CN103864575A - Method for preparing 1,2-pentanediol - Google Patents
Method for preparing 1,2-pentanediol Download PDFInfo
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- CN103864575A CN103864575A CN201210535329.9A CN201210535329A CN103864575A CN 103864575 A CN103864575 A CN 103864575A CN 201210535329 A CN201210535329 A CN 201210535329A CN 103864575 A CN103864575 A CN 103864575A
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- Prior art keywords
- pentanediol
- formic acid
- hydrogen peroxide
- reaction
- prepared
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- 238000000034 method Methods 0.000 title claims abstract description 41
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 56
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- 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 28
- 235000019253 formic acid Nutrition 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 25
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 abstract description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 abstract 4
- 239000004280 Sodium formate Substances 0.000 abstract 2
- 235000019254 sodium formate Nutrition 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 6
- SYURNNNQIFDVCA-UHFFFAOYSA-N 2-propyloxirane Chemical compound CCCC1CO1 SYURNNNQIFDVCA-UHFFFAOYSA-N 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- STJLVHWMYQXCPB-UHFFFAOYSA-N propiconazole Chemical compound O1C(CCC)COC1(C=1C(=CC(Cl)=CC=1)Cl)CN1N=CN=C1 STJLVHWMYQXCPB-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000005822 Propiconazole Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000002009 diols Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000003987 organophosphate pesticide Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A provided method for preparing 1,2-pentanediol mainly comprises the following steps: 1) mixing 1-pentene and formic acid in a reaction kettle, slowly dropwise adding hydrogen peroxide into the reaction kettle for 0.5-1.5 h, after addition is finished, keeping the temperature of 26-29 DEG C for 4-6 h, wherein the mass ratio of 1-pentene, formic acid and hydrogen peroxide is 3.5:0.5:0.2-3.5:2.5:1; and 2) dropwise adding a NaOH solution with a concentration of 50% into the reaction solution obtained in the step 1) for 30-60 min, controlling the pH value of the reaction solution to be 10-12, after addition is finished, keeping the temperature of 55-65 DEG C for 0.5-1.5 h. The advantages comprise that by changing the adding manner of the material, the usage amount of formic acid in the reaction process is reduced, and thus the usage amount of NaOH and the generation amount of sodium formate in hydrolysis process are reduced. The result shows that the method helps to reduce the usage amount of formic acid by 50%, and thus the generation amount of sodium formate is effectively reduced and the subsequent processing stress is mitigated.
Description
Technical field
The present invention relates to one and prepare the method for 1,2-pentanediol, particularly prepare the method for 1,2-pentanediol by the recycle of reaction mass.
Background technology
1,2-pentanediol is a kind of glycol of straight chain, has obvious polarity and nonpolar, thereby makes it have the character that is different from other glycol.1,2-pentanediol is widely used in the whole world, it is not only a kind of important industrial chemicals, be commonly used to produce polyester, tensio-active agent, 1,2-pentanediol is still prepared the main raw material of bactericide propiconazole, and Wocosin 50TK is a kind of sterilant that can replace organophosphorus pesticide, and it can be used as in the main component of the wetting Agent for Printing Inks of makeup simultaneously.
At present domestic 1, the synthetic method of 2-pentanediol mainly contains positive valeric acid method, Pentyl alcohol method, positive amylene method, acetic anhydride synthesis method, furfural method etc. according to the different synthetic methods of raw material also variation.Wherein positive amylene method is because technique is simple, and side reaction is few, and reaction yield is high and have certain advantage.But because the positive amylene of raw material is difficult to obtain, restricting the development of synthetic 1, the 2-pentanediol of positive amylene method.In recent years, separate the development of positive amylene through 1,2-pentanediol synthesis technique with oil C5 fraction, synthetic 1, the 2-pentanediol of positive amylene method more and more receives people's concern.For example: " with acetic anhydride synthesis method prepare adjacent glycol (" Tianjin chemical industry " 1996 (3): 28-29.) " literary composition introduced taking positive amylene as raw material, aceticanhydride is reaction medium, under the effect of the catalyzer vitriol oil, oxidized dose of Sodium peroxoborate direct oxidation of alkene is adjacent diol monoacetate, under alkaline condition, hydrolysis obtains required product 1,2-pentanediol again.The shortcoming of this technique is the more difficult control of catalyzer vitriol oil consumption, and by product is more, simultaneously poor safety performance.
US4605795 discloses a kind of synthetic method of 1,2-pentanediol, and the method is taking benzene as reaction medium, taking positive amylene, Perpropionic Acid as raw material is through the process such as epoxidation, saponification acquisition 1,2-pentanediol.The method easily generates by product and reclaims more difficult, equipment corrosion serious and used benzene that toxicity is high as solvent.
US447902 discloses a kind of method of synthetic 1,2-alkane glycol, and the method obtains 1,2-epoxy alkane with alkene and formic acid and hydroperoxidation, then is hydrolyzed and obtains 1,2-alkane glycol under alkaline condition.
