CN116102471A - Preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate - Google Patents
Preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate Download PDFInfo
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- CN116102471A CN116102471A CN202310122126.5A CN202310122126A CN116102471A CN 116102471 A CN116102471 A CN 116102471A CN 202310122126 A CN202310122126 A CN 202310122126A CN 116102471 A CN116102471 A CN 116102471A
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- zinc
- dimethyl
- formaldehyde
- hydroxymethylsulfinate
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- CAAIULQYGCAMCD-UHFFFAOYSA-L zinc;hydroxymethanesulfinate Chemical compound [Zn+2].OCS([O-])=O.OCS([O-])=O CAAIULQYGCAMCD-UHFFFAOYSA-L 0.000 title claims abstract description 57
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004280 Sodium formate Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 24
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 24
- 238000003860 storage Methods 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 150000002443 hydroxylamines Chemical class 0.000 claims abstract description 10
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical class C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 41
- 239000011259 mixed solution Substances 0.000 claims description 26
- -1 hydroxylamine compound Chemical class 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 18
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 13
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 12
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 8
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 7
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 6
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 claims description 6
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 claims description 6
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 claims description 6
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 6
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 6
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 5
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 5
- BDUPRNVPXOHWIL-UHFFFAOYSA-N dimethyl sulfite Chemical compound COS(=O)OC BDUPRNVPXOHWIL-UHFFFAOYSA-N 0.000 claims description 5
- AHLZREDQAWCTTL-UHFFFAOYSA-N 3-chloro-4,5-dimethylphthalic acid Chemical compound CC1=C(C(=C(C(C(=O)O)=C1)C(=O)O)Cl)C AHLZREDQAWCTTL-UHFFFAOYSA-N 0.000 claims description 4
- FCEXFJZCHYBECX-UHFFFAOYSA-N 3-(2-aminoethyl)-1h-indol-2-ol Chemical compound C1=CC=C2C(CCN)=C(O)NC2=C1 FCEXFJZCHYBECX-UHFFFAOYSA-N 0.000 claims description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- JFLCYRMPFSKFKJ-UHFFFAOYSA-N hydroxymethanesulfinic acid;zinc Chemical compound [Zn].OCS(O)=O JFLCYRMPFSKFKJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 61
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 15
- 238000004043 dyeing Methods 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 238000007639 printing Methods 0.000 description 7
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 6
- XUIVKWAWICCWIQ-UHFFFAOYSA-M sodium;formaldehyde;hydrogen sulfite Chemical compound [Na+].O=C.OS([O-])=O XUIVKWAWICCWIQ-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- 229940001584 sodium metabisulfite Drugs 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUNDKLAGHABJDI-UHFFFAOYSA-N dimethyl carbonate;methanol Chemical compound OC.COC(=O)OC GUNDKLAGHABJDI-UHFFFAOYSA-N 0.000 description 1
- YTFQGOTZEBLYNR-UHFFFAOYSA-N dimethyl sulfite;methanol Chemical compound OC.COS(=O)OC YTFQGOTZEBLYNR-UHFFFAOYSA-N 0.000 description 1
- 238000010018 discharge printing Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a formaldehyde-free reducing agent zinc hydroxymethylsulfinate, which comprises the steps of sequentially adding hydroxylamine compounds, dimethyl ester compounds, sodium formate and zinc catalyst powder into a reaction system, reacting to obtain a zinc hydroxymethylsulfinate solution, concentrating and drying the solution to obtain formaldehyde-free zinc hydroxymethylsulfinate with stable storage. The invention realizes the preparation of the zinc hydroxymethylsulfinate which has no free formaldehyde and stable storage, and the method can be stably produced in a conventional chemical plant and has no special requirement on equipment.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a preparation method of a formaldehyde-free reducer zinc hydroxymethylsulfinate.
