CN111499493A - Continuous condensation method and device for monopentaerythritol, dipentaerythritol and tripentaerythritol - Google Patents
Continuous condensation method and device for monopentaerythritol, dipentaerythritol and tripentaerythritol Download PDFInfo
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- 229940059574 pentaerithrityl Drugs 0.000 title claims abstract description 42
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000009833 condensation Methods 0.000 title claims abstract description 25
- 230000005494 condensation Effects 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 42
- 239000003513 alkali Substances 0.000 claims abstract description 32
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 235000019253 formic acid Nutrition 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000011541 reaction mixture Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 8
- 238000003860 storage Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 8
- -1 hydroxide ions Chemical class 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000014759 maintenance of location Effects 0.000 abstract description 3
- 238000007323 disproportionation reaction Methods 0.000 abstract description 2
- 150000001299 aldehydes Chemical class 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000005705 Cannizzaro reaction Methods 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- SSOONFBDIYMPEU-UHFFFAOYSA-N [3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COCC(CO)(CO)COC(=O)C=C SSOONFBDIYMPEU-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229960004321 pentaerithrityl tetranitrate Drugs 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004597 plastic additive Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
- B01F33/813—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles mixing simultaneously in two or more mixing receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1862—Stationary reactors having moving elements inside placed in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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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 belongs to the technical field of continuous condensation of monopentaerythritol, dipentaerythritol and tripentaerythritol, and particularly relates to a continuous condensation method of monopentaerythritol, dipentaerythritol and tripentaerythritol, which is characterized by comprising the following steps: step 1, adding 37% of formaldehyde solution, starting a circulating pump, and controlling the temperature in a continuous reaction heat exchanger to be 30-70 ℃; step 2, uniformly injecting acetaldehyde and formaldehyde into an aldehyde mixer according to the proportion for mixing, mixing alkali and water through the alkali mixer, and continuously injecting mixed aldehyde and alkali liquor into a continuous reaction heat exchanger at a constant speed; 3, continuously feeding the reaction mixture formed after the reaction in the step 2 into a continuous reactor through a continuous reaction heat exchanger, staying for 30-180 min in the continuous reactor, and controlling the temperature in the continuous reactor to be 30-70 ℃; step 4, continuously adding formic acid into the continuous neutralization reactor to perform neutralization reaction with the reaction mixture, and controlling the pH value to be weakly acidic; and obtaining a mixture of the target products of monopentaerythritol, dipentaerythritol, tripentaerythritol and by-product formate after the reaction is finished. The method has the advantages that the reaction temperature is accurately controlled, the overtemperature is avoided, and the yield is high; the method has the advantages of short average material retention time, less formaldehyde disproportionation reaction, low formaldehyde consumption, constant proportion of reaction raw materials and the like, and the reaction parameters are constant.
Description
Technical Field
The invention belongs to the technical field of continuous condensation of monopentaerythritol, dipentaerythritol and tripentaerythritol, and particularly relates to a continuous condensation method and device of monopentaerythritol, dipentaerythritol and tripentaerythritol.
Background
Monopentaerythritol (PE) is a few polyhydric alcohol products containing quaternary carbon atoms, has the advantages of good thermal stability, difficult decomposition and the like, contains 4 active hydroxyl groups, can form a polyester structure, is widely applied to high polymer materials, and is an important fine chemical product. Pentaerythritol is used primarily in the paint industry to make alkyd coatings with improved hardness, gloss and durability of the coating film. It is also used as raw material of rosin ester for colour paint, varnish and printing ink, etc. and can be used for preparing drying oil, flame-retardant coating and aviation lubricating oil, etc. Fatty acid esters of pentaerythritol are highly effective lubricants and plasticizers for polyvinyl chloride, and epoxy derivatives thereof are the starting materials for the production of nonionic surfactants. Pentaerythritol tends to form complexes with metals and is also used as a hard water softener in detergent formulations. In addition, the method is also used for the production of medicines, pesticides and the like. Pentaerythritol contains four equivalent hydroxymethyl groups in the molecule and has high symmetry, so that the pentaerythritol is often used as a raw material for preparing a multifunctional compound. Pentaerythritol tetranitrate (Taian, PETN) can be prepared by nitration of the compound, and is a strong explosive; esterification gives pentaerythritol triacrylate (PETA), which is used as coating material. Pentaerythritol and ammonium polyphosphate (APP) are matched to obtain an intumescent flame retardant which is used as a flame retardant of the adhesive. Also act as crosslinkers for the polyurethane, providing branching within the polyurethane.
