CN112661126B - Preparation method of solid hydroxylamine hydrochloride - Google Patents
Preparation method of solid hydroxylamine hydrochloride Download PDFInfo
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- CN112661126B CN112661126B CN202110004968.1A CN202110004968A CN112661126B CN 112661126 B CN112661126 B CN 112661126B CN 202110004968 A CN202110004968 A CN 202110004968A CN 112661126 B CN112661126 B CN 112661126B
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- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000007787 solid Substances 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000007864 aqueous solution Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- CDCMMFMDDMEKSC-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine;hydrochloride Chemical compound Cl.CCC(C)=NO CDCMMFMDDMEKSC-UHFFFAOYSA-N 0.000 claims abstract description 24
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000000746 purification Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000000066 reactive distillation Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 239000003463 adsorbent Substances 0.000 claims description 29
- 229910021645 metal ion Inorganic materials 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 20
- -1 propyl propylene disulfide Chemical compound 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000003707 silyl modified polymer Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- IBWXKMBLEOLOLY-UHFFFAOYSA-N dimethoxy(prop-2-enyl)silicon Chemical compound CO[Si](OC)CC=C IBWXKMBLEOLOLY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 3
- JWVTWJNGILGLAT-UHFFFAOYSA-N 1-ethenyl-4-fluorobenzene Chemical compound FC1=CC=C(C=C)C=C1 JWVTWJNGILGLAT-UHFFFAOYSA-N 0.000 claims description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- GULYEDQJRBYHJJ-UHFFFAOYSA-N [SiH4].CC=CC1=CC=CC=C1 Chemical compound [SiH4].CC=CC1=CC=CC=C1 GULYEDQJRBYHJJ-UHFFFAOYSA-N 0.000 claims description 3
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 claims description 3
- NAKOELLGRBLZOF-UHFFFAOYSA-N phenoxybenzene;pyrrole-2,5-dione Chemical compound O=C1NC(=O)C=C1.O=C1NC(=O)C=C1.C=1C=CC=CC=1OC1=CC=CC=C1 NAKOELLGRBLZOF-UHFFFAOYSA-N 0.000 claims description 3
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 3
- OZFIGURLAJSLIR-UHFFFAOYSA-N 1-ethenyl-2h-pyridine Chemical compound C=CN1CC=CC=C1 OZFIGURLAJSLIR-UHFFFAOYSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052742 iron Inorganic materials 0.000 abstract description 14
- 239000000243 solution Substances 0.000 abstract description 8
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229960005404 sulfamethoxazole Drugs 0.000 description 2
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 2
- 150000005672 tetraenes Chemical class 0.000 description 2
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 1
- NFPLJTNXOKFJRO-UHFFFAOYSA-N 1-ethenylpyridin-2-one Chemical compound C=CN1C=CC=CC1=O NFPLJTNXOKFJRO-UHFFFAOYSA-N 0.000 description 1
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- PGBVLOMZZHYJFP-UHFFFAOYSA-N 3-methyldithietane Chemical compound CC1CSS1 PGBVLOMZZHYJFP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229960001330 hydroxycarbamide Drugs 0.000 description 1
- UEKZEZKZACYYRQ-UHFFFAOYSA-N hydroxylamine iron hydrochloride Chemical compound [Fe].NO.Cl UEKZEZKZACYYRQ-UHFFFAOYSA-N 0.000 description 1
- BMMNWPYKMOFBBE-UHFFFAOYSA-N hydroxylamine;perchloric acid Chemical compound ON.OCl(=O)(=O)=O BMMNWPYKMOFBBE-UHFFFAOYSA-N 0.000 description 1
- 229960001680 ibuprofen Drugs 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of solid hydroxylamine hydrochloride, which comprises the following steps: step one, raw material purification: adding 50-60% butanone oxime hydrochloride aqueous solution raw material into a reaction kettle, standing for 30-90min, and layering to obtain siliconSeparating the oil phase layer from the silicic acid layer for recovery to obtain a water phase layer, and filtering the water phase layer by a filter to remove a small amount of silicic acid impurities to obtain a pure butanone oxime hydrochloride aqueous solution; step two, reactive distillation: obtaining hydroxylamine hydrochloride water solution; step three, purifying the product, adding the product into a centrifuge for centrifugation at the rotation speed of 8000-10000r/min, further removing water, and finally passing the product through a fluidized bed at 70-80 DEG CoAnd C, drying to obtain solid hydroxylamine hydrochloride. The solid hydroxylamine hydrochloride obtained by the method has high yield, high purity and low iron ion content.
