CN1911886A - Production technology of bi-tribydroxy methyl propane and/or trihydroxy methyl propane methylal - Google Patents
Production technology of bi-tribydroxy methyl propane and/or trihydroxy methyl propane methylal Download PDFInfo
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- CN1911886A CN1911886A CN 200610086255 CN200610086255A CN1911886A CN 1911886 A CN1911886 A CN 1911886A CN 200610086255 CN200610086255 CN 200610086255 CN 200610086255 A CN200610086255 A CN 200610086255A CN 1911886 A CN1911886 A CN 1911886A
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- tmp
- trimethylolpropane
- methylal
- ditrimethylolpropane
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000005516 engineering process Methods 0.000 title description 3
- GQPBUEXGBKVDDE-UHFFFAOYSA-N COCOC.OC(CCC)(O)O Chemical compound COCOC.OC(CCC)(O)O GQPBUEXGBKVDDE-UHFFFAOYSA-N 0.000 title 1
- 235000013847 iso-butane Nutrition 0.000 title 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 title 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 98
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 claims abstract description 90
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006266 etherification reaction Methods 0.000 claims abstract description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 64
- 238000000605 extraction Methods 0.000 claims description 53
- 239000002904 solvent Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 230000018044 dehydration Effects 0.000 claims description 18
- 238000006297 dehydration reaction Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 238000007701 flash-distillation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 5
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 5
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000003637 basic solution Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical compound CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 4
- UFZHRTLJOSFQNY-UHFFFAOYSA-N dimethoxymethane 2-ethyl-2-(hydroxymethyl)propane-1,3-diol Chemical compound COCOC.C(O)C(CC)(CO)CO UFZHRTLJOSFQNY-UHFFFAOYSA-N 0.000 abstract 2
- 238000005829 trimerization reaction Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 9
- 150000001241 acetals Chemical class 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses ditrimethylolpropane and/or trimethylolpropane methylal producing process. Butyl aldehyde, formaldehyde and alkaline water solution are added into reactor to produce Turonian reaction, Connizaros reaction, etherification and disproportionation so as to produce condensated liquid containing ditrimethylolpropane, trimethylolpropane methylal and trimethylolpropane mainly. The condensated liquid is then evaporated to eliminate water, extracted, rectified and purified to obtain the target product. The production process of the present invention has low power consumption, high yield, and simple and feasible separation.
Description
Affiliated technical field
The present invention relates to the production technique of ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal, particularly in basic solvent, react the production technique of producing high purity ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal of doing yield by formaldehyde and butyraldehyde-n.
Background technology
Ditrimethylolpropane (DTMP) is a kind of solid tetravalent alcohol, and its structural formula is as follows.TriMethylolPropane(TMP) methylal (CTF) is a kind of liquid monocycle monohydroxy-alcohol, and its structural formula is as follows.Highly purified ditrimethylolpropane (DTMP) and high-purity trimethylopropane methylal (CTF) are mainly used in light curing agent, coating, resin and specialty inks and PVC stablizer and synthetic grease.
Ditrimethylolpropane
The TriMethylolPropane(TMP) methylal
Usually, at alkaline aqueous solution, for example contain in the aqueous solution of sodium hydroxide, calcium hydroxide or potassium hydroxide, produce in TriMethylolPropane(TMP) (TMP) process by formaldehyde and butyraldehyde-n reaction, byproduct ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) methylal (CTF) be can generate, impurity trimerization TriMethylolPropane(TMP) (TTMP) and other acetals materials, salt etc. also generated simultaneously.Ditrimethylolpropane (DTMP) byproduct, mainly obtain by the mixture separation that reaction in TriMethylolPropane(TMP) (TMP) production process is generated, but because the existence of impurity such as trimerization TriMethylolPropane(TMP) (TTMP) and acetals material, cause separation to obtain very difficulty of highly purified ditrimethylolpropane (DTMP), and energy expenditure is too high, yield is also only less than 2%, purity is lower, have only 80-90%, can not satisfy growing demand ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) methylal (CTF).
