CN109206349A - A kind of production method of high-purity thiourea - Google Patents
A kind of production method of high-purity thiourea Download PDFInfo
- Publication number
- CN109206349A CN109206349A CN201711141587.8A CN201711141587A CN109206349A CN 109206349 A CN109206349 A CN 109206349A CN 201711141587 A CN201711141587 A CN 201711141587A CN 109206349 A CN109206349 A CN 109206349A
- Authority
- CN
- China
- Prior art keywords
- thiocarbamide
- exchange resin
- solution
- purity
- filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 114
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000012535 impurity Substances 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- 238000005342 ion exchange Methods 0.000 claims abstract description 4
- 230000005484 gravity Effects 0.000 claims description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003729 cation exchange resin Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 239000003957 anion exchange resin Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 description 10
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000004202 carbamide Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000006471 dimerization reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZRVUJXDFFKFLMG-UHFFFAOYSA-N Meloxicam Chemical compound OC=1C2=CC=CC=C2S(=O)(=O)N(C)C=1C(=O)NC1=NC=C(C)S1 ZRVUJXDFFKFLMG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- LMEKQMALGUDUQG-UHFFFAOYSA-N azathioprine Chemical compound CN1C=NC([N+]([O-])=O)=C1SC1=NC=NC2=C1NC=N2 LMEKQMALGUDUQG-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- XUFQPHANEAPEMJ-UHFFFAOYSA-N famotidine Chemical compound NC(N)=NC1=NC(CSCCC(N)=NS(N)(=O)=O)=CS1 XUFQPHANEAPEMJ-UHFFFAOYSA-N 0.000 description 1
- 229960001596 famotidine Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940073062 imuran Drugs 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229960001929 meloxicam Drugs 0.000 description 1
- GLVAUDGFNGKCSF-UHFFFAOYSA-N mercaptopurine Chemical compound S=C1NC=NC2=C1NC=N2 GLVAUDGFNGKCSF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 150000003583 thiosemicarbazides Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C335/02—Thiourea
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method using industrial thiocarbamide preparation high-purity thiocarbamide, industrial thiocarbamide is dissolved in pure water, solution ph is adjusted with ammonium hydroxide, formalin is added to be reacted, then ion exchange is carried out, organic impurities residual and impurity metal ion can be effectively removed, thiocarbamide purity is improved, meets requirement of the industries such as pharmacy, biological reagent, fine chemistry industry, chemical reagent to high-purity thiourea.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of method using industrial thiocarbamide preparation high-purity thiocarbamide.
Technical background
Sulphur arteries and veins also known as thiourea element, molecular formula are (NH2)2CS, relative molecular mass 76.12, white rectangle or needle-shaped light
Bright crystalline solid.Bitter, flammable, density 1.046, are reheated and are decomposed by 170-182 DEG C of fusing point.Decompression liter at 150-160 DEG C
China.It is dissolved in cold water, ammonium thiocyanate solution and ethyl alcohol, is practically insoluble in ether.
Currently, lime nitrogen and hydrogen sulfide gas are industrially used, the amino generated in synthesis reactor using lime nitrogen hydrolysis
Nitrile and calcium hydroxide and hydrogen sulfide gas carry out absorption synthetic reaction, are made the suspension containing thiocarbamide, solution by being filtered for multiple times,
After purification, it is concentrated into appropriate specific gravity, crystallisation by cooling, crystal centrifuge dripping after separation of solid and liquid, using drying finished product.The method
Process flow is shorter, at low cost, and most manufacturer adopts this method.Separately have the conditional enterprise in part using waste gypsum i.e.
Sulphur calcium waste residue is calcined with carbon, is leached, and leaching liquid is reacted in synthesis tank with lime nitrogen, solution through filtering, crystallization, point
From, drying obtain finished product, this process route reduces production cost, shortens process flow.Above-mentioned technique is due to by technique
Some impurity are inevitably brought in the limitation of method and raw material into the product, the calcium ion introduced such as raw material and other gold
Belong to ion, the organic impurities such as cyanamide, cyanamid dimerization, urea formed in reaction process, industrial thiocarbamide content is generally in 98.5wt%
Left and right.
Thiocarbamide can be used for producing in pharmaceuticals industry medicine intermediate ainothiazoly loximate, Meloxicam, famotidine, imidazoles this
The finings such as spit of fland, imuran, 6-MP and alkyl -5- sulfhydryl tetrazolium etc., and production thiourea dioxide, thiosemicarbazides
The raw material of chemical product.In these areas, there is higher quality requirement to thiocarbamide, it is desirable that with high content and lower miscellaneous
Matter.