CN1552684 discloses a kind of synthetic 1, the method of 2-pentanediol, the method is taking positive amylene, formic acid and hydrogen peroxide as raw material, under low temperature conditions, formic acid and hydrogen peroxide make peroxyformic acid with certain mol proportion reaction, and positive amylene generates 1,2-epoxy pentane under the effect of strong oxidizer peroxyformic acid, then under alkaline condition, hydrolysis obtains 1,2-pentanediol.Owing to using a large amount of acid and alkali in reaction process, this technique produces more waste liquid and formate.
The deficiencies such as can be seen here, in prior art, ubiquity production cost is higher, equipment corrosion is serious, environmental pollution is large.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provide one to prepare 1, the method of 2-pentanediol, the method is taking positive amylene as raw material, and hydrogen peroxide and formic acid are oxygenant, by the method to positive amylene and formic acid mixtures dropping hydrogen peroxide, reduce the consumption of formic acid in reaction process, thereby in minimizing hydrolysis reaction formate in amount, thereby alleviate the pressure of subsequent disposal formate, reduce production costs.
Below technical scheme of the present invention:
One is prepared the method for 1,2-pentanediol, and the method includes the steps of:
1) positive amylene and formic acid are blended in reactor, in reactor, slowly drip hydrogen peroxide, time for adding is 0.5 ~ 1.5h, after dropwising, at the temperature of 24 ~ 29 DEG C, is incubated 3 ~ 6h, and the mass ratio of positive amylene, formic acid and hydrogen peroxide is 3.5:0.5 ~ 2.5:0.2 ~ 1;
2) in the reaction solution obtaining to step 1), drip concentration and be 50% NaOH solution, time for adding is 30 ~ 60min, and controlling reacting liquid pH value is 10 ~ 12, after dropwising, at the temperature of 50 ~ 70 DEG C, is incubated 0.5 ~ 1.5h.
Described in step 1), hydrogen peroxide time for adding is 1 ~ 1.2h.
Described in step 1), holding temperature is 27 ~ 28 DEG C.
Described in step 1), soaking time is 4 ~ 5h.
Described in step 1), the mass ratio of positive amylene, formic acid and hydrogen peroxide is 3.5:1 ~ 2:0.5 ~ 1.
Step 2) described NaOH time for adding is 40 ~ 50min.
Step 2) described pH value in reaction is 10 ~ 11.
Step 2) described soaking time is 1 ~ 1.2h.
Step 2) described holding temperature is 55 ~ 65 DEG C.
In prior art, be generally that formic acid is first mixed with positive amylene, carry out oxidizing reaction by the mode that drips hydrogen peroxide in reactive system.Essence of the present invention is the recycle by formic acid, reduces the consumption of formic acid in reaction process, thereby reduces the growing amount of formate in hydrolysis reaction.Contriver is through research formic acid, the positive amylene of hydrogen peroxide oxidation synthetic 1, the reaction mechanism of 2-pentanediol operational path is found, in the process of the positive amylene of hydrogen peroxide oxidation, first formic acid oxidation is become peroxyformic acid by hydrogen peroxide, peroxyformic acid is a kind of strong oxidizer, and peroxyformic acid is reduced into formic acid after positive amylene is oxidized to 1,2-epoxy pentane, it is peroxyformic acid by formic acid oxidation that hydrogen peroxide continues, so circulation.In addition, contriver verifies by experiment, finds to change the dropping order of prior art Raw, and recycle formic acid, can reduce the consumption of the formic acid of 50% left and right, thereby has reduced the consumption of NaOH and the growing amount of sodium formiate.
Embodiment
Below by concrete embodiment, the invention will be further described.
[embodiment 1 ~ 10]
Formic acid and positive amylene being joined in reactor, in reactor, drip hydrogen peroxide, after completion of the reaction, is 50% NaOH solution to dripping concentration in system, and 1,2-epoxy pentane generates 1,2-pentanediol through hydrolysis.Reaction process Raw proportioning, technological reaction condition be in table 1.Adopt the each component concentration of gc analysis, obtain as calculated 1,2-pentanediol yield, the results are shown in Table 2.
[comparative example 1]
Hydrogen peroxide and positive amylene being joined in reactor, in reactor, drip formic acid, after completion of the reaction, is 50% NaOH solution to dripping concentration in system, and 1,2-epoxy pentane generates 1,2-pentanediol through hydrolysis.Reaction process Raw proportioning, technological reaction condition be in table 1.Adopt Gas chromatography to analyze each component concentration, obtain as calculated 1,2-pentanediol yield, the results are shown in Table 2.
[comparative example 2]
Hydrogen peroxide and formic acid are joined in reactor, in reactor, drip positive amylene, after completion of the reaction, in system, drip 50% NaOH solution, 1,2-epoxy pentane generates 1,2-pentanediol through hydrolysis.Reaction process Raw proportioning, technological reaction condition be in table 1.Adopt Gas chromatography to analyze each component concentration, obtain as calculated 1,2-pentanediol yield, the results are shown in Table 2.