Summary of the invention
The objective of the invention is in order to overcome above-mentioned deficiency, a kind of ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal production technique are provided, and the application of the invention technology is produced highly purified ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal with high yield.
Ditrimethylolpropane of the present invention and/or TriMethylolPropane(TMP) methylal production technique comprise following operation:
Step 1: butyraldehyde-n, formaldehyde, alkaline aqueous solution added in the reactor that has agitator react the condensated liquid that generation mainly contains ditrimethylolpropane, TriMethylolPropane(TMP) methylal and TriMethylolPropane(TMP), described alkaline aqueous solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH)
2) or yellow soda ash (Na
2CO
3) wait the aqueous solution, the mol ratio of described formaldehyde, butyraldehyde-n, alkali is 2.0-15.2: 1: 0.3-1.9, temperature of reaction is controlled at 15-90 ℃, and the reaction times was controlled at 30 minutes to 8 hours, and described reaction comprises Toulon's reaction, Cannizzaro's reaction, etherification reaction, disproportionation reaction.Its chemical reaction and route are:
The first step, Toulon's reaction and Cannizzaro's reaction:
Second step, etherificate and disproportionation reaction:
(ditrimethylolpropane)
(TriMethylolPropane(TMP) methylal)
Step 2: dehydration by evaporation.The condensated liquid that above-mentioned steps 1 reaction gained is contained ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) methylal (CTF) is imitated dehydration by evaporation by 1-5, removes the water in the condensated liquid, and dehydration rate is controlled at 30-90%, makes evaporated liquor.
Step 3: extraction.Can adopt conventional cross-flow or counter-current extraction method, the evaporated liquor that step 2 is made is 25 ℃-150 ℃ in temperature range, carry out the extraction of 1-15 level in solvent, to organic phase, salts substances and water are transferred to aqueous phase with ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF) and TriMethylolPropane(TMP) organic substance extractions such as (TMP).
Step 4: rectifying.Adopt rectifying tower that the organic phase liquid of extraction gained in the above-mentioned steps 3 is carried out rectifying, in temperature range is that 60-300 ℃, vacuum ranges are under the condition of 5Pa-200KPa, solvent, ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), TriMethylolPropane(TMP) (TMP) are progressively separated, adopt the side line extraction to obtain the TriMethylolPropane(TMP) methylal (CTF) that purity is 90-99.9%.
Step 5: purify.After above-mentioned steps 4 rectifying, obtaining major ingredient is the still raffinate mixture of ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) (TMP), this mixture is that 150-300 ℃, vacuum ranges are under the condition of 5Pa-200KPa in temperature, can obtain the ditrimethylolpropane that purity is 85-99.9% (DTMP) through flash distillation.
Further, the mass percent concentration of described formaldehyde is 5-99%, and the butyraldehyde mass percent concentration is 10-100%, and the mass percent concentration of alkali is 1-100%.
Further, the described reactor that has agitator is normal pressure or has the reactor that pressure range is 0-0.5MPa.
Further, the method in butyraldehyde-n, formaldehyde, the alkaline aqueous solution adding reactor adopts any one in following 4 kinds of feeding modes:
1, the feeding mode that adds simultaneously of formaldehyde, butyraldehyde-n, basic solution.
2, formaldehyde, butyraldehyde-n are made end water, the feeding mode that basic solution adds in batches or continuously.
3, formaldehyde, alkaline solution are made end water, the feeding mode that butyraldehyde-n adds in batches or continuously.
4, alkaline solution, butyraldehyde-n are made end water, the feeding mode that formaldehyde adds in batches or continuously.
Further, employed solvent is following any one in the extraction step:
1, aldehydes solvent is as butyraldehyde-n, differently decide aldehyde, valeraldehyde, isovaleric aldehyde.
2, alcoholic solvent is as methyl alcohol, ethanol, propyl alcohol, up to C
12Class straight or branched alcohol (comprising monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol).
3, lipid solvent is as methyl-formiate, ethyl formate, ethyl acetate, butylacetate, methylcarbonate etc.
4, varsol comprises hexanaphthene, benzene,toluene,xylene (o-Xylol or m-xylene or p-Xylol or its mixture).