CN1294124A disclose it is a kind of using general industry thiocarbamide through recrystallization, UF membrane and substep control crystallization technique system
The method of standby high-purity industrial thiocarbamide, general industry thiocarbamide is dissolved in soft water or mother liquor, thiourea solution is made, small with micro-pore diameter
In or equal to 3 microns membrane separator filtering, filtrate by adjust temperature control crystallization rate, obtain high-purity thiourea.This method
For common crystallisation, energy consumption water consume is big.
The method of purification of industry thiocarbamide disclosed in CN102584660A is using the anions and canons impurity removed in thiocarbamide respectively
Method, successively to industrial thiourea solution carry out positive and negative ion exchange, crystallization preparation high-quality thiocarbamide.
Sulfocarbamide crystallization purification technique disclosed in CN102976990A mainly uses surfactant to thiourea solution system
In impurity selectivity solubilising, reduce the crystallizing power of impurity, leave the impurity in liquid phase, to improve the purity of thiocarbamide.
Above method has preferable effect for the separation of metal ion, but has for cyanamide, cyanamid dimerization, urea etc.
Machine object impurity, separating effect are unsatisfactory.
Summary of the invention
The purpose of the present invention is to provide a kind of methods using industrial thiocarbamide preparation high-purity thiocarbamide.This method can be improved
Thiocarbamide purity reduces the content of impurity especially cyanamide, cyanamid dimerization, urea, meets pharmacy, biological reagent, fine chemistry industry, chemistry
Requirement of the industries such as reagent to high-purity thiourea.
Present invention is generally directed to influence the organic impurities of product quality residual and impurity metal ion to be handled.Wherein
To organic impurities cyanamide class main in thiourea solution, using being heated as cyanamid dimerization under ammonia catalytic condition, then it is poly- with formaldehyde
Conjunction forms oligomer precipitation, and the method being removed by filtration is handled, and can effectively remove cyanogen amine impurities, can also remove well
Remove the urea impurity in solution.For metal ion in solution impurity, using the method for ion exchange resin treatment to various gold
Belonging to ion has good result, can significantly reduce metal ion content, the production suitable for high quality thiocarbamide product.
Specific technical solution the following steps are included:
A, the polymerization reaction of impurity: industrial thiocarbamide is dissolved in pure water, and it is molten to be adjusted to the thiocarbamide that specific gravity is 1.04-1.06g/ml
Liquid, adjusting solution ph with ammonium hydroxide is 8-9, and the formalin of 0.1-2wt% of thiocarbamide amount is added, is stirred to react in 60-70 DEG C
1-10 hours, it is warming up to 70-100 DEG C of insulated and stirreds 1-10 hours；
B, ion exchange: it is 1.025-1.03g/ml that the solution after processing of step A, which is diluted to specific gravity, with the stream of 2-3BV/h
Speed passes sequentially through cation exchange resin and anion exchange resin, filtering, condensing crystallizing, dry obtained high-purity thiourea.
A further technical scheme of the invention is that the solution after the processing of step A is filtered with filter, then walked
The operation of rapid B.
In above-mentioned steps A, 70-100 DEG C during insulated and stirred 1-10 hours, are added the activity of thiocarbamide amount 0.5wt%
Charcoal can adsorb the oligomer of generation, be conducive to subsequent filter operation, also finer oligomer can be made to be adsorbed, reached more
Good removal effect.
Filter device therefor of the present invention is the polypropylene candle filter in 0.22 μm of aperture, sand core filter or stainless steel
Filter.
The model of above-mentioned cation exchange resin is preferred are as follows: 001 × 7(732), 001 × 4(734), IR-120 or IR-
118.The model of anion exchange resin is preferred are as follows: 201 × 7(717), 201 × 4(711), IRA-400 or IRA-401.
In above-mentioned steps B, before solution passes through cation exchange resin, it can also be adsorbed by macroporous absorbent resin.Macropore
Type resin model is preferred are as follows: D101, AB-8, HP-20, XAD-4 or XAD-16.
Macroporous absorbent resin, the activation of cation exchange resin and anion exchange resin and regeneration can be by well known sides
Method carries out.
The commercially available formalin that concentration is greater than 36wt% can be used in formalin of the present invention.
The present invention by adopting the above technical scheme, can effectively remove in thiocarbamide influence product quality organic impurities residual and
Impurity metal ion improves thiocarbamide purity, meets the industries such as pharmacy, biological reagent, fine chemistry industry, chemical reagent to high-purity thiourea
Requirement.