Description
Technical Field
The invention relates to the field of chemical industry, and particularly relates to a preparation method of solid hydroxylamine hydrochloride.
Background
The solid hydroxylamine hydrochloride has wide application in the fields of medicine, pesticide and analytical chemistry. It is intermediate of sulfamethoxazole (S.M.Z, compound sulfamethoxazole), VB6, VB12, semi-synthetic penicillin, ibuprofen, furan drugs, anticancer drugs (hydroxyurea) and the like, intermediate of novel nitrile synthetic perfumes such as citranitrile, jasmonitrile and the like, intermediate of hydroxylamine perchlorate, important intermediate in synthesizing products such as pesticide methomyl and the like, and intermediate for preparing oxime and antioxidant.
The prior four techniques are mature, but have the problems of high cost and a large amount of byproducts, wherein the concentration of iron ions in the hydroxylamine hydrochloride is too high, so that the application of the hydroxylamine hydrochloride is influenced.
Cn201710541998.x a process for preparing hydroxylamine hydrochloride, in particular a process for preparing hydroxylamine hydrochloride using hydrogen peroxide and ammonium chloride, comprising the steps of: firstly catalyzing hydrogen peroxide, ammonia gas and acetone or butanone to synthesize ketoxime, then reacting the ketoxime with ammonium chloride under negative pressure to generate hydroxylamine hydrochloride, ammonia gas, acetone or butanone, and recycling the acetone or butanone and ammonia gas. The method solves the problems of high cost of raw materials and more byproducts in the prior art for preparing the hydroxylamine hydrochloride, and can also promote the sustainable development of the soda industry by using low-value ammonium chloride to prepare the hydroxylamine hydrochloride with low cost.
CN201510582395.5 is a method for producing hydroxylamine hydrochloride by using industrial tail gas absorption waste liquid, belonging to the technical field of hydroxylamine hydrochloride production. The method for producing hydroxylamine hydrochloride by using industrial tail gas absorption waste liquid comprises the following steps: decolorizing industrial tail gas absorption waste liquid by utilizing urea; adding hydrochloric acid and nitromethane into the obtained decolored industrial tail gas absorption waste liquid, and carrying out hydrolysis reaction under a heating reflux state; and concentrating and post-treating the hydrolyzed liquid to obtain the hydroxylamine hydrochloride. The method for producing hydroxylamine hydrochloride by using the industrial tail gas absorption waste liquid fully utilizes the industrial tail gas absorption waste liquid, reduces the industrial water consumption, saves the cost, and is energy-saving and environment-friendly.
CN201810619737.X discloses a hydroxylamine hydrochloride synthesis method, which comprises the following steps of mixing pinacoloxime and concentrated hydrochloric acid solution according to a molar ratio of 1.2-1.5: 1, putting the mixture into a kettle, stirring the mixture strongly, heating the mixture to 70-80 ℃, and hydrolyzing the mixture. Cooling, standing, layering, distilling the water layer under reduced pressure to obtain white solid, adding ethanol, cooling, crystallizing, and filtering to obtain high-purity and high-yield hydroxylamine hydrochloride. The method avoids the generation of side reaction in the hydrolysis process, can improve the purity and the yield of the hydroxylamine hydrochloride, and has the characteristics of simple steps, easily obtained raw materials, small amount of waste water, environmental friendliness and the like.
Aiming at the problems of low purity and high content of iron ions of the prepared hydroxylamine hydrochloride, the prior art does not provide a better solution, so how to improve the purity of the hydroxylamine hydrochloride and reduce the content of the iron ions has great significance for expanding the application range of the hydroxylamine hydrochloride.
Disclosure of Invention
The invention provides a preparation method of solid hydroxylamine hydrochloride, and the solid hydroxylamine hydrochloride obtained by the method has high yield, high purity and low iron ion content.
