CN116283616B - Method for co-producing ZF-10 and BDMAEE - Google Patents
Method for co-producing ZF-10 and BDMAEE Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 238000006266 etherification reaction Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000007069 methylation reaction Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012223 aqueous fraction Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VXPJBVRYAHYMNY-UHFFFAOYSA-N n-methyl-2-[2-(methylamino)ethoxy]ethanamine Chemical group CNCCOCCNC VXPJBVRYAHYMNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims 1
- -1 amine ether compounds Chemical class 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 6
- 239000012972 dimethylethanolamine Substances 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- PVXVWWANJIWJOO-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-N-ethylpropan-2-amine Chemical compound CCNC(C)CC1=CC=C2OCOC2=C1 PVXVWWANJIWJOO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- QMMZSJPSPRTHGB-UHFFFAOYSA-N MDEA Natural products CC(C)CCCCC=CCC=CC(O)=O QMMZSJPSPRTHGB-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YSAANLSYLSUVHB-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]ethanol Chemical compound CN(C)CCOCCO YSAANLSYLSUVHB-UHFFFAOYSA-N 0.000 description 1
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005913 hydroamination reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013518 molded foam Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a production process of amine ether compounds, in particular to a method for co-producing two useful amine ether products, namely N, N, N '-trimethyl-N' -hydroxyethyl bis-aminoethyl ether (ZF 10 for short) and bis (dimethylaminoethyl ether (BDMAEE for short). The method comprises the following steps: MMEA is used as a raw material, and an etherified liquid containing BMAEE is prepared through sulfuric acid catalytic etherification; the BMAEE fraction, formaldehyde and hydrogen are subjected to selective N-methylation under the action of a catalyst to synthesize a solution containing TMAEE and BDMAEE, and the catalyst is recycled; and (3) carrying out hydroxyethylation reaction on the solution containing TMAEE and BDMAEE and EO under the protection of inert gas to obtain BDMAEE and ZF-10.
Description
Technical Field
The invention relates to a production process of amine ether compounds, in particular to a method for co-producing two useful amine ether products, namely N, N, N '-trimethyl-N' -hydroxyethyl bis-aminoethyl ether (ZF 10 for short) and bis (dimethylaminoethyl ether (BDMAEE for short).
Background
ZF-10 is colorless or pale yellow transparent liquid, is soluble in water, has a structural formula as S-1, is an important low-odor reactive polyurethane foaming catalyst, and is commonly used for preparing polyether polyurethane soft foam, molded foam, hard foam for packaging and the like.
S-1
BDMAEE is a colorless liquid, dissolved in water. The structural formula is shown as S-2, and the catalyst is used as a high-efficiency tertiary amine catalyst, is almost suitable for the production of all foam plastic products, is mainly used for soft foam products, and is particularly suitable for high-resilience products.
The main synthesis method of ZF-10 at present comprises the following steps:
1) The preparation method of ZF10 disclosed in patent CN 108084040A adopts dimethylaminoethoxy ethanol as a raw material, uses oxygen to oxidize an intermediate product under the action of a catalyst, mixes the intermediate product with N-methylethanolamine, and adopts Raney Ni to catalyze and aminate to synthesize ZF10. The method has high raw material cost and low yield.
The equation of the reaction is as follows:
2) The preparation method of ZF10 disclosed in patent CN108250088A adopts N, N-Dimethylethanolamine (DMEA) and chloroacetaldehyde dimethyl acetal as raw materials, and comprises the steps of nucleophilic substitution and hydrolysis to obtain an intermediate product, mixing with MMEA, and carrying out hydroamination by taking Raney Ni as a catalyst to synthesize ZF10. The method has low atom economy, the production process involves environment-friendly byproducts such as halogen, generated salt and the like, equipment corrosion is serious, and treatment is difficult.
The equation of the reaction is as follows:
3) Two methods for preparing ZF10 are disclosed in patent CN104341313A,
firstly, DMEA and N-methyldiethanolamine (MDEA for short) are used as main raw materials, firstly, DMEA reacts with sodium metal to obtain sodium alkoxide, methyl diethanolamine (MDEA for short) reacts with thionyl chloride to obtain monochloride, and then reacts with sodium salt of DMEA to synthesize ZF10.
