CN107011304A - A kind of catalytic hydrogenation prepares HHPA (HHPA) technique - Google Patents
A kind of catalytic hydrogenation prepares HHPA (HHPA) technique Download PDFInfo
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- CN107011304A CN107011304A CN201710311678.5A CN201710311678A CN107011304A CN 107011304 A CN107011304 A CN 107011304A CN 201710311678 A CN201710311678 A CN 201710311678A CN 107011304 A CN107011304 A CN 107011304A
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- hhpa
- sio
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
A kind of catalytic hydrogenation of the present invention prepares HHPA (HHPA) technique, using SiO2For carrier, infusion process is prepared for Pd NiO/SiO2Catalyst, in trickle bed reactor, THPA catalytic hydrogenation prepares HHPA (HHPA), has probed into optimum reaction condition and technological parameter.Using SiO2Loading type Pd, Ni binary metal catalyst, suitably reduce catalyst activity, increase hydrogen partial pressure, effectively improve purpose product HHPA (HHPA) selectivity.On hydrogen point, in, in lower three positions, into drip-flow reactor, reaction layout more uniform, controllable, side reaction is reduced, catalytic hydrogenation is exothermic reaction, increase the internal recycle rate of hydrogen in reactor, hydrogen is used as thermophore, timely transfer reaction heat, it is possible to prevente effectively from hot-spot is existing, reduces the generation of side reaction.
Description
Technical field
HHPA (HHPA) technique is prepared the present invention relates to catalytic hydrogenation, catalyst Pd-NiO/SiO is referred specifically to2's
Prepare, catalytic hydrogenation prepares HHPA (HHPA) technique, belongs to chemical field.
Background technology
HHPA full name hexahydrophthalic anhydride, English writes a Chinese character in simplified form HHPA, and molecular formula is C8H10O3, average molecular matter
Amount 154.2, relative density 1.2 is soluble in tetrahydrofuran, benzene,toluene,xylene equal solvent.
HHPA (HHPA) as polyesters high-grade paint basic material, by excellent product performance, such as adaptability
By force, viscosity is low, and vivid degree, glossiness are significantly improved, and can especially increase substantially the weatherability of coating, product quality substantially changes
It is kind.HHPA (HHPA) is also the important source material for producing plasticizer, insecticide, antirust agent, herbicide etc..
HHPA (HHPA) is widely used in semiconductor plastic package material and potting compound as epoxy curing agent, letter
Breath industry development is very swift and violent, and the demand to epoxy curing agent quickly increases, and increases to HHPA (HHPA)
The market demand, China only has the production of Some Enterprises small batch, far can not meet the market demand both domestic and external, set up HHPA
(HHPA) large industrialized is produced, with broader development prospect.
THPA catalytic hydrogenation prepares HHPA (HHPA), is industrially conventional process route.THPA adds
During hydrogen, because double bond is easily activated, this double bond is easy to shift, and causes hydrogenation not thorough, in entering for hydrogen atom
Capture, acid anhydrides is easier to occur condensation, hydrogenolysis, the side reaction such as crosslinking, generation is difficult to the product separated, the selectivity that influence is reacted with
Yield, and higher boiling product also easily 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 has a strong impact on product quality.Therefore, selection high activity is high
Catalysts selective, preparation process is simply controllable, reproducible, is the key technology of HHPA (HHPA) production.
Traditional THPA HHPA (HHPA) catalyst, the combined Pd/C generally loaded using different carriers,
Pd/Al2O3、Pd/Fe2O3、Pd/BaSO4、Pd/K2SO4, the catalytic hydrogenation activities of Pd series catalysts is very well, but expensive,
For example trans hexahydro phthalide of accessory substance and trans -4- cyclohexene -1,2- dioctyl phthalate can be produced, HHPA (HHPA) is directly affected
Purity and selectivity.The boiling point of particularly trans hexahydro phthalide and HHPA (HHPA) is very close to the difficulty being relatively kept completely separate
Very greatly, ultimately result in HHPA (HHPA) purity less than normal, be greatly affected using scope and added value.How tetrahydrochysene is improved
Phthalic anhydride hydrogenation selectivity, reduces the generation of side reaction to greatest extent, as exploitation THPA HHPA (HHPA) technique
Important technology bottleneck.
