CN116063248A - Method for continuously producing biomass glycidyl ether - Google Patents
Method for continuously producing biomass glycidyl ether Download PDFInfo
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- CN116063248A CN116063248A CN202211564760.6A CN202211564760A CN116063248A CN 116063248 A CN116063248 A CN 116063248A CN 202211564760 A CN202211564760 A CN 202211564760A CN 116063248 A CN116063248 A CN 116063248A
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- glycidyl ether
- continuously producing
- producing biomass
- alcohol
- oil
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- 238000000034 method Methods 0.000 title claims abstract description 25
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002028 Biomass Substances 0.000 title claims abstract description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 claims abstract description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 12
- 239000008158 vegetable oil Substances 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 239000003463 adsorbent Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000007670 refining Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000010924 continuous production Methods 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 11
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 10
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000007142 ring opening reaction Methods 0.000 claims description 5
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000391 magnesium silicate Substances 0.000 claims description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 4
- 235000019792 magnesium silicate Nutrition 0.000 claims description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- 239000004359 castor oil Substances 0.000 claims description 3
- 235000019438 castor oil Nutrition 0.000 claims description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 3
- 239000002540 palm oil Substances 0.000 claims description 3
- 239000003549 soybean oil Substances 0.000 claims description 3
- 235000012424 soybean oil Nutrition 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- -1 small molecule alcohols Chemical class 0.000 claims 1
- 150000003384 small molecules Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000012074 organic phase Substances 0.000 abstract description 7
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000003822 epoxy resin Substances 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229940009868 aluminum magnesium silicate Drugs 0.000 description 2
- WMGSQTMJHBYJMQ-UHFFFAOYSA-N aluminum;magnesium;silicate Chemical compound [Mg+2].[Al+3].[O-][Si]([O-])([O-])[O-] WMGSQTMJHBYJMQ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/24—Synthesis of the oxirane ring by splitting off HAL—Y from compounds containing the radical HAL—C—C—OY
- C07D301/26—Y being hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/22—Ethers with hydroxy compounds containing no oxirane rings with monohydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to a method for continuously producing biomass glycidyl ether, which comprises the steps of fully stirring micromolecular alcohol and/or vegetable oil with an acid catalyst, then carrying out mixed reaction with epoxy chloropropane, carrying out epoxy end capping on the synthesized chlorohydrin ether and alkali, centrifuging, separating liquid, adding an obtained organic phase into an adsorbent, refining and filtering to obtain a final required product. The reaction efficiency is greatly improved, the production period is shortened, and the temperature control is convenient through the tubular reactor; the reaction heat of the fixed bed reactor is exchanged with the heat carrier outside the tube through the tube wall, so that the fixed bed reactor is suitable for exothermic reaction and is convenient for temperature control. Meanwhile, the method of adding alkali for many times in batches for preventing overheat bumping is avoided, and manpower and material resources are greatly saved. The invention is suitable for mass production, can continuously produce, shortens the period and reduces the cost.
Description
Technical Field
The invention belongs to the field of epoxy resin, and particularly relates to a method for continuously producing biomass glycidyl ether.
Background
Epoxy resins are an important thermosetting resin. The epoxy resin condensate has good chemical stability, electrical insulation, corrosion resistance, excellent mechanical properties and physical properties, and good process operation performance, and is widely applied to the fields of coating industry, mechanical industry, electronic industry, transportation industry, automobile manufacturing industry, building industry, aerospace and the like.
At present, the main problems are that the production device is not economical enough in scale, the product specificity is low, and the product quality stability is poor.
The domestic pillar industry accelerates development, and brings unlimited business opportunities for the epoxy resin industry, such as the automobile field, the information industry, the energy, the transportation and the building industry, and the pillar industry with the outstanding development is the power generation field of applying the epoxy resin, and can bring huge market demands for the epoxy resin.