5, methyl iso-butyl ketone (MIBK).
6, methyl tertiary butyl ether.
Further, water backwash desalination again after the extraction makes the weight percent content of salt drop to 0.005-0.1%.
Further, the cat head of rectifying tower is furnished with condenser, is furnished with reboiler at the bottom of the tower, adopts and refluxes and the side line extraction.
Further, described rectifying tower has 3-10 valve tray column and/or packing tower and/or float valve, filler combination tower to combine continuously or periodical operation.
Ditrimethylolpropane of the present invention (DTMP) and/or TriMethylolPropane(TMP) methylal (CTF) production technique have that energy consumption is low, yield is high, separation is simple, can satisfy the growing demand to ditrimethylolpropane (DTMP) and/or TriMethylolPropane(TMP) methylal (CTF).
Embodiment
Embodiment 1:
Step 1: get mass percent concentration and be 10% formaldehyde 15mol, get mass percent concentration and be 85% butyraldehyde-n 1mol, getting mass percent concentration and be 55% NaOH solution 0.8mol adds in the normal pressure chemical reaction still that has agitator and stirs, temperature is controlled at 35 ℃, reaction times was controlled at 7 hours, at first generate TriMethylolPropane(TMP) (TMP) through Toulon's reaction and Cannizzaro's reaction, TriMethylolPropane(TMP) (TMP) is the condensated liquid of ditrimethylolpropane and TriMethylolPropane(TMP) methylal through etherificate and disproportionation reaction generation main component then, generates byproduct and impurity such as trimerization TriMethylolPropane(TMP) (TTMP) and acetals material simultaneously, sodium formiate, lighting end, Bis-TMP etc.
Step 2: dehydration by evaporation.Adopt 2 to imitate evaporative processes and remove water in the condensated liquid of step 1 gained, dehydration rate is controlled at 85%, obtains the evaporated liquor after the dehydration.
Step 3: extraction.Take the four-stage counter-current extraction that above-mentioned evaporated liquor is extracted in the butyraldehyde-n solvent.In extraction process TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organic substance extractions such as (TTMP) are arrived organic phase, sodium formiate and water are transferred to aqueous phase; Extraction temperature is controlled at 50 ℃; Wash the salt of removing trace after the extraction again with water, make the weight percent content of salt drop to 0.08%.
Step 4: rectifying.The organic phase liquid that obtains of extraction in the above-mentioned steps 3 is furnished with cat head is furnished with reboiler at the bottom of condenser, the tower and adopts and reflux and 7 valve tray columns of combining operate continuously of side line extraction, in temperature is rectifying under 80 ℃, the condition of vacuum tightness 180KPa, solvent is progressively separated with TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organism such as (TTMP), and it is 96% TriMethylolPropane(TMP) methylal (CTF) that the side line extraction obtains purity.
Step 5: purify.After above-mentioned rectifying, can mainly be comprised ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) (TMP), trimerization TriMethylolPropane(TMP) organic mixture kettle base solutions such as (TTMP).This mixture is that can to obtain purity through flash distillation under 180 ℃, the condition of vacuum tightness 15Pa be 95% ditrimethylolpropane (DTMP) in temperature again.
Embodiment 2:
Step 1: to get mass percent concentration and be 90% formaldehyde 2.5mol, get mass percent concentration be 20% butyraldehyde-n 1mol, get mass percent concentration is 30% calcium hydroxide (Ca (OH)
2) solution 1.2mol, formaldehyde and butyraldehyde-n are made end water, the feeding mode that aqua calcis is added in batches adds in the reactor of the 0.1mpa pressure that has agitator and stirs, temperature is controlled at 70 ℃, reaction times was controlled at 35 minutes, at first generate TriMethylolPropane(TMP) through Toulon's reaction and Cannizzaro's reaction, TriMethylolPropane(TMP) is the condensated liquid of ditrimethylolpropane and TriMethylolPropane(TMP) methylal through etherificate and disproportionation reaction generation main component then, generates byproduct and impurity such as trimerization TriMethylolPropane(TMP) and acetals material simultaneously, calcium formiate, lighting end, Bis-TMP etc.
