CN116814084A - Sustained-release sodium sarcosinate and preparation method thereof - Google Patents
Sustained-release sodium sarcosinate and preparation method thereof Download PDFInfo
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- CN116814084A CN116814084A CN202310820789.4A CN202310820789A CN116814084A CN 116814084 A CN116814084 A CN 116814084A CN 202310820789 A CN202310820789 A CN 202310820789A CN 116814084 A CN116814084 A CN 116814084A
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- solution
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- sodium
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- 108010077895 Sarcosine Proteins 0.000 title claims abstract description 73
- ZUFONQSOSYEWCN-UHFFFAOYSA-M sodium;2-(methylamino)acetate Chemical compound [Na+].CNCC([O-])=O ZUFONQSOSYEWCN-UHFFFAOYSA-M 0.000 title claims abstract description 72
- 229940048098 sodium sarcosinate Drugs 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 68
- 238000013268 sustained release Methods 0.000 title description 4
- 239000012730 sustained-release form Substances 0.000 title description 4
- 239000000243 solution Substances 0.000 claims abstract description 83
- 238000003756 stirring Methods 0.000 claims abstract description 63
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 33
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 32
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- LTYRAPJYLUPLCI-UHFFFAOYSA-N glycolonitrile Chemical compound OCC#N LTYRAPJYLUPLCI-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- PVVRRUUMHFWFQV-UHFFFAOYSA-N 2-(methylamino)acetonitrile Chemical compound CNCC#N PVVRRUUMHFWFQV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims abstract description 12
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 11
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 9
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 9
- 239000000661 sodium alginate Substances 0.000 claims abstract description 9
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 9
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 9
- 239000008157 edible vegetable oil Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 60
- 239000004005 microsphere Substances 0.000 claims description 40
- 239000010703 silicon Substances 0.000 claims description 40
- 229910052710 silicon Inorganic materials 0.000 claims description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 238000001035 drying Methods 0.000 claims description 36
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 30
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 30
- 229960004889 salicylic acid Drugs 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 20
- 239000002131 composite material Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 10
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical group N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- -1 alkyl orthosilicate Chemical compound 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- SXPWTBGAZSPLHA-UHFFFAOYSA-M cetalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SXPWTBGAZSPLHA-UHFFFAOYSA-M 0.000 claims description 3
- 229960000228 cetalkonium chloride Drugs 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 235000005687 corn oil Nutrition 0.000 claims description 3
- 239000002285 corn oil Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 19
- 230000000694 effects Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000007259 addition reaction Methods 0.000 description 7
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 7
- 229940106681 chloroacetic acid Drugs 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000013522 chelant Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001690 polydopamine Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- CVSVTCORWBXHQV-UHFFFAOYSA-N creatine Chemical compound NC(=[NH2+])N(C)CC([O-])=O CVSVTCORWBXHQV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229940043230 sarcosine Drugs 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- MEJYXFHCRXAUIL-UHFFFAOYSA-N 2-[carbamimidoyl(methyl)amino]acetic acid;hydrate Chemical compound O.NC(=N)N(C)CC(O)=O MEJYXFHCRXAUIL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 229960003624 creatine Drugs 0.000 description 1
- 239000006046 creatine Substances 0.000 description 1
- 229960004826 creatine monohydrate Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003405 delayed action preparation Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/02—Formation of carboxyl groups in compounds containing amino groups, e.g. by oxidation of amino alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
- B01J2231/343—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones to prepare cyanhydrines, e.g. by adding HCN or TMSCN
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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Abstract
The invention provides slow-release sodium sarcosinate and a preparation method thereof, and belongs to the technical field of sodium sarcosinate. Comprising the following steps: s1, adding a catalyst into formaldehyde solution, adjusting the pH value, adding hydrocyanic acid, stirring for reaction to obtain a hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution; s2, adding methylamine into the hydroxyacetonitrile solution, and stirring for reaction to obtain a methylaminoacetonitrile solution; s3, adding sodium hydroxide into the methylaminoacetonitrile solution, heating and stirring for reaction to obtain a sodium sarcosinate solution, and introducing generated gas into acid liquor to obtain byproducts; s4, mixing and dissolving sodium carboxymethyl cellulose, polyvinyl alcohol and sodium alginate in water to obtain a mixed solution, adding a sodium sarcosinate solution, stirring and mixing uniformly, adding edible oil, emulsifying, dripping a metal salt solution, and curing at normal temperature to obtain the slow-release sodium sarcosinate. The method of the invention obviously improves the yield and purity of the sodium sarcosinate product, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of sodium sarcosinate, in particular to slow-release sodium sarcosinate and a preparation method thereof.
Background
Sodium sarcosinate, also known as sodium N-methylglycinate, is a white triangular solid crystal, is very soluble in water and slightly soluble in ethanol. Sodium sarcosinate is mainly used for producing creatine monohydrate, sarcosine, N-acyl sarcosine and sodium salts thereof. Wherein creatine can effectively improve muscle strength, speed and endurance, improve physical ability and training level, and prevent fatigue. N-acyl sarcosines are useful as active agents for advanced skin care vanishing creams, toothpastes, shampoos, and advanced medical soaps and sarcosinates. Sodium sarcosinate can also be used as a dyeing assistant for quick dyes, a synthetic lubricating oil, an anti-rust agent fiber dyeing agent, an antistatic agent, a softening processing agent, a biochemical agent and the like, is an anionic surfactant with bactericidal property, and is widely used in daily chemical industry and the like.
