CN109280040A - A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride - Google Patents
A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride Download PDFInfo
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- CN109280040A CN109280040A CN201811061958.6A CN201811061958A CN109280040A CN 109280040 A CN109280040 A CN 109280040A CN 201811061958 A CN201811061958 A CN 201811061958A CN 109280040 A CN109280040 A CN 109280040A
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- mixed solvent
- hexahydrophthalic anhydride
- hydrogen
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- continuous production
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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
Abstract
The present invention provides a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride, technique uses continuous fixed bed reaction or continuous method, under the conditions of certain pressure and temperature, using the mixture that tetrahydrofuran and hexamethylene form as solvent, tetrahydrophthalic anhydride and hydrogen are raw material, add hydrogen that hexahydrophthalic anhydride crude product is prepared, then through vacuum flashing, continuous wipe film evaporation technology obtains hexahydrophthalic anhydride product, extra hydrogen and mixed solvent also passes through knockout drum and vacuum flasher respectively, thin film evaporator is recycled and is recycled, hydrogen and mixed solvent need to only supplement the amount of consumption in system, realize the recycling of atmosphere gas and mixed solution.Apply the present invention to the continuous production technology of hexahydrophthalic anhydride, it can be achieved that continuous feed, discharging, side reaction is few, product stability is high, and production efficiency improves.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of continuous production work of in the mixed solvent synthesis hexahydrophthalic anhydride
Skill.
Background technique
Hexahydrophthalic anhydride full name hexahydrophthalic anhydride, white to off-white color crystallize, and low melting point solid can be dissolved in tetrahydro
Furans, benzene, in acetone equal solvent.Hexahydrophthalic anhydride is the production indispensable raw material of polyesters coating, is replaced with hexahydrophthalic anhydride
Alkyd amino, polyurethane paint, the powdery paints etc. of aromatic polyvalent acid production, can significantly improve fresh degree of reflecting, the gloss of coating,
Hexahydrophthalic anhydride is alternatively arranged as curing agent, adhesive, plasticizer of epoxy resin etc. simultaneously.
Tetrahydrophthalic anhydride catalytic hydrogenation prepares hexahydrophthalic anhydride, is industrial common process route, there is melting batch process production
Technique and solvent continuity method production technology, batch process auto-processes degree is low, and product quality fluctuation is big, complicated for operation,
Yield is relatively small.Continuity method production technology is mainly reflected in that plant automation degree is high, and production capacity is big, stable product quality, behaviour
Make it is easy, while can also a variety of plasticizer products similar in raw materials for production property.The patent of domestic report is mostly to use at present
It melts batch process and prepares hexahydrophthalic anhydride, production efficiency is lower, and domestic hexahydrophthalic anhydride continuous process is using single molten
Agent, solvent is not easy to remove, while impurity content is higher.
Summary of the invention
To solve the above problems, the present invention provides a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride, it is raw
The hexahydrophthalic anhydride product stability of production is high, and production efficiency improves.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride, it is characterised in that: specific steps are as follows:
Step 1: tetrahydrofuran and hexamethylene are mixed to get mixed solvent according to a certain percentage, by tetrahydrophthalic anhydride and mix molten
Agent 1:4 in mass ratio is put into material-compound tank, and tetrahydrophthalic anhydride and mixed solvent pass through first circulation after mixing evenly in material-compound tank
It is pumped into the fixed bed reactors equipped with catalyst；
Step 2: the hydrogen in hydrogen gas tank is pressed into fixed reactor by compressor, the ratio of feed hydrogen and tetrahydrophthalic anhydride
For 1000:1 ~ 5000:1, controlling temperature in the fixed bed reactors is 40 ~ 60 DEG C, and reaction pressure is maintained at 2 ~ 4.0Mpa range
It is interior；
Step 3: the product that fixed reactor bottom comes out is continuously introduced into knockout drum, the hydrogen that knockout drum top row goes out
Gas introduces hydrogen gas tank and is recycled, and the liquid phase of gas-liquid separation tank bottom discharge is originally pumped into vacuum flasher by second circulation；
Step 4: temperature is 80 ~ 110 DEG C in vacuum flasher, vacuum pressure is -0.06 ~ 0.095Mpa, vacuum flasher top row
Gas phase out is sent into mixed solvent tank after the first condenser is condensed into liquid, recycles mixed solvent, vacuum flashing tower bottom
The liquid phase of discharge is pumped into thin film evaporator by third circulation and is evaporated in vacuo；
Step 5: thin film evaporator temperature is 80 ~ 110 DEG C, vacuum pressure is -0.08 ~ 0.095Mpa, what thin film evaporator obtained
Concentrated liquid is hexahydrophthalic anhydride, and hexahydrophthalic anhydride is also conveyed into product storage tank, and the gas that thin film evaporation is evaporated also passes through second
Condenser is sent into mixed solvent tank after being condensed into liquid, and the mixed liquor in mixed solvent tank, which is conveyed into again in material-compound tank, recycles benefit
With.