Background
The reducing agent is a substance that loses electrons or has electrons deviated in the oxidation-reduction reaction. The reducing agent itself has reducing property and is oxidized, and the product is called an oxidized product. The reduction and oxidation reactions are performed simultaneously, that is, the reducing agent itself is oxidized to become an oxide while the reducing agent is oxidized to the reduced material. The reactant containing a substance whose valence is increased is a reducing agent. The reducing agent is needed in the processes of bleaching, vat dye dyeing, sulfur dye dyeing, vat cleaning after disperse dye dyeing, even egg dye ground discharge printing and the like in the printing and dyeing process. The reducing agents commonly used in the printing and dyeing process include sodium hydrosulfite, thiourea dioxide, sodium sulfite, sodium sulfide, sodium thiosulfate, rongalite, sodium pyrophosphate and the like. Among the reducing agents, the sodium hydrosulfite and the rongalite are the most widely used varieties, but the sodium hydrosulfite is easy to release heat and spontaneous combustion when meeting water, has inflammability, explosiveness and toxicity, and belongs to dangerous chemicals; the rongalite is decomposed when meeting acid, and the aqueous solution starts to decompose harmful substances at the temperature of more than 60 ℃ and generates toxic gases such as formaldehyde, sulfur dioxide, hydrogen sulfide and the like when decomposing at the temperature of 120 ℃. Therefore, a green, safe, ecological and environment-friendly reducing agent is urgently needed in the printing and dyeing product processing process in China, and the green, healthy and stable development of the printing and dyeing industry in China is promoted.
The invention patent CN 107793305A discloses a preparation method of sodium bisulphite formaldehyde powder with low free formaldehyde and low zinc, sodium metabisulfite, zinc powder and formaldehyde solution are used as raw materials, inorganic acid is used as an activating agent, sodium bisulphite formaldehyde (diabro white block) is produced by a one-step method, free formaldehyde in the diabro white powder is reduced, and the reaction process needs to be kept at the temperature of 95-102 ℃ at the maximum for 90-120 min. The invention patent CN 104478682A discloses a method for improving the stability of a rongalite solution, which is characterized in that a buffer agent or a combination of the buffer agent, a chelating agent and a blocking agent is added into the rongalite solution prepared in the rongalite solution or rongalite product production process, the solution is filtered after being fully and uniformly mixed, and is packaged in a clean, dark and opaque plastic container for airtight preservation. CN109265379a discloses a preparation method of sodium metabisulfite, zinc powder, catalyst and formaldehyde are sequentially added into a reaction system under the condition of ultrasonic stirring to obtain sodium bisulphite formaldehyde solution, then polyphenol compound and drying agent are added into the sodium bisulphite formaldehyde solution to obtain sodium bisulphite formaldehyde stable storage solution which is uniformly mixed, and finally the solution is concentrated and dried to obtain the sodium bisulphite formaldehyde stable storage solution which is free of free formaldehyde and stable in storage. Sodium formaldehyde sulfoxylate is prepared by adopting a one-step ultrasonic method, and after the polyphenol compound and silica gel are added, the free formaldehyde-free and storage-stable rongalite powder is obtained. The method reduces the reaction temperature and the reaction time required by preparing sodium formaldehyde sulfoxylate, saves energy consumption and time, improves the production efficiency, reduces the production cost, and greatly improves the storage stability of the prepared rongalite without free formaldehyde.
According to the synthesis method of the rongalite, formaldehyde is used as a raw material in the synthesis process, or an auxiliary agent for removing free formaldehyde is added in the treatment of the synthesized finished product, and the final finished product does not meet the requirement of free formaldehyde. At present, no report on a synthetic method of formaldehyde-free zinc hydroxymethylsulfinate is available.
Disclosure of Invention
The invention aims to solve the technical problems that formaldehyde is needed to be used as a raw material in the current synthesis process of the rongalite reducing agent, the commercial rongalite reducing agent contains more free formaldehyde and has poor stability in the storage process, and the invention provides a method for realizing free formaldehyde and stable storage in the commercial rongalite reducing agent powder by not adding formaldehyde as a reactant in the synthesis process of the reducing agent.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps:
(1) Uniformly mixing 50 parts by weight of hydroxylamine compounds and dimethyl ester compounds according to a certain molar ratio, and dissolving the mixture in 100 parts by weight of organic alcohol solution to obtain an organic alcohol mixed solution A;
(2) Adding 30 parts by weight of sodium formate into the organic alcohol mixed solution A obtained in the step (1) to obtain an organic alcohol mixed solution B of hydroxylamine compounds, dimethyl ester compounds and sodium formate;
(3) Heating the organic alcohol mixed solution B to 70-100 ℃, adding 5-10 parts by weight of catalyst zinc powder, continuously preserving heat for 2-10 hours, washing the reacted product, and carrying out suction filtration to obtain a washing solution, namely a hydroxymethyl sulfinic acid zinc solution;
(4) Concentrating and drying the zinc hydroxymethylsulfinate solution obtained in the step (3) to obtain formaldehyde-free zinc hydroxymethylsulfinate with stable storage.