Along with the continuous expansion of the application field of the epoxy resin, new requirements on the environmental protection performance and the cost performance of the epoxy resin are put forward. The demand for biobased products in various countries is increasing, and despite the challenges, with the emphasis placed on environmentally friendly products in various countries, the applicability of the biomass glycidyl ether will gradually expand in the future, and the market competition will gradually increase.
Disclosure of Invention
The invention aims to provide a method for continuously producing biomass glycidyl ether, which greatly improves the reaction efficiency, shortens the production period and is convenient for controlling the temperature through a tubular reactor; the reaction heat of the fixed bed reactor is exchanged with the heat carrier outside the tube through the tube wall, so that the fixed bed reactor is suitable for exothermic reaction and is convenient for temperature control. Meanwhile, the method of adding alkali for many times in batches for preventing overheat bumping is avoided, and manpower and material resources are greatly saved. The invention is suitable for mass production, can continuously produce, shortens the period and reduces the cost.
The invention relates to a method for continuously producing biomass glycidyl ether, which comprises the steps of fully stirring micromolecular alcohol and/or vegetable oil with an acid catalyst, then carrying out mixed reaction with epoxy chloropropane, carrying out epoxy end capping on the synthesized chlorohydrin ether and alkali, centrifuging, separating liquid, obtaining an organic phase, adding an adsorbent, refining, and filtering to obtain a final required product.
The small molecular alcohol is one or more of 1, 4-butanediol, 1, 6-hexanediol, 1214 alcohol, 1618 alcohol, pentaerythritol or sorbitol; the vegetable oil comprises one or more of castor oil, soybean oil, palm oil, rapeseed oil, peanut oil or olive oil.
The acid catalyst is boron trifluoride diethyl etherate solution.
The molar ratio of the total hydroxyl number of the small molecular alcohol and the vegetable oil to the epichlorohydrin to the alkali is 1:1.1-2.8:1.2-2.9; the dosage of the acid catalyst is 1-2 per mill, and specifically the mass fraction of boron trifluoride diethyl etherate in the total mass of the micromolecular alcohol and the epichlorohydrin.
The small molecular alcohol, vegetable oil and epoxy chloropropane are subjected to ring opening under the action of an acid catalyst, the reaction temperature is 65-75 ℃, and the reaction time is 10-40min.
The alkali is one or more of potassium hydroxide, sodium hydroxide, cesium hydroxide or calcium hydroxide.
The adsorbent is one or more of magnesium silicate, aluminum silicate or magnesium aluminum silicate.
The mass fraction of the adsorbent is 1-7 per mill of the organic phase after centrifugation.
The epoxy end capping reaction temperature is 30-60 ℃ and the curing time is 2-3h.
During centrifugation, the centrifugation speed is 4000-9000r/min, and the centrifugation time is 10-60min. In the case of centrifugation, the centrifugation rate is preferably 4000r/min, and the centrifugation time is preferably 30min.
The small molecular alcohol, vegetable oil and epoxy chloropropane react in a tubular reactor in the ring opening stage, wherein the tubular reactor has the specification, the inner diameter of 3mm-20mm and the length of 10-100m, and the pressure resistance is more than 1Mpa.
The specific preparation method of the invention comprises the following steps:
(1) The ring-opening reaction, namely mixing vegetable oil, small molecular alcohol and acid according to the mass ratio of the catalyst, entering a 1# tank, connecting a 1# metering pump, and setting the flow rate to be 0-30ml/min; the epichlorohydrin tank is a No. 2 tank, which is connected with a No. 2 metering pump, and the flow rate is set to be 0-30ml/min. Placing the 3# tubular reactor in a constant-temperature water bath, simultaneously starting a 1# metering pump and a 2# metering pump, enabling a 1# tank and a 2# tank to simultaneously enter the 3# tubular reactor, carrying out mixed reaction, discharging 1 batch of chlorohydrin ether every 10min-1h, and entering a 4# buffer tank for cooling to a temperature lower than 60 ℃, so that the chlorohydrin ether is continuously produced;
(2) And (3) discharging the material of the No. 4 buffer tank into a No. 5 tube type fixed bed reactor after cooling, adding alkali into the tubes to carry out epoxy end sealing, and cooling water between the tubes in a circulating way. 1 batch of crude ether is discharged every 10min-1h and enters a No. 6 centrifuge, and every 10-60min of centrifugation, an organic phase is separated, so that continuous production of the crude ether is realized;
(3) The crude ether enters a 7# tube type fixed bed reactor, and an adsorbent is added into the tube. Meanwhile, the No. 8 metering pump pumps pure water into the No. 7 tube type fixed bed reactor, and water between the tubes is circularly heated. 1 batch of product is discharged every 10-30min, and continuous production is realized in the post-treatment process.