Step 2: dehydration by evaporation.Adopt 3 to imitate evaporative processes and remove water in the condensated liquid of step 1 gained, dehydration rate is controlled at 60%, obtains the evaporated liquor after the dehydration.
Step 3: extraction.Take 6 grades of extractions that above-mentioned evaporated liquor is extracted in alcohol solvent.In extraction process organic substance extractions such as TriMethylolPropane(TMP), ditrimethylolpropane, TriMethylolPropane(TMP) methylal, trimerization TriMethylolPropane(TMP) are arrived organic phase, calcium formiate and water are transferred to aqueous phase; The extraction temperature scope is controlled at 130 ℃.Wash the salt of removing trace after the extraction again with water, make the weight percent content of salt drop to 0.008%.
Step 4: rectifying.The organic phase liquid that obtains of extraction in the above-mentioned steps 3 is furnished with cat head is furnished with reboiler at the bottom of condenser, the tower and adopts and reflux and 5 float valve, filler combination towers of combining periodical operation of side line extraction, in temperature is rectifying under 280 ℃, the condition of vacuum tightness 10Pa, solvent is progressively separated with TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organism such as (TTMP), and it is 95% TriMethylolPropane(TMP) methylal (CTF) that the side line extraction obtains purity.
Step 5: purify.After above-mentioned rectifying, can mainly be comprised ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) (TMP) trimerization TriMethylolPropane(TMP) organic mixture kettle base solutions such as (TTMP).This mixture is that can to obtain purity through flash distillation under 250 ℃, the condition of vacuum tightness 120KPa be 97% ditrimethylolpropane (DTMP) in temperature again.
Embodiment 3:
Step 1: get mass percent concentration and be 50% formaldehyde 9mol, get mass percent concentration and be 85% butyraldehyde-n 1mol, get mass percent concentration and be 85% potassium hydroxide (KOH) solution 0.5mol, formaldehyde, potassium hydroxide solution is made end water, the feeding mode that butyraldehyde-n adds continuously adds in the reactor of the 0.4mpa pressure that has agitator and stirs, temperature is controlled at 20 ℃, reaction times was controlled at 5 hours, at first generate TriMethylolPropane(TMP) through Toulon's reaction and Cannizzaro's reaction, TriMethylolPropane(TMP) is the condensated liquid of ditrimethylolpropane and TriMethylolPropane(TMP) methylal through etherificate and disproportionation reaction generation main component then, generates byproduct and impurity such as trimerization TriMethylolPropane(TMP) (TTMP) and acetals material simultaneously, potassium formiate, lighting end, Bis-TMP etc.
Step 2: dehydration by evaporation.Adopt 4 to imitate evaporative processes and remove water in the condensated liquid of step 1 gained, dehydration rate is controlled at 35%, obtains the evaporated liquor after the dehydration.
Step 3: extraction.Take the extraction of 12 cross-flow levels that above-mentioned evaporated liquor is extracted in the ethyl formate solvent.In extraction process TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organic substance extractions such as (TTMP) are arrived organic phase, potassium formiate and water are transferred to aqueous phase; The extraction temperature scope is controlled at 90 ℃.Wash the salt of removing trace after the extraction again with water, make the weight percent content of salt drop to 0.015%.
Step 4: rectifying.The organic phase liquid that obtains of extraction in the above-mentioned steps 3 is furnished with cat head is furnished with reboiler at the bottom of condenser, the tower and adopts and reflux and 10 float valve, filler combination towers of combining operate continuously of side line extraction, in temperature is rectifying under 150 ℃, the condition of vacuum tightness 80KPa, solvent is progressively separated with TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organism such as (TTMP), and it is 98% TriMethylolPropane(TMP) methylal (CTF) that the side line extraction obtains purity.
Step 5: purify.After above-mentioned rectifying, can mainly be comprised ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) (TMP) trimerization TriMethylolPropane(TMP) organic mixture kettle base solutions such as (TTMP).This mixture is that can to obtain purity through flash distillation under 200 ℃, the condition of vacuum tightness 150KPa be 98% ditrimethylolpropane (DTMP) in temperature again.
