CN103130647B - Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate - Google Patents
Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate Download PDFInfo
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- CN103130647B CN103130647B CN201310015624.6A CN201310015624A CN103130647B CN 103130647 B CN103130647 B CN 103130647B CN 201310015624 A CN201310015624 A CN 201310015624A CN 103130647 B CN103130647 B CN 103130647B
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Abstract
The invention discloses a device for preparing 1, 2-cyclohexane dicyclohexyl phthalate. The device comprises an esterification kettle, a refining kettle, a filtering tank and a hydrogenation reaction unit. The hydrogenation reaction unit comprises an intermediate tank, a hydrogen compressing device and a hydrogenation reactor and further comprises a gas-liquid separation system. The intermediate tank is provided with a solution heater, the hydrogenation reactor is connected with the intermediate tank, and the gas-liquid separation system is connected with the hydrogenation reaction unit. The invention further discloses a preparation method. The preparation method includes the steps of esterification, neutralization, washing, refining and hydrogenation reacting. Compared with the prior art, the device for preparing the 1, 2-cyclohexane dicyclohexyl phthalate has the advantages of being applied to industrial large-scale production, low in cost and high in efficiency. The 1, 2-cyclohexane dicyclohexyl phthalate has a good toxicological property, is well compatible with polyvinyl chloride (PVC), odorless, environment-friendly and non-toxic. In the process of pelleting or plastifying, the 1, 2-cyclohexane dicyclohexyl phthalate is compatible with PVC materials quite well, low in viscosity and capable of being applied to a specific injection mold so that the service cycle of a plastification product is prolonged, and a final product is very low in mobility after plastified by the 1, 2-clohexane dicyclohexyl phthalate.
Description
Technical field
The present invention relates to a kind ofly prepare 1, the devices and methods therefor of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, this product is applicable to the responsive flexible PVC products such as food fresh keeping membrane, the interior pad of food sealing, Sport & Casual product, sealing agent, shower curtain, footwear, slipmat, water pipe, electric wire toy, food product pack, medical treatment product, can be used for producing three years old following toy for children, also can be used for low peculiar smell automobile for cable, medical nutrition supply pipe, adhesive membrane, domestic food contact gloves, the indoor wallpaper of environment-friendly type, decorative sheets of material, intravenously blood transfusion tube and Medical blood bag etc.
Background technology
In life, softening agent is ubiquitous, except plastic bottle, tableware, daily necessities, toy, even also can contain softening agent in preservative film.Fluidizer is widely used in the Industrial products such as food product pack, medical and hygiene article, paint, also has the phthalate things such as denier DEHP in environment, tap water.Softening agent is consumption maximum in all additives for plasticss.Wherein the use of the phthalate of cost performance optimum is the most extensive, and global annual usage quantity, more than 8,000,000 tons, wherein be take phthalate fluidizer as main body, has accounted for 75% share.It can increase the suppleness of plastics.But adjacent benzene class softening agent easily escapes in environment, what at this moment bring into play is all the bad effect of environment incretion interferent.Fluidizer can enter human body by approach such as Digestive tract, respiratory system and skin contact, has genotoxicity and development toxicity, and this harm is also hidden and very long.The focus that recently scientific research is paid close attention to, mainly concentrates on pregnancy period rat and is exposed in phthalate material, and the intergenerational impact producing by placenta and lactication, is mainly the impact that its male offspring's Development of Reproductive System is produced.Although human toxicity data are abundant not enough at present, that keeps someone at a respectful distance, throws and abandon worldwide reaches common understanding.Adjacent benzene class fluidizer consumption is huge, use range is wide, contaminated area and the number that affects are just all luxuriant is considerable, and phthalate can be described as a distribution on global class synthetic environment pollutent the most widely at present, in air, water, soil and dust, can detect.Phthalate has inrichment at organism escheat, has the significantly residue of this compounds in aquatic organism, and final people expose wherein by approach such as food and air.
Summary of the invention
The present invention is directed to deficiency of the prior art, provide a kind of preparation 1 that is applicable to industrial mass production, the device of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls.