The equation of the reaction is as follows:
in the second method, N-methylethanolamine (MMEA), DMEA and ethylene oxide are used as main raw materials, MMEA reacts with metallic sodium to obtain sodium salt of MMEA, DMEA reacts with thionyl chloride to obtain chloride, then MMEA sodium reacts with chloride to obtain N, N, N' -trimethyl diethyl amine ether (TMAEE), and finally TMAEE reacts with Ethylene Oxide (EO) to synthesize ZF10. The two methods are used for generating hydrogen by using active metal sodium, the process is high in risk, equipment is severely corroded by using thionyl chloride, and byproducts such as halogen salt and sulfur dioxide are generated, so that the method is not friendly to the environment.
The equation of the reaction is as follows:
disclosure of Invention
The invention aims to provide a ZF-10 and BDMAEE co-production method.
In order to solve the technical problems, the invention provides a method for co-producing ZF-10 and BDMAEE, which mainly comprises the following three steps:
1) Etherification:
MMEA is used as a raw material, and an etherified liquid containing BMAEE is prepared through sulfuric acid catalytic etherification; neutralizing, filtering, rectifying and separating the etherified liquid containing BMAEE, thereby recovering unconverted MMEA and obtaining BMAEE fraction;
the etherification temperature is 150-190 ℃, the time is 1-20 h, and the molar ratio of MMEA to sulfuric acid is 1:1-3;
MMEA is N-methylethanolamine and BMAEE is di (methylaminoethyl) ether;
description: in the etherification process, byproduct water is distilled out; cooling to be less than or equal to 40 ℃ after the reaction is finished, and obtaining etherified liquid containing BMAEE;
2) N-methylation:
the BMAEE fraction obtained in the step 1) is selectively N-methylated with formaldehyde and hydrogen under the action of a catalyst to synthesize a solution containing TMAEE and BDMAEE, and the catalyst is recycled;
the formaldehyde is 37 percent (mass percent) formaldehyde aqueous solution, and the molar ratio of BMAEE fraction to formaldehyde is 1:1.1-3; the Raney Ni catalyst accounts for 5-20% of the weight of the BMAEE fraction, the hydrogen pressure is 0.5-10 Mpa, and the temperature is 50-200 ℃; the reaction time is 3-6 h;
TMAEE is N, N, N' -trimethylbisethylamine ether, BDMAEE is bis (dimethylaminoethyl) ether;
3) Hydroxyethylation:
carrying out hydroxyethylation reaction on the solution containing TMAEE and BDMAEE and EO under the protection of inert gas (such as nitrogen), wherein the molar ratio of TMAEE to EO is 1:1-3, the reaction temperature is 40-160 ℃, and the reaction time is 3-6 h; after the reaction materials are cooled to room temperature, performing vacuum rectification to obtain BDMAEE and ZF-10 respectively;
EO is ethylene oxide; ZF10 is N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether.
As an improvement of the method for co-producing ZF-10 and BDMAEE of the invention:
the step 2) is as follows:
after the reaction is finished (the reaction is finished when no hydrogen is absorbed), cooling the obtained reaction liquid to room temperature, then, carrying out pressure filtration on inert gas (such as nitrogen), rectifying the filtrate at normal pressure (thereby evaporating water and unconverted raw materials in the filtrate), and obtaining a residual liquid, wherein the residual liquid is a solution containing TMAEE and BDMAEE; the filter cake is circularly used as a catalyst (hydrogenation catalyst) after alkali washing (the filter cake is soaked in 35-45 mass percent sodium hydroxide solution for about 20-40 min under the protection of inert gas nitrogen) and water washing until the pH value is 8+/-0.2;
description: after the set time is up, stopping hydrogenation, and stopping the reaction at the moment when the pressure in the kettle is kept unchanged, namely, the kettle does not absorb hydrogen.
And (3) rectifying filtrate at normal pressure: the unconverted feedstock is excess formaldehyde and BMAEE which may not be completely converted at 100-160 ℃. If the complete conversion of the raw material BMAEE can be ensured, the normal pressure rectification temperature is 100-108 ℃ so as to remove water and excessive formaldehyde in the filtrate.