The content of the invention
It is an object of the invention to：The technical problems to be solved by the invention are the present situations for prior art, using SiO2
For carrier, infusion process is prepared for Pd-NiO/SiO2In catalyst, trickle bed reactor, in 80~120 DEG C of temperature, pressure 3.0
~5.0 MPa, hydrogen-oil ratio 3000：Under the conditions of 1, THPA catalytic hydrogenations prepare crude product HHPA.In 180~230 DEG C of temperature, pressure-
Under the conditions of 0.098 MPa, rectification under vacuum obtains fine work HHPA.Result calculating is carried out by area normalization method, HHPA purity is
99.5%, state quality standard is reached, product total conversion and yield are respectively 97.3%, 84.1%., THPA, which is catalyzed, to be added
Hydrogen prepares HHPA (HHPA), has probed into optimum reaction condition and technological parameter.It is catalyzed using loading type Pd, Ni binary metals
Agent, suitably reduces catalyst activity, increases hydrogen partial pressure, effectively improves purpose product HHPA (HHPA) selectivity.Hydrogen
On point, in, in lower three positions, into drip-flow reactor, reaction layout more uniform, controllable reduces side reaction.Catalysis
Exothermic reaction is hydrogenated to, the internal recycle rate of hydrogen in reactor is increased, hydrogen is as thermophore, timely transfer reaction heat can
To be prevented effectively from hot-spot phenomenon, the generation of side reaction is reduced.Reaction product rectification under vacuum, obtained 99.5% qualified six
Hydrogen phthalic anhydride (HHPA) product.
The object of the present invention is achieved like this：A kind of catalytic hydrogenation prepares HHPA (HHPA) technique, and step is as follows：
Use N2 Leak test is suppressed to drip-flow reactor 4, hydrogen through compressor 2, it is point upper, in, in lower three positions press-in drip-flow reactor 4,
N in metathesis reactor 42, after 30 min, according to mol ratio THPA：Tetrahydrofuran=1：3 proportionings, solvent tetrahydrochysene furan
Mutter, material THPA is added to blending tank 1, by dnockout pumps 3 one, it is anti-that the mixed liquor of tetrahydrofuran and THPA squeezes into drip
Answer in device 4, catalyst Pt-NiO/SiO2In the fixed bed of drip-flow reactor 4, controlled by control system in drip-flow reactor 4
80~120 DEG C of reaction temperature is warming up to, the MPa of reaction pressure 3.0~5.0, reacting rear material is entered by the bottom of drip-flow reactor 4
Crude product storage tank 5, prepares HHPA (HHPA).
The described HHPA (HHPA) prepared enters rectifying column 7, rectifying by dnockout pumps 26 in the middle of rectifying column 7
Top of tower is vacuumized, the MPa of vacuum -0.098, and overhead components pass through complete condenser 8, and into top of tower 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, another part returns blending tank 1 by solvent circulating pump 11,
Solvents tetrahydrofurane is recycled, rectifier bottoms material is heated by reboiler 14, into bottom of towe storage tank 13, a part is by tower
Bottom reflux pump 12 is sent to the bottom of rectifying column 7, is flowed back as the gas phase of rectifying column, it is ensured that the continuous steady state operation of distillation operation, separately
A part is produced as tower bottom product.
Catalyst Pt-NiO/SiO2Preparation technology it is as follows：Added in hydrochloric acid solution of the concentration for 1 Mol/L 1 L
SiO2Carrier, 15~20 wt%；H2PdCl4, 1~3 wt% under 50~80 DEG C of temperature conditionss, is sufficiently stirred for 8~10 h, obtains
To Pd/SiO2, 80 DEG C are dried in vacuo 10~12 h, standby；
Take 0.5 Kg Pd/SiO2, nickel nitrate is added according to 5~8 wt%, 1 L distilled water, 80 DEG C of water bath with thermostatic control conditions is added
Under, 8~10 h, 80 DEG C of 10~12 h of vacuum drying are sufficiently stirred for, then 500 DEG C of 6 h of roasting, are made catalyst Pd-NiO/
SiO2。
Compared with prior art, the invention has the advantages that：On hydrogen point, in, in lower three positions, it is anti-into drip
Device is answered, reaction layout more uniform, controllable reduces side reaction, and 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.
Brief description of the drawings
Fig. 1 is that catalytic hydrogenation prepares HHPA (HHPA) process flow diagram.
Embodiment
Reference：1. the crude product storage tank 6. of one 4. drip-flow reactor of blending tank 2. hydrogen gas compressor, 3. dnockout pumps 5.
