CN107011304B - A kind of catalytic hydrogenation preparation hexahydrophthalic anhydride technique - Google Patents
A kind of catalytic hydrogenation preparation hexahydrophthalic anhydride technique Download PDFInfo
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- CN107011304B CN107011304B CN201710311678.5A CN201710311678A CN107011304B CN 107011304 B CN107011304 B CN 107011304B CN 201710311678 A CN201710311678 A CN 201710311678A CN 107011304 B CN107011304 B CN 107011304B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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Abstract
A kind of catalytic hydrogenation of the invention prepares hexahydrophthalic anhydride (HHPA) technique, using SiO2For carrier, infusion process is prepared for Pd-NiO/SiO2Catalyst, in trickle bed reactor, tetrahydrophthalic anhydride catalytic hydrogenation prepares hexahydrophthalic anhydride (HHPA), has probed into optimum reaction condition and technological parameter.Using SiO2Loading type Pd, Ni binary metal catalyst, suitably reduction catalyst activity, increase hydrogen partial pressure, effectively improve purpose product hexahydrophthalic anhydride (HHPA) selectivity.On hydrogen point, in, in lower three positions, into drip-flow reactor, reaction layout is more uniform controllable, side reaction is reduced, catalytic hydrogenation is exothermic reaction, increases the internal recycle rate of hydrogen in reactor, hydrogen is as thermophore, timely transfer reaction heat reduces the generation of side reaction it is possible to prevente effectively from hot-spot is existing.
Description
Technical field
The present invention relates to catalytic hydrogenations to prepare hexahydrophthalic anhydride (HHPA) technique, refers specifically to catalyst Pd-NiO/SiO2's
Preparation, catalytic hydrogenation prepare hexahydrophthalic anhydride (HHPA) technique, belong to chemical field.
Background technique
Hexahydrophthalic anhydride full name hexahydrophthalic anhydride, English write a Chinese character in simplified form HHPA, molecular formula C8H10O3, relative molecular mass
154.2, relative density 1.2 is soluble in tetrahydrofuran, benzene,toluene,xylene equal solvent.
Basic material of the hexahydrophthalic anhydride (HHPA) as polyesters high-grade paint relies on excellent product performance, such as adaptability
By force, viscosity is low, and vivid degree, glossiness significantly improve, and can especially increase substantially the weatherability of coating, product quality obviously changes
It is kind.Hexahydrophthalic anhydride (HHPA) is also the important source material of production plasticizer, insecticide, antirust agent, herbicide etc..
Hexahydrophthalic anhydride (HHPA) is used as epoxy curing agent, is widely used in semiconductor plastic package material and potting compound, believes
It is very swift and violent to cease industry development, the demand of epoxy curing agent is quicklyd increase, is increased to hexahydrophthalic anhydride (HHPA)
The market demand, China only have the production of Some Enterprises small batch, are far from satisfying the market demand both domestic and external, establish hexahydrophthalic anhydride
(HHPA) large industrialized produces, and has broader development prospect.
Tetrahydrophthalic anhydride catalytic hydrogenation prepares hexahydrophthalic anhydride (HHPA), is industrial common process route.Tetrahydrophthalic anhydride adds
During hydrogen, since double bond is easy activation, this double bond is easy to shift, cause that hydrogen is added to be not thorough, hydrogen atom into
Capture, acid anhydrides is easier to that condensation, hydrogenolysis, the side reactions such as crosslinking occur, and generation is difficult to isolated product, influence the selectivity of reaction with
Yield, and high boiling point product also be easy coking at high temperature, cause to be attached to catalyst surface so that catalyst poisoning and lose
Deactivation.Raw material is close with product boiling point, and conventional method is difficult to separate, and seriously affects product quality.Therefore, selection high activity is high
Catalysts selective, preparation process is simply controllable, reproducible, is the key technology of hexahydrophthalic anhydride (HHPA) production.
