CN113831210A - Post-treatment method of cyclododecatriene reaction liquid - Google Patents
Post-treatment method of cyclododecatriene reaction liquid Download PDFInfo
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- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1892—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns the sorbent material moving as a whole, e.g. continuous annular chromatography, true moving beds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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- C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered
Abstract
The invention discloses a post-treatment method of cyclododecatriene synthetic reaction liquid, which takes amine modified beta-cyclodextrin cross-linked resin as an adsorbent, adopts a moving bed adsorption device to adsorb active catalyst components in the cyclododecatriene synthetic reaction liquid, and effectively solves the problems of complex post-treatment, incomplete quenching, difficult separation and the like in the existing quenching mode.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a post-treatment method of a cyclododecatriene reaction solution produced by cyclotrimerization of butadiene.
Background
Cyclododecatriene, abbreviated as CDT, is industrially obtained by performing a liquid-phase cyclotrimerization reaction on butadiene (abbreviated as BD) serving as a raw material under the action of a Ziegler-Natta catalyst. The CDT belongs to a chemical raw material, and the main downstream chemicals are hexabromocyclododecane (HBCD for short) and nylon 12 (PA 12 for short).
The cyclododecatriene is obtained by adopting butadiene as a raw material and performing catalytic cyclotrimerization, the process belongs to the oligomerization process of butadiene, a catalyst is a Ziegler-Natta system, a general main catalyst is titanium tetrachloride, a cocatalyst is aluminum sesquiethylate chloride, and in addition, different other electron donors can be added. Under different electron donor conditions, the activity and selectivity of the catalyst for the reaction are different. If the catalyst activity is not high, longer residence time and larger reactor volume are needed; meanwhile, when the selectivity of the main product is low and the amount of the by-produced polymer is large, the production process is troublesome. At present, domestic manufacturers all adopt batch kettle type reactors, and the reaction residence time is over 10 hours; the foreign manufacturers all adopt continuous reactors, and the residence time is slightly short. Because the catalyst adopts the alkyl aluminum as a cocatalyst, the post-treatment of the alkyl aluminum-containing system is also one of the process difficulties. The conventional post-treatment method is to quench the reaction solution with an alkali solution and wash and extract the catalyst. In order to avoid the aluminum compound from forming a colloid, the concentration and the dosage of the alkali liquor need to be increased, and then a large amount of waste alkali liquor is generated.
Quenching agents for trimerization have been variously attempted in continuing industrial practice. The butadiene cyclotrimerization reaction takes place in the form of solution polymerization, for example, toluene is used as a solvent, the polymerization temperature is 75 ℃, a five-kettle series process of '3 + reaction kettle → aging kettle → quenching kettle' is adopted, butadiene is respectively introduced into three reaction kettles, the lower monomer concentration of each kettle is convenient to control, and the occurrence of side reactions is reduced. And further converting the residual small amount of butadiene in the aging kettle, and quenching the obtained reaction liquid in a quenching kettle by a quenching agent (such as ethanol) and then separating and purifying the reaction liquid in a rectifying tower. The separation and purification adopts a weight removal mode to remove quenched catalyst and oligomer (heavy component) generated in the reaction, then the rectification is carried out in sequence to remove excessive ethanol and recover solvent toluene to obtain a cyclododecatriene pure product, and the light component is further separated to obtain vinylcyclohexene and 1, 5-cyclooctadiene. And the heavy component and the ethanol-butadiene-toluene mixture are treated in the form of three wastes.
After the reaction is finished, quenching the reaction. The primary purpose of the quenching is to quench the aluminum alkyl, ensuring the safety of the subsequent separation process, while it is desirable to remove the catalyst from the system by suitable means. The similar process in industry mainly has the following solutions:
water quenching or lye quenching. The aluminum hydrolysate is inevitably formed by adopting water quenching or alkali quenching, exists in a colloid form, adsorbs a large amount of organic matters to be suspended or hung on the wall in a system, and is difficult to process. The concentrated alkali liquor can process the aluminum compound into a metaaluminate solution, and the practical verification shows that the concentration of the alkali liquor needs to reach more than 40 percent, and the metal is difficult to be completely removed because the organic phase (containing CDT) has certain solubility with water.
And (5) quenching by heavy alcohol. The method is suitable for the process of ethylene oligomerization to prepare 1-C6/1-C8, and adopts higher-boiling alcohol such as 2-ethylhexanol, and the excessive alcohol exists in a heavy component form. However, if the catalyst activity is low, the amount of alcohol used is increased and the cost is not negligible.