The existing sodium sarcosinate production process mainly comprises a chloroacetic acid method and a hydroxyacetonitrile method. The chloroacetic acid method is to take chloroacetic acid as a raw material, perform condensation reaction with monomethylamine under alkaline condition, finally obtain aqueous solution of sodium sarcosinate and sodium chloride in the presence of sodium hydroxide, and remove sodium chloride to obtain sodium sarcosinate product. The chloroacetic acid method needs to be carried out under the condition of pressure, the reaction condition is relatively high, the equipment requirement for industrial mass production is high, and the yield is low. In the preparation process, the hydrogen chloride gas with strong corrosiveness is generated, and is very easy to dissolve in water to form hydrochloric acid with strong corrosiveness, so that acid corrosion-resistant materials are required to be adopted for reaction equipment and a gas recovery device, and investment cost is high. And because the activity of chlorine in chloroacetic acid is weaker, the reaction can be normally performed only when the using amount of methylamine and chloroacetic acid reaches more than 8:1 molar ratio. After the reaction, the surplus methylamine is very large and requires subsequent recovery treatment. Thus, the chloroacetic acid process is very limited in its industrial application.
The hydroxy acetonitrile method is mainly that hydroxy acetonitrile (or hydrocyanic acid and formaldehyde directly participate in reaction) and monomethylamine are subjected to condensation reaction, and then are subjected to alkaline hydrolysis with liquid alkali to generate sodium sarcosinate. Because the hydroxy acetonitrile method finally generates sodium sarcosinate and byproduct ammonia, the byproduct ammonia can be removed from the system in a negative pressure mode during alkaline hydrolysis, and the method does not generate three wastes, thus being a clean and green process. The hydroxyacetonitrile method is a relatively common production method of sodium sarcosinate in China at present, but the method has the problems of low yield and the like in practical application.
In addition, sodium sarcosinate is taken as a common amino acid raw material, can be degraded at the temperature higher than 80 ℃, and can obviously prolong the service life of the sodium sarcosinate after being embedded to prepare a slow-release material, thereby prolonging the use effect and obtaining wider application prospect.
Disclosure of Invention
The invention aims to provide the slow-release sodium sarcosinate and the preparation method thereof, which reduce the occurrence of side reactions through controlling reaction conditions, can obviously improve the yield and purity of sodium sarcosinate products, and can play a role in good water resistance, moisture resistance and temperature resistance, thereby obviously prolonging the service life of sodium sarcosinate, prolonging the use effect and obtaining wider application prospects.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of slow-release sodium sarcosinate, which comprises the following steps:
s1, preparing sodium sarcosinate: adding a catalyst into formaldehyde solution, dispersing uniformly, adjusting the pH value to be a first pH value, adding hydrocyanic acid, stirring for reaction to obtain a hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution to be a second pH value;
the catalyst is a Pt-loaded modified carrier catalyst for fixing proline and salicylic acid;
s2, adding methylamine into the hydroxyacetonitrile solution prepared in the step S1, and stirring for reaction to prepare a methylaminoacetonitrile solution;
s3, adding sodium hydroxide into the methylaminoacetonitrile solution prepared in the step S2, heating and stirring for reaction to prepare a sodium sarcosinate solution, and introducing generated gas into acid liquor to prepare a byproduct;
s4, preparation of slow-release sodium sarcosinate: and (3) mixing and dissolving sodium carboxymethylcellulose, polyvinyl alcohol and sodium alginate in water to obtain a mixed solution, adding the sodium sarcosinate solution prepared in the step (S3), stirring and mixing uniformly, adding edible oil, emulsifying, dripping a metal salt solution, solidifying at normal temperature, centrifuging, washing and drying to obtain the slow-release sodium sarcosinate.
As a further improvement of the present invention, the catalyst is prepared as follows:
t1, preparing hollow mesoporous silicon microspheres: dissolving alkyl orthosilicate in an organic solvent, adding an aqueous solution containing a pore-forming agent, emulsifying, adjusting the pH value of the solution, stirring for reaction, centrifuging, washing and drying to obtain hollow mesoporous silicon microspheres;
t2 preparation of diatomite composite silicon microsphere: cleaning diatomite, ball milling, drying, adding the diatomite into water, adding the hollow mesoporous silicon microspheres prepared in the step T1, stirring and uniformly mixing, centrifuging and drying to prepare diatomite composite silicon microspheres;
and T3, modification: adding the diatomite composite silicon microsphere prepared in the step T2 into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing and drying to obtain a modified carrier;
t4. immobilization of proline and salicylic acid: dissolving proline and salicylic acid in ethanol water solution, adding the modified carrier prepared in the step T3, heating, stirring, reacting, centrifuging, washing, and drying to obtain a modified carrier for fixing proline and salicylic acid;
deposition of pt metal: dissolving chloroplatinic acid in water, regulating the pH value of the solution to 3-4, adding the modified carrier for fixing proline and salicylic acid prepared in the step T4, adding citric acid, regulating the pH value of the solution to 5-6, heating and stirring for reaction, centrifuging, washing and drying to obtain the catalyst.
