CN106220513B - A method of preparing nonamethylene diamine - Google Patents
A method of preparing nonamethylene diamine Download PDFInfo
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- CN106220513B CN106220513B CN201610601807.XA CN201610601807A CN106220513B CN 106220513 B CN106220513 B CN 106220513B CN 201610601807 A CN201610601807 A CN 201610601807A CN 106220513 B CN106220513 B CN 106220513B
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- Prior art keywords
- reaction
- catalyst
- azelaic
- nonamethylene diamine
- dinitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
Abstract
The invention discloses a kind of methods preparing nonamethylene diamine, it is using azelaic acid as raw material, and azelaic dinitrile is prepared in neutralized reaction, dehydration and Depressor response successively, and nonamethylene diamine is prepared in the hydrogenated reaction of azelaic dinitrile.Compared with prior art, the present invention provides a kind of process is simple, efficiency and the high process route of yield, and using renewable biomass resources as raw material, derive from a wealth of sources, while process is relatively simple and can implement, and has great social effect and economic value.
Description
Technical field
The invention belongs to field of chemical engineering, and in particular to a method of preparing nonamethylene diamine.
Background technology
Azelaic acid also known as azalaic acid, 1,7- heptane dicarboxylic acid is white under room temperature to faint yellow monoclinic prism, needle-shaped crystalline substance
Body or powder.It is slightly soluble in cold water, ether and benzene, hot water, ether is dissolved in, is soluble in ethyl alcohol, property is stablized.Azelaic acid has been important
Machine synthetic intermediate can be used to synthesize the products such as dioctyl azelate plasticizer, synthetic perfume, lubricating oil and polyamide；Nonyl two
Acid is additionally operable to the production of nylon-6 9 and nylon-9.In addition to this, the other application of azelaic acid further includes dielectric liquid, demulsification
Agent, mothproofing agent, polyurethane methyl vinegar foam, hydraulic oil, turbine oil, high molten coating, adhesive, water-soluble resin and cosmetics
Deng.The current main production process of azelaic acid is that saponification obtains ricinoleic acid, is further obtained by potassium permanganate or hydrogen peroxide oxidation
Obtain azelaic acid (new agricultural, 2015,10 (1)：16-18；Mining science technology, 2005,33 (4)：30-33), above method process
It is simple to operation, but by-product is more, and the utilization ratio of raw material is relatively low.
Nonamethylene diamine is C9 aliphatic diamines, is the important monomer as high temperature resistant nylon PA9T.PA9T has excellent low
It is the advantages that water imbibition, heat resistance, high resistance to rigidity, resistance to medicinal solvent borne, toughness, dimensional stability, sliding, mouldability, and same
High-temperature nylon PA46, PA6T of type are compared, and due to not having to be copolymerized large scale Third monomer, crystallinity is high, and crystallization rate is fast,
It can rapid shaping.
Existing literature is less to the preparation method report of nonamethylene diamine, and Kuraray company is using butadiene as raw material, through more
Step reaction prepare nonamethylene diamine and 2- methyl octamethylenediamines mixture (related patents such as US4417079, US4510331,
EP1489087, JP58167547), the technology is advanced, but nonamethylene diamine content and conversion ratio are relatively low.Chinese patent
CN201210180845.4 disclosed a kind of method preparing nonamethylene diamine as raw material using azelaic acid in 2012, and this method passes through chlorine
Change, amidation, dehydration, Hydrogenation is standby to obtain nonamethylene diamine, but total recovery about 84%, needs to further increase realization by technology
It is prepared by the high yield of product.
The invention mainly relates to castor oil to be aoxidized by saponification and molecular sieve, and the coarse-grain of azelaic acid is obtained through simple process
Body, while relating to the use of azelaic acid coarse crystal, take neutralization, two step dehydrations to obtain azelaic dinitrile and by adding hydrogen finally to obtain
Nonamethylene diamine.
Invention content
It is of the existing technology to solve the technical problem to be solved in the present invention is to provide a kind of method preparing nonamethylene diamine
Lack the problems such as azelaic acid prepares the technique and low feed stock conversion of nonamethylene diamine.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A method of nonamethylene diamine being prepared, it includes the following steps：
(1) azelaic acid is soluble in water, neutralization reaction, dehydration and Depressor response are carried out after heating for dissolving successively, is received
Collect distillate, i.e. azelaic dinitrile；
(2) after mixing the azelaic dinitrile being prepared in step (1), reaction dissolvent, catalyst and co-catalyst, to reaction
It is passed through hydrogen in system, carries out hydrogenation reaction, nonamethylene diamine is prepared.
In step (1), the azelaic acid is azelaic acid sterling or azelaic acid coarse crystal, purchased from market or by as follows
Method is prepared：
After castor oil is by saponification and oxidation reaction, through being separated by solid-liquid separation and crystallizing, azelaic acid coarse crystal is obtained；
Wherein, alkali used in saponification is NaOH or KOH, and oxidation reaction used catalyst is mesoporous molecular sieve catalyst
MO/HZSM-5, MO PbO, CuO, MgO, MoO3, MnO or ZnO.