For solving the problems of the technologies described above, the present invention is solved by following technical proposals: a kind ofly prepare 1, the device of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, comprise esterifying kettle, refining kettle, hay tank and hydrogenation reaction unit, described hydrogenation reaction unit comprises the tundish that are provided with solution heater, hydrogen gas booster compressor, the hydrogenator being connected with described tundish, an outlet of described hydrogen gas booster compressor is communicated with the lower section catalyst bed of described hydrogenator, another outlet communication loop hydrogen preheater, described circulating hydrogen preheater communication loop hydrogen well heater, described circulating hydrogen well heater is communicated with described hydrogenator, described hydrogenator is connected with hp flash drum, one of them outlet of described hp flash drum connects 4.5MPa separating tank, another outlet ligation device water cooler, described reactor water cooler connects circulation gas separating tank, one of them outlet of described circulation gas separating tank connects described hydrogen gas booster compressor, another outlet connects boiler systems, also have an outlet to connect described 4.5MPa separating tank, one of them outlet of described 4.5MPa separating tank connects described boiler plant, another outlet is connected with low pressure flash chamber, one of them outlet of described low pressure flash chamber connects described boiler systems, another outlet connects decolouring groove, described decolouring groove is connected with reactor product cooler, in wherein said esterifying kettle, be provided with stir shaft, on this stir shaft, be provided with paddle, evenly offer some holes on the blade face of this paddle, described hole is evenly opened in the edge of described paddle.Device of the present invention is applicable to industrial mass production, have advantages of that production cost is low, and hole on paddle makes a part of liquid be stirred leaf to promote in whipping process, a part is by this hole, make liquid speed difference everywhere obvious, easily form turbulent flow, mixing effect is better, makes reaction more abundant.
As preferably, the medullary ray in above-mentioned hole and the angle on described blade face are less than 90 degree.Said structure, by changing liquid flow direction, more easily causes turbulent flow, makes mixing effect better.
The present invention also provides a kind of preparation 1 that is applicable to industrial mass production simultaneously, the method of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, it is characterized in that comprising the following steps: 1) esterification: open nitrogen and pass into described esterifying kettle, after air drains, open and stir, drop into hexalin, put into after catalyzer, input is faced phthalate anhydride, wherein, face phthalate anhydride and hexalin charging capacity mol ratio is 1:3, feed intake complete, close solid dog-house and nitrogen, start to heat up, carry out esterification, be warming up to 220 ℃ ~ 230 ℃, when esterification acid number reaches 1mgKOH/g when following, esterification finishes, steam off, open cooling water temperature to 100 ℃, by vacuum, proceed to described refining kettle, 2) neutralization, washing: open described refining kettle and stir, in described refining kettle, pump into the buck preparing, neutralize, after material fully mixes with liquid caustic soda, stop stirring, standing minute water, acid number reaches below 0.05mgKOH/g, open and stir, in described refining kettle, pump into esterification generation water and a small amount of steam condensation water, wash stir about 10min, stop stirring standing minute water, 3) refining: minute water is complete, open described refining kettle vacuum and the heating of described refining kettle, more than treating that vacuum tightness reaches negative 0.09Mpa, be warming up to 170 ~ 175 ℃, in described refining kettle, pass into open steam, carry out stripping, stripping 240min, close open steam, flash-point is surveyed in sampling, after flash-point is qualified, open nitrogen at the bottom of described refining kettle, dry 30min, measures moisture content of finished products content and acid number, pumps into described hay tank after qualified to filter, 4) hydrogenation: material after filtering enters described tundish, through raw material fresh feed pump, be forced into 12.9MPa, through described solution heater, by 3.0MPa, being steam heated to 200 ℃ again enters hydrogenator and carries out hydrogenation reaction, from the circulating hydrogen after the de-oiling of hydrogen gas booster compressor, a part rises to 180 ℃ in circulating hydrogen preheater temperature, through circulating hydrogen well heater, by 3.0MPa, be steam heated to 200 ℃ again and enter hydrogenator and carry out hydrogenation reaction, a part is removed hydrogenator lower section catalyst bed as cold hydrogen, reflect material mixture through gas-liquid separation, liquidus temperature is down to after 100 ℃, enters that decolouring groove decolours and de-heavy, finally by after cooling 40 ℃ of reactor product cooler, delivers to battery limit (BL), obtains finished product 1,2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls.