As a further improvement of the invention, the alkyl orthosilicate in the step T1 is methyl orthosilicate or ethyl orthosilicate, the pore-forming agent is at least one selected from cetyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride, tetradecyltrimethylammonium chloride and octadecyl trimethyl ammonium bromide, the mass ratio of the alkyl orthosilicate to the pore-forming agent is 15-20:1-2, the pH value of the solution is adjusted to 9-10, and the stirring reaction time is 5-7h.
As a further improvement of the invention, the mass ratio of the diatomite to the hollow mesoporous silicon microsphere in the step T2 is 5-10:12-15, and the ball milling time is 2-3h.
As a further improvement of the invention, in the step T3, the mass ratio of the diatomite composite silicon microsphere, the dopamine hydrochloride and the catalyst is 12-15:15-17:1-2, and the catalyst contains 3-5wt% of CoCl 2 The temperature of the heating and stirring reaction is 40-50 ℃ and the time is 2-3h.
As a further improvement of the invention, in the step T4, the mass ratio of the proline to the salicylic acid to the modified carrier is 3-5:1-2:15-20, the concentration of the ethanol in the ethanol aqueous solution is 50-70wt%, the temperature of the heating and stirring reaction is 50-60 ℃ and the time is 30-40min.
As a further improvement of the invention, the mass ratio of the chloroplatinic acid, the citric acid, the immobilized proline and the salicylic acid modified carrier in the step T5 is 12-15:7-10:25-30, the temperature of the heating and stirring reaction is 50-55 ℃ and the time is 1-2h.
As a further improvement of the invention, the concentration of the formaldehyde solution in the step S1 is 30-40wt%, and the molar ratio of formaldehyde to hydrocyanic acid is 1:1-1.1, wherein the addition amount of the catalyst is 3-5wt% of the total mass of the system, the temperature of the stirring reaction is 15-20 ℃, the time is 0.5-1h, the first pH value is 7.2-7.5, and the second pH value is 1.2-1.5; in the step S2, the molar ratio of the hydroxyacetonitrile to the methylamine is 1:1-1.05, the temperature of the stirring reaction is 10-15 ℃, and the time is 2-3h.
As a further improvement of the invention, in the step S3, the mol ratio of the methylaminoacetonitrile to the sodium hydroxide is 1:2-4, the temperature of the heating and stirring reaction is 80-90 ℃ for 1-2 hours, the acid liquor is 2-4mol/L sulfuric acid solution, and the by-product is ammonium sulfate; in the step S4, the mass ratio of the sodium carboxymethyl cellulose to the polyvinyl alcohol to the sodium alginate to the sodium sarcosinate is 3-5:4-7:7-10:15-20, the metal salt is at least one of calcium chloride, aluminum chloride, ferric chloride, ferrous chloride, magnesium chloride, aluminum nitrate, calcium nitrate, magnesium nitrate and ferric nitrate, the concentration of the metal salt solution is 3-5wt%, the normal-temperature curing time is 20-40min, and the edible oil is at least one of peanut oil, corn oil, rapeseed oil, soybean oil, olive oil and linseed oil.
The invention further provides the slow-release sodium sarcosinate prepared by the preparation method.
The invention has the following beneficial effects: in the invention, the first step is an addition reaction: hcho+hcn=hoch 2 CN
In the addition reaction, adding a catalyst into formaldehyde solution, adjusting the pH value to a specified range, dripping hydrocyanic acid after adjusting the temperature to ensure that the two are fully reacted, continuously reacting for a period of time at the specified temperature after the dripping of the hydrocyanic acid is finished, and storing an intermediate glycolonitrile qualified in the reaction after adding a stabilizer for the next procedure;
the proper pH value is obvious in reaction promotion, if the pH value is too low, the addition reaction is insufficient, the formaldehyde and hydrocyanic acid content in glycolonitrile after the reaction exceeds the standard, if the pH value is too high, the reaction speed is high, the addition reaction is not easy to control, the production is dangerous, flash explosion can occur, and safety accidents are caused.
Diatomite is an important nonmetallic mineral material, and the main component of the diatomite is SiO 2 Has multiple holes,Large specific surface area, strong adsorptivity, good thermal stability and the like. The diatomite molecule surface has a large number of hydroxyl groups, and can play a role in complexing metal ions under the action of hydrogen bonds. The silicon dioxide has stable property, low cost and easy obtainment, has larger specific surface area and is rich in silicon hydroxyl (Si-OH), so the silicon dioxide is often used as a carrier supported catalyst for catalyzing addition reaction.
The proline has a simple molecular structure, can be used as acid or alkali, and is a chiral bidentate ligand. Salicylic acid is also a good lewis acid with carboxyl groups. The chelate ligand contained in the catalyst can react with a substrate to synergistically promote the catalytic action of the addition reaction, and meanwhile, the chelate ligand can chelate the solid with Pt metal, so that the loading amount of the Pt metal is increased.