Specific embodiment:
Embodiment 1:
In 2m3Pure water 1000Kg is added in reaction kettle and is heated to 70 DEG C, is added with stirring industrial thiocarbamide 500Kg, dissolves to obtain thiocarbamide
Solution, measuring specific gravity is 1.06g/ml, and adjusting solution ph with ammonium hydroxide is 8, and 5Kg formalin is added, is stirred to react 2 in 70 DEG C
Hour, it is warming up to 90 DEG C of insulated and stirreds 2 hours, is cooled to 60 DEG C, by the polypropylene material filter core mistake in 0.22 μm of aperture of feed liquid
Filter filtering, filtrate add water 720Kg to dilute, and specific gravity 1.025g/ml is down to room temperature, passes sequentially through 732 with the flow velocity of 2BV/h
Type cation exchange resin and 717 type anion exchange resin, solution filter again, and filtrate squeezes into concentration kettle and is concentrated in vacuo to 1/
2 volumes stir lower decrease temperature crystalline, after crystallization is completed, separate crystal and mother liquor, gained crystal pure water eluted, centrifugal drying
High-purity thiourea is made in dry, 80 DEG C of dryings.
Embodiment 2:
In 2m3Pure water 1000Kg is added in reaction kettle and is heated to 60 DEG C, is added with stirring industrial thiocarbamide 430Kg, dissolves to obtain thiocarbamide
Solution, measuring specific gravity is 1.05 g/ml, and adjusting solution ph with ammonium hydroxide is 9, and 5Kg formalin and 3Kg active carbon is added, in
70 DEG C are stirred to react 2 hours, are warming up to 90 DEG C of insulated and stirreds 2 hours, are cooled to 60 DEG C, by poly- the third of 0.22 μm of aperture of feed liquid
The filtering of alkene material filter element filter, filtrate add water 600Kg to dilute, and specific gravity 1.026g/ml is down to room temperature, with the flow velocity of 3BV/h
732 type cation exchange resins and 717 type anion exchange resin are passed sequentially through, solution filters again, and filtrate squeezes into concentration kettle
It is concentrated in vacuo to 1/2 volume, lower decrease temperature crystalline is stirred, after crystallization is completed, crystal and mother liquor is separated, by gained crystal pure water
High-purity thiourea is made in elution, centrifuge dripping, 80 DEG C of dryings.
Embodiment 3:
In 2m3Pure water 1000Kg is added in reaction kettle and is heated to 70 DEG C, is added with stirring industrial thiocarbamide 450Kg, dissolves to obtain thiocarbamide
Solution, measuring specific gravity is 1.05g/ml, and adjusting solution ph with ammonium hydroxide is 8, and 5Kg formalin is added, is stirred to react 2 in 70 DEG C
Hour, it is warming up to 90 DEG C of insulated and stirreds 2 hours, filtrate adds water 700Kg to dilute, and specific gravity 1.025g/ml is down to room temperature, with
The flow velocity of 2BV/h passes sequentially through D101 type macroporous absorbent resin, 732 type cation exchange resins and 717 type anion exchange trees
Rouge, 0.22 μm of solution via hole diameter of polypropylene material candle filter filtering, filtrate squeeze into concentration kettle and are concentrated in vacuo to 1/2 body
Product stirs lower decrease temperature crystalline, after crystallization is completed, separates crystal and mother liquor, by the pure water elution of gained crystal, centrifuge dripping,
High-purity thiourea is made in 80 DEG C of dryings.