Traditional tetrahydrophthalic anhydride hexahydrophthalic anhydride (HHPA) catalyst, generally use different carriers load combined Pd/C,
Pd/Al2O3、Pd/Fe2O3、Pd/BaSO4、Pd/K2SO4, the catalytic hydrogenation activity of Pd series catalysts is fine, but expensive,
For example trans- hexahydro phthalide of by-product and trans- -4- cyclohexene -1,2- dioctyl phthalate can be generated, hexahydrophthalic anhydride (HHPA) is directly affected
Purity and selectivity.Especially trans- hexahydro phthalide and the boiling point of hexahydrophthalic anhydride (HHPA) are very close to the difficulty being relatively kept completely separate
It is very big, eventually lead to that hexahydrophthalic anhydride (HHPA) purity is less than normal, and use scope and added value are greatly affected.How tetrahydro is improved
Phthalic anhydride hydrogenation selectivity reduces the generation of side reaction to greatest extent, becomes exploitation tetrahydrophthalic anhydride hexahydrophthalic anhydride (HHPA) technique
Important technology bottleneck.
Summary of the invention
It is an object of the invention to: the technical problems to be solved by the invention are the statuses for the prior art, using SiO2
For carrier, infusion process is prepared for Pd-NiO/SiO2Catalyst, in trickle bed reactor, at 80~120 DEG C of temperature, pressure 3.0~
Under the conditions of 5.0MPa, hydrogen-oil ratio 3000:1, THPA catalytic hydrogenation prepares crude product HHPA.At 180~230 DEG C of temperature, pressure-
Under the conditions of 0.098MPa, rectification under vacuum obtains fine work HHPA.Result calculating is carried out by area normalization method, the purity of HHPA is
99.5%, reach state quality standard, product total conversion and yield are respectively 97.3%, 84.1%., tetrahydrophthalic anhydride catalysis
Add hydrogen to prepare hexahydrophthalic anhydride (HHPA), probes into optimum reaction condition and technological parameter.It is urged using loading type Pd, Ni binary metal
Agent, suitably reduction catalyst activity, increase hydrogen partial pressure, effectively improve purpose product hexahydrophthalic anhydride (HHPA) selectivity.Hydrogen
On gas point, in, in lower three positions, into drip-flow reactor, reaction layout is more uniform controllable, reduces side reaction.It urges
Change is hydrogenated to exothermic reaction, increases the internal recycle rate of hydrogen in reactor, and for hydrogen as thermophore, timely transfer reaction is hot,
It is possible to prevente effectively from hot-spot phenomenon, reduces the generation of side reaction.Reaction product rectification under vacuum has obtained 99.5% qualification
Hexahydrophthalic anhydride (HHPA) product.
The object of the present invention is achieved like this: a kind of catalytic hydrogenation preparation hexahydrophthalic anhydride (HHPA) technique, steps are as follows:
Use N2Leak test suppressed to drip-flow reactor 4, hydrogen through compressor 2, it is point upper, in, in lower three positions be pressed into drip
Reactor 4 replaces the N in drip-flow reactor 42, after 30min, according to molar ratio tetrahydrophthalic anhydride: tetrahydrofuran=1:3 proportion,
Solvents tetrahydrofurane, material tetrahydrophthalic anhydride are added to blending tank 1, by dnockout pumps 1, the mixed liquor of tetrahydrofuran and tetrahydrophthalic anhydride
It squeezes into drip-flow reactor 4, catalyst Pd-NiO/SiO2In the fixed bed of drip-flow reactor 4, drip is controlled by control system
It is warming up to 80~120 DEG C of reaction temperature in reactor 4, under the conditions of 3.0~5.0Mpa of reaction pressure, hydrogen-oil ratio 3000:1, reaction
Material enters crude product storage tank 5 by 4 bottom of drip-flow reactor afterwards, prepares hexahydrophthalic anhydride (HHPA).