The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding 50-60% butanone oxime hydrochloride aqueous solution raw materials into a reaction kettle, standing for 30-90min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer from the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: according to the mass portion, 100-110 portions of pure butanone oxime hydrochloride aqueous solution is introduced into a pre-reactor, 7-15 portions of butanone oxime are added, mixed evenly and then introduced into a rectifying tower, 65-80 portionsoC, staying for 150-300s, rectifying and separating butanone and water generated by the reaction, then adding a metal ion selective adsorbent into the kettle liquid, stirring for 30-60min at 300r/min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: introducing the obtained hydroxylamine hydrochloride aqueous solution into a concentration tower, wherein the concentration tower is 70-80 percentoC, staying for 150-300s, separating to obtain butanone and recovering part of water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.08 to-0.09 MPa, and the temperature is 70 to 80 DEGoC, keeping 150-oAnd C, drying to obtain solid hydroxylamine hydrochloride.
Preferably, the preparation method of the metal ion selective adsorbent described in the second step comprises:
according to the mass parts, adding 120 parts of silane modified polymer powder of 100-one, 15-30 parts of propyl propylene disulfide, 0.02-0.3 part of N-vinyl pyridine, 0.5-1.8 parts of chloroplatinic acid and 200 parts of isoamyl alcohol of 100-one into a reaction kettle, stirring at 100-one and 300r/min, heating to 65-75 ℃, reacting for 2-6 hours, washing and drying to obtain the metal ion selective adsorbent.
Preferably, the preparation method of the silane modified polymer powder comprises the following steps:
adding 120 parts by mass of non-polar monomer 100-fold, 5-20 parts by mass of cross-linking agent, 1-10 parts by mass of silicon modifier, 40-60 parts by mass of toluene and 1.1-3.2 parts by mass of benzoyl peroxide into a reaction kettle, heating to 85-95 ℃, stirring for reaction for 7-10 hours at 100-fold at 200r/min, after the reaction is finished, adding 1500 parts by mass of solvent naphtha 1000-fold, extracting the toluene completely, and drying to remove the participating solvent, thereby obtaining the silane modified polystyrene powder.
Preferably, the non-polar monomer is one or a combination of styrene, methyl styrene, p-fluoro styrene and vinyl naphthalene.
Preferably, the crosslinking agent is one or a combination of divinyl benzene, bismaleimide, N' -m-phenylene bismaleimide and diphenyl ether bismaleimide.
Preferably, the silicon modifier is one or a combination of allyl dimethoxy silane, tetraene silane, methyl styrene silane and triethyl vinyl silane.
Part of reaction mechanism in the preparation process of the solid hydroxylamine hydrochloride is shown as follows:
part of reaction mechanisms in the preparation process of the metal ion selective adsorbent are shown as follows:
compared with the prior art, the invention has the beneficial effects that:
1. the raw materials and the byproducts generated in the reaction process are effectively recycled, so that the whole production process is kept closed-loop, the environmental pollution is greatly reduced, and the production cost is reduced.
2. According to the invention, a metal ion selective adsorbent is added into the system to adsorb iron ions in the system, so that the content of the iron ions is greatly reduced.
3. The solid hydroxylamine hydrochloride product obtained by the method has high yield and high purity.
Drawings
FIG. 1 is a Fourier infrared spectrum of the selective adsorbent obtained in example 1:
at 1612/1502/1447cm-1An absorption peak of benzene ring is present nearby, and is 2964cm-1The expansion and contraction absorption peak of the hydrocarbon exists nearby, and is 1080/1032/804cm-1The antisymmetric stretching/symmetric stretching absorption peak of the silicon oxygen exists nearby, which indicates that the silane modified polymer powder participates in the reaction; at 685cm-1A telescopic absorption peak of a carbon-sulfur bond exists nearby, which indicates that the propylpropylene disulfide participates in the reaction; at 1779cm-1The absorption peak of carbonyl group of amide at 1377cm-1The presence of a stretching absorption peak of the carbon-nitrogen single bond of the amide in the vicinity indicates that the N-vinylpyridinone participates in the reaction.
FIG. 2 is a Fourier infrared spectrum of hydroxylamine hydrochloride prepared in example 2.
Detailed Description
The raw materials used in the following examples are all commercially available products, and the examples are further illustrative of the present invention and do not limit the scope of the present invention;
the performance test methods are as follows:
1. product yield test, calculating the amount of material and calculating the molar yield by weighing the mass of the product obtained and the raw materials used.