As a further improvement of the process for co-production of ZF-10 and BDMAEE according to the invention, in said step 1):
the neutralization and filtration steps of the etherification solution are as follows: adding inorganic alkali liquor into the etherified liquid to adjust the pH value to 11-13, and filtering to obtain filtrate and filter cake respectively;
the rectification separation steps are as follows: the filtrate is rectified under normal pressure to obtain water fraction (used for preparing neutralized alkali solution) at 100-105 ℃, and is decompressed and rectified to obtain unconverted raw material MMEA fraction (recycled as etherified raw material) at 60-70 ℃/7mmHg and BMAEE fraction (recycled as N-methylated raw material) at 95-105 ℃/7 mmHg.
As a further improvement of the process for co-production of ZF-10 and BDMAEE according to the invention, in said step 1):
and collecting condensate generated in the filter cake heating and drying process, combining the condensate with filtrate, and then carrying out a subsequent rectifying and separating step.
As a further improvement of the process for co-production of ZF-10 and BDMAEE of the invention, the reduced pressure rectification in step 3) is: collecting 100-108 ℃/7mmHg fractions to obtain BDMAEE fractions; 120-130 ℃/7mmHg fraction, which is ZF-10 fraction.
As a further improvement of the process for co-production of ZF-10 and BDMAEE of the present invention,
in step 1): the etherification temperature is 190 ℃, the time is 12h, and the molar ratio of MMEA to sulfuric acid is 1:1.5;
in step 2): the molar ratio of BMAEE fraction to formaldehyde is 1:1.1-2, the hydrogen pressure is 1-5 Mpa, and the temperature is 60-180 ℃;
in the step 3), the molar ratio of TMAEE to EO is 1:1-1.5, and the temperature is 60-120 ℃.
The method used in the invention is that firstly, the cheap and easily available raw material MMEA is used for synthesizing BMAEE by etherification technology, thus the atom economy is high and the pollution is small; the product BMAEE obtained by etherification is subjected to N-methylation and hydroxyethylation to obtain a target product, and the target product does not relate to strong pollution factors such as chlorine compounds, halogen salts and the like and is easy to treat.
The method for coproducing and synthesizing ZF-10 and BDMAEE comprises the following three chemical reactions and related operation steps:
1) MMEA is catalyzed and etherified by sulfuric acid to synthesize BMAEE,
the etherification process comprises the following steps: adding N-methylethanolamine (MMEA) and concentrated sulfuric acid into a reaction kettle, heating and etherification to obtain an etherification solution, neutralizing the etherification solution, filtering (solid-liquid separation), and rectifying to obtain BMAEE.
2) BMAEE, formaldehyde, hydrogen and the like are subjected to N-methylation reaction under Raney Ni catalyst to synthesize TMAEE and BDMAEE.
The N-methylation process comprises the following steps: adding BMAEE and formaldehyde aqueous solution into a reaction kettle, maintaining a certain hydrogen pressure in the system, heating, stirring for reaction, and performing post-treatment on the reaction liquid to obtain a raffinate (solution containing TMAEE and BDMAEE).
3) And (3) carrying out hydroxyethylation reaction on the distilled residual liquid and EO, converting the distilled residual liquid and EO into ZF-10 and BDMAEE solutions, and carrying out reduced pressure rectification to obtain two useful amine ether products BDMAEE and ZF-10 respectively.
Namely, the hydroxyethylation process is as follows: adding the residual liquid obtained in the step 2) into an autoclave, pumping EO into the autoclave in a metering way, heating, stirring for reaction, cooling the reaction materials to room temperature, and rectifying under reduced pressure to obtain BDMAEE and ZF-10 respectively.
The invention has the advantages compared with the method II in the background art that: the invention uses MMEA to synthesize BMAEE by etherification, and then methylates to synthesize a mixed solution containing TMAEE and BDMAEE. Compared with the method II for synthesizing TMAEE, the etherification and methylation technology adopted by the invention is mature and can be used for industrialization; and does not generate SO 2 And the like; active metal sodium is not used in the raw materials, so that the risk is reduced; no sulfoxide chloride which is seriously corroded by equipment and is not friendly to environment is usedThe method comprises the steps of carrying out a first treatment on the surface of the The byproduct sodium sulfate is easier to handle than sodium chloride.