Dipentaerythritol (Di-PE) contains 2 quaternary carbon atoms and 6 active hydroxyl groups in the molecule, and is a 6-membered alcohol with excellent thermal stability. The dipentaerythritol serving as an important fine chemical intermediate is regarded as a medium-high grade product in the pentaerythritol industry and is mainly used for the high-grade coating industry. Producing polyether, polyester, polyurethane, high-grade alkyd resin and photosensitive resin film. The dipentaerythritol higher fatty acid ester is used for high-grade aviation lubricating oil, and the lower fatty acid ester can be used as a polyvinyl chloride plasticizer. In the aspect of photosensitive coating, the dipentaerythritol acrylate can be used as a stainless steel color plate and a high-grade granite spraying surface film, and has the excellent performances of strong adhesion, friction resistance, aging resistance and the like. The application of the dipentaerythritol is very wide, but the yield is low and the additional value is high.
Tripentaerythritol (Ti-PE) contains 3 quaternary carbon atoms and 8 active hydroxyl groups in its molecule, and is an 8-membered alcohol with excellent thermal stability. The acrylic resin is mainly used in the fields of high-performance acrylic resin, fireproof paint, high-grade aviation lubricating oil, high-grade color printing ink, plastic additives, high-molecular modified materials and the like.
The monopentaerythritol is prepared by condensing acetaldehyde, formaldehyde and alkali as raw materials, wherein the condensation process comprises a aldol condensation reaction and a Cannizzaro reaction to obtain monopentaerythritol and formate. The monopentaerythritol condensation reaction is also accompanied by dipentaerythritol, tripentaerythritol and other by-products, the side yield of dipentaerythritol is low, the price is 2-4 times of that of monopentaerythritol, the amount of the by-products of tripentaerythritol is less, and the price is 5-8 times of that of monopentaerythritol. Because dipentaerythritol and tripentaerythritol have wide application, low yield, no supply, high additional value and good economic benefit, production enterprises hope that the condensation reaction produces more byproducts dipentaerythritol and tripentaerythritol. The monopentaerythritol condensation reaction usually adopts a batch reaction process, the material retention time is long, the equipment investment is large, the production capacity is low, the formaldehyde consumption is high, the amount of the byproduct of dipentaerythritol in the batch reaction process is small, usually less than 5%, and the amount of the byproduct of tripentaerythritol is less than 2%.
In the prior art, a continuous production method with low formaldehyde consumption and high yield of dipentaerythritol and tripentaerythritol is not disclosed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method and a device for continuously condensing monopentaerythritol, dipentaerythritol and tripentaerythritol so as to solve the defects in the prior art.
The invention discloses a continuous condensation method of monopentaerythritol, dipentaerythritol and tripentaerythritol, which comprises the following steps:
step 1, filling a formaldehyde solution with the mass percent of 37% into a continuous reaction heat exchanger, starting a circulating pump, and controlling the temperature in the continuous reaction heat exchanger to be 30-70 ℃;
3, continuously feeding a reaction mixture formed after the reaction in the step 2 into a continuous reactor through a continuous reaction heat exchanger, staying for 30-180 min in the continuous reactor, and controlling the temperature in the continuous reactor to be 30-70 ℃;
Further, in step 2, the amount of the base is calculated by the amount of the substance of hydroxide ion, n, in terms of mole fractionAcetaldehyde：nFormaldehyde (I)：nAlkali1: 4.2-15.0: 1.05-1.4; the addition of water is calculated according to the condensation liquid of 800-1500kg obtained by feeding 1kmol acetaldehyde.
The alkali is at least one of a potassium hydroxide aqueous solution, a sodium hydroxide aqueous solution, and a calcium hydroxide suspension.
Preferably, the alkali is calcium hydroxide suspension.
Further, the continuous condensation method of monopentaerythritol, dipentaerythritol and tripentaerythritol further comprises the following steps:
and 5, introducing the reaction mixture formed after the reaction in the step 4 into a condensation liquid storage tank for temporary storage, and then separating and refining to obtain qualified monopentaerythritol, dipentaerythritol, tripentaerythritol and formate.