2. And (3) testing the purity of the product, weighing about 1g of sample, weighing to 0.00012g, dissolving in oxygen-free water, transferring into a 250mL volumetric flask, diluting to a scale, shaking up, transferring 25mL of solution into a 250mL conical flask by using a pipette, adding 10mL of sulfuric acid solution and 20mL of ferric ammonium sulfate solution, and shaking up. Slowly heating to boil, boiling for 5min, adding 100mL of oxygen-free water, adding 2mL of phosphoric acid, and titrating to pink with a potassium permanganate standard titration solution at about 60 ℃. Meanwhile, a blank test is carried out, and the purity of the product is calculated.
3. And (3) testing the content of the solid hydroxylamine hydrochloride iron, namely preparing the solid hydroxylamine hydrochloride into a deionized water solution, and then testing by adopting a spectrophotometry method.
Example 1
The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding 50% butanone oxime hydrochloride aqueous solution raw materials into a reaction kettle, standing for 30min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer and the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: 100kg of pure butanone oxime hydrochloride aqueous solution is introduced into a pre-reactor, 7kg of butanone oxime is added, the mixture is uniformly mixed and then introduced into a rectifying tower, 65 kg of pure butanone oxime hydrochloride aqueous solution is addedoC, staying for 300s, rectifying and separating butanone and water generated by the reaction, then adding 10kg of metal ion selective adsorbent into the kettle liquid, stirring at 200r/min for 60min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: the aqueous solution of hydroxylamine hydrochloride obtained is introduced into a concentration column, 70oC, staying for 300s, separating to obtain butanone and partially recovering water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.08 MPa, and the temperature is 80oC, keeping the temperature for 150s, removing most of water for recycling, adding the product into a centrifugal machine for centrifugation at the rotating speed of 8000r/min, further removing water, and finally passing the product through a fluidized bed at 70 DEG CoAnd C, drying to obtain solid hydroxylamine hydrochloride.
The preparation method of the metal ion selective adsorbent comprises the following steps:
adding 100kg of silane modified polymer powder, 15kg of propyl propylene disulfide, 0.02kg of N-vinyl pyridine ketone, 0.5kg of chloroplatinic acid and 100kg of isoamyl alcohol into a reaction kettle, stirring at 100r/min, heating to 65 ℃, reacting for 6 hours, washing and drying to obtain the metal ion selective adsorbent.
The preparation method of the silane modified polymer powder comprises the following steps:
100kg of styrene, 5kg of divinylbenzene, 1kg of allyl dimethoxysilane, 40kg of toluene and 1.1-3.2kg of benzoyl peroxide are added into a reaction kettle, the temperature is raised to 85 ℃, the mixture is stirred for reaction for 10 hours at 100r/min, 1000kg of solvent naphtha is added after the reaction is finished, the toluene is extracted completely, and the participating solvent is dried to obtain the silane modified polystyrene powder.
The yield of the obtained product is 96%, the purity is 99.1%, and the iron content is 0.0005%.
Example 2
The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding a butanone oxime hydrochloride aqueous solution raw material with the concentration of 53% into a reaction kettle, standing for 50min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer from the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain a pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: 103kg of pure butanone oxime hydrochloride aqueous solution is introduced into a pre-reactor, 10kg of butanone oxime is added, the mixture is uniformly mixed and then introduced into a rectifying tower, 67 g of pure butanone oxime hydrochloride aqueous solution is introduced into the rectifying toweroC, staying for 265s, rectifying and separating butanone and water generated by the reaction, then adding 12kg of metal ion selective adsorbent into the kettle liquid, stirring for 50min at 243r/min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: the aqueous solution of hydroxylamine hydrochloride obtained is introduced into a concentration column, 71oC, staying for 270s, separating to obtain butanone and partially recovering water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.09 MPa, and the temperature is 75oMaintaining for 190s, removing most of water, recovering, centrifuging at 8800r/min, removing water, and passing through fluidized bed (72)oAnd C, drying to obtain solid hydroxylamine hydrochloride.
The preparation method of the metal ion selective adsorbent comprises the following steps:
adding 109kg of silane modified polymer powder, 18kg of propyl propylene disulfide, 0.1kg of N-vinyl pyridine ketone, 0.8kg of chloroplatinic acid and 143kg of isoamyl alcohol into a reaction kettle, stirring at 146r/min, heating to 69 ℃, reacting for 4 hours, washing and drying to obtain the metal ion selective adsorbent.