Wherein, the intermediate product chlorohydrin ether can not be left in the production process, and the epoxy end capping is carried out to obtain the crude ether only by adding alkali according to the proportion of alkali.
The invention researches the production process of biomass glycidyl ether and explores the continuous process for shortening the production period.
The epoxy end capping process is carried out by changing the process conditions of the metering pump such as the feeding speed, the reaction temperature, the material proportion and the like. The feeding speed is adjusted to control the production period to be shortened, and the benefit is improved; the reaction temperature and the material proportion are changed to mainly improve the quality of the product so as to obtain the highest epoxy end capping rate.
The glycidyl ether is added into epoxy resin as diluent to reduce viscosity.
Compared with the prior art, the invention has the beneficial effects that:
the invention can greatly improve the reaction efficiency, shorten the production period and facilitate temperature control by utilizing the tubular reactor. In addition, the reaction heat of the fixed bed reactor is exchanged with the heat carrier outside the tube through the tube wall, so that the reactor is very suitable for exothermic reaction and is convenient for temperature control. Compared with a reaction kettle, the method avoids adding alkali for a plurality of times in batches due to overheat bumping, and greatly saves manpower and material resources. The invention is suitable for mass production, has mature process, realizes continuous production, shortens the period and reduces the cost.
Detailed Description
The invention is further illustrated below with reference to examples.
Example 1
Feeding the mixed material into a 1# tank (material density is 0.955 g/ml) according to the mass ratio of castor oil/boron trifluoride diethyl ether= 933.5/1.8, connecting a 1# metering pump, and setting the flow rate to be 24.44ml/min; the epichlorohydrin tank is a No. 2 tank (material density 1.18 g/ml), which is connected with a No. 2 metering pump, and the set flow rate is 5.49ml/min. The 3# tubular reactor is placed in a constant-temperature water bath at 65 ℃, and a 1# metering pump and a 2# metering pump are started simultaneously, so that materials in the 1# tank and the 2# tank enter the 3# tubular reactor simultaneously, the materials are mixed for reaction, 1 batch of chlorohydrin ether is discharged every 40min and enters a 4# buffer tank for cooling, and the chlorohydrin ether is continuously produced.
The material of the No. 4 buffer tank is discharged into a No. 5 tube type fixed bed reactor after being cooled, and potassium hydroxide solid is added into the tube, so that 162.4g of potassium hydroxide is consumed for epoxy end capping per 1192.5g of material. The water between the pipes is circularly cooled, and the reaction temperature is controlled to be 30-50 ℃.1 batch of crude ether is discharged every 40min and enters a No. 6 centrifugal machine, the rotating speed is 4000r/min, and every 20min of the centrifugal machine, 1084g of organic phase is separated, so that continuous production of the crude ether is realized.
The crude ether was fed into a 7# shell and tube fixed bed reactor, and 600# magnesium silicate was added to the tube, and 3.3g of 600# magnesium silicate was required for adsorption per 1084g of crude ether. Meanwhile, a No. 8 metering pump is used for pumping 32.5g of pure water into the No. 7 tubular fixed bed reactor. The water circulation between the pipes is heated, and the reaction temperature is controlled to be 80-110 ℃.1 batch of product is discharged every 20min, and continuous production is realized in the post-treatment process.