Furthermore, the invention also discloses a monopentaerythritol, dipentaerythritol and tripentaerythritol continuous condensation device, which comprises a raw material mixing device, a reaction device and a neutralization device;
the raw material mixing device comprises an aldehyde mixer and an alkali mixer; the aldehyde mixer is used for mixing formaldehyde and acetaldehyde raw materials, and the alkali mixer is used for mixing alkali and water;
the reaction device comprises a continuous reaction heat exchanger and a continuous reactor; the inlet of the continuous reaction heat exchanger is respectively connected with the outlet of the aldehyde mixer and the outlet of the alkali mixer; the outlet of the continuous reaction heat exchanger is connected with the inlet of the continuous reactor; the continuous reaction heat exchanger is provided with a circulating pump in parallel, the outlet of the circulating pump is connected with the inlet of the continuous reaction heat exchanger, and the inlet of the circulating pump is connected with the outlet of the continuous reaction heat exchanger;
the neutralization device comprises a neutralization reactor, a formic acid storage tank and a pH meter; the outlet of the continuous reactor is connected with the inlet of the neutralization reactor; the outlet of the formic acid storage tank is connected with the inlet of the neutralization reactor; the pH meter is arranged on the neutralization reactor and used for testing the pH value of materials in the neutralization reactor.
Preferably, the aldehyde mixer is a pipeline mixer or a stirred tank mixer; the alkali mixer adopts a pipeline mixer or a stirring tank mixer.
Preferably, the continuous reaction heat exchanger adopts at least one of a tube heat exchanger, a plate heat exchanger or a coil heat exchanger.
Preferably, the continuous reaction heat exchanger is in a heat exchanger form with a large heat exchange area and a small effective volume.
Preferably, the continuous reactor adopts at least one of a pipeline reactor and a multi-kettle serial stirring reactor, and has both a heat exchange function and a stirring function.
Furthermore, an automatic control regulating valve is arranged at the outlet of the formic acid storage tank, and the pH meter is interlocked with the opening of the automatic control regulating valve at the outlet of the formic acid storage tank in an automatic control mode.
Further, the continuous condensation device of mono-pentaerythritol, di-pentaerythritol and tri-pentaerythritol also comprises a temperature control device, wherein the temperature control device comprises a thermometer and a temperature control device; the temperature control device is arranged on at least one of the continuous reaction heat exchanger, the continuous reactor and the neutralization reactor.
Further, the thermometer is interlocked with the switch of the temperature adjusting device in a self-control mode and used for automatically adjusting the temperature.
Furthermore, the temperature adjusting device adopts at least one of a refrigerant, a heating medium and electric heating.
The invention has the beneficial effects that:
1. compared with a simple tubular reactor, the tubular reactor has the advantages of large heat exchange area, rapid reaction heat exchange, accurate control of reaction temperature, no over temperature and high yield of dipentaerythritol and tripentaerythritol;
2. compared with a simple multi-kettle continuous reactor, the method has the advantages of rapid heat removal, less material back mixing, high reaction speed and high yield of dipentaerythritol and tripentaerythritol;
3. compared with a batch reactor, the method has the advantages of short average material retention time, less formaldehyde disproportionation reaction, low formaldehyde consumption, constant proportion of reaction raw materials and the like, and the method has the advantages of constant reaction temperature, no change along with the feeding time, large production load, high equipment utilization rate and high yield of dipentaerythritol and tripentaerythritol.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a flow diagram of the feed mixing apparatus;
FIG. 3 is a flow diagram of the reaction apparatus;
FIG. 4 is a flow chart of the neutralization apparatus;
FIG. 5 is a flow chart of the temperature control device.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are only some embodiments, but not all embodiments, of the present invention. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without any creative effort, belong to the protection scope of the present invention.
Example 1
The invention discloses a continuous condensation method of monopentaerythritol, dipentaerythritol and tripentaerythritol, which comprises the following steps:
step 1, filling a formaldehyde solution with the mass percent of 37% into a continuous reaction heat exchanger, starting a circulating pump, and controlling the temperature in the continuous reaction heat exchanger to be 40 +/-1 ℃;
3, continuously feeding a reaction mixture formed after the reaction in the step 2 into a continuous reactor through a continuous reaction heat exchanger, staying for 40min in the continuous reactor, and controlling the temperature in the continuous reactor to be 45 +/-1 ℃;
And (4) detecting the mixture obtained after the reaction in the step (4) by using a liquid chromatography area normalization method (deducting a formaldehyde peak and a sodium formate peak), wherein the content of the monopentaerythritol is 82%, the content of the dipentaerythritol is 11% and the content of the tripentaerythritol is 1%.
