condensing recovery re-use, and reaction temperature early period control is 70 DEG C, time for adding control
It is made as 2h, after being added dropwise, is to slowly warm up to 85 DEG C, the i.e. fully reacting when not having carbon disulfide to steam in kettle；
Step 4: by acquired solution vacuum distillation concentration after step 3 fully reacting, when liquor capacity is reduced to about in kettle
After 800L, sodium sulfate crystal and sodium chloride crystal is precipitated in cooling down, and sodium sulfate crystal and chlorination is then removed by filtration
Sodium crystal, residual filtrate are the aqueous solution of mercaptoethylamine hydrochloride；
Step 5: the aqueous solution for the mercaptoethylamine hydrochloride that step 4 is obtained carries out vacuum distillation until removing all water
Point, it is 95.1% through detection purity, total recovery is about 93.03% up to solid mercaptoethylamine hydrochloride 570kg after cooling.
Embodiment 2
A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride, comprising the following steps:
It is reacted Step 1: 3000ml enamel is added with the sodium sulfide solution that 600kg concentration is 35% in 200kg carbon disulfide
In kettle reaction kettle, stirring, slow heating reflux are opened, control reaction temperature is 40-45 DEG C, mixing speed 60r/min, reaction
Thiocarbonic acid sodium solution is obtained after 2.5h；
It is reacted Step 2: the 2-chloroethyl amine HCI solution that 613kg concentration is 25% is added drop-wise to above-mentioned 3000ml enamel
In kettle, controlled at 40-45 DEG C, time for adding 2h during dropwise addition, to warm 0.5h after being added dropwise, then slowly heating
It to 60 DEG C, and keeps the temperature the reaction was continued, until the color (peony or isabelline) of thiocarbonic acid sodium solution thoroughly disappears
It loses and reaches reaction end；
Step 3: the hydrochloric acid that 660kg concentration is 30% is slowly added in reaction kettle, the carbon disulfide for reacting generation passes through
The reaction raw materials that can be used as in step 1 after condensing recovery re-use, and reaction temperature early period control is 70 DEG C, time for adding control
It is made as 2h, after being added dropwise, is to slowly warm up to 85 DEG C, the i.e. fully reacting when not having carbon disulfide to steam in kettle；
Step 4: by acquired solution vacuum distillation concentration after step 3 fully reacting, when liquor capacity is reduced to about in kettle
After 800L, then sodium chloride crystal is removed by filtration in cooling down precipitated sodium chloride crystal, residual filtrate is mercaptoethylmaine
The aqueous solution of hydrochloride；
Step 5: the aqueous solution for the mercaptoethylamine hydrochloride that step 4 is obtained carries out vacuum distillation until removing all water
Point, it is 95.05% through detection purity, total recovery is about 93.27% up to solid mercaptoethylamine hydrochloride 575kg after cooling.
It will be apparent to those skilled in the art embodiment 1 enumerated above and embodiment 2 respectively correspond step
The case where 2- amino-ethyl sodium sulfovinate salting liquid and 2-chloroethyl amine HCI solution are added in two.In addition, will step in step 3
The S=C (- SNa) (- SCH reacted in rapid two2CH2NH2) and the mercaptoethylmaine hydrochloric acid that reacts of certain density hydrochloric acid
Salting liquid, there is also sodium sulphate and sodium chloride that reaction generates in the mercaptoethylamine hydrochloride solution in embodiment 1 at this time, implement
There is also the sodium chloride that reaction generates in mercaptoethylamine hydrochloride solution in example 2, and mercaptoethylamine hydrochloride in water molten
Solution degree is very big, can reach 300g/100g water, and cooling down is crystallized in step 4, can make the pair of the overwhelming majority
Product is precipitated in the form of crystal, to improve the purity of final products therefrom solid mercaptoethylamine hydrochloride.
In addition, those skilled in the art is understood that the control of the dosage and concentration, heating temperature of each raw material in the present invention
System and other reaction condition parameters have larger impact for yield, temperature control, dropwise addition during being added dropwise in step 2
Heating is conducive to sodium thiocarbonate fully reacting all in solution in half an hour after complete, and S=C (- SNa) in step 3 (-
SCH2CH2NH2) and the temperature control of hydrochloric acid reaction can also effectively facilitate the progress of reaction, factors above, which interacts, simultaneously finally to be mentioned
The high yield of products therefrom solid mercaptoethylamine hydrochloride.
Claims (8)
1. a kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride, it is characterised in that: the following steps are included:
Step 1: carbon disulfide and sodium sulfide solution are added in reaction kettle, stir and be heated to reflux, reaction obtains thiocarbonic acid
Sodium solution；
Step 2: the 2- amino-ethyl sodium sulfovinate salting liquid or 2-chloroethyl amine HCI solution that concentration is 25%-30% are dripped
It is added in the thiocarbonic acid sodium solution that step 1 is prepared, controlled at 40-45 DEG C during dropwise addition, time for adding is
1.5h-2.5h after half an hour is added dropwise, is warming up to 58-62 DEG C, and the reaction was continued thoroughly disappears to the color of thiocarbonic acid sodium solution
It loses；
It is reacted Step 3: hydrochloric acid is added in step 2 acquired solution, temperature control is 70-85 DEG C in reaction process, and
The carbon disulfide that reaction generates is re-used in return step one after condenser pipe recycles, when carbon disulfide does not regenerate i.e.
Fully reacting；
Step 4: acquired solution vacuum distillation concentration after step 3 fully reacting is filtered, gained filtrate is mercapto after crystallisation by cooling
The aqueous solution of base ethylamine hydrochloride；
Step 5: the aqueous solution for the mercaptoethylamine hydrochloride that step 4 obtains is evaporated under reduced pressure, remove cold after all moisture
But product mercaptoethylamine hydrochloride can be obtained.
2. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 1, it is characterised in that: step 1
The molar ratio of middle carbon disulfide and vulcanized sodium is 1:1.05-1:1, and reaction temperature is 40-45 DEG C, reaction time 2-3h.
3. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 2, it is characterised in that: step 1
Middle mixing speed is 60r/min.
4. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 1, it is characterised in that: step 1
The concentration of middle gained thiocarbonic acid sodium solution is 45%-50%.
5. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 1, it is characterised in that: step 2
Temperature after middle heating is 60 DEG C.
6. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 1-5, feature exist
In: it is 70 DEG C that reaction, which starts to control temperature in rear 2h, in step 3, and reaction temperature is promoted to 85 DEG C after 2h and the reaction was continued
Completely.
7. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 1, it is characterised in that: step 3
The concentration of middle hydrochloric acid is 25-35%.
8. the method for sodium thiocarbonate synthesis mercaptoethylamine hydrochloride according to claim 7, it is characterised in that: step 3
The concentration of middle hydrochloric acid is 30%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110818602A (en) * | 2019-11-27 | 2020-02-21 | 衡阳丰联精细化工有限公司 | Method for preparing high-purity cysteamine hydrochloride |
| CN110845375A (en) * | 2019-11-27 | 2020-02-28 | 衡阳丰联精细化工有限公司 | Method for preparing cysteamine hydrochloride |
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| CN110818602A (en) * | 2019-11-27 | 2020-02-21 | 衡阳丰联精细化工有限公司 | Method for preparing high-purity cysteamine hydrochloride |
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