In step (1), the operation of the neutralization reaction is：Ammonium hydroxide is added into azelaic acid aqueous solution, adjusts pH to 7.5
~9.0.
In step (1), the operation of the dehydration is：By gained mixed system after the completion of neutralization reaction 188~
2~5h is reacted at 219 DEG C.
In step (1), the operation of the Depressor response is：By gained mixed system after the completion of dehydration 185~
2~5h is reacted at 215 DEG C, it is 8~9kpa to answer vacuum degree in system.
In step (2), the reaction dissolvent is ethyl alcohol, methanol or butanol, and the catalyst is Raney's nickel, described
Co-catalyst is potassium hydroxide, sodium hydroxide or calcium hydroxide.
In step (2), the volume ratio of azelaic dinitrile and reaction dissolvent is 1：1~1.2.
In step (2), the solid-to-liquid ratio of the quality and azelaic dinitrile of catalyst and the total volume of reaction dissolvent is 3~10g：
The solid-to-liquid ratio of 100mL, the quality and azelaic dinitrile of co-catalyst and the total volume of solvent is 0.05~0.5g：100mL.
In step (2), the temperature of the hydrogenation reaction is 60~100 DEG C, and the reaction time is 0.5~1.0h, reactant
Pressure is 1.5~2.5MPa in system.
Advantageous effect：
The present invention obtains nonamethylene diamine using azelaic acid as raw material, by neutralization reaction, dehydration and hydrogenation reaction.Meanwhile
The technique that preparation method above-mentioned can also prepare azelaic acid with saponification, mesopore molecular sieve MO/HZSM-5 blown castor oils carries out
Coupling obtains azelaic acid coarse crystal, further by being simply separated by solid-liquid separation under conditions of non-purifies and separates with crystallization process
Nonamethylene diamine is prepared in reaction.Whole process provides that a kind of process is simple, efficiency and the high process route of yield, and with can
Renewable biomass resource is raw material, is derived from a wealth of sources, while process is relatively simple and can implement, therefore the technology is with great
Social effect and economic value.
Specific implementation mode
Embodiment 1
The preparation method of molecular sieve catalyst of the present embodiment narration containing different oxidants.
Metal oxide-loaded HZSM-5 catalyst is prepared using chemical precipitation method, to prepare 25wt%-ZnO/HZSM-
It is illustrated for 5 catalyst (10.00g)：Weigh 17.84g Zn (NO3)2·6H2O is dissolved in equipped with 50mL deionized waters
In 250mL beakers, after fully dissolving nitrate, the HZSM-5 of 7.50g is added in beaker, mixed liquor stirs 4h, then slowly
3mol/L (the NH of 30.00g are added4)2CO3Solution, stirring while adding, gained precipitation mixture is still aging for 24 hours, then uses successively
Deionization is washed, and absolute ethyl alcohol washing filters, and filter cake is put into 120 DEG C of baking ovens dry 12h, then roast 5h at 550 DEG C,
The grinding of gained catalyst fines is abundant, in the pressure lower sheeting of 10MPa, screens out 20~60 mesh particles up to 25wt%-ZnO/
HZSM-5。
The metal oxide PbO, CuO, MgO, MoO of other loads3, MnO also uses its corresponding nitrate as oxygen respectively
Compound donor.
Embodiment 2
The molecular sieve catalyst that the present embodiment has investigated different loads oxide prepares azelaic acid crude product process to castor oil
The influence of committed step oxidation reaction.
The preparation method of azelaic acid crude product illustrates：200 grams of castor oil are weighed, 1 liter containing 40 grams of KOH of addition is water-soluble
Liquid, being sufficiently stirred makes into emulsion.It measures 200mL absolute ethyl alcohols and is heated to 80 DEG C, be gradually added under the state that is sufficiently stirred
Molecular sieve catalyst carries out oxidation reaction 12h.After reaction, 500 milliliter 33% of aqueous sulfuric acid is added, continues heating and stirs
Simultaneously heat filtering is mixed, filter cake is washed with hot water and refilters, filtrate is concentrated after merging, and azelaic acid coarse crystal is precipitated after cooling.