The preparation method of the silane modified polymer powder comprises the following steps:
108kg of methyl styrene, 10kg of bismaleimide, 3kg of tetraene silane, 46kg of toluene and 1.6kg of benzoyl peroxide are added into a reaction kettle, the temperature is raised to 88 ℃, the mixture is stirred and reacted for 9 hours at 143r/min, 1100kg of solvent naphtha is added after the reaction is finished, the toluene is extracted completely, and the participating solvent is dried to obtain the silane modified polystyrene powder.
The yield of the obtained product is 96%, the purity is 99.1%, and the iron content is 0.0005%.
Example 3
The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding the butanone oxime hydrochloride aqueous solution raw material with the concentration of 56% into a reaction kettle, standing for 64min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer from the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain a pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: 107kg of pure butanone oxime hydrochloride aqueous solution is introduced into a pre-reactor, 13kg of butanone oxime is added, the mixture is uniformly mixed and then introduced into a rectifying tower, 71 kg of pure butanone oxime hydrochloride aqueous solution is addedoC, staying for 240s, rectifying and separating butanone and water generated by the reaction, then adding 14kg of metal ion selective adsorbent into the kettle liquid, stirring at 289r/min for 42min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: the aqueous solution of hydroxylamine hydrochloride obtained is passed into a concentration column, 75oC, staying for 230s, separating to obtain butanone and partially recovering water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.1 MPa, and the temperature is 72 DEGoC, keeping 245s, removing most of water for recovery, adding the product into a centrifuge for centrifugation at the rotating speed of 9133r/min, further removing water, and finally passing the product through a fluidized bed at 75 DEG CoAnd C, drying to obtain solid hydroxylamine hydrochloride.
The preparation method of the metal ion selective adsorbent comprises the following steps:
adding 115kg of silane modified polymer powder, 23kg of propyl propylene disulfide, 0.23kg of N-vinyl pyridine ketone, 1.4kg of chloroplatinic acid and 176kg of isoamyl alcohol into a reaction kettle, stirring at 206r/min, heating to 71 ℃, reacting for 2 hours, washing and drying to obtain the metal ion selective adsorbent.
The preparation method of the silane modified polymer powder comprises the following steps:
adding 116kg of p-fluorostyrene, 14kg of N, N' -m-phenylene bismaleimide, 5kg of methyl styrene silane, 50kg of toluene and 3.2kg of benzoyl peroxide into a reaction kettle, heating to 91 ℃, stirring at 159r/min for reaction for 8 hours, adding 1233kg of solvent naphtha after the reaction is finished, extracting the toluene cleanly, and drying to remove the participating solvent to obtain the silane modified polystyrene powder.
The yield of the obtained product is 96%, the purity is 99.1%, and the iron content is 0.0004%.
Example 4
The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding 60% butanone oxime hydrochloride aqueous solution raw materials into a reaction kettle, standing for 90min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer and the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: introducing 110kg of pure butanone oxime hydrochloride aqueous solution into a pre-reactor, adding 15kg of butanone oxime, uniformly mixing, introducing into a rectifying tower, and introducing 80 kg of butanone oxime hydrochloride aqueous solution into the rectifying toweroC, staying for 150s, rectifying and separating butanone and water generated by the reaction, then adding 20kg of metal ion selective adsorbent into the kettle liquid, stirring at 300r/min for 30min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: the aqueous solution of hydroxylamine hydrochloride obtained is introduced into a concentration column, 80oC, staying for 150s, separating to obtain butanone and partially recovering water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.09 MPa, and the temperature is 70 DEGoC, protectionMaintaining for 300s, removing most water, recovering, centrifuging at 10000r/min, removing water, and passing the product through fluidized bed at 80%oAnd C, drying to obtain solid hydroxylamine hydrochloride.
The preparation method of the metal ion selective adsorbent comprises the following steps:
adding 120kg of silane modified polymer powder, 30kg of propyl propylene disulfide, 0.3kg of N-vinyl pyridine ketone, 1.8kg of chloroplatinic acid and 200kg of isoamyl alcohol into a reaction kettle, stirring at 300r/min, heating to 75 ℃, reacting for 2 hours, washing and drying to obtain the metal ion selective adsorbent.