The surface of the hollow mesoporous silicon microsphere prepared by the emulsion method and the sol-gel method contains a large number of mesopores, and meanwhile, the hollow mesoporous silicon microsphere has a hollow structure, so that the hollow mesoporous silicon microsphere has a large specific surface area, and after the hollow mesoporous silicon microsphere is compounded with diatomite, a large number of hydroxyl, carboxyl, amino and other active groups are formed on the surface under the modification effect of polydopamine, on one hand, proline and salicylic acid can be conveniently reacted and fixed, and on the other hand, pt metal can be also fixed under the effect of hydrogen bond and coordination bond, so that the Pt loading capacity is improved, the Pt crystal formation is promoted, the catalytic effect is improved, the prepared catalyst can perform efficient catalysis, the reaction temperature and pressure are reduced, the reaction selectivity is improved, and the product yield is improved.
The catalyst prepared by the method can obviously improve the addition reaction efficiency of formaldehyde and hydrocyanic acid, greatly improve the addition rate, shorten the reaction time, greatly improve the conversion rate and have milder reaction conditions.
The second step is condensation reaction: HOCH 2 CN+CH 3 NH 2 =CH 3 NHCH 2 CN+H 2 O
In the condensation reaction, a small excess of methyl amine is added into the glycolonitrile solution generated by the reaction, and the condensation reaction is completed by controlling the reaction temperature and the dripping time.
The third step is hydrolysis reaction:
CH 3 NHCH 2 CN+H 2 O+NaOH=CH 3 NHCH 2 COONa+NH 3 ↑
in the hydrolysis reaction, the condensation liquid after the reaction is finished is added into a hydrolysis reaction kettle with quantitative water and excessive sodium hydroxide for hydrolysis reaction, the initial temperature, the hydrolysis temperature and the hydrolysis speed of the hydrolysis kettle are regulated and controlled, the prescribed temperature is kept until the hydrolysis is fully finished, and then the sodium sarcosinate solution is obtained after heating and concentrating.
In the preparation of the sustained-release preparation, the sodium sarcosinate solution is added into coating liquid (carboxymethyl cellulose sodium, polyvinyl alcohol and sodium alginate aqueous solution), after edible oil is added, water-in-oil emulsion is formed by emulsification, and metal salt solution is added, so that metal ions, the sodium carboxymethyl cellulose, the polyvinyl alcohol and the sodium alginate form a crosslinked network structure, and the sodium sarcosinate is embedded in microspheres to prepare the sustained-release sodium sarcosinate, so that the sustained-release sodium sarcosinate has good water resistance, moisture resistance and temperature resistance effects, the service life of the sodium sarcosinate is obviously prolonged, the use effect is prolonged, and the wider application prospect is achieved.
By-product reaction: h 2 SO 4 +2NH 3 =(NH 4 ) 2 SO 4
In tail gas absorption, ammonia gas generated in the hydrolysis process enters excessive sulfuric acid liquid, sulfuric acid is used for absorbing the ammonia gas, and the saturated ammonium sulfate solution is subjected to centrifugal separation to obtain a byproduct ammonium sulfate product. The sulfuric acid solution is replaced after adsorption saturation in time, so that further dissipation of ammonia tail gas is avoided, and environment pollution is avoided.
The method reduces the occurrence of side reaction by controlling the reaction condition, can obviously improve the yield and purity of the sodium sarcosinate product, and prepares the slow-release sodium sarcosinate with good water resistance, moisture resistance and temperature resistance effects, thereby obviously prolonging the service life of the sodium sarcosinate, prolonging the use effect and obtaining wider application prospect.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is a TEM image of the hollow mesoporous silica microspheres prepared in the step T1 of preparation example 1.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Diatomite is purchased from Ningbo Ding Innovative materials Co., ltd, has a water content of less than 0.5%, a silicon dioxide content of more than 85% and a tap density of less than 0.53g/mL.
Preparation example 1 preparation of catalyst
The method comprises the following steps:
t1, preparing hollow mesoporous silicon microspheres: dissolving 15 parts by weight of methyl orthosilicate in 100 parts by weight of petroleum ether, adding 50 parts by weight of an aqueous solution containing 1 part by weight of tetradecyl trimethyl ammonium chloride, emulsifying for 15min at 12000r/min, regulating the pH value of the solution to 9, stirring and reacting for 5h, centrifuging, washing and drying to obtain hollow mesoporous silicon microspheres; FIG. 1 is a TEM image of a hollow mesoporous silicon microsphere, which is a hollow structure;
t2 preparation of diatomite composite silicon microsphere: washing 5 parts by weight of diatomite, ball-milling for 2 hours, drying, adding 100 parts by weight of water, adding 12 parts by weight of the hollow mesoporous silicon microsphere prepared in the step T1, stirring and mixing for 20 minutes, centrifuging, and drying to obtain the diatomite composite silicon microsphere;
and T3, modification: adding 12 parts by weight of the diatomite composite silicon microsphere prepared in the step T2 into 100 parts by weight of water, adding 15 parts by weight of dopamine hydrochloride and 1 part by weight of catalyst, heating to 40 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to prepare a modified carrier;
the catalyst was 3wt% CoCl 2 Tris-HCl solution at ph=5;
t4. immobilization of proline and salicylic acid: dissolving 3 parts by weight of proline and 1 part by weight of salicylic acid in 100 parts by weight of 50wt% ethanol water solution, adding 15 parts by weight of the modified carrier prepared in the step T3, heating to 50 ℃, stirring and reacting for 30min, centrifuging, washing and drying to obtain the modified carrier for fixing proline and salicylic acid;
deposition of pt metal: dissolving 12 parts by weight of chloroplatinic acid in 100 parts by weight of water, regulating the pH value of the solution to be 3, adding 25 parts by weight of the modified carrier for fixing proline and salicylic acid prepared in the step T4, adding 7 parts by weight of citric acid, regulating the pH value of the solution to be 5, heating to 50 ℃, stirring and reacting for 1h, centrifuging, washing and drying to obtain the catalyst.