In summary, the synthesis method of the invention has the following technical advantages:
1. the raw materials are simple and easy to obtain, the cost is low, and the toxicity is low.
3. Halogen acid is not used, halogen salt is not generated, and the environmental impact is small.
4. The Raney Ni catalyst and unconverted raw materials can be recycled and reused, and the atom utilization rate is high.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
sulfuric acid refers to concentrated sulfuric acid having a concentration of 98%.
The correctness of the obtained product is verified in all the following cases.
Example 1, a synthetic method of BMAEE, using MMEA as raw material and sulfuric acid (concentrated sulfuric acid) as catalyst for etherification reaction; neutralizing, filtering (solid-liquid separation) and rectifying the etherified liquid to obtain the target product BMAEE.
600g of sulfuric acid and 300g of MMEA (sulfuric acid: MMEA molar ratio: 1.5:1) were charged into a 2000mL reactor equipped with a stirrer, a condenser, a heater and the like, and the reaction system was etherified at 190℃under stirring for 12 hours, and by-product water was distilled off, and the temperature was lowered to 40℃after the completion of the reaction to obtain an etherified liquid. Dropwise adding an inorganic alkali solution (40% sodium hydroxide solution in mass concentration) into the etherified liquid at the temperature of 40-70 ℃ under stirring until the pH value of the system is=12-13, and stopping dropwise adding to obtain a solid-liquid mixture; solid-liquid separation is carried out on the solid-liquid mixture to obtain filtrate and wet sodium sulfate, heating and drying (drying to constant weight at 70-90 ℃) the wet sodium sulfate to obtain 811.95g of dried sodium sulfate, and gas phase condensate (condensate for short) in the drying process is recovered, wherein the main content is water mixture, and the mixture contains a little of raw material MMEA and product BMAEE); the filtrate and condensate are combined and separated by rectification to obtain 100-105 ℃/760mmHg water fraction, 60-70 ℃/7mmHg MMEA fraction (137 g, content 98.5 percent, recovered for etherification raw material), 95-105 ℃/7mmHg BMAEE fraction (113.6 g, content 99.4 percent) in sequence.
In examples 2 to 5, the amount of MMEA used was kept constant, only the molar ratio of sulfuric acid to MMEA in example 1 was changed (see in particular Table 1); the remainder was identical to example 1.
In examples 6 to 9, only the etherification temperature in example 1 was changed (see Table 1 for details); the remainder was identical to example 1.
Examples 10 to 13, only the etherification time in example 1 was changed (see table 1 for details); the remainder was identical to example 1.
The results of examples 1 to 13 are shown in Table 1.
TABLE 1
Remarks: the MMEA conversion% = 100 x 1-MMEA recovered mass/MMEA added mass,
BMAEE yield% = 100 × [ BMAEE mass/132 ]/[ MMEA addition/(75 x 2) ]/MMEA conversion%.
Example 14N-methylating BMAEE with formaldehyde and hydrogen to obtain a kettle liquid containing TMAEE and BDMAEE, and post-treating the kettle liquid to obtain a raffinate.
A500 ml autoclave was charged with 1.5mol (about 198 g) of the BMAEE fraction obtained in example 1, a 37% aqueous formaldehyde solution (about 182.4 g) containing 2.25mol of formaldehyde and 19.8g of Raney Ni (Raney Ni) as a catalyst, and the autoclave was charged with hydrogen to 3.0MPa at room temperature, heated to 120℃and stirred for 5 hours to thereby maintain the pressure in the autoclave at 3.0 to 3.2MPa.
After the reaction is finished, cooling the obtained reaction liquid to room temperature, performing pressure filtration by using nitrogen, performing alkali washing on the obtained filter cake under the protection of the nitrogen (the filter cake is soaked in 40% sodium hydroxide solution for 30min under the protection of the nitrogen), performing water washing until the pH value is 8+/-0.2, and then circularly using the filter cake as a hydrogenation catalyst; the conversion of BMAEE was 99.7%, the filtrate was subjected to rectification (atmospheric rectification, 100-160 ℃) and water and small amounts of unconverted material (excess formaldehyde and possibly unconverted BMAEE) in the filtrate were distilled off, yielding 228.9g of raffinate (TMAEE, BDMAEE content 52.7% and 47.2%, respectively).