Further, the hydroxylamine compound in the step (1) is one or more of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine-O-sulfonic acid, 2-hydroxytryptamine, N-phenylhydroxylamine and N, N-diethylhydroxylamine.
Further, the dimethyl ester compound in the step (1) is one or more of dimethyl carbonate, dimethyl adipate, dimethyl chlorophthalic acid, dimethyl phosphate, dimethyl oxalate, dimethyl sulfite, dimethyl fumarate, dimethyl succinate and dimethyl maleate.
Further, in the step (1), the molar ratio of the hydroxylamine compound to the dimethyl ester compound is 1:1-4:1.
Further, the organic alcohol in the step (1) is one or more of methanol, ethanol, propanol and n-butanol.
Further, the particle size of the catalyst zinc powder in the step (3) is 1-100 nm.
The invention also provides the formaldehyde-free reducer zinc hydroxymethanesulfinate prepared by the preparation method.
The invention has the beneficial effects that: the invention discloses a preparation method of formaldehyde-free zinc hydroxymethylsulfinate, which is characterized in that organic alcohol and sodium formate are adopted for synthesizing hydroxylamine compounds as synthesis intermediates, and then hydroxylamine compounds and dimethyl ester compounds are utilized to react to prepare formaldehyde-free zinc hydroxymethylsulfinate, so that the final finished product does not contain free formaldehyde unlike the traditional process requiring formaldehyde as an intermediate, and the requirements of the current printing and dyeing processing on green printing and dyeing auxiliary agents and clean printing and dyeing production are met. The technical scheme of the invention has simple and feasible process, no special requirement on synthetic raw materials, and can realize large-scale production by utilizing conventional chemical plant equipment, thereby having wide application prospect.
Drawings
FIG. 1 is an infrared spectrum of the product obtained in example 1 of the present invention.
FIG. 2 is a graph showing the hydrogen spectrum of the product obtained in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the invention, and that numerous insubstantial modifications and adaptations can be made by those skilled in the art in light of the foregoing disclosure.
The preparation method of the formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine compounds and dimethyl ester compounds according to a certain molar ratio, dissolving the mixture in 100 parts by weight of organic alcohol solution, adding 30 parts by weight of sodium formate into the organic alcohol solution of the hydroxylamine compounds and the dimethyl ester compounds to obtain an organic alcohol mixed solution of the hydroxylamine compounds, the dimethyl ester compounds and the sodium formate, heating the mixed solution to 70-100 ℃, adding 5-10 parts by weight of catalyst zinc powder into the system, continuously preserving heat for 2-10 hours, washing and suction-filtering the reacted product, and obtaining a washing liquid, namely the hydroxymethyl zinc sulfinate solution.
Preferably, the hydroxylamine compound is one or more of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine-O-sulfonic acid, 2-hydroxytryptamine, N-phenylhydroxylamine, N-diethylhydroxylamine.
Preferably, the dimethyl ester compound is one or more of dimethyl carbonate, dimethyl adipate, dimethyl chlorophthalic acid, dimethyl phosphate, dimethyl oxalate, dimethyl sulfite, dimethyl fumarate, dimethyl succinate and dimethyl maleate.
Preferably, the molar ratio of the hydroxylamine compound to the dimethyl ester compound is 1:1-4:1.
Preferably, the organic alcohol is one or more of methanol, ethanol, propanol and n-butanol.
Preferably, the zinc powder serving as the catalyst has the particle size of 1-100 nm.