The hexahydrophthalic anhydride (HHPA) prepared enters rectifying column 7, rectifying by dnockout pumps 26 among rectifying column 7
It is vacuumized at the top of tower 7, vacuum degree -0.098MPa, overhead components pass through complete condenser 8, and into tower top storage tank 10, a part is by tower top
Reflux pump 9 sends rectifying column 7 back to, and as the liquid-phase reflux of rectifying column 7, another part returns blending tank 1 by solvent circulating pump 11, follows
Ring utilizes solvents tetrahydrofurane, and 7 bottoms material of rectifying column is heated by reboiler 14, and into tower bottom storage tank 13, a part is by tower
Bottom reflux pump 12 is sent to 7 bottom of rectifying column, and the gas phase as rectifying column flows back, it is ensured that the continuous steady state operation of distillation operation, separately
A part is produced as tower bottom product.
Catalyst Pd-NiO/SiO2Preparation process it is as follows: concentration be 1Mol/L 1L hydrochloric acid solution in SiO is added2
Carrier, 15~20wt%；H2PdCl4, 1~3wt% is sufficiently stirred 8~10h under the conditions of 50~80 DEG C of temperature, obtains Pd/
SiO2, 80 DEG C of vacuum drying 10~12h are spare；
Take 0.5KgPd/SiO2, nickel nitrate is added according to 5~8wt%, 1L distilled water, 80 DEG C of water bath with thermostatic control conditions are added
Under, 8~10h, 80 DEG C of 10~12h of vacuum drying are sufficiently stirred, then 500 DEG C of roasting 6h, catalyst Pd-NiO/SiO is made2。
Described uses N21h, pressure 6MPa are no less than to the time that drip-flow reactor (4) suppresses leak test.
Compared with prior art, the present invention has the advantage that on hydrogen point, in, in lower three positions, it is anti-into drip
Device is answered, reaction layout is more uniform controllable, reduces side reaction, hydrogen is as thermophore, timely transfer reaction heat, Ke Yiyou
Effect avoids hot-spot phenomenon, reduces the generation of side reaction.Reaction product rectification under vacuum has obtained 99.5% qualified hexahydrobenzene
Acid anhydride (HHPA) product.
Detailed description of the invention
Fig. 1 is catalytic hydrogenation preparation hexahydrophthalic anhydride (HHPA) process flow diagram.
Specific embodiment
Appended drawing reference: 1. blending tanks；2. hydrogen gas compressor；3. dnockout pumps one；4. drip-flow reactor；5. crude product storage tank；6.
Dnockout pumps two；7. rectifying column；8. complete condenser；9. tower top return pump；10. tower top storage tank；11. solvent circulating pump；12. tower bottom flows back
Pump；13 tower bottom storage tanks；14. reboiler.
Firstly, handling SiO using supercritical methanol2Carrier reduces its Surface oxygen-containing groups, in the 1L that concentration is 1Mol/L
Hydrochloric acid solution in SiO is added2Carrier, 15~20wt%；H2PdCl4, 1~3wt%, under the conditions of 50~80 DEG C of temperature, sufficiently
8~10h is stirred, Pd/SiO is obtained2, 80 DEG C of vacuum drying 10~12h are spare.
Take 0.5KgPd/SiO2, nickel nitrate is added according to 5~8wt%, 1L distilled water, 80 DEG C of water bath with thermostatic control conditions are added
Under, 8~10h, 80 DEG C of 10~12h of vacuum drying is sufficiently stirred.Then 500 DEG C of roasting 6h, obtain Pd-NiO/SiO2, spare.
Use N2Leak test is suppressed to drip-flow reactor 4, pressure does not change after pressure 6MPa, 1h, can determine reaction kettle
Sealing has reached the requirement of trial production.