Examples 15 to 16, the bmaee fraction and the amount used remain unchanged; only the molar ratio of BMAEE to formaldehyde in example 14 was changed (see table 2 for details); the remainder was identical to example 14.
Examples 17 to 19, the amount of catalyst used in example 14 was changed only (see Table 2 for details); the remainder was identical to example 14.
Examples 20 to 21, only the hydrogen pressure in example 14 was changed (see specifically table 2); the remainder was identical to example 14.
Examples 22 to 23, in which only the reaction temperature in example 14 was changed (see Table 2 for details); the remainder was identical to example 14.
The specific parameters and the final data are shown in Table 2.
TABLE 2
Remarks description: BMAEE was prepared as described in example 1, resulting in the data described in table 2.
Example 24, the resulting raffinate and EO were hydroxyethylated to produce ZF-10, BDMAEE.
50g of the raffinate obtained in example 14, TMAEE and BDMAEE-containing solution (TMAEE and BDMAEE contents of 52.7% and 47.2% respectively) were added to a 100ml autoclave, so that TMAEE was 0.18mol, and after nitrogen substitution, the autoclave was stirred and warmed to 75℃and maintained at a stable temperature, 9.53g (0.2166 mol) of EO was pumped into the autoclave and reacted for 6 hours; TMAEE in the raw materials in the kettle liquid is completely converted; cooling the obtained kettle liquid to room temperature, and then performing vacuum rectification, and respectively collecting fractions of 100-108 ℃/7mmHg to obtain BDMAEE fractions; 120-130 ℃/7mmHg fraction, which is ZF-10 fraction.
The content of 33.1. 33.1gZF-10 is 98.1 percent and the yield is 94.7 percent respectively; 23.5g BDMAEE, content 99.2% yield: 98.6%.
Examples 25 to 26, in which only the reaction temperature in example 24 was changed (see Table 3 for details); the remainder was identical to example 24.
Examples 27 to 28, the molar ratio of the starting materials in example 24 (see in particular Table 3) was varied while the amount of the raffinate and the amount were kept constant; the remainder was identical to example 24.
The specific parameters and the final data are shown in Table 3.
TABLE 3 Table 3
Remarks description: the preparation of the retentate was performed as described in example 14, giving the data of Table 3.
ZF-10 yield% = 100 x (ZF-10 mass)/(addition of raffinate) (TMAEE content in raffinate)/146 x 190].
BDMAEE yield% = 100 x (BDMAEE mass)/(amount of raffinate added) ].
Examples 29 to 31, the catalyst Raney Ni was recycled in the N-methylation reaction.
The Raney Ni catalyst recovered in example 14 (about 19 g) was subjected to the test for reuse after adding 19.8g of fresh catalyst, and the other conditions were the same as those in example 14, and the test for recycling was performed four times, and the results are shown in Table 4:
TABLE 4 Table 4
The MMEA fraction recovered in example 33 or example 1 was used as an etherification raw material;
the MMEA fraction recovered in example 1 (137 g, 98.5% content) was supplemented with new MMEA to a total amount of 300g of MMEA; the remaining conditions were identical to those of example 1.
The results obtained were: MMEA fraction (138.7 g, content 98.4%) at 60-70 ℃/7mmHg and BMAEE fraction (112.18 g, content 99.4%) at 95-105 ℃/7mmHg were obtained.
Comparative example 1 the inorganic alkaline solution in example 1 was changed from "40% sodium hydroxide solution by mass" to liquid ammonia, and the raw material conversion was 52% and the product yield was 74.7% in the same manner as in example 1.
