CN110003068A - A kind of method that one-step method prepares thiocarbamide - Google Patents
A kind of method that one-step method prepares thiocarbamide Download PDFInfo
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- CN110003068A CN110003068A CN201910423756.XA CN201910423756A CN110003068A CN 110003068 A CN110003068 A CN 110003068A CN 201910423756 A CN201910423756 A CN 201910423756A CN 110003068 A CN110003068 A CN 110003068A
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 77
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000004202 carbamide Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 8
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- CFHGBZLNZZVTAY-UHFFFAOYSA-N lawesson's reagent Chemical compound C1=CC(OC)=CC=C1P1(=S)SP(=S)(C=2C=CC(OC)=CC=2)S1 CFHGBZLNZZVTAY-UHFFFAOYSA-N 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 43
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000006227 byproduct Substances 0.000 abstract description 9
- 239000011261 inert gas Substances 0.000 abstract description 3
- 239000011575 calcium Substances 0.000 description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 17
- 229910052791 calcium Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 13
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- MYFXBBAEXORJNB-UHFFFAOYSA-N calcium cyanamide Chemical compound [Ca+2].[N-]=C=[N-] MYFXBBAEXORJNB-UHFFFAOYSA-N 0.000 description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 10
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- STRTXDFFNXSZQB-UHFFFAOYSA-N calcium;cyanamide Chemical compound [Ca+2].NC#N STRTXDFFNXSZQB-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 7
- JLCRXCPXQLBSEM-UHFFFAOYSA-N calcium diisocyanate Chemical compound [Ca++].[N-]=C=O.[N-]=C=O JLCRXCPXQLBSEM-UHFFFAOYSA-N 0.000 description 7
- 239000000920 calcium hydroxide Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000005997 Calcium carbide Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- -1 amine salt Chemical class 0.000 description 5
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- KKZBGEAWRXFNSW-UHFFFAOYSA-N (cyanoamino)urea Chemical compound NC(=O)NNC#N KKZBGEAWRXFNSW-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013558 reference substance Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- NMOJAXCSURVGEY-UHFFFAOYSA-N N#CC#N.[S] Chemical compound N#CC#N.[S] NMOJAXCSURVGEY-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- YNNGZCVDIREDDK-UHFFFAOYSA-N aminocarbamodithioic acid Chemical compound NNC(S)=S YNNGZCVDIREDDK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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 relates to the preparation method of thiocarbamide, a kind of method for preparing thiocarbamide more specifically to one-step method, it is intended to solve when prior art preparation thiocarbamide that preparation process is complicated, by-product is more, yield is low and technical problem at high cost.The method that the one-step method prepares thiocarbamide is that urea and thio reagents are added in solvent, is reacted 2~5 hours under inert gas protection, up to product after drying.The thiocarbamide yield that preparation method according to the invention obtains can achieve 78% or more, and this preparation process is simple, product yield is high, reaction condition is mild.
Description
Technical field
The present invention relates to the preparation method of thiocarbamide, a kind of method for preparing thiocarbamide more specifically to one-step method.
Background technique
Thiocarbamide synthetic method mainly has lime nitrogen method, urea-lime nitrogen method, cyanamide method, urea-cyanamide method, two sulphur
Change the process routes such as carbon method, is the method that multistep prepares thiocarbamide.