Hydrogen through compressor 2, it is point upper, in, in lower three positions be pressed into drip-flow reactor 4, take the lead in replacing drip-flow reactor 4
Interior N2, after 30min, according to molar ratio tetrahydrophthalic anhydride: tetrahydrofuran=1:3, i.e. n (tetrahydrophthalic anhydride): n (tetrahydrofuran)=1:
Solvents tetrahydrofurane, material tetrahydrophthalic anhydride, are added to blending tank 1, i.e., every 152.14Kg tetrahydrophthalic anhydride and 144.22Kg tetra- by 3 proportions
Hydrogen furans or the mixing of 146L tetrahydrofuran liquid, the tetrahydrofuran concentration of tetrahydrophthalic anhydride are 0.33Mol/L, by dnockout pumps 1,
Mixed liquor squeezes into drip-flow reactor 4, catalyst Pd-NiO/SiO2In the fixed bed of drip-flow reactor 4, controlled by control system
It is warming up to 80~120 DEG C of reaction temperature in drip-flow reactor 4, under the conditions of 3.0~5.0MPa of reaction pressure, hydrogen-oil ratio 3000:1,
Reacting rear material enters crude product storage tank 5 by 4 bottom of drip-flow reactor, then by dnockout pumps 26, from 7 intermediate feed of rectifying column, crude product
It into rectifying column 7, is vacuumized at the top of rectifying column 7, vacuum degree -0.098MPa, overhead components pass through complete condenser 8, store up into tower top
Tank 10, a part send rectifying column 7 back to by tower top return pump 9, and as the liquid-phase reflux of rectifying column 7, another part is recycled by solvent
Pump 11 returns blending tank 1, recycles solvents tetrahydrofurane.Rectifier bottoms material is heated by reboiler 14, into tower bottom
Storage tank 13, a part are sent to 7 bottom of rectifying column by tower bottom reflux pump 12, and the gas phase as rectifying column flows back, it is ensured that distillation operation
Continuous steady state operation；A part is produced as tower bottom product.
By Agilent gas chromatograph-mass spectrometer Agilent5977AGC/MSD analysis detection, determine that the purity of product and quality are closed
After lattice, it is sent to dry and packing department.Instrument is used in conjunction using Agilent 5977A makings, chromatographic condition: DB-INNOWAX polyethylene glycol
20000 highly polar columns, 30m × 0.32mm × 0.25 μm, 290 DEG C of detector temperature, are gasified 280 DEG C of room temperature by 120 DEG C of column temperature.
The purity for detecting HHPA is 99.5%, has reached national product standard.
Claims (3)
1. a kind of catalytic hydrogenation prepares hexahydrophthalic anhydride technique, its step are as follows:
Use N2Leak test suppressed to drip-flow reactor (4), hydrogen through compressor (2), it is point upper, in, in lower three positions indentation drip it is anti-
It answers device (4), the N in displacement drip-flow reactor (4)2, after 30min, according to molar ratio tetrahydrophthalic anhydride: tetrahydrofuran=1:3 proportion,
Solvents tetrahydrofurane, material tetrahydrophthalic anhydride are added to blending tank (1), by dnockout pumps one (3), tetrahydrofuran and tetrahydrophthalic anhydride
Mixed liquor is squeezed into drip-flow reactor (4), catalyst Pd-NiO/SiO2Fixed bed in drip-flow reactor (4), by control system
80~120 DEG C of reaction temperature are warming up in system control drip-flow reactor (4), 3.0~5.0MPa of reaction pressure, hydrogen-oil ratio 3000:1
Under the conditions of, reacting rear material enters crude product storage tank (5) by drip-flow reactor (4) bottom, prepares hexahydrophthalic anhydride；
Catalyst Pd-NiO/SiO2Preparation process it is as follows: concentration be 1Mol/L 1L hydrochloric acid solution in SiO is added2It carries
Body, 15~20wt%；H2PdCl4, 1~3wt% is sufficiently stirred 8~10h under the conditions of 50~80 DEG C of temperature, obtains Pd/
SiO2, 80 DEG C of vacuum drying 10~12h are spare；
Take 0.5KgPd/SiO2, nickel nitrate is added according to 5~8wt%, 1L distilled water is added, under the conditions of 80 DEG C of waters bath with thermostatic control, sufficiently
8~10h, 80 DEG C of 10~12h of vacuum drying are stirred, then 500 DEG C of roasting 6h, catalyst Pd-NiO/SiO is made2。
2. a kind of catalytic hydrogenation as described in claim 1 prepares hexahydrophthalic anhydride technique, it is characterised in that: described to prepare
Hexahydrophthalic anhydride enters rectifying column (7) by dnockout pumps two (6), from rectifying column (7) is intermediate, vacuumizes at the top of rectifying column (7), vacuum
Degree -0.098MPa, overhead components pass through complete condenser (8), and into tower top storage tank (10), a part is sent back to by tower top return pump (9)
Rectifying column (7), as the liquid-phase reflux of rectifying column (7), another part is returned blending tank (1) by solvent circulating pump (11), circulation
Using solvents tetrahydrofurane, rectifying column (7) bottoms material is heated by reboiler (14), into tower bottom storage tank (13), a part
Rectifying column (7) bottom is sent to by tower bottom reflux pump (12), as rectifying column (7) gas phase flow back, it is ensured that distillation operation it is continuous
Steady state operation, another part are produced as tower bottom product.