And (4) complexing and adsorbing. The polyethylene prepared by the smoothening petrochemical solution method adopts octanoic acid and acetylacetone as a quenching agent, and the catalyst is removed by adsorption of activated alumina after quenching. The adsorption process is irreversible and uneconomical if the catalyst activity is low.
And (4) ammonia quenching. The Invista CDT device which is permanently shut down in the United states adopts ammonia gas quenching, then is subjected to two-stage scraper de-weighting, and then is washed by alkali washing to remove a small amount of residual catalyst. In fact, ammonia gas is immiscible with reaction liquid in the process, so that quenching is difficult, if the purpose of quenching is achieved, the quenching time needs to be prolonged, and the method is matched with a method of adding water and the like. Basf patent application CN105793214A discloses a CDT reaction solution post-treatment method, which comprises contacting with gaseous ammonia for more than 1h, then adding a small amount of water, stirring for more than 2h, filtering to remove a small amount of precipitate, and removing the residual catalyst and heavy components by distillation to remove heavy components.
The complex adsorption quenching requires high catalyst activity, quenching and adsorption are carried out by adopting quenchers such as alcohols, quenching is incomplete, the subsequent separation system and the product quality are influenced, ammonia gas and water are used as the quenchers, multi-step centrifugation and alkaline washing are required, and the separation process is complicated.
Therefore, it is necessary to develop a new quenching post-treatment method for cyclododecatriene synthesis reaction solution to solve the problems in CDT production and separation.
Disclosure of Invention
The invention aims to provide a post-treatment method of cyclododecatriene synthesis reaction liquid, which utilizes modified cyclodextrin cross-linked resin (CDP) as an adsorbent and a moving bed adsorption device to effectively quench the cyclododecatriene synthesis reaction liquid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a post-treatment method of cyclododecatriene synthesis reaction liquid is characterized by comprising the step of effectively quenching a catalyst in the cyclododecatriene synthesis reaction liquid by using modified beta-cyclodextrin cross-linked resin (CDP) as an adsorbent and adopting an adsorption device.
In a specific embodiment, the adsorbent is an amine-modified beta-cyclodextrin cross-linked resin; preferably, the amine is selected from one or more of triethylamine, diethylamine, ethylenediamine and the like; more preferably, the adsorbent is triethylamine modified beta-cyclodextrin resin TEA-beta-CDP.
In a specific embodiment, the adsorbent is prepared by the following method:
1) synthesis of beta-CDP: preparing beta-CDP by adopting the beta-CD and epoxy chloropropane;
2) preparing a p-toluenesulfonylated resin (Ts- β -CDP) by reacting p-toluenesulfonyl chloride with β -CDP;
3) the prepared Ts-beta-CDP is then reacted with the amine to prepare an amine modified beta-cyclodextrin resin, preferably, the amine is selected from triethylamine to prepare a triethylamine modified beta-cyclodextrin resin (TEA-beta-CDP).
In a specific embodiment, in the step 1), the charging molar ratio of the beta-CD to the epichlorohydrin is 1: 10.
in a specific embodiment, the preparation method of step 2) is as follows: adding a proper amount of beta-CDP into 4-5 times of dry pyridine for swelling for 0.5h, adding benzene with equal mass, uniformly mixing, and heating, refluxing and steaming to remove a toluene fraction; cooling, adding TsCl, oscillating at room temperature, washing, extracting, and vacuum drying to obtain Ts-beta-CDP light yellow particles; preferably, the mass ratio of the beta-CDP to the TsCl is as follows: oscillating at room temperature for 22h at a ratio of 5-6:1, washing with ethanol for several times, extracting with ethanol for 8h, and vacuum drying at 50 ℃ for 10h to obtain Ts-beta-CDP light yellow particles; preferably, the particle size of the beta-CDP is 40-60 mesh, and the sulfur content of the product Ts-beta-CDP is 2-3 wt%.
In a specific embodiment, the preparation method of step 3) is as follows: adding 25mL of benzene into 5.0 gTs-beta-CDP, refluxing to remove 20mL of fraction, adding 20mL of triethylamine, and refluxing for 24 h; cooling, filtering, washing with water and dilute sodium hydroxide solution for 3 times, and washing with water to neutral; air-drying, and vacuum-drying at 50 deg.C for 10 hr to obtain TEA-beta-CDP light yellow granule.