The invention also discloses a continuous condensation device of monopentaerythritol, dipentaerythritol and tripentaerythritol, which comprises a raw material mixing device 1, a reaction device 2 and a neutralization device 3;
the raw material mixing device 1 comprises an aldehyde mixer 11 and an alkali mixer 12; the aldehyde mixer 11 is used for mixing formaldehyde and acetaldehyde raw materials, and the alkali mixer 12 is used for mixing alkali and water;
the reaction device 2 comprises a continuous reaction heat exchanger 21 and a continuous reactor 22; the inlet of the continuous reaction heat exchanger 21 is respectively connected with the outlet of the aldehyde mixer 11 and the outlet of the alkali mixer 12; the outlet of the continuous reaction heat exchanger 21 is connected with the inlet of the continuous reactor 22; a circulating pump 23 is arranged on the continuous reaction heat exchanger 21 in parallel, an outlet of the circulating pump 23 is connected with an inlet of the continuous reaction heat exchanger 21, and an inlet of the circulating pump 23 is connected with an outlet of the continuous reaction heat exchanger 21;
the neutralization device 3 comprises a neutralization reactor 31, a formic acid storage tank 32 and a pH meter 33; the outlet of the continuous reactor 22 is connected with the inlet of the neutralization reactor 31; the outlet of the formic acid storage tank 32 is connected with the inlet of the neutralization reactor 31; the pH meter 33 is disposed on the neutralization reactor 31 for testing the pH value of the contents of the neutralization reactor 31.
Preferably, the aldehyde mixer 11 employs a line mixer or a stirred tank mixer; the alkali mixer 12 is a pipeline mixer or a stirred tank mixer.
Preferably, the continuous reaction heat exchanger 21 is at least one of a tube and tube heat exchanger, a plate heat exchanger or a coil heat exchanger.
Preferably, the continuous reaction heat exchanger 21 is in the form of a heat exchanger having a large heat exchange area and a small effective volume.
Preferably, the continuous reactor 22 is at least one of a pipeline reactor and a multi-kettle serial stirring reactor, and has both heat exchange function and stirring function.
In this embodiment, the outlet of the formic acid storage tank 32 is provided with an automatic control regulating valve, and the pH meter 33 is interlocked with the opening of the automatic control regulating valve at the outlet of the formic acid storage tank 32 in an automatic control manner.
In this embodiment, the continuous condensation device of mono-pentaerythritol, di-pentaerythritol, and tri-pentaerythritol further includes a temperature control device 4, where the temperature control device 4 includes a thermometer 41 and a temperature control device 42; the temperature control device 4 is disposed on at least one of the continuous reaction heat exchanger 21, the continuous reactor 22, and the neutralization reactor 31.
In this embodiment, the thermometer 41 and the temperature adjustment device 42 are linked by a switch for automatic control, so as to automatically adjust the temperature.
In this embodiment, the temperature adjusting device 42 uses at least one of a refrigerant, a heating medium, and an electric heater.
Examples 2 to 3
Examples 2-3 were the same apparatus and similar methods as those used in example 1, except for the following parameters (tables 1-2):
table 1 raw material selection table
TABLE 2 reaction parameters Table
The product parameters obtained are shown in the following table (table 2):
TABLE 3 product parameters table
| Group of | Content of monopentaerythritol (n/n%) | Dipentaerythritol content (n/n%) | Tripentaerythritol content (n/n%) |
| Example 2 | 88 | 5 | 0.8 |
| Example 3 | 92 | 3 | 0.3 |
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A method for continuously condensing monopentaerythritol, dipentaerythritol and tripentaerythritol is characterized by comprising the following steps:
step 1, filling a formaldehyde solution with the mass percent of 37% into a continuous reaction heat exchanger, starting a circulating pump, and controlling the temperature in the continuous reaction heat exchanger to be 30-70 ℃;
step 2, uniformly injecting acetaldehyde and formaldehyde into an aldehyde mixer according to the proportion for mixing, mixing alkali and water through the alkali mixer, and continuously injecting mixed aldehyde and alkali liquor into a continuous reaction heat exchanger at a constant speed; the reaction materials stay in the continuous reaction heat exchanger for 1min to 30min, and the temperature in the continuous reaction heat exchanger is controlled to be 30 ℃ to 70 ℃;
3, continuously feeding the reaction mixture formed after the reaction in the step 2 into a continuous reactor through a continuous reaction heat exchanger, staying for 30-180 min in the continuous reactor, and controlling the temperature in the continuous reactor to be 30-70 ℃;
step 4, the reaction mixture formed after the reaction in the step 3 continuously enters a continuous neutralization reactor from the continuous reactor, stays in the continuous neutralization reactor for 1-30 min, and the temperature in the continuous neutralization reactor is controlled at 40-70 ℃; simultaneously continuously adding formic acid into the continuous neutralization reactor to perform neutralization reaction with the reaction mixture, and controlling the pH value to be weakly acidic; and obtaining a mixture of the target products of monopentaerythritol, dipentaerythritol, tripentaerythritol and by-product formate after the reaction is finished.