Embodiment 4:
Step 1: to get mass percent concentration and be 70% formaldehyde 6mol, get mass percent concentration be 50% butyraldehyde-n 1mol, get mass percent concentration is 10% yellow soda ash (Na
2CO
3) solution 1.8mol, sodium carbonate solution, butyraldehyde-n is made end water, feeding mode that formaldehyde adds in batches adds in the reactor of the 0.3mpa pressure that has agitator and stirs, temperature is controlled at 50 ℃, reaction times was controlled at 3 hours, at first generate TriMethylolPropane(TMP) through Toulon's reaction and Cannizzaro's reaction, TriMethylolPropane(TMP) is the condensated liquid of ditrimethylolpropane and TriMethylolPropane(TMP) methylal through etherificate and disproportionation reaction generation main component then, generates byproduct and impurity such as trimerization TriMethylolPropane(TMP) (TTMP) and acetals material simultaneously, sodium formiate, lighting end, Bis-TMP etc.
Step 2: dehydration by evaporation.Adopt 5 to imitate evaporative processes and remove water in the condensated liquid of step 1 gained, dehydration rate is controlled at 80%, obtains the evaporated liquor after the dehydration.
Step 3: extraction.Take the extraction of 10 stage countercurrents that above-mentioned evaporated liquor is extracted in methyl isobutyl ketone solvent.In extraction process TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organic substance extractions such as (TTMP) are arrived organic phase, sodium formiate and water are transferred to aqueous phase; The extraction temperature scope is controlled at 70 ℃.Wash the salt of removing trace after the extraction again with water, make the weight percent content of salt drop to 0.03%.
Step 4: rectifying.The organic phase liquid that obtains of extraction in the above-mentioned steps 3 is furnished with cat head is furnished with reboiler at the bottom of condenser, the tower and adopts and reflux and 3 packing towers of combining periodical operation of side line extraction, in temperature is rectifying under 200 ℃, the condition of vacuum tightness 1KPa, solvent is progressively separated with TriMethylolPropane(TMP) (TMP), ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), trimerization TriMethylolPropane(TMP) organism such as (TTMP), and it is 98% TriMethylolPropane(TMP) methylal (CTF) that the side line extraction obtains purity.
Step 5: purify.After rectifying, can mainly be comprised ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) (TMP) trimerization TriMethylolPropane(TMP) organic mixture kettle base solutions such as (TTMP).This mixture is that can to obtain purity through flash distillation under 280 ℃, the condition of vacuum tightness 5KPa be 96% ditrimethylolpropane (DTMP) in temperature again.
Claims (8)
1, a kind of ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal production technique is characterized in that this ditrimethylolpropane and/or TriMethylolPropane(TMP) methylal production technique comprise following operation:
Step 1: butyraldehyde-n, formaldehyde, alkaline aqueous solution added in the reactor that has agitator react the condensated liquid that generation mainly contains ditrimethylolpropane, TriMethylolPropane(TMP) methylal and TriMethylolPropane(TMP), described alkaline aqueous solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), calcium hydroxide (Ca (OH)
2) or yellow soda ash (Na
2CO
3) wait the aqueous solution, the mol ratio of described formaldehyde, butyraldehyde-n, alkali is 2.0-15.2: 1: 0.3-1.9, temperature of reaction is controlled at 15-90 ℃, and the reaction times was controlled at 30 minutes to 8 hours, and described reaction comprises Toulon's reaction, Cannizzaro's reaction, etherification reaction, disproportionation reaction.Its chemical reaction and route are:
The first step, Toulon's reaction and Cannizzaro's reaction:
Second step, etherificate and disproportionation reaction:
(TriMethylolPropane(TMP) methylal)
Step 2: dehydration by evaporation.The condensated liquid that above-mentioned steps 1 reaction gained is contained ditrimethylolpropane (DTMP) and TriMethylolPropane(TMP) methylal (CTF) is imitated dehydration by evaporation by 1-5, removes the water in the condensated liquid, and dehydration rate is controlled at 30-90%, makes evaporated liquor.
