A membrane catalysis-separation reactor and its preparation method and application

Abstract

The application provides a membrane catalysis-separation reactor and a preparation method and application thereof, the membrane catalysis-separation reactor comprises a catalyst-alumina hollow fiber carrier, an outer surface of the catalyst-alumina hollow fiber carrier is coated with a hafnium-based metal organic framework material film, and an inner surface of the catalyst-alumina hollow fiber carrier is provided with a polymer film of carbon nanofiber wrapped carbon nanosheet; the membrane catalysis-separation reactor uses MOFs material and mixed dimension COFs material with metal catalytic center as a membrane material, forms a novel membrane catalysis reactor with the structure of (MOFs membrane) / (catalyst-alumina hollow fiber carrier) / (COFs membrane) from outside to inside, has double functions of separation and catalysis, can realize conversion of phenyl isocyanate, avoids occurrence of further side reactions, obtains a hydrolysis-resistant stabilizer, and moreover, the membrane catalysis-separation reactor has high catalytic activity and separation stability and a long service cycle.

Description

Technical Field

[0001] This invention belongs to the field of reaction-separation bifunctional catalytic membrane technology, specifically relating to a membrane catalytic-separation reactor, its preparation method, and its application. Background Technology

[0002] Diphenylmethyl diisocyanate (MDI) is an important raw material for polyurethane, and the most mature preparation process currently is the phosgene process. In industrial production, polyamines are first generated by the catalytic reaction of aniline and formaldehyde, then crude MDI is generated through a phosgene reaction, and finally, a product with a specific isomer composition is obtained by distillation.

[0003] Due to the high boiling point of isocyanates at atmospheric pressure and their tendency to self-polymerize at high temperatures, the industry often uses high-vacuum, reduced-pressure side-stream distillation columns or partitioned-wall columns for separation. However, the crude MDI obtained from phosgenation contains not only heavy components such as MDI and polymeric MDI, but also light component impurities such as chlorobenzene, phenyl isocyanate (PI), and HCl. Under high vacuum, these light components accumulate at the top of the distillation column and are condensed before being collected as waste liquid in a storage tank. The main component of the waste liquid is chlorobenzene, along with small amounts of MDI and phenyl isocyanate. The MDI in the waste liquid is not effectively utilized, and the phenyl isocyanate must be removed before the chlorobenzene solvent can be recycled. Therefore, the harmless and resource-efficient treatment of this waste liquid is of great significance.

[0004] N,N-Diphenylcarbodiimide, as the most widely used anti-hydrolysis stabilizer in industry, is applied in polymers such as thermoplastic elastomers, polyurethanes, polyesters, and polyamides. It reacts with carboxylic acids generated from the hydrolysis of ester groups in the polyurethane rubber structure to form acylurea derivatives, thereby eliminating carboxyl groups, preventing the spread of hydrolysis, and acting as a chain-breaking and rejoining agent. Simultaneously, N,N-diphenylcarbodiimide also has a high melting point, allowing for easy mixing with plastics. It not only prevents material hydrolytic aging but also acts as a processing aid, reacting with the acidic substances produced during the material processing to avoid or reduce polymer degradation and improve the processing safety of the polymer.

[0005] In the presence of an effective amount of carbodiimide catalyst, phenyl isocyanate reacts in a liquid nonpolar solvent to convert into N,N-diphenylcarbodiimide, such as the phosphorene compounds and phosphonidine compounds disclosed in CN113474388A. However, because the generated product is not directly separated, the N,N-diphenylcarbodiimide further reacts with phenyl isocyanate to form urea-ketene imide, thus affecting the viscosity, isocyanate content, and isocyanate functionality of the product. Therefore, a novel technology combining separation and catalysis is expected to be key to solving this problem.