(1) lime nitrogen method prepares thiocarbamide
Lime nitrogen method is traditional one of the method for China's synthesizing thiourea, in the early 1990s the phase, Ju Hua calcium carbide company, Zhejiang Province
Special research of technique group has been set up, has been proved by various researchs, medium-sized time of up to ten thousand tons of annual output of final design
Converter, and be constructed and put into operation, only trial production once just achieves success.The process flow of this method is first to go out carbon with lime production
Change calcium (CaC2) calcirm-fluoride (CaF) of certain mass is added as catalyst, fresh foundry returns is incorporated after they are ground,
It is blown into nitriding furnace with spreading mouth, it is ensured that gas phase is higher than 800 DEG C in furnace, and the material of positive furnace and interior furnace and 450 DEG C of nitrogen is enabled to carry out
Nitridation reaction.It needs to preheat before the reaction, the temperature of nitrogen is made to reach 450 DEG C, using this partial heat heat, make that material is added
Temperature reach 900-1200 DEG C.The material in this temperature range is maintained to be melt into block and enter lower single order by gravitational settling
Section, next stage preheat and are water-cooled using nitrogen, discharging when gradually cooling has reached 300 DEG C or less.Object after coming out of the stove
Material is again with mortar grinder at powdered lime nitrogen finished product.This method has used sedimentation oven process to be produced first with carbonization
Calcium prepares lime nitrogen solid: its key reaction equation is as follows.
Calcium sulfhydrate is made with milk of lime again.
Ca(OH)2+2H2S→Ca(HS)2+2H2O
Lime nitrogen and calcium sulfhydrate are finally mixed to prepare thiocarbamide.
The process flow is to prepare lime nitrogen, and need first to go to prepare calcium carbide first, calcium carbide continue to prepare again lime nitrogen this
Two processes, operation equipment is more complicated in reaction process, contains more free state calcium carbide in the product.Because calcium carbide and
Two kinds of substances of lime nitrogen belong to high energy losses, seriously polluted product, this energy that this method production thiocarbamide is paid
Source higher cost, environmental cost is larger, and most producer has eliminated this method.
(2) urea-lime nitrogen method prepares thiocarbamide
Utilize urea and calcium oxide (CaO), calcium hydroxide (Ca (OH)2) or calcium carbonate (CaCO3) three kinds of calcium containing oxidation
Object is closed, nitrolim is first generated, calcium cyanate is calcined to obtain nitrolim, obtains sulphur using hydrogen sulfide and calcium hydroxide reaction and hydrogenates
Then calcium carries out reaction with nitrolim and calcium sulfhydrate and generates thiocarbamide, the method that obtained product recycles freezing and crystallizing obtains
To the thiocarbamide of purification.Cyanogen is prepared using urea and containing the oxygenatedchemicals of calcium, such as calcium oxide, calcium hydroxide or calcium carbonate reaction
The reaction of sour calcium is as shown in following equation.In urea-lime nitrogen method production thiocarbamide technical process, urea and quick lime are closed
It is calcined to obtain nitrolim this two step at calcium cyanate and calcium cyanate and requires relatively high temperature.
Firstly, a certain amount of urea is put into heating in reactor, the powder that addition was selected with sieve after it melts
Broken blocky calcium oxide, calcium hydroxide or calcium carbonate is put by the feed ratio that the oxide mol ratio of urea and calcium is 2.5-3.0
Fragment, stirring, reacts 1.0h at 160~400 DEG C, and calcium cyanate can be made in cooling, and the product that this single step reaction generates removes
Gas entirely other than calcium cyanate, can with reaction carry out leave reaction system, 600~900 DEG C at a temperature of, grinding
The calcium cyanate after grinding is put into tube furnace by calcium cyanate (previous step is made) under conditions of nitrogen makees reaction protection gas afterwards,
Reaction carries out 1.5h, cooling, finally obtains nitrolim.
The preparation of calcium sulfhydrate solution, it is desirable that be passed through hydrogen sulfide gas in lime milk solution, agitating solution and cooling makes
Stopping reaction just obtaining calcium sulfhydrate after it becomes celadon.
Ca(OH)2+2H2S→Ca(HS)2+2H2O
Nitrolim and calcium sulfhydrate are added in reactor, and according to the molar ratio of nitrolim and calcium sulfhydrate 1:1
It is reacted, first calcium sulfhydrate is put into reactor, after reaction temperature reaches 50~60 DEG C, then the nitrolim of handle is put
It is stirred after entering to reactor, reacts one hour, filtered after being cooled to room temperature, in crystallisation by cooling when temperature is 75~80 DEG C
Filtrate is added in device, temperature control is freezed, then obtained crystal solution is centrifuged under crystallization, finally crystal is dried
Thiocarbamide finished product is obtained after dry.