In a specific embodiment, the adsorption apparatus employs a moving bed adsorption apparatus as the adsorption carrier.
In a specific embodiment, the modified cyclodextrin cross-linked resin enters the moving bed from an upper inlet of the moving bed body and exits the moving bed from a lower outlet of the moving bed body; the reaction liquid enters from a lower inlet of the moving bed main body and flows out from an upper outlet of the moving bed main body; and a plurality of isolation sieve plates are arranged in the moving bed main body along the direction from the resin inlet to the resin outlet, and the isolation sieve plates isolate the moving bed main body into a plurality of resin bins.
In a specific embodiment, the reaction liquid inlet of the moving bed main body adopts a divergent structure, and the reaction liquid outlet adopts a microporous plate structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a post-treatment method of cyclododecatriene synthesis reaction liquid, which adopts amine modified beta-cyclodextrin cross-linked resin (CDP) as an adsorbent and can effectively inactivate active alkyl aluminum and titanium tetrachloride in a catalyst.
(2) The invention adopts the modified TEA-beta-CDP, increases the pore volume of the adsorption resin, enhances the adsorption effect and reduces the occurrence probability of bed layer blockage.
(3) The invention adopts a movable adsorption bed device, has the adsorption effects of cross flow and convection, improves the contact time of reaction liquid and resin, enhances the quenching effect, and effectively solves the problem of separating light and heavy components.
Drawings
FIG. 1 is a schematic view of the structure of a moving adsorbent bed of the present invention.
Wherein, 1 is a resin inlet, 2 resin outlets, 3 reaction liquid inlets, 4 reaction liquid outlets, 5 catalyst adsorption sections, 6 louver inlets, 7 microporous plates and 8 isolation sieve plates.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
The Cyclodextrin (CD) is a glucose cyclic oligomer formed by 1, 4 glycosidic bonds, has a plurality of types of alpha, beta, gamma and the like, has small holes in alpha-CD molecules, can only be used for coating guest substances with small molecules, and has a small application range; the molecular hole of gamma-CD is large, but the production cost is high, the mass production cannot be realized industrially, and the application is limited; the beta-CD has moderate molecular hole, wide application range and low production cost, and is the cyclodextrin product which is used most in industry at present. However, the hydrophobic region of beta-CD and the catalytic activity are limited, so that the application of the beta-CD is limited. Thus, the present invention selects beta-CD for modification, but those skilled in the art will appreciate that alpha-CD and gamma-CD are less effective than beta-CD, but are within the scope of the present invention. The new recognition factors are introduced through chemical modification, so that the CD has higher binding selectivity, namely multiple molecular recognition. Similarly, if a new recognition factor is introduced to the selective modification of cyclodextrin cross-linked resin (CDP for short), the adsorption selectivity of CDP is expected to be further improved.
Modifying cyclodextrin:
according to the invention, an amine-modified CD derivative is adopted to prepare triethylamine-modified beta-cyclodextrin resin TEA-beta-CDP which is used as a catalyst adsorbent in a cyclododecatriene synthesis reaction liquid, and creative research shows that on one hand, a sesquiethyl alkyl aluminum cocatalyst selected in a trimerization reaction system belongs to Lewis acid, and amine modification is adopted, and an amino group and an acidic adsorbate have an acid-base action and can cooperate with beta-CDP to enhance the adsorption effect on active substances; on the other hand, the amino group has the same function with the hydroxyl in the beta-cyclodextrin, can combine with the alkyl aluminum and the titanium tetrachloride, release ethane and hydrogen chloride, and form a complex structure with the main body to enhance the function with the active catalyst component.
beta-CDP: the beta-CDP is prepared by adopting the beta-CD and epichlorohydrin, and the specific preparation method can refer to Komiyama M document (doi: 10.1016/0304-5102(86)85083-0), wherein the feeding ratio of the beta-CD to the epichlorohydrin is 1: 10 (molar ratio), and the mass content of the beta-CD in the prepared beta-CDP resin product is 61.6 percent by adopting gas chromatography analysis.
P-toluenesulfonylated resin Ts- β -CDP: 20.0g of beta-CDP (40-60 mesh) was taken, 100mL of dry pyridine was added and swollen for 0.5h, 25mL of benzene was added and about 25mL of fractions were distilled off under reflux. After cooling, 3.5g of TsCl was added, the mixture was shaken at room temperature for 22h, washed with ethanol several times, extracted with ethanol for 8h, and vacuum-dried at 50 ℃ for 10h to obtain 22.1g of pale yellow particles with a sulfur content of 2.11%.