Products obtained therefrom test results in the following table:
| Industrial thiocarbamide | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Content ((NH2)2CS), % | 98.65 | 99.82 | 99.90 | 99.80 |
| Water-insoluble, % | 0.15 | 0.001 | 0.001 | 0.0015 |
| Loss on drying, % | 0.38 | 0.05 | 0.05 | 0.05 |
| Ignition residue (in terms of sulfate), % | 0.035 | 0.005 | 0.003 | 0.005 |
| Cyanamide, (ppm) | 1250 | 0.2 | 0.15 | 0.2 |
| Cyanamid dimerization, (ppm) | 565 | 0.04 | 0.05 | 0.05 |
| Urea, (ppm) | 850 | 0.2 | 0.4 | 0.3 |
| Rhodanate (in terms of CNS), % | 0.105 | 0.004 | 0.004 | 0.005 |
| Chloride (Cl), ppm | 120 | 0.5 | 0.4 | 0.8 |
| Sulfate (SO4), ppm | 52 | 0.4 | 0.4 | 0.5 |
| Phosphate (PO4), ppm | 13 | 0.2 | 0.3 | 0.2 |
| Aluminium (Al), ppm | 0.5 | 0.002 | 0.002 | 0.003 |
| Arsenic (As), ppm | 0.2 | 0.001 | 0.001 | 0.001 |
| Calcium (Ca), ppm | 0.15 | 0.0015 | 0.002 | 0.002 |
| Chromium (Cr), ppm | 0.012 | 0.001 | 0.001 | 0.001 |
| Copper (Cu), ppm | 1.2 | 0.005 | 0.004 | 0.006 |
| Iron (Fe), ppm | 2.5 | 0.05 | 0.03 | 0.05 |
| Potassium (K), ppm | 5.5 | 0.06 | 0.05 | 0.05 |
| Magnesium (Mg), ppm | 0.8 | 0.001 | 0.002 | 0.002 |
| Manganese (Mn), ppm | 0.2 | 0.001 | 0.001 | 0.003 |
| Sodium (Na), ppm | 8.5 | 0.05 | 0.10 | 0.08 |
| Nickel (Ni), ppm | 0.3 | 0.001 | 0.001 | 0.002 |
| Lead (Pb), ppm | 0.02 | 0.001 | 0.001 | 0.001 |
| Tin (Sn), ppm | 0.02 | 0.002 | 0.001 | 0.002 |
| Titanium (Ti), ppm | 0.01 | 0.002 | 0.002 | 0.002 |
| Zinc (Zn), ppm | 0.19 | 0.03 | 0.01 | 0.02 |
Claims (8)
1. a kind of production method of high-purity thiourea, which comprises the following steps:
A, the polymerization reaction of impurity: industrial thiocarbamide is dissolved in pure water, and it is molten to be adjusted to the thiocarbamide that specific gravity is 1.04-1.06g/ml
Liquid, adjusting solution ph with ammonium hydroxide is 8-9, and the formalin of 0.1-2wt% of thiocarbamide amount is added, is stirred to react in 60-70 DEG C
1-10 hours, it is warming up to 70-100 DEG C of insulated and stirreds 1-10 hours；
B, ion exchange: it is 1.025-1.03g/ml that the solution after processing of step A, which is diluted to specific gravity, with the stream of 2-3BV/h
Speed passes sequentially through cation exchange resin and anion exchange resin, filtering, condensing crystallizing, dry obtained high-purity thiourea.
2. method according to claim 1, which is characterized in that the solution after the processing of step A is filtered with filter, then
Carry out the operation of step B.
3. method according to claim 2, which is characterized in that in the step A, 70-100 DEG C insulated and stirred 1-10 hours
In the process, the active carbon of thiocarbamide amount 0.5wt% is added.
4. method according to claim 2, which is characterized in that the filter is the polypropylene filter element filtering in 0.22 μm of aperture
Device, sand core filter or stainless steel filter.
5. method according to claim 1, which is characterized in that the model of the cation exchange resin are as follows: 001 × 7
(732), 001 × 4(734), IR-120 or IR-118.
6. method according to claim 1, which is characterized in that the model of the anion exchange resin are as follows: 201 × 7
(717), 201 × 4(711), IRA-400 or IRA-401.
7. method according to claim 1, which is characterized in that in the step B, the solution passes through cation exchange resin
Before, it is adsorbed by macroporous absorbent resin.
8. method according to claim 7, which is characterized in that the macroporous ion-exchange resin model are as follows: D101, AB-8, HP-20,
XAD-4 or XAD-16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711141587.8A CN109206349B (en) | 2017-11-17 | 2017-11-17 | Production method of high-purity thiourea |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711141587.8A CN109206349B (en) | 2017-11-17 | 2017-11-17 | Production method of high-purity thiourea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109206349A true CN109206349A (en) | 2019-01-15 |
| CN109206349B CN109206349B (en) | 2020-10-02 |
Family
ID=64991952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711141587.8A Active CN109206349B (en) | 2017-11-17 | 2017-11-17 | Production method of high-purity thiourea |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109206349B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614068A (en) * | 2019-09-23 | 2019-12-27 | 天津大学 | Device and method for uniform feeding in water-soluble urea-formaldehyde resin synthesis process |
| CN110759838A (en) * | 2019-11-12 | 2020-02-07 | 山东益丰生化环保股份有限公司 | Treatment method of thiourea feed liquid |