The method of urea and lime nitrogen thiocarbamide, although being reduced compared to traditional method for preparing thiocarbamide with lime nitrogen
Pollution, but solubility is small in water for the by-product calcium hydroxide generated during hydrogen sulfide absorption, is eventually reacting
In kettle in thick and agglomerate, the continuation of reaction is made be restricted, which prepares calcium sulfhydrate using hydrogen sulfide,
Hydrogen sulfide waste gas is largely consumed, this handles a large amount of exhaust gas hydrogen sulfide problem of petroleum chemical enterprise, improves production ring
Border and living environment, and it absorbs exhaust gas hydrogen sulfide and removes polluting and without generating new exhaust emission to environment
Object has been accomplished to turn waste into wealth, has prepared thiocarbamide.But the method prepares the solid slag generated when thiocarbamide and whole process and only generates less
The cyanamide method for measuring soluble amine salt waste residue does not solve pollution problem fundamentally, and produces higher cost, and profit margin is small.
(3) cyanamide method prepares thiocarbamide
Cyanamide method is to generate H with ammonia and carbon dioxide reaction2CN2, H2CN2Again with H2S reaction generates thiocarbamide.
Since the inertia of carbon dioxide causes reaction to be difficult to occur, yield does not exceed 30%, causes reaction yield low, at
This height.
(4) urea-cyanamide method synthesizing thiourea
Urea-cyanamide method is to be dehydrated atmospheric-pressure urea to generate cyanamide H2CN2, further utilize cyanamide and vulcanization
Hydrogen synthesizing thiourea and by-product sodium hydroxide, hydrogen sulfide gas is passed into the sodium hydroxide of generation and converts sodium hydroxide to
Vulcanized sodium, the vulcanized sodium of generation can participate in reacting.
This method is first to be dehydrated atmospheric-pressure urea to generate cyanamide H2CN2, the H of generation2CN2Further reacted with hydrogen sulfide
Thiocarbamide is made；Urea may generate different thermal decomposition products at different temperatures, with the raising of reaction temperature, at temperature
When 130 DEG C -180 DEG C, biuret and ammonia may be generated.As reaction continues, when temperature continues to be increased to 180 DEG C
When above, isocyanic acid and cyanuric acid may be generated, when continuing heating makes temperature be in 190 DEG C -220 DEG C, may be generated
Double fleshes, peptamine and melamine；And when temperature is 250 DEG C -400 DEG C, cyanuric acid and melamine may be generated.Work as temperature
Miller amine is had when degree is more than 400 DEG C and Mi Bai amine generates.When reacting progress, heating is rapidly performed by avoid life
At these by-products, so system must supply enough heats.Urea makees catalyst using molecular sieve and be dehydrated under normal pressure,
In ammonia atmosphere, synthesis cyanamide is dehydrated in urea under the reaction condition of regular hour, temperature etc..Then at concentrated ammonia solution
It is middle to carry out reacting obtained thiocarbamide, during the reaction, urea in 50 DEG C or so in temperature with hydrogen sulfide and the cyanamide of generation
Head step conversion ratio can reach 80%, and cyanamide has the selectivity greater than 37%, generate the byproduct of only 1.2%-2%, this
The result is that being sieved derived from catalyst molecule.Ethyl acetate cyanamide solution extracted is added in concentrated ammonia solution, by stink damp
It is passed into wherein in body, and adequately stirs, obtain a large amount of crystal thiocarbamide.It can occur in the reaction process a large amount of secondary anti-
It answers, general yield is no more than 32%, and reaction yield is low.