Further, the catalyst is made of active component and carrier, and active component is the NiO of mass ratio 5 ~ 15%,
Carrier is SiO2。
Further, catalyst also passes through reduction treatment using preceding, hydrogen as also Primordial Qi, volume space velocity is 500 ~
5000h-1, restores 0 ~ 3.0Mpa of pressure, 8 ~ 48h of recovery time by 100 ~ 150 DEG C of reduction temperature.
Further, the volume ratio of the in the mixed solvent tetrahydrofuran and hexamethylene is 3:1 ~ 10:1.
Further, the vacuum evaporation is evaporated using continuous wipe film.
Further, the fixed bed reactors are trickle bed reactor.
The invention has the benefit that
1, the continuous production processes of a kind of in the mixed solvent of the invention synthesis hexahydrophthalic anhydride, using continuous feed, discharging, tetrahydro
The residence time is very short in the reactor for phthalic anhydride and mixed solvent, and product stability is high, and production efficiency improves, the abrasion journey of catalyst
Degree substantially reduces, and process route cleaning rationally meets environmentally protective production theory；
2, hydrogenation reaction of the invention is carried out in the in the mixed solvent of tetrahydrofuran and hexamethylene, and generation impurity is less, and product is pure
Degree is high, and single solvent tetrahydrofuran is similar to product hexahydrophthalic anhydride structure, is not readily separated removing and hexamethylene composition mixed solvent
Afterwards, azeotropic mixture can be formed, the difficulty of solvent removal is reduced, improves production efficiency；
3, the present invention passes through reasonable process route, and hydrogen and mixed solvent need to only supplement the amount of consumption in system, most of
Ke Xunhuanliyong, synthetical recovery reduces the generation of the three wastes.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Wherein, each label in figure are as follows: 1, material-compound tank, 2, first circulation pump, 3, hydrogen gas tank, 4, compressor, 5, fixed bed it is anti-
Answer device, 6, knockout drum, 7, second circulation pump, 8, vacuum flasher, the 9, first condenser, 10, mixed solvent tank, 11, the
Three circulating pumps, 12, thin film evaporator, the 13, second condenser, 14, product storage tank.
Specific embodiment
In order to which those skilled in the art better understood when technical solution provided by the present invention, below with reference to specific
Embodiment income illustrates.
Fig. 1 is process flow chart of the invention, and NiO/SiO2 is catalyzed by the fixed catalyst first on fixed bed reactors
Agent is loaded on fixed bed reactors 5.First with nitrogen displacement reaction system, make its oxygen content lower than 0.2%(volume), then cut
Change hydrogen carry out catalyst reduction, control hydrogen charging volume space velocity 2000h-1,130 DEG C of temperature of reactor, pressure
3.0Mpa, reductase 12 4h.
Then hydrogenation reaction is carried out, it is molten that tetrahydrofuran and hexamethylene are that 5:1 is configured to mix in solvent tank by volume
Tetrahydrophthalic anhydride and mixed solvent 1:4 in mass ratio are put into material-compound tank 1 by agent, are sent by first circulation pump 2 equipped with catalyst
In fixed bed reactors 5, hydrogen is sent into fixed bed reactors 5 by compressor 4 in hydrogen gas tank 3, and charging hydrogen-oil ratio is 3000:
1, controlling temperature in the fixed bed reactors is 50 DEG C, and reaction pressure is maintained at 3.0Mpa.The product that tower bottom comes out is continuously introduced into
In knockout drum 6, the hydrogen that knockout drum top row goes out introduces hydrogen gas tank 3 and is recycled, the liquid of gas-liquid separation tank bottom discharge
Mutually by second circulation pump 7 be sent into vacuum flashers 8 in, control vacuum flasher in temperature be 100 DEG C, vacuum pressure for-
0.080Mpa, the gas phase that vacuum flasher top row goes out, i.e. sudden strain of a muscle top gas are sent to mixed solvent after the first condenser 9 is condensed into liquid
Tank 10, recycles mixed solvent, and the liquid phase of vacuum flashing tower bottom discharge, i.e. sudden strain of a muscle bottom liquid are sent into scraper plate by third circulating pump 11
Formula thin film evaporator 12 is evaporated in vacuo, and control thin film evaporator temperature is 100 DEG C, and vacuum pressure is -0.080Mpa, is obtained
Hexahydrophthalic anhydride product is sent into product storage tank 14, and product purity reaches 99.3%.The gas being evaporated is condensed through the second condenser 13
It is recycled to be sent to mixed solvent tank 10 after liquid.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
The present invention will not be limited to the embodiments shown herein, and is to fit to special with principles disclosed herein and novelty
The consistent widest scope of point.