The bottom of towe of 11. solvent circulating pump of dnockout pumps 2 7. rectifying column, 8. complete condenser, 9. overhead reflux pump, 10. tower top storage tank 12. flows back
The reboiler of 13 bottom of towe storage tank of pump 14..
First, SiO is handled using supercritical methanol2Carrier, reduces its Surface oxygen-containing groups, is 1 Mol/L's in concentration
SiO is added in 1 L hydrochloric acid solution2Carrier, 15~20 wt%；H2PdCl4, 1~3 wt%, under 50~80 DEG C of temperature conditionss,
8~10 h are sufficiently stirred for, Pd/SiO is obtained2, 80 DEG C are dried in vacuo 10~12 h, standby.
Take 0.5 Kg Pd/SiO2, nickel nitrate is added according to 5~8 wt%, 1 L distilled water, 80 DEG C of water bath with thermostatic control bars is added
Under part, 8~10 h, 80 DEG C of 10~12 h of vacuum drying are sufficiently stirred for.Then 500 DEG C of 6 h of roasting, obtain Pd-NiO/
SiO2, it is standby.
Use N2 Suppress leak test to drip-flow reactor 4, pressure is that pressure does not change after 6 MPa, 1 h, it may be determined that reaction
Kettle sealing has reached the requirement of trial production.
Hydrogen through compressor 2, it is point upper, in, in lower three positions press-in drip-flow reactor 4, the metathesis reactor that takes the lead in N2, 30
After min, according to mol ratio THPA：Tetrahydrofuran=1：3, i.e. n(THPA):n(tetrahydrofuran)=1:3 proportionings, solvent tetrahydrochysene furan
Mutter, material THPA is added to blending tank 1, i.e., per 152.14Kg THPAs and 144.22Kg tetrahydrofurans or 146 L tetrahydrochysenes
Furan liquid is mixed, and the tetrahydrofuran concentration of THPA is 0.33 Mol/L, and by dnockout pumps 3 one, mixed liquor squeezes into drip
Reactor 4, catalyst Pt-NiO/SiO2In the fixed bed of drip-flow reactor 4, controlled by control system in drip-flow reactor 4
It is warming up to 80~120 DEG C of reaction temperature, 3.0~5.0MPa of reaction pressure, hydrogen-oil ratio 3000：Under the conditions of 1, reacting rear material is by dripping
The bottom of flow reactor 4 enters crude product storage tank 5, then by dnockout pumps 26, from the intermediate feed of rectifying column 7, crude product enters rectifying column 7, essence
Evaporate top of tower to vacuumize, vacuum -0.098MPa, overhead components pass through complete condenser 8, into top of tower storage tank 10, a part by
Overhead reflux pump 9 sends rectifying column 7 back to, as the liquid-phase reflux of rectifying column, and another part returns blending tank by solvent circulating pump 11
1, recycle solvents tetrahydrofurane.Rectifier bottoms material is heated by reboiler 14, into bottom of towe storage tank 13, a part by
Bottom of towe reflux pump 12 is sent to the bottom of rectifying column 7, is flowed back as the gas phase of rectifying column, it is ensured that the continuous steady state operation of distillation operation；
A part is produced as tower bottom product.
Analyze and detect by Agilent gas chromatograph-mass spectrometer Agilent 5977A GC/MSD, determine the purity and quality of product
After qualified, it is sent to and dries and packing department.
Instrument, chromatographic condition are used in conjunction using Agilent 5977A makings：The highly polar post of DB-INNOWAX PEG 20000s, 30
Mm × 0.25 μm of m × 0.32,120 DEG C of column temperature, 290 DEG C of detector temperature, gasify 280 DEG C of room temperature.Detection
HHPA purity is 99.5%, has reached national product standard.
Claims (4)
1. a kind of catalytic hydrogenation prepares HHPA (HHPA) technique, its step is as follows：
With N2 to drip-flow reactor（4）Leak test is suppressed, hydrogen is through compressor（2）, it is point upper, in, in lower three positions press-in drip
Reactor（4）, metathesis reactor（4）After interior N2,30 min, according to mol ratio THPA：Tetrahydrofuran=1：3 proportionings,
Solvents tetrahydrofurane, material THPA are added to blending tank（1）, by dnockout pumps one（3）, tetrahydrofuran and THPA it is mixed
Close liquid and squeeze into drip-flow reactor（4）It is interior, catalyst Pt-NiO/SiO2In drip-flow reactor（4）Fixed bed, by control system
Control drip-flow reactor（4）Inside it is warming up to 80~120 DEG C of reaction temperature, the MPa of reaction pressure 3.0~5.0, hydrogen-oil ratio 3000：1
Under the conditions of, reacting rear material is by drip-flow reactor（4）Bottom enters crude product storage tank（5）, prepare HHPA (HHPA).