Example 1
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine and dimethyl carbonate in total into 100 parts by weight of methanol solution according to a molar ratio of 1:1, adding 30 parts by weight of sodium formate into the hydroxylamine and dimethyl carbonate methanol solution to obtain a methanol mixed solution of the hydroxylamine, the dimethyl carbonate and the sodium formate, heating the mixed solution to 70 ℃, adding 5 parts by weight of catalyst zinc powder with the particle size of 1nm into the system, continuously preserving heat for 2 hours, and washing and suction-filtering a product after the reaction to obtain a lotion which is the hydroxymethyl zinc sulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 2
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine sulfate and dimethyl adipate in total in a molar ratio of 2:1, dissolving in 100 parts by weight of ethanol solution, adding 30 parts by weight of sodium formate into the ethanol solution of the hydroxylamine sulfate and the dimethyl adipate to obtain an ethanol mixed solution of the hydroxylamine sulfate, the dimethyl adipate and the sodium formate, heating the mixed solution to 100 ℃, adding 10 parts by weight of 100nm catalyst zinc powder into the system, continuously preserving heat for 10 hours, and washing and suction-filtering a product after the reaction to obtain a lotion, namely the hydroxymethyl zinc sulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 3
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine hydrochloride and dimethyl chlorophthalic acid ester in a molar ratio of 2:1, dissolving in 100 parts by weight of propanol solution, adding 30 parts by weight of sodium formate into the hydroxylamine hydrochloride and dimethyl chlorophthalic acid ester propanol solution to obtain a propanol mixed solution of the hydroxylamine hydrochloride, the dimethyl chlorophthalic acid ester and the sodium formate, heating the mixed solution to 90 ℃, adding 6 parts by weight of catalyst zinc powder with the particle size of 40nm into the system, continuously preserving heat for 7 hours, washing and suction-filtering a product after reaction, and obtaining a washing liquid, namely the hydroxymethyl zinc sulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 4
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine-O-sulfonic acid and dimethyl phosphate in total in a molar ratio of 4:1, dissolving in 100 parts by weight of n-butanol solution, adding 30 parts by weight of sodium formate into the hydroxylamine-O-sulfonic acid and dimethyl phosphate n-butanol solution to obtain an n-butanol mixed solution of hydroxylamine-O-sulfonic acid, dimethyl phosphate and sodium formate, heating the mixed solution to 80 ℃, adding 7 parts by weight of catalyst zinc powder with the particle size of 55nm into the system, continuously preserving heat for 6 hours, washing and suction-filtering the reacted product, and obtaining a washing solution, namely the hydroxymethyl zinc sulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 5
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of N-phenylhydroxylamine and dimethyl oxalate according to a molar ratio of 4:1, dissolving in 100 parts by weight of N-butanol solution, adding 30 parts by weight of sodium formate into the N-phenylhydroxylamine and dimethyl oxalate N-butanol solution to obtain an N-butanol mixed solution of N-phenylhydroxylamine, dimethyl oxalate and sodium formate, heating the mixed solution to 75 ℃, adding 9 parts by weight of catalyst zinc powder with the particle size of 65nm into the system, continuously preserving heat for 3 hours, washing and suction-filtering the reacted product, and obtaining a washing solution, namely the hydroxymethyl zinc sulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 6
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: uniformly mixing 50 parts by weight of hydroxylamine sulfate and dimethyl sulfite in total in a molar ratio of 3:1, dissolving in 100 parts by weight of methanol solution, adding 30 parts by weight of sodium formate into the hydroxylamine sulfate and dimethyl sulfite methanol solution to obtain a methanol mixed solution of hydroxylamine sulfate, dimethyl sulfite and sodium formate, heating the mixed solution to 95 ℃, adding 10 parts by weight of 85nm catalyst zinc powder into the system, continuously preserving the temperature for 4.5 hours, washing and suction-filtering the reacted product, and obtaining a lotion, namely the hydroxymethyl zinc sulfite solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 7
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: and uniformly mixing 50 parts by weight of hydroxylamine hydrochloride and dimethyl fumarate according to a molar ratio of 2.5:1, dissolving in 100 parts by weight of ethanol solution, adding 30 parts by weight of sodium formate into the ethanol solution of the hydroxylamine hydrochloride and the dimethyl fumarate to obtain an ethanol mixed solution of the hydroxylamine hydrochloride, the dimethyl fumarate and the sodium formate, heating the mixed solution to 70 ℃, adding 6 parts by weight of 5nm catalyst zinc powder into the system, continuously preserving the temperature for 7.5 hours, washing and suction-filtering the reacted product, and obtaining a washing liquid, namely the hydroxymethyl sulfinic acid zinc solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Example 8
A preparation method of formaldehyde-free reducer zinc hydroxymethylsulfinate comprises the following steps: and uniformly mixing 50 parts by weight of hydroxylamine sulfate, dimethyl succinate and dimethyl maleate (the molar ratio of the dimethyl succinate to the dimethyl maleate is 1:1) in total into 100 parts by weight of ethanol solution according to the molar ratio of 3.5:1, adding 30 parts by weight of sodium formate into the ethanol solution of the hydroxylamine sulfate, the dimethyl succinate and the dimethyl maleate to obtain an ethanol mixed solution of the hydroxylamine sulfate, the dimethyl succinate and the sodium formate, heating the mixed solution to 90 ℃, adding 9 parts by weight of catalyst zinc powder with the particle size of 15nm into the system, continuously preserving the heat for 3.5 hours, and washing and suction-filtering the reacted product to obtain a washing liquid, namely the zinc hydroxymethylsulfinate solution. Concentrating and drying the zinc hydroxymethanesulfinate solution to obtain formaldehyde-free zinc hydroxymethanesulfinate with stable storage.