Comparative example 2 the conversion of raw material BMAEE was 95.6% in the remaining equivalent example 14, except that the 37% aqueous formaldehyde solution in example 14 was changed to paraformaldehyde and 225ml of methanol (methanol as solvent), and 221.8g of a raffinate was finally obtained, in which the TMAEE content was 41% and the BDMAEE content was 58.8%.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (8)
1. A method for co-producing ZF-10 and BDMAEE, which is characterized by comprising the following steps:
1) Etherification:
MMEA is used as a raw material, and an etherified liquid containing BMAEE is prepared through sulfuric acid catalytic etherification; neutralizing, filtering, rectifying and separating the etherified liquid containing BMAEE, thereby recovering unconverted MMEA and obtaining BMAEE fraction;
the etherification temperature is 150-190 ℃, the time is 1-20 h, and the molar ratio of MMEA to sulfuric acid is 1:1-3;
MMEA is N-methylethanolamine and BMAEE is di (methylaminoethyl) ether;
2) N-methylation:
the BMAEE fraction obtained in the step 1) is selectively N-methylated with formaldehyde and hydrogen under the action of a catalyst to synthesize a solution containing TMAEE and BDMAEE, and the catalyst is recycled;
the molar ratio of BMAEE fraction to formaldehyde is 1:1.1-3; the Raney Ni catalyst accounts for 5-20% of the weight of the BMAEE fraction, the hydrogen pressure is 0.5-10 Mpa, and the temperature is 50-200 ℃; the reaction time is 3-6 h;
TMAEE is N, N, N' -trimethylbisethylamine ether, BDMAEE is bis (dimethylaminoethyl) ether;
3) Hydroxyethylation:
carrying out hydroxyethylation reaction on the solution containing TMAEE and BDMAEE and EO under the protection of inert gas, wherein the molar ratio of TMAEE to EO is 1:1-3, the reaction temperature is 40-160 ℃, and the reaction time is 3-6 h; after the reaction materials are cooled to room temperature, performing vacuum rectification to obtain BDMAEE and ZF-10 respectively;
EO is ethylene oxide; ZF10 is N, N, N '-trimethyl-N' -hydroxyethyl-bis-aminoethyl ether.
2. The method for co-producing ZF-10 and BDMAEE according to claim 1, characterized in that:
the step 2) is as follows:
after the reaction is finished, cooling the obtained reaction solution to room temperature, performing inert gas filter pressing, and rectifying the filtrate at normal pressure to obtain a residual steam, wherein the residual steam is a solution containing TMAEE and BDMAEE; the filter cake is circularly used as a catalyst after alkali washing and water washing until the pH value is 8+/-0.2.
3. The process for co-production of ZF-10 and BDMAEE according to claim 2, characterized in that in said step 1):
the neutralization and filtration steps of the etherification solution are as follows: adding inorganic alkali liquor into the etherified liquid to adjust the pH value to 11-13, and filtering to obtain filtrate and filter cake respectively;
the rectification separation steps are as follows: the filtrate is rectified under normal pressure to obtain water fraction at 100-105 ℃, and is rectified under reduced pressure to obtain unconverted raw material MMEA fraction at 60-70 ℃/7mmHg and BMAEE fraction at 95-105 ℃/7 mmHg.
4. A process for co-production of ZF-10 and BDMAEE according to claim 3, characterized in that in said step 1):
and collecting condensate generated in the filter cake heating and drying process, combining the condensate with filtrate, and then carrying out a subsequent rectifying and separating step.
5. The method for co-producing ZF-10 and BDMAEE according to claim 4, characterized in that the vacuum rectification in step 3) is: collecting 100-108 ℃/7mmHg fractions to obtain BDMAEE fractions; 120-130 ℃/7mmHg fraction, which is ZF-10 fraction.
6. The method for co-producing ZF-10 and BDMAEE according to any one of claims 1 to 5, characterized in that:
the formaldehyde is 37% formaldehyde aqueous solution.
7. The method for co-producing ZF-10 and BDMAEE according to claim 6, characterized in that:
in step 1): the etherification temperature is 190 ℃, the time is 12h, and the molar ratio of MMEA to sulfuric acid is 1:1.5;
in step 2): the molar ratio of BMAEE fraction to formaldehyde is 1:1.1-2, the hydrogen pressure is 1-5 Mpa, and the temperature is 60-180 ℃;
in the step 3), the molar ratio of TMAEE to EO is 1:1-1.5, and the temperature is 60-120 ℃.
8. The method for co-producing ZF-10 and BDMAEE according to claim 2, characterized in that:
the alkaline washing in the step 2) is as follows: the filter cake is soaked in 35-45% sodium hydroxide solution for 20-40 min under the protection of inert gas.
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