As preferably, above-mentioned gas-liquid separation comprises the following steps: reflect material mixture after hp flash drum carries out gas-liquid separation, gas phase temperature after interchanger and circulating hydrogen heat exchange is down to 84 ℃ by 215 ℃, again through reaction gas water cooler by circulating water to 40 ℃, then go circulation gas separating tank to carry out gas-liquid separation, through the isolated gas phase major part of described circulation gas separating tank as recycle hydrogen dehydrogenation gas gas booster compressor, part gas phase is removed boiler systems, through the isolated liquid phase of described circulation gas separating tank, removes 4.5MPa separating tank after being decompressed to 4.5MPa; From hp flash drum liquid phase after being decompressed to 4.5MPa with interchanger heat exchange after temperature by 215 ℃, be down to 80 ℃, go described 4.5MPa separating tank to carry out gas-liquid separation, flashed vapour goes to remove boiler systems as fuel gas, and liquid phase goes low pressure flash chamber to carry out gas-liquid separation through being decompressed to 0.4MPa; The flashed vapour of low pressure flash chamber removes boiler systems as fuel gas after being decompressed to 0.3MPa, and liquidus temperature is down to after 100 ℃, enters decolouring groove and decolours and take off heavy.
Compared with prior art, the invention has the beneficial effects as follows: 1) product of the present invention is through rigorous toxicity test, and the toxicological characteristics of its excellence makes it to be applicable to the responsive flexible PVC products such as toy, food product pack, medical treatment product; 2) product of the present invention has fine consistency to PVC, has the low-temperature performance of good processing characteristics, low volatility, excellence, and odorlessness, environment-protecting asepsis; 3) when granulation or plasticising production, product of the present invention is fairly good with PVC material compatibleness; 4) product viscosity of the present invention is low, applicable to specific injection mould, even can be used for very accurate careful design, thereby extends the life cycle of plastified prod; 5) the finished product transport property of product plasticising of the present invention is very low, can with the safe combinations of resin material such as ABS, SAN, PC, guarantee that product has longer work-ing life and excellent properties; 6) apparatus and method of the present invention are suitable for large-scale industrialization production, and production cost is low, and production efficiency is high.
Accompanying drawing explanation
Fig. 1 is workflow schematic diagram of the present invention.
Fig. 2 is the structural representation of esterifying kettle in the present invention.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail: embodiment 1: a kind ofly prepare 1, the device of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, comprise esterifying kettle 1, refining kettle 2, hay tank 3 and hydrogenation reaction unit, described hydrogenation reaction unit comprises the tundish 4 that are provided with solution heater, hydrogen gas booster compressor 6, the hydrogenator 5 being connected with described tundish 4, an outlet of described hydrogen gas booster compressor 6 is communicated with the lower section catalyst bed of described hydrogenator 5, another outlet communication loop hydrogen preheater 7, described circulating hydrogen preheater 7 communication loop hydrogen well heaters 8, described circulating hydrogen well heater 8 is communicated with described hydrogenator 5, described hydrogenator 5 is connected with hp flash drum 9, one of them outlet of described hp flash drum 9 connects 4.5MPa separating tank 13, another outlet ligation device water cooler 10, described reactor water cooler 10 connects circulation gas separating tank 11, described circulation gas separating tank 11 one of them outlet connect described hydrogen gas booster compressor 6, another outlet connects boiler systems 12, also have an outlet to connect described 4.5MPa separating tank 13, one of them outlet of described 4.5MPa separating tank 13 connects described boiler systems 12, another outlet is connected with low pressure flash chamber 14, one of them outlet of described low pressure flash chamber 14 connects described boiler systems 12, another outlet connects decolouring groove 15, described decolouring groove 15 is connected with reactor product cooler 16, in wherein said esterifying kettle 1, be provided with stir shaft 17, on this stir shaft 17, be provided with paddle 18, the outer end of described paddle 18 is rotatably connected to movable plate 22, and the height of this movable plate is greater than the height of described paddle 18, and one end of described movable plate 22 and the inwall of described esterifying kettle contact.On the blade face of this paddle, evenly offer some holes 23, described hole 23 is evenly opened in the edge of described paddle 18.
Wherein, the angle on the medullary ray in above-mentioned hole 23 and described paddle 18 blade faces is less than 90 degree.