Triethylamine modified resin TEA- β -CDP: 5.0 gTs-. beta. -CDP 25mL of benzene were added, 20mL of fractions were removed by refluxing, 20mL of triethylamine were added, and refluxing was carried out for 24 h. Cooling, filtering, washing with water and diluted sodium hydroxide solution for 3 times, and washing with water to neutral. After air drying, vacuum drying is carried out for 10h at 50 ℃ to obtain 4.3g of light yellow particles. The TEA-. beta. -CDP resin modified with triethylamine had an acid-base exchange amount of 0.590 mmol/g.
Moving bed adsorption apparatus:
the moving bed adsorption device shown in fig. 1 comprises a moving bed main body, wherein the upper end of the moving bed main body is a modified cyclodextrin cross-linked resin inlet 1, the lower end of the moving bed main body is a resin outlet 2, a plurality of isolation sieve plates 8 are arranged in the moving bed main body along the direction from the resin inlet to the resin outlet, the isolation sieve plates 8 isolate the moving bed main body into a plurality of resin bins, and the bins are respectively filled with resin; the lower part of the moving bed main body is provided with a reaction liquid inlet 3, the entering reaction liquid is fully adsorbed by an adsorption section 5 and flows out through a reaction liquid outlet 4 at the upper part, the reaction liquid inlet adopts a gradually expanding structure and is provided with a shutter 6, and the outlet adopts a micropore plate 7 structure.
The invention adopts the following instruments and conditions:
gas phase analysis conditions: the instrument model is as follows: shimadzu 2010Plus, injection port temperature: 280 ℃; the split ratio is as follows: 30: 1; a chromatographic column: DB-5(30m 0.25mm 0.25 μm); temperature rising procedure: keeping the temperature at 50 ℃ for 2 minutes, heating to 80 ℃ at 5 ℃/min, keeping the temperature for 10 minutes, heating to 300 ℃ at 15 ℃/min, and keeping the temperature for 10 minutes; FID detector temperature: at 300 ℃.
The metal analysis conditions were as follows: the instrument model is as follows: spectra plasma emission spectrometer ICP; and (3) testing conditions are as follows: after the sample is subjected to ultrasonic nitrolysis, the sample is measured, the carrier gas is argon, the collision gas is helium, the flow rate of the plasma gas is 14.5L/min, the flow rate of the auxiliary gas is 1.2L/min, the radio frequency power is 1300W, the flow rate of the atomizer is 0.9L/min, the sampling depth is 8.0mm, the analysis time is 0.1s, and the sample lifting amount is 1.0 mL/min.
The invention relates to the following reagents and samples:
beta-cyclodextrin (more than or equal to 97%): purchased from sigma reagent net;
p-toluenesulfonyl chloride TsCl (AR): purchased from chemical industry of jujude;
triethylamine (≥ 99%), epichlorohydrin (98%), pyridine (99%), benzene (AR), absolute ethanol, sodium hydroxide: purchased from alatin reagent;
d101 macroporous adsorption resin, mixed bed ion exchange resin: purchased from new scientific and technological materials, inc;
cyclododecatriene synthesis reaction solution: the device is produced by itself.
Example 1
The modified cyclodextrin resin (55 mesh) prepared by the foregoing procedure was filled into a moving bed adsorption apparatus as shown in FIG. 1 at a filling density of 0.80g/cm3The modified cyclodextrin cross-linked resin enters the moving bed from an inlet at the upper end of the moving bed main body and is discharged from an outlet at the lower end of the moving bed main body; the reaction liquid enters from the lower inlet of the moving bed main body and flows out from the upper outlet of the moving bed main body.