| CN112876393A (en) * | 2021-01-19 | 2021-06-01 | 浙江工业大学 | Method for continuously synthesizing and purifying thiourea by using ammonium thiocyanate |
| CN115494174A (en) * | 2022-09-23 | 2022-12-20 | 南京瑞孚医药科技有限公司 | Method for detecting thiourea in meloxicam by high performance liquid chromatography |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294124A (en) * | 1999-10-28 | 2001-05-09 | 湖南大荣化工农药有限公司 | Process for preparing high-purity thiourea |
| CN102584660A (en) * | 2011-12-27 | 2012-07-18 | 山东益丰生化环保股份有限公司 | Method for purifying thiocarbamide |
-
2017
- 2017-11-17 CN CN201711141587.8A patent/CN109206349B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1294124A (en) * | 1999-10-28 | 2001-05-09 | 湖南大荣化工农药有限公司 | Process for preparing high-purity thiourea |
| CN102584660A (en) * | 2011-12-27 | 2012-07-18 | 山东益丰生化环保股份有限公司 | Method for purifying thiocarbamide |
Non-Patent Citations (2)
| Title |
|---|
| 潘凤荣: "《甜樱桃高产优质栽培》", 30 September 2010, 辽宁科学技术出版社 * |
| 马建中: "《皮革化学品（第二版）》", 31 March 2008, 化学工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110614068A (en) * | 2019-09-23 | 2019-12-27 | 天津大学 | Device and method for uniform feeding in water-soluble urea-formaldehyde resin synthesis process |
| CN110759838A (en) * | 2019-11-12 | 2020-02-07 | 山东益丰生化环保股份有限公司 | Treatment method of thiourea feed liquid |
| CN110759838B (en) * | 2019-11-12 | 2021-08-20 | 山东益丰生化环保股份有限公司 | Treatment method of thiourea feed liquid |
| CN112876393A (en) * | 2021-01-19 | 2021-06-01 | 浙江工业大学 | Method for continuously synthesizing and purifying thiourea by using ammonium thiocyanate |
| CN115494174A (en) * | 2022-09-23 | 2022-12-20 | 南京瑞孚医药科技有限公司 | Method for detecting thiourea in meloxicam by high performance liquid chromatography |
| CN115494174B (en) * | 2022-09-23 | 2024-03-29 | 南京瑞孚医药科技有限公司 | Method for detecting thiourea in meloxicam by high performance liquid chromatography |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109206349B (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109206349A (en) | A kind of production method of high-purity thiourea | |
| CN102963933B (en) | Preparation method of ammonium paratungstate | |
| CN102923776B (en) | Method for producing high-purity vanadium pentoxide | |
| CN103343239B (en) | Method for separating and purifying rhodium | |
| CN108622938B (en) | Method for preparing ammonium dimolybdate from molybdenum-containing solution | |
| CN112607777A (en) | Production process of ammonium molybdate | |
| CN112209441A (en) | Method for preparing high-purity vanadium pentoxide by purifying ammonium metavanadate | |
| CN113073202A (en) | Method for comprehensively treating liquid after vanadium precipitation of acidic ammonium salt in vanadium slag extraction | |
| CN112777641A (en) | Method for simultaneously preparing battery-grade manganese sulfate and feed-grade manganese sulfate | |
| CN104692461A (en) | Method for preparing high-purity powdered vanadium oxide | |
| CN102430266A (en) | Method for purifying vanadium-containing solution and method for preparing ammonium metavanadate and vanadium oxide | |
| CN114606396A (en) | Resource utilization method for limonite type laterite-nickel ore leaching solution | |
| CN114702075A (en) | Purification preparation method of manganese sulfate | |
| CN101838750A (en) | Method for performing direct acid adjusting closed cycle on ammonium paratungstate crystallization mother liquor | |
| CN110817907A (en) | Treatment system and method for purifying high-purity lithium carbonate | |
| CN112758983A (en) | Preparation method of ammonium heptamolybdate | |
| CN109534369B (en) | Membrane integrated lithium chloride preparation equipment and method thereof | |
| CN111018747A (en) | Method for refining guanidine nitrate | |
| CN103172122A (en) | Method for purifying high purity ammonium rhenate from liquid containing ammonium rhenate | |
| CN113735136B (en) | Process method for preparing potassium salt and byproduct magnesium salt by using corn soaking water | |
| CN103012115B (en) | Production process of medicinal potassium citrate | |
| CN113800566B (en) | Method for preparing ammonium molybdate from crude molybdic acid | |
| CN109748307A (en) | A method of producing High-Purity Aluminum Ammonium Sulfate | |
| CN211445070U (en) | Ammonium molybdate three-line-in-one production line | |
| CN104694769B (en) | A kind of production method of clean vanadium liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A production method of high-purity thiourea Granted publication date: 20201002 Pledgee: Shantou Bay Rural Commercial Bank Co.,Ltd. Pledgor: XILONG SCIENTIFIC Co.,Ltd. Registration number: Y2024980010255 |