[0006] Membrane catalytic separation reactors are a novel technology that integrates catalysis and separation, emerging in recent years. Their numerous catalytic reaction nests and abundant catalytic active sites give them advantages such as simplicity, high efficiency, and low energy consumption, effectively solving the aforementioned problems. Therefore, how to utilize membrane reactors to achieve efficient separation and utilization of impurities in MDI wastewater has become an urgent technical issue to be addressed. Summary of the Invention

[0007] To address the problems existing in the prior art, the present invention aims to provide a membrane catalytic separation reactor, its preparation method, and its application. The membrane catalytic separation reactor first designs a hollow fiber support with catalytic function. Then, considering the characteristics of MDI, chlorobenzene, phenyl isocyanate, and N,N-diphenylcarbodiimide, a MOF (Metal-O-Foil) film is deposited on the outer surface of the hollow fiber support, and a mixed-dimensional COF (Co-Fiber) film is deposited on the inner surface of the hollow fiber support. This simultaneously achieves the separation of MDI, chlorobenzene, and phenyl isocyanate, as well as the reaction of phenyl isocyanate, while avoiding the influence of further reactions of phenyl isocyanate, thus demonstrating good application prospects.

[0008] To achieve this objective, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a membrane catalytic-separation reactor, the membrane catalytic-separation reactor comprising a catalyst-alumina hollow fiber support, the outer surface of the catalyst-alumina hollow fiber support being coated with a hafnium-based metal-organic framework material film, and the inner surface of the catalyst-alumina hollow fiber support being provided with a polymer film of carbon nanofibers encapsulating carbon nanosheets.

[0010] In this invention, the membrane catalysis-separation reactor is first designed with a hollow fiber support with catalytic function. A hafnium-based metal-organic framework material film with high hydrothermal and chemical stability is prepared on the outer surface of the catalyst-alumina hollow fiber support. A polymer film of carbon nanofibers encapsulating carbon nanosheets with high affinity to N,N-diphenylcarbodiimide is assembled on the inner surface, resulting in a novel membrane catalysis-separation reactor with a structure of (MOF membrane) / (catalyst-alumina hollow fiber support) / (mixed-dimensional COF membrane).

[0011] Among them, MOF membranes possess high thermal and chemical stability, as well as a large specific surface area. The metal catalytic centers they provide, along with defects created by chemical coordination, offer abundant substrate sites for catalytic reactions, thereby significantly improving conversion rates. Simultaneously, the long-chain organic framework greatly enhances the hydrothermal stability of MOF materials, ensuring the service life of the catalytic membrane-separation reactor. The specific selectivity of COF membranes guarantees the sieving of specific molecules.

[0012] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. The technical objectives and beneficial effects of the present invention can be better achieved and realized through the following technical solutions.

[0013] As a preferred technical solution of the present invention, the catalyst in the alumina hollow fiber support includes any one or a combination of at least two of the following: dimethylcyclopentadienyl samarium, phosphorene compounds, phosphonic oxides, phosphate esters, phosphine oxides, and metal oxides of acetylacetone. Typical but non-limiting examples of such combinations include: a combination of dimethylcyclopentadienyl samarium and phosphorene compounds, a combination of phosphonic oxides and metal oxides of acetylacetone, etc.

[0014] Preferably, in the catalyst-alumina hollow fiber support, the mass ratio of alumina to catalyst is (0.2-100):1, for example, 0.2:1, 0.3:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0015] Preferably, the hafnium-based metal-organic framework material film includes an Hf-NU-1000 film.

[0016] Preferably, the polymer film containing carbon nanofibers encapsulating carbon nanosheets comprises TpTG. Cl @CNFs film.

[0017] As a preferred technical solution of the present invention, the outer diameter of the catalyst-alumina hollow fiber carrier is 1.5-1.7 mm, such as 1.5 mm, 1.6 mm or 1.7 mm; the inner diameter is 0.8-1 mm, such as 0.8 mm, 0.9 mm or 1 mm. The selection of the above values ​​is not limited to the listed values, and other unlisted values ​​within their respective ranges are also applicable.