The final product index is 2ppm of potassium ion, PH7.16 acid value, 0.015mgKOH/g moisture, 0.023% epoxy value, 0.19mol/100g end-capping rate, 76.2%.
Example 2
Feeding the mixed material into a 1# tank (material density is 0.84 g/ml) according to the mass ratio of soybean oil/1214 alcohol/boron trifluoride diethyl ether=20/200.4/0.3, connecting a 1# metering pump, and setting the flow rate to be 13.12ml/min; the epichlorohydrin tank is a No. 2 tank (material density 1.18 g/ml), which is connected with a No. 2 metering pump, and the set flow rate is 4.31ml/min. Placing the tubular reactor in a constant-temperature water bath at 70 ℃, simultaneously starting a 1# metering pump and a 2# metering pump, enabling materials in a 1# tank and a 2# tank to enter the 3# tubular reactor at the same time, carrying out mixed reaction, and discharging 1 batch of chlorohydrin ether into a 4# buffer tank for cooling every 20min in the residence time; the chlorohydrin ether realizes continuous production.
The material of the No. 4 buffer tank is discharged into a No. 5 tube type fixed bed reactor after being cooled, sodium hydroxide solid is added into the tube, and 48g of sodium hydroxide is consumed for epoxy end capping per 322.2g of material. The water between the pipes is circularly cooled, and the reaction temperature is controlled to be 35-50 ℃.1 batch of crude ether is discharged every 20min and enters a 6# centrifugal machine (the rotating speed is 4000 r/min), 256g of organic phase is separated out every 15min, and continuous production of the crude ether is realized.
The crude ether was fed into a 7# tubular fixed bed reactor, and the inside of the tube was charged with an aluminum magnesium silicate adsorbent, and 0.5g of aluminum magnesium silicate was required for adsorption per 256g of the crude ether. Meanwhile, a No. 8 metering pump is used for pumping 10.3g of pure water into the No. 7 tubular fixed bed reactor. The water circulation between the pipes is heated, and the reaction temperature is controlled to be 90-120 ℃.1 batch of product is discharged every 15min, and continuous production is realized in the post-treatment process.
The final product index was sodium ion 1ppm PH7.23 acid value 0.018mgKOH/g moisture 0.021% epoxy value 0.3042mol/100g end-capping 78%.
Example 3
Mixing palm oil/1, 4-butanediol/boron trifluoride diethyl ether=18/90.12/0.57 according to the mass ratio, feeding the mixture into a No. 1 tank (the material temperature is 60 ℃, the density is 1.0 g/ml), connecting a No. 1 metering pump, and setting the flow rate to 7.2ml/min; the epichlorohydrin tank is a No. 2 tank (material density 1.18 g/ml), which is connected with a No. 2 metering pump, and the flow rate is set to be 10.98ml/min. Placing the tubular reactor in a 75 ℃ constant-temperature water bath, simultaneously starting a 1# metering pump and a 2# metering pump, enabling a 1# tank and a 2# tank to simultaneously enter a 3# tubular reactor, carrying out mixed reaction, and discharging 1 batch of chlorohydrin ether into a 4# buffer tank for cooling every 15min in the residence time; the chlorohydrin ether realizes continuous production.
The material of the No. 4 buffer tank is discharged into a No. 5 tube type fixed bed reactor after being cooled, cesium hydroxide solid is added into the tube, and 96g of sodium hydroxide is consumed for epoxy end capping per 302.5g of the material. The water between the pipes is circularly cooled, and the reaction temperature is controlled to be 40-60 ℃.1 batch of crude ether is discharged every 15min and enters a 6# centrifugal machine (the rotating speed is 4000 r/min), and 200g of organic phase is separated out every 10min, so that continuous production of the crude ether is realized.
The crude ether was fed into a 7# tubular fixed bed reactor, and aluminum silicate was added to the tube, and 0.8g of aluminum silicate was required for adsorption per 200g of crude ether. Meanwhile, a No. 8 metering pump is used for pumping 6g of pure water into the No. 7 tubular fixed bed reactor. The water circulation between the pipes is heated, and the reaction temperature is controlled to be 90-110 ℃.1 batch of product is discharged every 15min, and continuous production is realized in the post-treatment process.