And continuously introducing the synthetic reaction liquid of the cyclododecatriene into a moving bed device, controlling the flow rate of an inlet to be 40mL/min and the pressure to be 0.2MPa, obtaining the reaction liquid without the active catalyst from an outlet, and entering a subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid after sampling and ICP testing are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 438 | 76 |
| Outlet reaction liquid | 2.2 | 1.3 |
Example 2
The difference from example 1 is that the filled resin is modified with ethylenediamine, and in the synthesis step, the ethylenediamine is used to replace triethylamine, and other conditions are kept unchanged, and the cyclododecatriene synthesis reaction solution is continuously fed into a moving bed device, and the reaction solution without active catalyst is obtained from the outlet and enters a subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid after sampling and ICP testing are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 432 | 75 |
| Outlet reaction liquid | 7.8 | 2.2 |
Example 3
The difference from example 1 is that the filled resin is modified by diethylamine, and triethylamine is replaced by diethylamine in the synthesis step, other conditions are kept unchanged, the synthesis reaction solution of cyclododecatriene is continuously fed into a moving bed device, and the reaction solution without active catalyst is obtained from an outlet and enters a subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid sampled by the national ICP are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 443 | 76 |
| Outlet reaction liquid | 8.9 | 3.5 |
Comparative example 1
The difference from the example 1 is that the filling material adopts beta-cyclodextrin, the cyclododecatriene synthesis reaction solution is continuously introduced into a moving bed device, and the reaction solution without active catalyst is obtained from an outlet and enters a subsequent separation system.
After the reaction liquid is continuously introduced for 20min, the bed layer collapses, the moving bed is blocked, the material can not be normally fed and discharged, and the experiment is terminated.
The early-stage outlet reaction liquid is sampled and tested by ICP to have the following Al and Ti catalyst contents:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 423 | 79 |
| Outlet reaction liquid | 2.0 | <1 |
The comparison experiment result shows that the beta-cyclodextrin group contains a large amount of hydroxyl groups, can effectively combine the components of the aluminum alkyl and the titanium tetrachloride to form a complex, but the untreated beta-cyclodextrin is in a powder state, does not form a magnetic sphere shape, is easy to collapse when used in a moving bed, and causes blockage to cause parking. If the catalyst is used in a slurry bed, centrifugal separation is needed subsequently, and the post-treatment process is complicated and is not suitable for industrial production.
Comparative example 2
The difference from the example 1 is that D101 macroporous adsorption resin is adopted for filling, the cyclododecatriene synthesis reaction liquid is continuously introduced into a moving bed device, and the reaction liquid without active catalyst is obtained from an outlet and enters a subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid after sampling and ICP testing are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 436 | 63 |
| Outlet reaction liquid | 413 | 57 |
As can be seen from the comparative example 2, the Ziegler-Natta catalyst has a complex structure, the metal components in the catalyst cannot be effectively complexed by using the common macroporous adsorption resin, the contents of the catalyst metals Ti and Al in the outlet reaction liquid are still high, and modification are required.
Comparative example 3
The difference from example 1 is that the mixed bed ion exchange resin is used as adsorbent for the packing, the cyclododecatriene synthesis reaction solution is continuously introduced into the moving bed apparatus, and the reaction solution without active catalyst is obtained from the outlet and enters the subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid after sampling and ICP testing are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 425 | 73 |
| Outlet reaction liquid | 289 | 65 |
The mixed bed ion exchange resin has weak adsorption effect on Al and Ti, and the reaction solution after adsorption still contains a large amount of catalyst active components, which is obviously not the same as the modified cyclodextrin resin adsorbent of the invention.
Comparative example 4
The difference from example 1 is that Ts-beta-CDP adsorbent resin is used for filling, the reaction liquid for synthesizing cyclododecatriene is continuously fed into the moving bed device, and the reaction liquid without active catalyst is obtained from the outlet and enters the subsequent separation system.
The contents of Al and Ti catalysts in the outlet reaction liquid after sampling and ICP testing are as follows:
| name (R) | Al/ppm | Ti/ppm |
| Inlet reaction liquid | 436 | 63 |
| Outlet reaction liquid | 132 | 16 |
From the results of the catalyst content test of the outlet reaction solution, it can be seen that the adsorption of beta-CDP which is not modified by amine to the catalyst is not complete, and thus modification and modification are required. The reason is that the amine modified TEA-beta-CDP increases the pore volume of the adsorption resin, enhances the adsorption effect and reduces the probability of bed layer blockage.