Step 3: extraction.The evaporated liquor that step 2 is made is 25 ℃-150 ℃ in temperature range, carry out the extraction of 1-15 level in solvent, to organic phase, salts substances and water are transferred to aqueous phase with ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF) and TriMethylolPropane(TMP) organic substance extractions such as (TMP).
Step 4: rectifying.Adopt rectifying tower that the organic phase liquid of extraction gained in the above-mentioned steps 3 is carried out rectifying, in temperature is that 60-300 ℃, pressure are under the condition of vacuum tightness 5Pa-200KPa, solvent, ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) methylal (CTF), TriMethylolPropane(TMP) (TMP) are progressively separated, adopt the side line extraction to obtain the TriMethylolPropane(TMP) methylal (CTF) that purity is 90-99.9%.
Step 5: purify.After above-mentioned steps 4 rectifying, obtaining major ingredient is the still raffinate mixture of ditrimethylolpropane (DTMP), TriMethylolPropane(TMP) (TMP), this mixture is that 150-300 ℃, pressure are under the condition of vacuum tightness 5Pa-200KPa in temperature, can obtain the ditrimethylolpropane that purity is 85-99.9% (DTMP) through flash distillation.
2, ditrimethylolpropane according to claim 1 and/or TriMethylolPropane(TMP) methylal production technique, the mass percent concentration that it is characterized in that described formaldehyde is 5-99%, the butyraldehyde mass percent concentration is 10-100%, and the mass percent concentration of alkali is 1-100%.
3, ditrimethylolpropane according to claim 1 and 2 and/or TriMethylolPropane(TMP) methylal production technique is characterized in that the described reactor that has agitator is normal pressure or has the reactor that pressure range is 0-0.5mpa.
4, ditrimethylolpropane according to claim 3 and/or TriMethylolPropane(TMP) methylal production technique is characterized in that butyraldehyde-n, formaldehyde, the interior method of alkaline aqueous solution adding reactor adopt any one in following 4 kinds of feeding modes:
(1) feeding mode that adds simultaneously of formaldehyde, butyraldehyde-n, basic solution.
(2) formaldehyde, butyraldehyde-n are made end water, the feeding mode that basic solution adds in batches or continuously.
(3) formaldehyde, alkaline solution are made end water, the feeding mode that butyraldehyde-n adds in batches or continuously.
(4) alkaline solution, butyraldehyde-n are made end water, the feeding mode that formaldehyde adds in batches or continuously.
5,, it is characterized in that described extraction solvent is following any one according to claim 1 or 4 described ditrimethylolpropanes and/or TriMethylolPropane(TMP) methylal production technique:
(1) aldehydes solvent is as butyraldehyde-n, differently decide aldehyde, valeraldehyde, isovaleric aldehyde.
(2) alcoholic solvent is as methyl alcohol, ethanol, propyl alcohol, up to C
12Class straight or branched alcohol (comprising monohydroxy-alcohol, dibasic alcohol, trivalent alcohol, tetravalent alcohol).
(3) lipid solvent is as methyl-formiate, ethyl formate, ethyl acetate, butylacetate, methylcarbonate etc.
(4) varsol comprises hexanaphthene, benzene,toluene,xylene (o-Xylol or m-xylene or p-Xylol or its mixture).
(5) methyl iso-butyl ketone (MIBK).
(6) methyl tertiary butyl ether.
6, ditrimethylolpropane according to claim 5 and/or TriMethylolPropane(TMP) methylal production technique is characterized in that water backwash desalination again after the extraction, make the weight percent content of salt drop to 0.005-0.1%.
7, according to claim 1,4 or 6 described ditrimethylolpropanes and/or TriMethylolPropane(TMP) methylal production technique, it is characterized in that the cat head of rectifying tower is furnished with condenser, be furnished with reboiler at the bottom of the tower, adopt and reflux and the side line extraction.
8, ditrimethylolpropane according to claim 7 and/or TriMethylolPropane(TMP) methylal production technique is characterized in that described rectifying tower has 3-10 valve tray column and/or packing tower and/or float valve, filler combination tower to combine continuously or periodical operation.
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