(5) carbon disulfide method prepares thiocarbamide
Carbon disulfide method prepares ammonium dithiocarbamate using carbon disulfide and ammonia as raw material, and then is decomposed into sulphur cyanogen
Sour ammonium, ammonium thiocyanate isomery generate thiocarbamide.
This process by-product hydrogen sulfide.The main reason for highest yield of this technique of document report is 11.5%, and yield is low
It is ammonium thiocyanate isomerization.Since intermediate ammonium thiocyanate and product thiocarbamide are isomer, physics, chemical property are non-
It is often close, it there is no the method for efficiently separating at present.
Currently, it is complicated using there are still preparation process when prior art preparation thiocarbamide, by-product is more, yield is low and cost
The problems such as high.
Summary of the invention
Present invention aim to address the complexity of thiocarbamide preparation process in the prior art, the problem that by-product is more, yield is low, mention
A kind of method for preparing thiocarbamide for one-step method.
To achieve the purpose of the present invention, the present invention provides technical solutions below:
Urea and thio reagents are added in tetrahydrofuran a kind of method that one-step method prepares thiocarbamide, protect in inert gas
The lower reaction of shield 2~5 hours, up to product after drying.
Further, the mass ratio of the urea and thio reagents is 3:1~1:1.
Further, the temperature of the reaction is 60~100 DEG C.
Further, the temperature of the reaction is 70~80 DEG C.
Further, the solvent is the mixed of one or more of benzene, tetrahydrofuran, ethyl alcohol, hexamethylene and petroleum ether
It closes.
Further, every 1g urea uses the solvent of 1~40mL.
Further, the thio reagents are one or more of lawesson reagent, tetraphosphorus decasulfide and phosphorus pentasulfide
Mixing.
Compared with prior art, the invention has the benefit that
1. the method that one-step method of the invention prepares thiocarbamide is obtained using urea and thio reagents as raw material by single step reaction
Thiocarbamide, the process flow of reaction is simple, side reaction is few.
2. the method that one-step method of the invention prepares thiocarbamide, whole process carries out under inert gas protection, reaction temperature is suitable for,
Reaction time is short, and reaction process is easily controllable, at low cost.
3. the method that one-step method of the invention prepares thiocarbamide, obtained thiocarbamide yield can achieve 78% or more, and product is received
Rate improves a lot.
Detailed description of the invention
Technical solution of the present invention is described in further detail with reference to the accompanying drawing, but does not constitute and of the invention is appointed
What is limited.
Fig. 1 is the infrared spectrogram of thiocarbamide product of the present invention；
Fig. 2 is the XRD analysis comparison diagram of thiocarbamide product of the present invention and thiocarbamide reference substance；
Fig. 3 is the thermogravimetric analysis comparison diagram of thiocarbamide product of the present invention and thiocarbamide reference substance.
Specific embodiment
Embodiment 1
Phosphorus pentasulfide and urea are added by the quality proportioning of 2.5:1 equipped with tetrahydrofuran (the corresponding use of 1g urea
30mL tetrahydrofuran) three-necked flask in be condensed back, and three-necked flask is placed in heat in water-bath and is reacted, bath temperature sets
It is set to 70 DEG C, reacts under nitrogen protection, stops experiment after reacting and reaching 4.5h, the transferred product of collection is used into beaker
Baking oven dry out solvent simultaneously obtains product.Measuring product yield is 77.15%.
The reaction equation of phosphorus pentasulfide and urea is as follows:
Phosphorus pentasulfide isomerization is generated containing there are four the substance of phosphorus sulphur double bond structure (P=S) first, and the substance is again into one
Step is changed into the ion for having positive and negative charge, and necleophilic reaction occurs with urea, forms unstable quaternary transition state, and finally convert
For stable thiocarbamide.