It is shown in Table 1 using the corresponding azelaic acid conversion ratio of different loads oxide：
Table 1
| Carried metal chemicals | Substrate conversion efficiency |
| ZnO | 99% |
| PbO | 89% |
| CuO | 95% |
| MgO | 96% |
| MoO3 | 96% |
| MnO | 99% |
Embodiment 3
This example demonstrates that clarification azelaic acid coarse crystal prepares the technique of nonamethylene diamine, in order to obtain nonamethylene diamine, establish with
Lower technique：
Azelaic acid coarse crystal adjusts pH to 8.5 with ammonium hydroxide, further in the way of vacuum distillation, controls concentration tank tank
Supernatant is evaporated until obtaining ammonium azelate coarse crystal by pressure -0.09Mpa, temperature at 60 DEG C；It is anti-that the crystal is transferred to 500mL
It answers in kettle, under normal pressure, 3h is reacted in temperature control at 190 DEG C, and effluent is mainly water and part ammonia, can directly be received with waste water
Collect tank connection；Vacuum pump control reaction kettle vacuum degree is connect in 8~9kpa, temperature control reacts 2h at 180 DEG C, collects distillate,
That is azelaic dinitrile；Hydrogenation reaction kettle is added in distillate, ethyl alcohol is solvent, and additive amount is 1.1 times (volume ratios) of azelaic dinitrile, thunder Buddhist nun
Nickel is catalyst, and quality (g) is the 5% of ethyl alcohol and azelaic dinitrile total volume (mL), and potassium hydroxide is co-catalyst, and quality (g) is
The 0.1% of ethyl alcohol and azelaic dinitrile total volume (mL) after being replaced with nitrogen, leads to hydrogen reaction, temperature upper limit scope control is 100
DEG C, pressure control reacts 1.0h in 2MPa, finally obtains nonamethylene diamine, and the final molar yield of product nonamethylene diamine is 95~
99%, product purity>99%.
Above-mentioned technique realizes the target of union diacid coarse-grain system nonamethylene diamine sterling, has significant economical.
Claims (5)
1. a kind of method preparing nonamethylene diamine, which is characterized in that it includes the following steps：
(1) azelaic acid is soluble in water, neutralization reaction, dehydration and Depressor response are carried out after heating for dissolving successively, is prepared into
To azelaic dinitrile；
(2) after mixing the azelaic dinitrile being prepared in step (1), reaction dissolvent, catalyst and co-catalyst, to reaction system
It is inside passed through hydrogen, hydrogenation reaction is carried out, nonamethylene diamine is prepared；
In step (1), the operation of the neutralization reaction is：Be added ammonium hydroxide into azelaic acid aqueous solution, adjust pH to 7.5~
9.0；
In step (1), the operation of the dehydration is：By gained mixed system after the completion of neutralization reaction at 188~219 DEG C
2~5h of lower reaction；
In step (1), the operation of the Depressor response is：By gained mixed system after the completion of dehydration at 185~215 DEG C
2~5h of lower reaction, it is 8~9kpa to answer vacuum degree in system.
2. preparation method according to claim 1, which is characterized in that in step (2), the reaction dissolvent be ethyl alcohol,
Methanol or butanol, the catalyst are Raney's nickel, and the co-catalyst is potassium hydroxide, sodium hydroxide or calcium hydroxide.
3. preparation method according to claim 1, which is characterized in that in step (2), the volume of azelaic dinitrile and reaction dissolvent
Than being 1：1~1.2.
4. preparation method according to claim 1, which is characterized in that in step (2), the quality and azelaic dinitrile of catalyst with
The solid-to-liquid ratio of the total volume of reaction dissolvent is 3~10g：100mL, the quality and azelaic dinitrile of co-catalyst and the total volume of solvent
Solid-to-liquid ratio is 0.05~0.5g：100mL.
5. preparation method according to claim 1, which is characterized in that in step (2), the temperature of the hydrogenation reaction is
60~100 DEG C, the reaction time is 0.5~1.0h, and pressure is 1.5~2.5MPa in reaction system.
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| CN107382740B (en) * | 2017-08-09 | 2020-10-27 | 无锡殷达尼龙有限公司 | Method for synthesizing heptylamine |
| CN107325022B (en) * | 2017-08-09 | 2021-06-18 | 无锡殷达尼龙有限公司 | Preparation method of long-carbon-chain cyano acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701991A (en) * | 2012-06-05 | 2012-10-03 | 河北亚诺化工有限公司 | Method for preparing nonane diamine |
| KR20140137490A (en) * | 2013-05-22 | 2014-12-03 | 서울대학교산학협력단 | Method for Preparing α,ω-diamine |
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| JPS55157553A (en) * | 1979-05-25 | 1980-12-08 | Dainippon Ink & Chem Inc | Preparation of alpha,omega-polymethylenedinitrile compound |
| JPS55157554A (en) * | 1979-05-28 | 1980-12-08 | Dainippon Ink & Chem Inc | Preparation of alpha,omega-aliphatic long-chain dinitrile compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701991A (en) * | 2012-06-05 | 2012-10-03 | 河北亚诺化工有限公司 | Method for preparing nonane diamine |
| KR20140137490A (en) * | 2013-05-22 | 2014-12-03 | 서울대학교산학협력단 | Method for Preparing α,ω-diamine |
Non-Patent Citations (2)
| Title |
|---|
| 癸二胺的合成工艺及其应用研究;潘宇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20140815(第8期);第9-14页1.5 同类二胺的生产技术研究，第28-29页3.2.2 实验方法 * |
| 蓖麻油制取工程之癸二酸制取癸二腈工艺设计研究;赵云发 等;《粮油加工》;20150831;第26-29页 * |
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