The prepared catalyst was subjected to infrared analysis: 3520cm -1 、3420cm -1 、3270cm -1 Is a hydroxyl telescopic vibration peak, 3070cm -1 Is C-H telescopic vibration peak at aromatic ring, 1570cm -1 Is NH bending vibration peak, 1595cm -1 1580cm -1 The vibration wave number at the position has higher signal intensity, which marks the interaction of Van der Waals force generated in the polydopamine molecular chain, 1277cm -1 Is the stretching vibration peak of C-N. Therefore, polydopamine, proline and salicylic acid are successfully immobilized on the catalyst.
Preparation example 2 preparation of catalyst
The method comprises the following steps:
t1, preparing hollow mesoporous silicon microspheres: dissolving 20 parts by weight of ethyl orthosilicate in 100 parts by weight of ethyl acetate, adding 50 parts by weight of aqueous solution containing 2 parts by weight of hexadecyldimethylbenzyl ammonium chloride, emulsifying for 15min at 12000r/min, regulating the pH value of the solution to 10, stirring and reacting for 7h, centrifuging, washing and drying to obtain hollow mesoporous silicon microspheres;
t2 preparation of diatomite composite silicon microsphere: washing 10 parts by weight of diatomite, ball-milling for 3 hours, drying, adding 100 parts by weight of water, adding 15 parts by weight of the hollow mesoporous silicon microsphere prepared in the step T1, stirring and mixing for 20 minutes, centrifuging, and drying to obtain the diatomite composite silicon microsphere;
and T3, modification: adding 15 parts by weight of the diatomite composite silicon microsphere prepared in the step T2 into 100 parts by weight of water, adding 17 parts by weight of dopamine hydrochloride and 2 parts by weight of catalyst, heating to 50 ℃, stirring and reacting for 3 hours, centrifuging, washing and drying to prepare a modified carrier;
the catalyst is a catalyst containing 5wt% of CoCl 2 Tris-HCl solution at ph=6;
t4. immobilization of proline and salicylic acid: dissolving 5 parts by weight of proline and 2 parts by weight of salicylic acid in 100 parts by weight of 70wt% ethanol aqueous solution, adding 20 parts by weight of the modified carrier prepared in the step T3, heating to 60 ℃, stirring and reacting for 40min, centrifuging, washing and drying to obtain the modified carrier for fixing proline and salicylic acid;
deposition of pt metal: dissolving 15 parts by weight of chloroplatinic acid in 100 parts by weight of water, regulating the pH value of the solution to be 4, adding 30 parts by weight of the modified carrier for fixing proline and salicylic acid prepared in the step T4, adding 10 parts by weight of citric acid, regulating the pH value of the solution to be 6, heating to 55 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain the catalyst.
Preparation example 3 preparation of catalyst
The method comprises the following steps:
t1, preparing hollow mesoporous silicon microspheres: dissolving 17 parts by weight of tetraethoxysilane in 100 parts by weight of ethyl acetate, adding 50 parts by weight of aqueous solution containing 1.5 parts by weight of cetyltrimethylammonium bromide, emulsifying for 15min at 12000r/min, regulating the pH value of the solution to 9.5, stirring and reacting for 6h, centrifuging, washing and drying to obtain hollow mesoporous silicon microspheres;
t2 preparation of diatomite composite silicon microsphere: cleaning 7 parts by weight of diatomite, ball-milling for 2.5 hours, drying, adding into 100 parts by weight of water, adding 13.5 parts by weight of the hollow mesoporous silicon microsphere prepared in the step T1, stirring and mixing for 20 minutes, centrifuging, and drying to prepare the diatomite composite silicon microsphere;
and T3, modification: adding 13.5 parts by weight of the diatomite composite silicon microsphere prepared in the step T2 into 100 parts by weight of water, adding 16 parts by weight of dopamine hydrochloride and 1.5 parts by weight of catalyst, heating to 45 ℃, stirring and reacting for 2.5 hours, centrifuging, washing and drying to prepare a modified carrier;
the catalyst was 4wt% CoCl 2 Tris-HCl solution at ph=5.5;
t4. immobilization of proline and salicylic acid: dissolving 4 parts by weight of proline and 1.5 parts by weight of salicylic acid in 100 parts by weight of 60wt% ethanol water solution, adding 17 parts by weight of the modified carrier prepared in the step T3, heating to 55 ℃, stirring and reacting for 35min, centrifuging, washing and drying to prepare the modified carrier for fixing the proline and the salicylic acid;
deposition of pt metal: 13.5 parts by weight of chloroplatinic acid is dissolved in 100 parts by weight of water, the pH value of the solution is regulated to 3.5, 27 parts by weight of the modified carrier for fixing proline and salicylic acid prepared in the step T4 is added, 8.5 parts by weight of citric acid is added, the pH value of the solution is regulated to 5.5, the solution is heated to 52 ℃, and the reaction is carried out for 1.5 hours under stirring, and the catalyst is prepared by centrifugation, washing and drying.