Embodiment 2
By phosphorus pentasulfide and urea, by the quality proportioning addition of 2:1, equipped with tetrahydrofuran, (1g urea is corresponding to use 25mL
Tetrahydrofuran) three-necked flask in be condensed back, three-necked flask is placed in heat in water-bath and is reacted, bath temperature is set as 80
DEG C, it reacts under nitrogen protection, stops experiment after reacting and reaching 4h, the transferred product of collection is dried into beaker with baking oven
Solvent simultaneously obtains product.Measuring product yield is 78.27%.Reaction mechanism is same as Example 1.
Embodiment 3
By lawesson reagent and urea, by the quality proportioning addition of 3:1, equipped with tetrahydrofuran, (1g urea is corresponding to use 40mL tetra-
Hydrogen furans) three-necked flask in be condensed back, and three-necked flask is placed in heat in water-bath and is reacted, bath temperature is set as
It 100 DEG C, reacts under nitrogen protection, stops experiment after reacting and reaching 3.7h, by the transferred product of collection into beaker with baking
Case dry out solvent simultaneously obtains product.Measuring product yield is 75.69%.
The reaction equation of lawesson reagent and urea is such as:
Lawesson reagent is heated to be decomposed into two moleculesUrea is typical amide structure,
Containing carbonyl, C atom carries part positive electricity core, and O atom carries part negative electricity core, it may occur that necleophilic reaction, the sulphur of lawesson reagent
The carbonium ion of anion attack urea, the phosphorus cation of lawesson reagent and the negative oxygen ion of urea are closed to form C, O, P, S tetra-
Member ring transition state.Quaternary transition rings are unstable, the electron transfer of phosphorus sulfide linkage to phosphorus oxygen key, at thio phosphorus ylide, while carbon oxygen
Singly-bound is broken, and double bond is closed between carbon-sulfur bond and forms thiocarbamide.
In order to further prove the structure of product, the thiocarbamide product that embodiment 3 obtains is detected:
(1) IR Characterization
Sample tabletting is taken, Fourier transform infrared spectroscopy (FT-IR) detection is carried out, it is as shown in Figure 1 to measure spectrogram.Infrared
Spectrum 4000cm-1~400cm-1It can be seen that 3429cm-1, 3216cm-1, 1081cm-1And 1190cm-1There is characteristic absorption peak at place,
In 3429cm-1To 3216cm-1Between peak be primary amine characteristic absorption peak, in 1081cm-1-1190cm-1Between peak be C=S
Characteristic absorption peak, 1503cm-1Place is the characteristic absorption peak of C-N.
(2) X-ray diffraction characterizes
Thiocarbamide product and standard sample are characterized.As shown in Fig. 2, figure a indicates standard thiocarbamide sample XRD spectrum, b is schemed
Indicate thiocarbamide product X RD map.From the graph it can be found that the diffraction peak of standard specimen is in 20 in Plays thiocarbamide sample XRD spectrum
DEG C, 21 DEG C, 23 DEG C, 26 DEG C, 30 DEG C, 32 DEG C, 35 DEG C and 36 DEG C, and these diffraction maximums are also deposited in the XRD spectra of thiocarbamide product
Illustrating that the substance is thiocarbamide.It there are also some small peaks is some impurity contained in experimental product thiocarbamide in product map.
(3) TGA thermogravimetric characterizes
Thiocarbamide product and thiocarbamide standard sample is taken to measure thermogravimetric, the thermogravimetric curve of product at a temperature of measuring from 30 to 800,
As shown in Figure 3.A is the standard sample of thiocarbamide, and b is the TGA curve of product, can be divided into three in the thermogravimetric curve of thiocarbamide standard specimen
Stage is temperature respectively lower than 175 DEG C, and temperature is between 175 DEG C -250 DEG C and temperature is higher than 250 DEG C.Temperature is lower than 175 DEG C,
Belong to the molten condition of thiocarbamide, for this process with the isomerization of thiocarbamide, some tautomerizes to ammonium thiocyanate.When temperature rises to
At 175 DEG C -250 DEG C, the weight loss rate of thiocarbamide is maximum at this time, generates with gas, illustrates that thiocarbamide has decomposed.Temperature is higher than
250 DEG C, significant reaction is slack-off, and isomerization product and decomposition product resolve into arc substance.And the thermogravimetric curve of product is also classified into
Three phases are less than 150 DEG C, 150 DEG C -230 DEG C, are higher than 230 DEG C of three parts, and two lines are similar in preceding two sections of variation tendencies,
Then product main component is thiocarbamide.And curve slowly reduces after 230, the nubbin that should be by-product lawesson reagent of reduction
The guanidine substance that the ammonium thiocyanate and product that isomerization generates resolve into.