Table 1
Table 2
| 1,2-pentanediol content/% | 1,2-pentanediol yield/% | By-product sodium formiate amount/g | |
| Embodiment 1 | 67.5 | 78.2 | 62.3 |
| Embodiment 2 | 61.2 | 70.9 | 64.4 |
| Embodiment 3 | 66.9 | 77.5 | 63.9 |
| Embodiment 4 | 65.3 | 75.7 | 65.6 |
| Embodiment 5 | 67.2 | 77.8 | 64.5 |
| Embodiment 6 | 62.4 | 72.6 | 64.8 |
| Embodiment 7 | 54.1 | 62.1 | 62.6 |
| Embodiment 8 | 67.8 | 78.6 | 153.1 |
| Embodiment 9 | 52.3 | 78.3 | 122.4 |
| Embodiment 10 | 54.6 | 62.5 | 32.4 |
| Comparative example 1 | 53.4 | 61.9 | 218.1 |
| Comparative example 2 | 50.7 | 58.7 | 214.5 |
Claims (9)
1. prepare the method for 1,2-pentanediol for one kind, it is characterized in that, the method includes the steps of:
1) positive amylene and formic acid are blended in reactor, in reactor, slowly drip hydrogen peroxide, time for adding is 0.5 ~ 1.5h, after dropwising, at the temperature of 24 ~ 29 DEG C, is incubated 3 ~ 6h, and the mass ratio of positive amylene, formic acid and hydrogen peroxide is 3.5:0.5 ~ 2.5:0.2 ~ 1;
2) in the reaction solution obtaining to step 1), drip concentration and be 50% NaOH solution, time for adding is 30 ~ 60min, and controlling reacting liquid pH value is 10 ~ 12, after dropwising, at the temperature of 50 ~ 70 DEG C, is incubated 0.5 ~ 1.5h.
2. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that described in step 1) that hydrogen peroxide time for adding is 1 ~ 1.2h.
3. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that described in step 1) that holding temperature is 27 ~ 28 DEG C.
4. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that described in step 1) that soaking time is 4 ~ 5h.
5. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that the mass ratio of positive amylene, formic acid and hydrogen peroxide described in step 1) is 3.5:1 ~ 2:0.5 ~ 1.
6. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that step 2) described NaOH time for adding is 40 ~ 50min.
7. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that step 2) described pH value in reaction is 10 ~ 11.
8. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that step 2) described soaking time is 1 ~ 1.2h.
9. one according to claim 1 is prepared the method for 1,2-pentanediol, it is characterized in that step 2) described holding temperature is 55 ~ 65 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210535329.9A CN103864575A (en) | 2012-12-12 | 2012-12-12 | Method for preparing 1,2-pentanediol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210535329.9A CN103864575A (en) | 2012-12-12 | 2012-12-12 | Method for preparing 1,2-pentanediol |
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| Publication Number | Publication Date |
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| CN103864575A true CN103864575A (en) | 2014-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210535329.9A Pending CN103864575A (en) | 2012-12-12 | 2012-12-12 | Method for preparing 1,2-pentanediol |
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| Country | Link |
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| CN (1) | CN103864575A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104926600A (en) * | 2015-05-12 | 2015-09-23 | 佛山市德品高新材料有限公司 | Method for synthesizing 1,2-pentanediol by one-pot method |
| CN105461511A (en) * | 2014-08-27 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of 1,2-pentanediol through oxidative hydrolysis of alpha-amylene |
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552684A (en) * | 2003-05-29 | 2004-12-08 | 浙江联盛化学工业有限公司 | Preparing method for 1,2-pentadiol |
-
2012
- 2012-12-12 CN CN201210535329.9A patent/CN103864575A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552684A (en) * | 2003-05-29 | 2004-12-08 | 浙江联盛化学工业有限公司 | Preparing method for 1,2-pentadiol |
Non-Patent Citations (2)
| Title |
|---|
| 李文: "高纯度1,2-己二醇的合成研究", 《研发前沿》 * |
| 林昌志: "1，2-辛二醇的合成", 《合肥学院学报(自然科学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461511A (en) * | 2014-08-27 | 2016-04-06 | 中国石油化工股份有限公司 | Preparation of 1,2-pentanediol through oxidative hydrolysis of alpha-amylene |
| CN104926600A (en) * | 2015-05-12 | 2015-09-23 | 佛山市德品高新材料有限公司 | Method for synthesizing 1,2-pentanediol by one-pot method |
| CN104926600B (en) * | 2015-05-12 | 2018-02-09 | 佛山市德品高新材料有限公司 | A kind of method of the pentanediol of one pot process 1,2 |
| CN110283046A (en) * | 2019-07-31 | 2019-09-27 | 新乡市巨晶化工有限责任公司 | A kind of preparation method of 1,2- pentanediol |
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Application publication date: 20140618 |