Effect of the invention
After the treatments of examples 1 to 8, the products were subjected to the following tests, the test results of which are shown in Table 1.
1) Determination of free formaldehyde
The content of free formaldehyde in the zinc hydroxymethylsulfinate is tested according to GB/T5543-2006 method for measuring the total formaldehyde content in a resin finishing agent.
2) Determination of storage stability
After the zinc hydroxymethanesulfinate sample was exposed to air for half a month, the effective content of zinc hydroxymethanesulfinate was measured by an iodometry method to test its storage stability.
Table 1 free formaldehyde emission and storage stability of the zinc hydroxymethylsulfinate product prepared in the examples
As shown in Table 1, the zinc hydroxymethylsulfinate synthesized by the technical scheme provided by the invention has no free formaldehyde, and the effective content of the zinc hydroxymethylsulfinate sample is 100% after the zinc hydroxymethylsulfinate sample is exposed to air and stored for half a month. Therefore, the technical scheme provided by the invention can endow the zinc hydroxymethanesulfinate with zero free formaldehyde release amount and stable storage stability.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. The preparation method of the formaldehyde-free reducer zinc hydroxymethylsulfinate is characterized by comprising the following steps of:
(1) Uniformly mixing 50 parts by weight of hydroxylamine compounds and dimethyl ester compounds according to a certain molar ratio, and dissolving the mixture in 100 parts by weight of organic alcohol solution to obtain an organic alcohol mixed solution A;
(2) Adding 30 parts by weight of sodium formate into the organic alcohol mixed solution A obtained in the step (1) to obtain an organic alcohol mixed solution B of hydroxylamine compounds, dimethyl ester compounds and sodium formate;
(3) Heating the organic alcohol mixed solution B to 70-100 ℃, adding 5-10 parts by weight of catalyst zinc powder, continuously preserving heat for 2-10 hours, washing the reacted product, and carrying out suction filtration to obtain a washing solution, namely a hydroxymethyl sulfinic acid zinc solution;
(4) Concentrating and drying the zinc hydroxymethylsulfinate solution obtained in the step (3) to obtain formaldehyde-free zinc hydroxymethylsulfinate with stable storage.
2. The method for preparing formaldehyde-free reducer zinc hydroxymethylsulfinate according to claim 1, characterized in that: the hydroxylamine compound in the step (1) is one or more of hydroxylamine, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine-O-sulfonic acid, 2-hydroxytryptamine, N-phenylhydroxylamine and N, N-diethylhydroxylamine.
3. The method for preparing formaldehyde-free reducer zinc hydroxymethylsulfinate according to claim 1, characterized in that: the dimethyl ester compound in the step (1) is one or more of dimethyl carbonate, dimethyl adipate, dimethyl chlorophthalic acid, dimethyl phosphate, dimethyl oxalate, dimethyl sulfite, dimethyl fumarate, dimethyl succinate and dimethyl maleate.
4. The method for preparing formaldehyde-free reducer zinc hydroxymethylsulfinate according to claim 1, characterized in that: the molar ratio of the hydroxylamine compound to the dimethyl ester compound in the step (1) is 1:1-4:1.
5. The method for preparing formaldehyde-free reducer zinc hydroxymethylsulfinate according to claim 1, characterized in that: the organic alcohol in the step (1) is one or more of methanol, ethanol, propanol and n-butanol.
6. The method for preparing formaldehyde-free reducer zinc hydroxymethylsulfinate according to claim 1, characterized in that: the particle size of the catalyst zinc powder in the step (3) is 1-100 nm.
7. Zinc hydroxymethanesulfinate, a formaldehyde-free reducing agent, made by the process of any one of claims 1-6.
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