2. Process according to claim 1, wherein in step 2, the base is present in the amount of hydroxide ions, n is the molar fraction of the substanceAcetaldehyde：nFormaldehyde (I)：nAlkali1: 4.2-15.0: 1.05-1.4; the addition amount of water is calculated according to the condensation liquid of 800-1500kg obtained by feeding 1kmol acetaldehyde.
3. The continuous condensation method of monopentaerythritol, dipentaerythritol, and tripentaerythritol according to claim 1, wherein the alkali is at least one of an aqueous potassium hydroxide solution, an aqueous sodium hydroxide solution, and a suspension of calcium hydroxide.
4. A process for the continuous condensation of monopentaerythritol, dipentaerythritol and tripentaerythritol according to any one of claims 1 to 3, characterized by further comprising the steps of:
and 5, introducing the reaction mixture formed after the reaction in the step 4 into a condensation liquid storage tank for temporary storage, and then separating and refining to obtain qualified monopentaerythritol, dipentaerythritol, tripentaerythritol and formate.
5. A continuous condensation device of monopentaerythritol, dipentaerythritol and tripentaerythritol is characterized by comprising a raw material mixing device (1), a reaction device (2) and a neutralization device (3);
the raw material mixing device (1) comprises an aldehyde mixer (11) and an alkali mixer (12); the aldehyde mixer (11) is used for mixing formaldehyde and acetaldehyde raw materials, and the alkali mixer (12) is used for mixing alkali and water;
the reaction device (2) comprises a continuous reaction heat exchanger (21) and a continuous reactor (22); the inlet of the continuous reaction heat exchanger (21) is respectively connected with the outlet of the aldehyde mixer (11) and the outlet of the alkali mixer (12); the outlet of the continuous reaction heat exchanger (21) is connected with the inlet of the continuous reactor (22); a circulating pump (23) is arranged on the continuous reaction heat exchanger (21) in parallel, an outlet of the circulating pump (23) is connected with an inlet of the continuous reaction heat exchanger (21), and an inlet of the circulating pump (23) is connected with an outlet of the continuous reaction heat exchanger (21);
the neutralization device (3) comprises a neutralization reactor (31), a formic acid storage tank (32) and a pH meter (33); the outlet of the continuous reactor (22) is connected with the inlet of the neutralization reactor (31); the outlet of the formic acid storage tank (32) is connected with the inlet of the neutralization reactor (31); the pH meter (33) is arranged on the neutralization reactor (31) and is used for testing the pH value of the materials in the neutralization reactor (31).
6. The continuous condensation apparatus of mono-, di-and tripentaerythritol according to claim 5, characterized in that the aldehyde mixer (11) is a pipeline mixer or a stirred tank mixer; the alkali mixer (12) adopts a pipeline mixer or a stirring tank mixer; the continuous reaction heat exchanger (21) adopts at least one of a tube heat exchanger, a plate heat exchanger or a coil heat exchanger; the continuous reactor (22) adopts at least one of a pipeline reactor and a multi-kettle serial stirring reactor, and has the functions of heat exchange and stirring.
7. The continuous mono-, di-and tripentaerythritol condensation plant according to claim 5, characterized in that the formic acid storage tank (32) outlet is provided with a self-regulating valve, and the pH meter (33) is interlocked with the self-regulating valve opening degree of the formic acid storage tank (32) outlet in a self-regulating manner.
8. The continuous condensation apparatus of mono-, di-and tripentaerythritol according to any one of claims 5 to 7, characterized in that it further comprises a temperature control device (4), said temperature control device (4) comprising a thermometer (41), a temperature control device (42); the temperature control device (4) is arranged on at least one of the continuous reaction heat exchanger (21), the continuous reactor (22) and the neutralization reactor (31).
9. The continuous condensation apparatus of mono-, di-and tripentaerythritol according to claim 8, characterized in that the thermometer (41) is self-control interlocked with the switch of the temperature adjusting means (42) for automatic temperature adjustment.
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