Embodiment 2, a kind of preparation 1 that is applicable to industrial mass production, the method of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, it is characterized in that comprising the following steps: 1) esterification: open nitrogen and pass into described esterifying kettle, after air drains, open and stir, drop into hexalin, put into after catalyzer, input is faced phthalate anhydride, wherein, face phthalate anhydride and hexalin charging capacity mol ratio is 1:3, feed intake complete, close solid dog-house and nitrogen, start to heat up, carry out esterification, be warming up to 220 ℃ ~ 230 ℃, when esterification acid number reaches 1mgKOH/g when following, esterification finishes, steam off, open cooling water temperature to 100 ℃, by vacuum, proceed to described refining kettle, 2) neutralization, washing: open described refining kettle and stir, in described refining kettle, pump into the buck preparing, neutralize, after material fully mixes with liquid caustic soda, stop stirring, standing minute water, acid number reaches below 0.05mgKOH/g, open and stir, in described refining kettle, pump into esterification generation water and a small amount of steam condensation water, wash stir about 10min, stop stirring standing minute water, 3) refining: minute water is complete, open described refining kettle vacuum and the heating of described refining kettle, more than treating that vacuum tightness reaches negative 0.09Mpa, be warming up to 170 ~ 175 ℃, in described refining kettle, pass into open steam, carry out stripping, stripping 240min, close open steam, flash-point is surveyed in sampling, after flash-point is qualified, open nitrogen at the bottom of described refining kettle, dry 30min, measures moisture content of finished products content and acid number, pumps into described hay tank after qualified to filter, 4) hydrogenation: material after filtering enters described tundish, through raw material fresh feed pump, be forced into 12.9MPa, through described solution heater, by 3.0MPa, being steam heated to 200 ℃ again enters hydrogenator and carries out hydrogenation reaction, from the circulating hydrogen after the de-oiling of hydrogen gas booster compressor, a part rises to 180 ℃ in circulating hydrogen preheater temperature, through circulating hydrogen well heater, by 3.0MPa, be steam heated to 200 ℃ again and enter hydrogenator and carry out hydrogenation reaction, a part is removed hydrogenator lower section catalyst bed as cold hydrogen, reflect material mixture after hp flash drum carries out gas-liquid separation, gas phase temperature after interchanger and circulating hydrogen heat exchange is down to 84 ℃ by 215 ℃, again through reaction gas water cooler by circulating water to 40 ℃, then go circulation gas separating tank to carry out gas-liquid separation, through the isolated gas phase major part of described circulation gas separating tank as recycle hydrogen dehydrogenation gas gas booster compressor, part gas phase is removed boiler systems, through the isolated liquid phase of described circulation gas separating tank, removes 4.5MPa separating tank after being decompressed to 4.5MPa, from hp flash drum liquid phase after being decompressed to 4.5MPa with interchanger heat exchange after temperature by 215 ℃, be down to 80 ℃, go described 4.5MPa separating tank to carry out gas-liquid separation, flashed vapour goes to remove boiler systems as fuel gas, and liquid phase goes low pressure flash chamber to carry out gas-liquid separation through being decompressed to 0.4MPa, the flashed vapour of low pressure flash chamber removes boiler systems as fuel gas after being decompressed to 0.3MPa, liquidus temperature is down to after 100 ℃, enters that decolouring groove decolours and de-heavy, finally by after cooling 40 ℃ of reactor product cooler, delivers to battery limit (BL), obtain finished product 1,2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls.
Claims (4)
1. prepare 1 for one kind, the device of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, it is characterized in that: comprise esterifying kettle, refining kettle, hay tank and hydrogenation reaction unit, described hydrogenation reaction unit comprises the tundish that are provided with solution heater, hydrogen gas booster compressor, the hydrogenator being connected with described tundish, an outlet of described hydrogen gas booster compressor is communicated with the lower section catalyst bed of described hydrogenator, another outlet communication loop hydrogen preheater, described circulating hydrogen preheater communication loop hydrogen well heater, described circulating hydrogen well heater is communicated with described hydrogenator, described hydrogenator is connected with hp flash drum, one of them outlet of described hp flash drum connects 4.5MPa separating tank, another outlet ligation device water cooler, described reactor water cooler connects circulation gas separating tank, one of them outlet of described circulation gas separating tank connects described hydrogen gas booster compressor, another outlet connects boiler systems, also have an outlet to connect described 4.5MPa separating tank, one of them outlet of described 4.5MPa separating tank connects described boiler systems, another outlet is connected with low pressure flash chamber, one of them outlet of described low pressure flash chamber connects described boiler systems, another outlet connects decolouring groove, described decolouring groove is connected with reactor product cooler, in wherein said esterifying kettle, be provided with stir shaft, on this stir shaft, be provided with paddle, offer some holes on the blade face of this paddle, described hole is uniformly distributed in the edge of described paddle.
2. a kind of device of preparing 1,2-cyclohexane cyclohexanedimethanodibasic, two cyclohexyls according to claim 1, is characterized in that: the central axis in described hole and the angle on described blade face are less than 90 degree.