Comparative preparation example 1
In comparison with preparation example 3, the difference is that step T1 is not carried out.
Comparative preparation example 2
In comparison with preparation example 3, the difference is that step T2 is not carried out.
Comparative preparation example 3
In comparison with preparation example 3, the difference is that step T3 is not carried out.
Comparative preparation example 4
In comparison with preparation example 3, the difference is that no proline was added in step T4.
Comparative preparation example 5
In comparison with preparation example 3, the difference is that salicylic acid was not added in step T4.
Comparative preparation example 6
In comparison with preparation example 3, the difference is that step T4 is not carried out.
Comparative preparation example 7
In comparison with preparation example 3, the difference is that step T5 is not performed.
Test example 1
The catalysts prepared in preparation examples 1 to 3 and comparative preparation examples 1 to 7 were subjected to performance test, and the results are shown in Table 1.
0.5g of the catalyst was weighed and dissolved in a volumetric flask containing aqua regia, and the Pt content of the catalyst was measured by ICP (ICP is commonly referred to as inductively coupled plasma emission spectrometer Inductively coupled plasma atomic emission spectroscopy) and expressed in ppm
The specific surface area and pore volume parameters of the samples were measured using an ASAP2460 full-automatic specific surface and porosity analyzer manufactured by Micromeritics instruments, inc. of America.
TABLE 1
| Group of | Pt content (ppm) | Specific surface area (m) 2 /g） | Aperture (nm) | Pore volume (cm) 3 /g） |
| Preparation example 1 | 13.25 | 38.55 | 3.75 | 0.145 |
| Preparation example 2 | 13.27 | 38.59 | 3.77 | 0.147 |
| Preparation example 3 | 13.31 | 38.62 | 3.78 | 0.149 |
| Comparative preparation example 1 | 9.77 | 32.54 | 3.24 | 0.102 |
| Comparative preparation example 2 | 10.56 | 34.55 | 3.41 | 0.117 |
| Comparative preparation example 3 | 10.37 | 39.42 | 3.84 | 0.156 |
| Comparative preparation example 4 | 11.72 | 38.78 | 3.79 | 0.151 |
| Comparative preparation example 5 | 11.57 | 38.82 | 3.78 | 0.152 |
| Comparative preparation example 6 | 10.89 | 39.13 | 3.82 | 0.154 |
| Comparative preparation example 7 | / | 38.98 | 3.80 | 0.153 |
As is clear from the above table, the catalysts prepared in preparation examples 1-3 of the present invention have high Pt metal loading, large specific surface area and large pore volume.
Example 1
The embodiment provides a preparation method of slow-release sodium sarcosinate, which comprises the following steps:
s1, preparing sodium sarcosinate: adding a catalyst prepared in preparation example 1 into a 30wt% formaldehyde solution, wherein the addition amount of the catalyst is 3wt% of the total mass of the system, performing 1000W ultrasonic dispersion for 15min, adjusting the pH value to 7.2, adding hydrocyanic acid, stirring at 15 ℃ for reaction for 0.5h, obtaining a hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution to 1.2; the molar ratio of formaldehyde to hydrocyanic acid is 1:1, a step of;
s2, adding methylamine into the hydroxyacetonitrile solution prepared in the step S1, and stirring at 10 ℃ for reacting for 2 hours to prepare a methylaminoacetonitrile solution; the molar ratio of the hydroxyacetonitrile to the methylamine is 1:1;
s3, adding sodium hydroxide into the methylaminoacetonitrile solution prepared in the step S2, heating and stirring at 80 ℃ for reaction for 1h to prepare a sodium sarcosinate solution, and introducing the generated gas into 2mol/L sulfuric acid solution to prepare ammonium sulfate as a byproduct; the molar ratio of the methylaminoacetonitrile to the sodium hydroxide is 1:2;
s4, preparation of slow-release sodium sarcosinate: mixing 3 parts by weight of sodium carboxymethyl cellulose, 4 parts by weight of polyvinyl alcohol and 7 parts by weight of sodium alginate in 100 parts by weight of water to obtain a mixed solution, adding 15 parts by weight of the sodium sarcosinate solution prepared in the step S3, stirring and mixing for 20min, adding 200 parts by weight of corn oil, emulsifying for 10min at 12000r/min, dripping 3wt% of calcium nitrate solution, solidifying for 20min at normal temperature, centrifuging, washing and drying to obtain the slow-release sodium sarcosinate.