Pass through FTIR spectrum (FI-IR) characterization, X-ray diffraction (XRD) characterization and heat carried out to thiocarbamide product
Weight analysis (TGA) characterization the result shows that, synthesized substance be target product thiocarbamide.The research process flow is short, product yield
It is higher, reaction condition is mild, research achievement be thiocarbamide product industrialized production lay a good foundation.
The above is some embodiments of the invention, is not restricted to the present invention.It will be understood by those skilled in the art that
The several improvements and modifications made without departing from the principle of the present invention, also should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of method that one-step method prepares thiocarbamide, which is characterized in that urea and thio reagents are added in solvent, in indifferent gas
The lower reaction of body protection 2~5 hours, up to product after drying.
2. the method that one-step method described in claim 1 prepares thiocarbamide, which is characterized in that the quality of the urea and thio reagents
Than for 3:1~1:1.
3. the method that one-step method of any of claims 1 or 2 prepares thiocarbamide, which is characterized in that the temperature of the reaction be 60~
100℃。
4. the method that one-step method according to claim 3 prepares thiocarbamide, which is characterized in that the temperature of the reaction be 70~
80℃。
5. the method that one-step method described in claim 1 prepares thiocarbamide, which is characterized in that the solvent is benzene, tetrahydrofuran, second
The mixing of one or more of alcohol, hexamethylene and petroleum ether.
6. the method that one-step method described in claim 1 or 5 prepares thiocarbamide, which is characterized in that every 1g urea uses 1~40mL's
Solvent.
7. the method that one-step method described in claim 1 prepares thiocarbamide, which is characterized in that the thio reagents be lawesson reagent,
The mixing of one or more of tetraphosphorus decasulfide and phosphorus pentasulfide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343060A (en) * | 2019-08-27 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of synthetic method of thiocarbamide |
| CN110724079A (en) * | 2019-11-07 | 2020-01-24 | 山东益丰生化环保股份有限公司 | Method for synthesizing thiourea by using petrochemical waste gas |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844521A (en) * | 2014-02-13 | 2015-08-19 | 成都伊诺达博医药科技有限公司 | Novel method for compounding medicament of Enzalutamide for resisting prostate cancer |
| CN107903199A (en) * | 2017-11-23 | 2018-04-13 | 黄河三角洲京博化工研究院有限公司 | A kind of technique for preparing thiocarbamide |
-
2019
- 2019-05-21 CN CN201910423756.XA patent/CN110003068A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104844521A (en) * | 2014-02-13 | 2015-08-19 | 成都伊诺达博医药科技有限公司 | Novel method for compounding medicament of Enzalutamide for resisting prostate cancer |
| CN107903199A (en) * | 2017-11-23 | 2018-04-13 | 黄河三角洲京博化工研究院有限公司 | A kind of technique for preparing thiocarbamide |
Non-Patent Citations (1)
| Title |
|---|
| MANOJ MANICKAM ET AL: ""Exploration of flexible phenylpropylurea scaffold as novel cardiac myosin activators for the treatment of systolic heart failure", 《EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343060A (en) * | 2019-08-27 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of synthetic method of thiocarbamide |
| CN110724079A (en) * | 2019-11-07 | 2020-01-24 | 山东益丰生化环保股份有限公司 | Method for synthesizing thiourea by using petrochemical waste gas |
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