From the above examples and comparative examples, it can be seen that the modified triethylamine or diethylamine modified β -cyclodextrin resin provided by the present invention can effectively adsorb Al and Ti metals in the cyclododecatriene synthesis reaction solution, the metal content in the reaction solution after adsorption is less than 9ppm, particularly, the metal content in the reaction solution after adsorption by the β -cyclodextrin resin modified by triethylamine is less than 3ppm, effectively quenching the active components in the reaction solution, and providing a method for post-treatment of the reaction solution using a ziegler-natta catalyst system. On the other hand, the modified triethylamine modified beta-cyclodextrin resin combined moving adsorption bed device provided by the invention is used for post-treatment of cyclododecatriene synthesis reaction liquid, has the adsorption effects of cross flow and convection, improves the contact time of the reaction liquid and the resin, enhances the quenching effect, and effectively solves the problem of separation of light and heavy components.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A post-treatment method of cyclododecatriene synthesis reaction liquid is characterized by comprising the step of effectively quenching a catalyst in the cyclododecatriene synthesis reaction liquid by using modified beta-cyclodextrin cross-linked resin (CDP) as an adsorbent and adopting an adsorption device.
2. The method for post-treating cyclododecatriene synthesis reaction liquid according to claim 1, wherein the adsorbent is an amine-modified β -cyclodextrin cross-linked resin; preferably, the amine is selected from one or more of triethylamine, diethylamine, ethylenediamine and the like; more preferably, the adsorbent is triethylamine modified beta-cyclodextrin resin TEA-beta-CDP.
3. The method for post-treating cyclododecatriene synthesis reaction solution according to claim 1 or 2, wherein the adsorbent is prepared by the following method:
1) synthesis of beta-CDP: preparing beta-CDP by adopting the beta-CD and epoxy chloropropane;
2) preparing a p-toluenesulfonylated resin (Ts- β -CDP) by reacting p-toluenesulfonyl chloride with β -CDP;
3) the prepared Ts-beta-CDP is then reacted with the amine to prepare an amine modified beta-cyclodextrin resin, preferably, the amine is selected from triethylamine to prepare a triethylamine modified beta-cyclodextrin resin (TEA-beta-CDP).
4. The method for post-treating cyclododecatriene synthesis reaction liquid according to claim 3, wherein in the step 1), the charging molar ratio of β -CD to epichlorohydrin is 1: 10.
5. the method for post-treating cyclododecatriene synthesis reaction solution according to claim 3, wherein the preparation method of step 2) is as follows: adding a proper amount of beta-CDP into 4-5 times of dry pyridine for swelling for 0.5h, adding benzene with equal mass, uniformly mixing, and heating, refluxing and steaming to remove a toluene fraction; cooling, adding TsCl, oscillating at room temperature, washing, extracting, and vacuum drying to obtain Ts-beta-CDP light yellow particles; preferably, the mass ratio of the beta-CDP to the TsCl is as follows: oscillating at room temperature for 22h at a ratio of 5-6:1, washing with ethanol for several times, extracting with ethanol for 8h, and vacuum drying at 50 ℃ for 10h to obtain Ts-beta-CDP light yellow particles.
6. The method of claim 5, wherein the beta-CDP has a particle size of 40-60 mesh, and the product Ts-beta-CDP has a sulfur content of 2-3 wt%.
7. The method for post-treating cyclododecatriene synthesis reaction liquid according to claim 3, wherein the preparation method of step 3) is as follows: adding 25mL of benzene into 5.0 gTs-beta-CDP, refluxing to remove 20mL of fraction, adding 20mL of triethylamine, and refluxing for 24 h; cooling, filtering, washing with water and dilute sodium hydroxide solution for 3 times, and washing with water to neutral; air-drying, and vacuum-drying at 50 deg.C for 10 hr to obtain TEA-beta-CDP light yellow granule.
8. The method for post-treating cyclododecatriene synthesis reaction liquid according to claim 1 or 2, wherein the adsorption apparatus employs a moving bed adsorption apparatus as an adsorption carrier.
9. The method for post-treating cyclododecatriene synthesis reaction liquid according to claim 8, wherein the modified cyclodextrin cross-linked resin enters the moving bed from an upper inlet of the moving bed main body and is discharged from a lower outlet of the moving bed main body; the reaction liquid enters from a lower inlet of the moving bed main body and flows out from an upper outlet of the moving bed main body; and a plurality of isolation sieve plates are arranged in the moving bed main body along the direction from the resin inlet to the resin outlet, and the isolation sieve plates isolate the moving bed main body into a plurality of resin bins.
10. The method for post-treating cyclododecatriene synthesis reaction solution according to claim 9, wherein the reaction solution inlet of the moving bed main body has a gradually expanding structure, and the reaction solution outlet has a microplate structure.
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