Example 2
The embodiment provides a preparation method of slow-release sodium sarcosinate, which comprises the following steps:
s1, preparing sodium sarcosinate: adding a catalyst prepared in preparation example 2 into 40wt% formaldehyde solution, wherein the addition amount of the catalyst is 5wt% of the total mass of the system, performing 1000W ultrasonic dispersion for 15min, adjusting the pH value to 7.5, adding hydrocyanic acid, stirring at 20 ℃ for reaction for 1h, obtaining hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution to 1.5; the molar ratio of formaldehyde to hydrocyanic acid is 1:1.1;
s2, adding methylamine into the hydroxyacetonitrile solution prepared in the step S1, and stirring and reacting for 3 hours at 15 ℃ to prepare a methylaminoacetonitrile solution; the molar ratio of the hydroxyacetonitrile to the methylamine is 1:1.05;
s3, adding sodium hydroxide into the methylaminoacetonitrile solution prepared in the step S2, heating and stirring at 90 ℃ for reaction for 2 hours to prepare a sodium sarcosinate solution, and introducing the generated gas into a sulfuric acid solution with the concentration of 4mol/L to prepare ammonium sulfate as a byproduct; the molar ratio of the methylaminoacetonitrile to the sodium hydroxide is 1:4;
s4, preparation of slow-release sodium sarcosinate: mixing 5 parts by weight of sodium carboxymethyl cellulose, 7 parts by weight of polyvinyl alcohol and 10 parts by weight of sodium alginate in 100 parts by weight of water to obtain a mixed solution, adding 20 parts by weight of the sodium sarcosinate solution prepared in the step S3, stirring and mixing for 20min, adding 200 parts by weight of peanut oil, emulsifying for 10min with 12000r/min, dripping 5wt% of ferric chloride solution, solidifying for 40min at normal temperature, centrifuging, washing and drying to obtain the slow-release sodium sarcosinate.
Example 3
The embodiment provides a preparation method of slow-release sodium sarcosinate, which comprises the following steps:
s1, preparing sodium sarcosinate: adding a catalyst prepared in preparation example 3 into 37wt% formaldehyde solution, wherein the addition amount of the catalyst is 4wt% of the total mass of the system, performing 1000W ultrasonic dispersion for 15min, adjusting the pH value to 7.35, adding hydrocyanic acid, stirring at 17 ℃ for reaction for 1h, obtaining hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution to 1.35; the molar ratio of formaldehyde to hydrocyanic acid is 1:1.05;
s2, adding methylamine into the hydroxyacetonitrile solution prepared in the step S1, and stirring and reacting for 2.5 hours at the temperature of 12 ℃ to prepare a methylaminoacetonitrile solution; the molar ratio of the hydroxyacetonitrile to the methylamine is 1:1.02;
s3, adding sodium hydroxide into the methylaminoacetonitrile solution prepared in the step S2, heating and stirring at 85 ℃ for reaction for 1.5 hours to prepare a sodium sarcosinate solution, and introducing the generated gas into a sulfuric acid solution with the concentration of 3mol/L to prepare ammonium sulfate as a byproduct; the molar ratio of the methylaminoacetonitrile to the sodium hydroxide is 1:3;
s4, preparation of slow-release sodium sarcosinate: mixing and dissolving 4 parts by weight of sodium carboxymethyl cellulose, 5 parts by weight of polyvinyl alcohol and 8.5 parts by weight of sodium alginate in 100 parts by weight of water to obtain a mixed solution, adding 17 parts by weight of the sodium sarcosinate solution prepared in the step S3, stirring and mixing for 20min, adding 200 parts by weight of soybean oil, emulsifying for 10min at 12000r/min, dripping 4wt% of calcium nitrate and calcium chloride solution, solidifying for 30min at normal temperature, centrifuging, washing and drying to obtain the slow-release sodium sarcosinate.
Example 4
The difference compared to example 3 is that the first pH value in step S1 is adjusted to 5.
Example 5
In comparison with example 3, the difference is that the first pH value in step S1 is adjusted to 11, and the reaction is stopped in time because the reaction is too severe, so that the next reaction is not performed.
Comparative examples 4 to 7
In comparison with example 3, the catalysts were prepared from comparative preparations 1-7.
Comparative example 8
In comparison with example 3, the difference is that step S4 was not performed, and the sodium sarcosinate solution obtained in step S3 was directly concentrated and dehydrated to obtain sodium sarcosinate.
Test example 2
The products prepared in examples 1-4 and comparative examples 1-8 were subjected to performance testing, and the results are shown in Table 2.
Stability test:
and (3) testing the cyclic freeze thawing stability: putting the sample into a low-temperature box at the temperature of minus 20 ℃ for 24 hours, immediately putting the sample into a blast drying box at the temperature of 50 ℃ for heating for 8 hours after taking out, performing 3 cycles in this way, and standing the sample for 24 hours under the condition of normal temperature and normal pressure after taking out;
high temperature stability test: the sample is put into an oven at 80 ℃ for 7d and 14d, and is placed for 24h under normal temperature and normal pressure after being taken out.
TABLE 2
As is clear from the table above, the sodium sarcosinate prepared in examples 1 to 3 of the present invention has high yield, and the prepared slow-release sodium sarcosinate can withstand high temperature and has good stability to circulating freeze thawing.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A method for preparing slow-release sodium sarcosinate, which is characterized by comprising the following steps:
s1, preparing sodium sarcosinate: adding a catalyst into formaldehyde solution, dispersing uniformly, adjusting the pH value to be a first pH value, adding hydrocyanic acid, stirring for reaction to obtain a hydroxyacetonitrile solution, filtering the catalyst, recycling the catalyst, and adjusting the pH value of the solution to be a second pH value;
the catalyst is a Pt-loaded modified carrier catalyst for fixing proline and salicylic acid;
s2, adding methylamine into the hydroxyacetonitrile solution prepared in the step S1, and stirring for reaction to prepare a methylaminoacetonitrile solution;
s3, adding sodium hydroxide into the methylaminoacetonitrile solution prepared in the step S2, heating and stirring for reaction to prepare a sodium sarcosinate solution, and introducing generated gas into acid liquor to prepare a byproduct;
s4, preparation of slow-release sodium sarcosinate: and (3) mixing and dissolving sodium carboxymethylcellulose, polyvinyl alcohol and sodium alginate in water to obtain a mixed solution, adding the sodium sarcosinate solution prepared in the step (S3), stirring and mixing uniformly, adding edible oil, emulsifying, dripping a metal salt solution, solidifying at normal temperature, centrifuging, washing and drying to obtain the slow-release sodium sarcosinate.