Claims (6)
1. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride, it is characterised in that: specific steps are as follows:
Step 1: tetrahydrofuran and hexamethylene are mixed to get mixed solvent according to a certain percentage, by tetrahydrophthalic anhydride and mix molten
Agent 1:4 in mass ratio is put into material-compound tank, and tetrahydrophthalic anhydride and mixed solvent pass through first circulation after mixing evenly in material-compound tank
It is pumped into the fixed bed reactors equipped with catalyst；
Step 2: the hydrogen in hydrogen gas tank is pressed into fixed reactor by compressor, the ratio of feed hydrogen and tetrahydrophthalic anhydride
For 1000:1 ~ 5000:1, controlling temperature in the fixed bed reactors is 40 ~ 60 DEG C, and reaction pressure is maintained at 2 ~ 4.0Mpa range
It is interior；
Step 3: the product that fixed reactor bottom comes out is continuously introduced into knockout drum, the hydrogen that knockout drum top row goes out
Gas introduces hydrogen gas tank and is recycled, and the liquid phase of gas-liquid separation tank bottom discharge is originally pumped into vacuum flasher by second circulation；
Step 4: temperature is 80 ~ 110 DEG C in vacuum flasher, vacuum pressure is -0.06 ~ 0.095Mpa, vacuum flasher top row
Gas phase out is sent into mixed solvent tank after the first condenser is condensed into liquid, recycles mixed solvent, vacuum flashing tower bottom
The liquid phase of discharge is pumped into thin film evaporator by third circulation and is evaporated in vacuo；
Step 5: thin film evaporator temperature is 80 ~ 110 DEG C, vacuum pressure is -0.08 ~ 0.095Mpa, what thin film evaporator obtained
Concentrated liquid is hexahydrophthalic anhydride, and hexahydrophthalic anhydride is also conveyed into product storage tank, and the gas that thin film evaporation is evaporated also passes through second
Condenser is sent into mixed solvent tank after being condensed into liquid, and the mixed liquor in mixed solvent tank, which is conveyed into again in material-compound tank, recycles benefit
With.
2. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride according to claim 1, it is characterised in that:
The catalyst is made of active component and carrier, and active component is the NiO, carrier SiO of mass ratio 5 ~ 15%2。
3. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride according to claim 2, it is characterised in that:
Catalyst also passes through reduction treatment using preceding, and for hydrogen as also Primordial Qi, volume space velocity is 500 ~ 5000h-1, and reduction temperature 100 ~
150 DEG C, restore 0 ~ 3.0Mpa of pressure, 8 ~ 48h of recovery time.
4. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride according to claim 1, it is characterised in that:
The volume ratio of the in the mixed solvent tetrahydrofuran and hexamethylene is 3:1 ~ 10:1.
5. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride according to claim 1, it is characterised in that:
The vacuum evaporation is evaporated using continuous wipe film.
6. a kind of continuous production processes of in the mixed solvent synthesis hexahydrophthalic anhydride according to claim 1, it is characterised in that:
The fixed bed reactors are trickle bed reactor.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811061958.6A CN109280040B (en) | 2018-09-12 | 2018-09-12 | Continuous production process for synthesizing hexahydrophthalic anhydride in mixed solvent |
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| CN201811061958.6A CN109280040B (en) | 2018-09-12 | 2018-09-12 | Continuous production process for synthesizing hexahydrophthalic anhydride in mixed solvent |
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| CN109280040A true CN109280040A (en) | 2019-01-29 |
| CN109280040B CN109280040B (en) | 2021-02-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841161A (en) * | 2020-07-29 | 2020-10-30 | 濮阳市盛源能源科技股份有限公司 | Gas-liquid separation device and pressure removal reaction kettle |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003335769A (en) * | 2002-03-14 | 2003-11-28 | New Japan Chem Co Ltd | Method for producing hexahydrophthalic anhydrides |
| CN106674172A (en) * | 2016-11-24 | 2017-05-17 | 大连理工大学 | Method for preparing hexahydrophthalic anhydride |
| CN106866365A (en) * | 2017-03-30 | 2017-06-20 | 荣成市科盛化工有限公司 | A kind of continuous preparation method of hydrogenated bisphenol A |
| CN107011304A (en) * | 2017-05-05 | 2017-08-04 | 安阳工学院 | A kind of catalytic hydrogenation prepares HHPA (HHPA) technique |
-
2018
- 2018-09-12 CN CN201811061958.6A patent/CN109280040B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003335769A (en) * | 2002-03-14 | 2003-11-28 | New Japan Chem Co Ltd | Method for producing hexahydrophthalic anhydrides |
| CN106674172A (en) * | 2016-11-24 | 2017-05-17 | 大连理工大学 | Method for preparing hexahydrophthalic anhydride |
| CN106866365A (en) * | 2017-03-30 | 2017-06-20 | 荣成市科盛化工有限公司 | A kind of continuous preparation method of hydrogenated bisphenol A |
| CN107011304A (en) * | 2017-05-05 | 2017-08-04 | 安阳工学院 | A kind of catalytic hydrogenation prepares HHPA (HHPA) technique |
Non-Patent Citations (1)
| Title |
|---|
| 李大东: "《加氢处理工艺与工程》", 31 December 2004, 北京:中国石化出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841161A (en) * | 2020-07-29 | 2020-10-30 | 濮阳市盛源能源科技股份有限公司 | Gas-liquid separation device and pressure removal reaction kettle |
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