The final product index was sodium ion 1ppm PH7.23 acid value 0.013mgKOH/g moisture 0.024% epoxy value 0.78mol/100g end-capping 79%.
Performance testing
The glycidyl ether of the above example was added to the epoxy resin E51 (if the operation temperature was low, the epoxy resin was heated first for easy operation), stirred uniformly and then left to stand for 5 minutes, and the bubbles generated during stirring were eliminated for use. The amine curing agent is ready for use (note sealed to protect against exposure to air when not in use, to protect the surface of the cured article from moisture from whitening).
The mould is processed and the required ornaments are installed.
The two materials prepared in advance are epoxy resin according to the mass ratio: after mixing uniformly, curing agent=3:1, slowly pour from the side of the inner wall of the prepared mold until the desired amount. The mixture is placed in an oven at a certain temperature or in an environment suitable for curing. After curing is completed, the article is safely removed from the mold.
| Project | Example 1 | Example 2 | Example 3 |
| Tensile Strength (kg/cm) 2 ) | 750 | 720 | 830 |
| Flexural Strength (kg/cm) 2 ) | 1100 | 1000 | 1200 |
| Compressive Strength (kg/cm) 2 ) | 1200 | 1100 | 1300 |
| Impact Strength (kg.cm/cm) 2 ) | 15 | 10 | 20 |
| Heat resistance (. Degree. C. Ma Dingfa) | 120 | 110 | 120 |
| Breakdown voltage (kilovolt/millimeter, room temperature) | 35 | 32 | 35 |
Claims (10)
1. A method for continuously producing biomass glycidyl ether is characterized in that micromolecular alcohol and/or vegetable oil and an acid catalyst are fully stirred, then mixed with epichlorohydrin for reaction, the synthesized chlorohydrin ether and alkali are subjected to epoxy end capping, centrifuging and separating liquid, and finally a required product is obtained by adding an adsorbent for refining and filtering.
2. The method for continuous production of biomass glycidyl ether according to claim 1, wherein the small molecule alcohol is one or more of 1, 4-butanediol, 1, 6-hexanediol, 1214 alcohol, 1618 alcohol, pentaerythritol or sorbitol; the vegetable oil comprises one or more of castor oil, soybean oil, palm oil, rapeseed oil, peanut oil or olive oil.
3. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the acidic catalyst is boron trifluoride etherate solution.
4. The continuous process for producing biomass glycidyl ethers according to claim 1, wherein the total hydroxyl number of the small molecule alcohols and vegetable oils, the molar ratio of epichlorohydrin to base is 1:1.1-2.8:1.2-2.9; the dosage of the acid catalyst is 1-2 per mill, and specifically the mass fraction of boron trifluoride diethyl etherate in the total mass of the micromolecular alcohol and the epichlorohydrin.
5. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the small molecular alcohol, the vegetable oil and the epichlorohydrin are subjected to ring opening under the action of an acid catalyst, the reaction temperature is 65-75 ℃, and the reaction time is 10-40min.
6. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the small molecular alcohol, the vegetable oil and the epichlorohydrin are reacted in a tubular reactor in a ring-opening stage in the specification of the tubular reactor, wherein the inner diameter is 3mm-20mm, the length is 10-100m, and the pressure resistance is more than 1Mpa.
7. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the alkali is one or more of potassium hydroxide, sodium hydroxide, cesium hydroxide or calcium hydroxide.
8. The method for continuously producing biomass glycidyl ethers according to claim 1, wherein the adsorbent is one or more of magnesium silicate, aluminum silicate, magnesium aluminum silicate, and the like.
9. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the epoxy capping reaction temperature is 30-60 ℃ and the curing time is 2-3h.
10. The method for continuously producing biomass glycidyl ether according to claim 1, wherein the centrifugation rate is 4000-9000r/min and the centrifugation time is 10-60min.
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