2. a kind of catalytic hydrogenation as claimed in claim 1 prepares HHPA (HHPA) technique, it is characterised in that：Described system
For the HHPA (HHPA) gone out by dnockout pumps two（6）, from rectifying column（7）Centre enters rectifying column（7）, rectifying column top takes out true
Sky, vacuum -0.098MPa, overhead components pass through complete condenser（8）, into top of tower storage tank（10）, a part is by overhead reflux
Pump（9）Send rectifying column back to（7）, as the liquid-phase reflux of rectifying column, another part is by tower top storage tank（11）Return blending tank（1）,
Solvents tetrahydrofurane is recycled, rectifier bottoms material passes through reboiler（14）Heating, into bottom of towe storage tank（13）, a part
By solvent circulating pump（12）The bottom of rectifying column 7 is sent to, is flowed back as the gas phase of rectifying column, it is ensured that the continuous stable state behaviour of distillation operation
Make, another part is produced as tower bottom product.
3. a kind of catalytic hydrogenation as claimed in claim 1 or 2 prepares HHPA (HHPA) technique, it is characterised in that：Catalysis
Agent Pt-NiO/SiO2Preparation technology it is as follows：SiO is added in hydrochloric acid solution of the concentration for 1Mol/L 1L2Carrier, 15~20
wt%；H2PdCl4, 1~3 wt% under 50~80 DEG C of temperature conditionss, is sufficiently stirred for 8~10h, obtains Pd/SiO2, 80 DEG C true
Sky dries 10~12 h, standby；
Take 0.5 Kg Pd/SiO2, nickel nitrate is added according to 5~8 wt%, 1 L distilled water is added, under the conditions of 80 DEG C of waters bath with thermostatic control,
8~10 h, 80 DEG C of 10~12 h of vacuum drying are sufficiently stirred for, then 500 DEG C of 6 h of roasting, are made catalyst Pd-NiO/
SiO2。
4. a kind of catalytic hydrogenation as claimed in claim 1 prepares HHPA (HHPA) technique, it is characterised in that：Described use
N2 To drip-flow reactor（4）The time for suppressing leak test is no less than 1h, and pressure is 6MPa.
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| CN201710311678.5A CN107011304B (en) | 2017-05-05 | 2017-05-05 | A kind of catalytic hydrogenation preparation hexahydrophthalic anhydride technique |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108392899A (en) * | 2018-03-15 | 2018-08-14 | 濮阳市盛源能源科技股份有限公司 | A kind of device and its technique of removing 1,2- cyclohexane cyclohexanedimethanodibasics |
| CN109225227A (en) * | 2018-09-12 | 2019-01-18 | 濮阳市盛源能源科技股份有限公司 | A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride |
| CN109280040A (en) * | 2018-09-12 | 2019-01-29 | 濮阳市盛源能源科技股份有限公司 | A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride |
| 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 |
|---|
| J.LI等: ""Nickel and nickel–platinum as active and selective catalyst for the maleic anhydride hydrogenation to succinic anhydride"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| W. -P. TIAN等: ""Selective Hydrogenation of Maleic Anhydride to Succinic Anhydride Over Nickel-palladium Catalysts"", 《PETROLEUM SCIENCE AND TECHNOLOGY》 * |
| 李文超: ""四氢苯酐催化加氢合成六氢苯酐及动力学研究"", 《北京化工大学硕士学位论文》 * |
| 杨瑞娜: ""六氢苯二甲酸酐的制备"", 《热固性树脂》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN108392899A (en) * | 2018-03-15 | 2018-08-14 | 濮阳市盛源能源科技股份有限公司 | A kind of device and its technique of removing 1,2- cyclohexane cyclohexanedimethanodibasics |
| CN109225227A (en) * | 2018-09-12 | 2019-01-18 | 濮阳市盛源能源科技股份有限公司 | A kind of order mesoporous C catalyst and preparation method thereof being used to prepare hexahydrophthalic anhydride |
| CN109280040A (en) * | 2018-09-12 | 2019-01-29 | 濮阳市盛源能源科技股份有限公司 | A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride |
| 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 |
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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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