3. one kind is used device as claimed in claim 1 to prepare 1, the method of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, it is characterized in that comprising the following steps: 1) esterification: open nitrogen and pass into described esterifying kettle, after air drains, open and stir, drop into hexalin, put into after catalyzer, drop into Tetra hydro Phthalic anhydride, wherein, Tetra hydro Phthalic anhydride and hexalin charging capacity mol ratio are 1:3, feed intake complete, close solid dog-house and nitrogen, start to heat up, carry out esterification, be warming up to 220 ℃～230 ℃, when esterification acid number reaches 1mgKOH/g when following, esterification finishes, steam off, open cooling water temperature to 100 ℃, by vacuum, proceed to described refining kettle, 2) neutralization, washing: open refining kettle and stir, in described refining kettle, pump into the buck preparing, neutralize, after material fully mixes with liquid caustic soda, stop stirring, standing minute water, acid number reaches below 0.05mgKOH/g, open and stir, in described refining kettle, pump into esterification generation water and a small amount of steam condensation water, wash stir about 10min, stop stirring standing minute water, 3) refining: minute water is complete, open refining kettle vacuum and refining kettle heating, more than treating that vacuum tightness reaches negative 0.09MPa, be warming up to 170～175 ℃, in described refining kettle, pass into open steam, carry out stripping, stripping 240min, close open steam, flash-point is surveyed in sampling, after flash-point is qualified, nitrogen at the bottom of unlatching refining kettle, dry 30min, measures moisture content of finished products content and acid number, pumps into described hay tank after qualified to filter, 4) hydrogenation: material after filtering enters described tundish, through raw material fresh feed pump, be forced into 12.9MPa, through described solution heater, by 3.0MPa, being steam heated to 200 ℃ again enters hydrogenator and carries out hydrogenation reaction, from the circulating hydrogen after the de-oiling of hydrogen gas booster compressor, a part rises to 180 ℃ in circulating hydrogen preheater temperature, through circulating hydrogen well heater, by 3.0MPa, be steam heated to 200 ℃ again and enter hydrogenator and carry out hydrogenation reaction, a part is removed hydrogenator lower section catalyst bed as cold hydrogen, reflect material mixture through gas-liquid separation, liquidus temperature is down to after 100 ℃, enters that decolouring groove decolours and de-heavy, finally by after cooling 40 ℃ of reactor product cooler, delivers to battery limit (BL), obtains finished product 1,2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls.
4. according to claim 3ly a kind ofly prepare 1, the method of 2-cyclohexane cyclohexanedimethanodibasic two cyclohexyls, it is characterized in that: described gas-liquid separation comprises the following steps: reflect material mixture after hp flash drum carries out gas-liquid separation, gas phase temperature after interchanger and circulating hydrogen heat exchange is down to 84 ℃ by 215 ℃, again through reactor water cooler by circulating water to 40 ℃, then go circulation gas separating tank to carry out gas-liquid separation, through the isolated gas phase major part of described circulation gas separating tank as recycle hydrogen dehydrogenation gas gas booster compressor, part gas phase is removed boiler systems, through the isolated liquid phase of described circulation gas separating tank, after being decompressed to 4.5MPa, remove 4.5MPa separating tank, from hp flash drum liquid phase after being decompressed to 4.5MPa with interchanger heat exchange after temperature by 215 ℃, be down to 80 ℃, go described 4.5MPa separating tank to carry out gas-liquid separation, flashed vapour goes to remove boiler systems as fuel gas, and liquid phase goes low pressure flash chamber to carry out gas-liquid separation through being decompressed to 0.4MPa, the flashed vapour of low pressure flash chamber removes boiler systems as fuel gas after being decompressed to 0.3MPa, and liquidus temperature is down to after 100 ℃, enters decolouring groove and decolours and take off heavy.
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| CN201310015624.6A CN103130647B (en) | 2013-01-16 | 2013-01-16 | Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate |
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| CN201310015624.6A CN103130647B (en) | 2013-01-16 | 2013-01-16 | Device and method for preparing 1, 2-cyclohexane dicyclohexyl phthalate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223631A (en) * | 1996-06-28 | 1999-07-21 | 新日本理化株式会社 | Process for the preparation of cyclohexanedimethanol |
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1223631A (en) * | 1996-06-28 | 1999-07-21 | 新日本理化株式会社 | Process for the preparation of cyclohexanedimethanol |
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
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