2. The preparation method according to claim 1, wherein the preparation method of the catalyst is as follows:
t1, preparing hollow mesoporous silicon microspheres: dissolving alkyl orthosilicate in an organic solvent, adding an aqueous solution containing a pore-forming agent, emulsifying, adjusting the pH value of the solution, stirring for reaction, centrifuging, washing and drying to obtain hollow mesoporous silicon microspheres;
t2 preparation of diatomite composite silicon microsphere: cleaning diatomite, ball milling, drying, adding the diatomite into water, adding the hollow mesoporous silicon microspheres prepared in the step T1, stirring and uniformly mixing, centrifuging and drying to prepare diatomite composite silicon microspheres;
and T3, modification: adding the diatomite composite silicon microsphere prepared in the step T2 into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing and drying to obtain a modified carrier;
t4. immobilization of proline and salicylic acid: dissolving proline and salicylic acid in ethanol water solution, adding the modified carrier prepared in the step T3, heating, stirring, reacting, centrifuging, washing, and drying to obtain a modified carrier for fixing proline and salicylic acid;
deposition of pt metal: dissolving chloroplatinic acid in water, regulating the pH value of the solution to 3-4, adding the modified carrier for fixing proline and salicylic acid prepared in the step T4, adding citric acid, regulating the pH value of the solution to 5-6, heating and stirring for reaction, centrifuging, washing and drying to obtain the catalyst.
3. The preparation method according to claim 2, wherein in the step T1, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, the pore-forming agent is at least one selected from cetyltrimethylammonium bromide, cetyldimethylbenzyl ammonium chloride, tetradecyltrimethylammonium chloride and octadecyl trimethyl ammonium bromide, the mass ratio of the alkyl orthosilicate to the pore-forming agent is 15-20:1-2, the pH value of the solution is adjusted to 9-10, and the stirring reaction time is 5-7h.
4. The preparation method according to claim 2, wherein the mass ratio of the diatomite to the hollow mesoporous silicon microsphere in the step T2 is 5-10:12-15, and the ball milling time is 2-3h.
5. The preparation method according to claim 2, wherein in the step T3, the mass ratio of the diatomite composite silicon microsphere, the dopamine hydrochloride and the catalyst is 12-15:15-17:1-2, and the catalyst is 3-5wt% CoCl 2 The temperature of the heating and stirring reaction is 40-50 ℃ and the time is 2-3h.
6. The preparation method according to claim 2, wherein in the step T4, the mass ratio of the proline to the salicylic acid to the modified carrier is 3-5:1-2:15-20, the concentration of the ethanol in the ethanol aqueous solution is 50-70wt%, the temperature of the heating and stirring reaction is 50-60 ℃ and the time is 30-40min.
7. The preparation method according to claim 2, wherein the mass ratio of the chloroplatinic acid, the citric acid, the immobilized proline and the salicylic acid modified carrier in the step T5 is 12-15:7-10:25-30, the temperature of the heating and stirring reaction is 50-55 ℃ and the time is 1-2h.
8. The method according to claim 1, wherein the concentration of the formaldehyde solution in the step S1 is 30-40wt%, and the molar ratio of formaldehyde to hydrocyanic acid is 1:1-1.1, wherein the addition amount of the catalyst is 3-5wt% of the total mass of the system, the temperature of the stirring reaction is 15-20 ℃, the time is 0.5-1h, the first pH value is 7.2-7.5, and the second pH value is 1.2-1.5; in the step S2, the molar ratio of the hydroxyacetonitrile to the methylamine is 1:1-1.05, the temperature of the stirring reaction is 10-15 ℃, and the time is 2-3h.
9. The preparation method according to claim 1, wherein in the step S3, the molar ratio of the methylaminoacetonitrile to the sodium hydroxide is 1:2-4, the temperature of the heating and stirring reaction is 80-90 ℃ for 1-2 hours, the acid solution is 2-4mol/L sulfuric acid solution, and the by-product is ammonium sulfate; in the step S4, the mass ratio of the sodium carboxymethyl cellulose to the polyvinyl alcohol to the sodium alginate to the sodium sarcosinate is 3-5:4-7:7-10:15-20, the metal salt is at least one of calcium chloride, aluminum chloride, ferric chloride, ferrous chloride, magnesium chloride, aluminum nitrate, calcium nitrate, magnesium nitrate and ferric nitrate, the concentration of the metal salt solution is 3-5wt%, the normal-temperature curing time is 20-40min, and the edible oil is at least one of peanut oil, corn oil, rapeseed oil, soybean oil, olive oil and linseed oil.
10. A slow release sodium sarcosinate produced by the production process as claimed in any one of claims 1 to 9.
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