3. a kind of catalytic hydrogenation as described in claim 1 prepares hexahydrophthalic anhydride technique, it is characterised in that: described uses N2To drop
The time that flow reactor (4) suppresses leak test is no less than 1h, pressure 6MPa.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108033936A (en) * | 2017-12-27 | 2018-05-15 | 上海迅凯新材料科技有限公司 | Hexahydrophthalic anhydride process units and production method |
| CN108392899B (en) * | 2018-03-15 | 2020-08-18 | 濮阳市盛源石油化工（集团）有限公司 | Device and process for removing 1, 2-cyclohexanedicarboxylic acid |
| CN109280040B (en) * | 2018-09-12 | 2021-02-05 | 濮阳市盛源能源科技股份有限公司 | Continuous production process for synthesizing hexahydrophthalic anhydride in mixed solvent |
| CN109225227B (en) * | 2018-09-12 | 2021-08-31 | 濮阳市盛源能源科技股份有限公司 | Ordered mesoporous carbon catalyst for preparing hexahydrophthalic anhydride and preparation method thereof |
| CN109293611A (en) * | 2018-09-30 | 2019-02-01 | 濮阳市盛源能源科技股份有限公司 | A kind of continuous synthesis device and its synthetic method of hexahydrophthalic anhydride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244877A (en) * | 1979-05-23 | 1981-01-13 | Bayer Aktiengesellschaft | Process for the preparation of hexahydrophthalic acid anhydride |
| CN103769105A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application |
-
2017
- 2017-05-05 CN CN201710311678.5A patent/CN107011304B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4244877A (en) * | 1979-05-23 | 1981-01-13 | Bayer Aktiengesellschaft | Process for the preparation of hexahydrophthalic acid anhydride |
| CN103769105A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst for hydrogenating cis-butenedioic anhydride to prepare butanedioic anhydride and its preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| "Nickel and nickel–platinum as active and selective catalyst for the maleic anhydride hydrogenation to succinic anhydride";J.Li等;《Chemical Engineering Journal》;20111115;第175卷;第417-422页 |
| "Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride Over Nickel-palladium Catalysts";W. -P. Tian等;《Petroleum Science and Technology》;20140519;第32卷(第15期);第1784-1790页 |
| "六氢苯二甲酸酐的制备";杨瑞娜;《热固性树脂》;20020731;第17卷(第4期);第5-7页 |
| "四氢苯酐催化加氢合成六氢苯酐及动力学研究";李文超;《北京化工大学硕士学位论文》;20110115;第1-7页 |
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Effective date of registration: 20171109 Address after: Puyang City, Henan province 457000 Industrial Agglomeration District Fanxian Industrial Park Applicant after: Puyang Sheng Yuan energy science and technology limited company Address before: 455000 west section of the Yellow River Road, Anyang, Henan Province, Anyang Institute of Technology Applicant before: Anyang Institute of Technology |
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