The preparation method of the silane modified polymer powder comprises the following steps:
adding 120kg of naphthylethylene, 20kg of diphenyl ether bismaleimide, 10kg of triethylvinylsilane, 60kg of toluene and 3.1kg of benzoyl peroxide into a reaction kettle, heating to 95 ℃, stirring at 200r/min for reaction for 7 hours, adding 1500kg of solvent naphtha after the reaction is finished, extracting the toluene cleanly, and drying to remove the participating solvent to obtain the silane modified polystyrene powder.
The yield of the obtained product is 98%, the purity is 99.3%, and the iron content is 0.0004%.
Comparative example 1
Relative to example 1, the amount of the metal ion adsorbent added was 0kg, and the remainder was the same as in example 1, and the obtained product had a yield of 95.2%, a purity of 98.5% and an iron content of 0.03%.
Comparative example 2
Compared with the example 1, the preparation process of the metal ion selective adsorbent does not add propylene disulfide, and the obtained product has the yield of 95.5%, the purity of 98.7% and the iron content of 0.001%.
Comparative example 3
In comparison with example 1, no allyldimethoxysilane was added during the preparation of the silane-modified polymer powder, giving a product yield of 95.3%, a purity of 98.6% and an iron content of 0.003%.
Claims (5)
1. The preparation method of the solid hydroxylamine hydrochloride is characterized by comprising the following steps:
step one, raw material purification: adding 50-60% butanone oxime hydrochloride aqueous solution raw materials into a reaction kettle, standing for 30-90min, layering to obtain a silicic acid layer, a water phase layer and an oil phase layer, separating the oil phase layer from the silicic acid layer, recovering to obtain the water phase layer, and filtering the water phase layer through a filter to remove a small amount of silicic acid impurities to obtain pure butanone oxime hydrochloride aqueous solution;
step two, reactive distillation: according to the mass portion, 100-110 portions of pure butanone oxime hydrochloride aqueous solution is introduced into a pre-reactor, 7-15 portions of butanone oxime are added, mixed evenly and then introduced into a rectifying tower, 65-80 portionsoC, staying for 150-300s, rectifying and separating butanone and water generated by the reaction, then adding 10-20 parts of metal ion selective adsorbent into the kettle liquid, stirring for 30-60min at 300r/min, and filtering and separating the adsorbent to obtain a hydroxylamine hydrochloride aqueous solution;
step three, product purification: introducing the obtained hydroxylamine hydrochloride aqueous solution into a concentration tower, wherein the concentration tower is 70-80 percentoC, staying for 150-300s, separating to obtain butanone and recovering part of water, introducing the residual hydroxylamine hydrochloride aqueous solution into a crystallization kettle, wherein the vacuum degree is-0.08 to-0.09 MPa, and the temperature is 70 to 80 DEGoC, keeping 150-oC, drying to obtain solid hydroxylamine hydrochloride;
the preparation method of the metal ion selective adsorbent in the second step comprises the following steps:
according to the mass parts, adding 120 parts of silane modified polymer powder of 100-one, 15-30 parts of propyl propylene disulfide, 0.02-0.3 part of N-vinyl pyridine, 0.5-1.8 parts of chloroplatinic acid and 200 parts of isoamyl alcohol of 100-one into a reaction kettle, stirring at 100-one and 300r/min, heating to 65-75 ℃, reacting for 2-6 hours, washing and drying to obtain the metal ion selective adsorbent.
2. The method of claim 1, wherein the silane-modified polymer powder is prepared by:
adding 120 parts by mass of non-polar monomer 100-fold, 5-20 parts by mass of cross-linking agent, 1-10 parts by mass of silicon modifier, 40-60 parts by mass of toluene and 1.1-3.2 parts by mass of benzoyl peroxide into a reaction kettle, heating to 85-95 ℃, stirring for reaction for 7-10 hours at 100-fold at 200r/min, after the reaction is finished, adding 1500 parts by mass of solvent naphtha 1000-fold, extracting the toluene completely, and drying to remove the participating solvent, thereby obtaining the silane modified polystyrene powder.
3. The method of claim 2, wherein the non-polar monomer is one or more of styrene, methyl styrene, p-fluoro styrene, and vinyl naphthalene.
4. The method of claim 2, wherein the crosslinking agent is one or more of divinylbenzene, bismaleimide, N' -m-phenylenebismaleimide, and diphenyloxide bismaleimide.
5. The method of claim 2, wherein the silicon modifier is one or more selected from the group consisting of allyldimethoxysilane, tetraenylsilane, methylstyrene silane and triethylvinylsilane.
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