[0018] Preferably, the thickness of the hafnium-based metal-organic framework material film is 180-240 nm, such as 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 210 nm, 220 nm, 230 nm or 240 nm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0019] Preferably, the loading of the hafnium-based metal-organic framework material relative to the catalyst-alumina hollow fiber support is 3-280 mg / cm³. 2 For example, 3mg / cm 2 5mg / cm 210mg / cm 2 30mg / cm 2 50mg / cm 2 100mg / cm 2 150mg / cm 2 200mg / cm 2 250mg / cm 2 Or 280mg / cm 2 This applies to, but is not limited to, the listed values; other unlisted values ​​within this range also apply.

[0020] Preferably, the thickness of the polymer film encapsulating carbon nanosheets with carbon nanofibers is 450-540 nm, such as 450 nm, 460 nm, 470 nm, 480 nm, 490 nm, 500 nm, 520 nm, 530 nm or 540 nm, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0021] Preferably, the loading of carbon nanofibers encapsulating carbon nanosheets relative to the catalyst-alumina hollow fiber support is 10-300 mg / cm³. 2 For example, 10 mg / cm 2 30mg / cm 2 50mg / cm 2 100mg / cm 2 150mg / cm 2 200mg / cm 2 250mg / cm 2 Or 300mg / cm 2 This applies to, but is not limited to, the listed values; other unlisted values ​​within this range also apply.

[0022] In this invention, the loading amounts of hafnium-based metal-organic framework (HOM) materials and carbon nanofiber-encapsulated carbon nanosheets are particularly important for the separation performance of the membrane reactor. If the loading amount of HOM is too low, it will lead to excessively large grain boundary gaps, causing membrane defects of varying degrees and thus affecting the membrane separation effect. If the loading amount of HOM is too high, it will cause disordered membrane orientation deposited on the alumina-catalyst hollow fiber support, and will also increase the membrane thickness, resulting in a sharp decrease in the membrane's throughput per unit time. If the loading amount of carbon nanofiber-encapsulated carbon nanosheets is too low, the carbon nanosheets will be incompletely encapsulated, directly exposed, affecting the specific selectivity of the mixed-dimensional COFs membrane. If the loading amount of carbon nanofiber-encapsulated carbon nanosheets is too high, it will be difficult to assemble on the alumina-catalyst hollow fiber support during vacuum filtration, leading to a decrease in the bonding force between the COFs membrane and the support, resulting in COFs membrane detachment.

[0023] In a second aspect, the present invention provides a method for preparing the membrane catalytic separation reactor described in the first aspect, the method comprising the following steps:

[0024] (1) After mixing α-Al2O3 powder, catalyst, ether sulfone polymer and first solvent, the mixture is degassed, spun, phase-inverted and calcined in sequence to obtain catalyst-alumina hollow fiber carrier;

[0025] (2) The hafnium-based metal-organic framework material is mixed with the second solvent and the auxiliary regulator, and then dipped into the outer surface of the catalyst-alumina hollow fiber support. After the reaction, a catalyst-alumina hollow fiber support loaded with hafnium-based metal-organic framework material film is obtained.

[0026] (3) Carbon nanofibers are used to encapsulate carbon nanosheets on the inner surface of a catalyst-alumina hollow fiber carrier supported by a hafnium-based metal-organic framework material film by vacuum filtration coating to obtain a membrane catalysis-separation reactor.

[0027] Steps (2) and (3) are not in any particular order.

[0028] As a preferred technical solution of the present invention, the ether sulfone polymer in step (1) includes polyphenylene ether sulfone.

[0029] Preferably, in step (1), the first solvent comprises a nitrogen heterocyclic compound, preferably N-methyl-2-pyrrolidone.

[0030] Preferably, the mass ratio of α-Al2O3 powder to catalyst in step (1) is (0.2-100):1, for example, 1:5, 1:3, 1:2, 1:1, 2:1, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0031] Preferably, the mass ratio of the α-Al2O3 powder to the polyphenylene ether sulfone in step (1) is 1:(0.05-1), such as 1:0.05, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9 or 1:1, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0032] Preferably, stirring is performed during the mixing process in step (1).

[0033] Preferably, the stirring time is 24-72h, such as 24h, 30h, 36h, 42h, 48h, 54h, 60h, 66h or 72h, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0034] Preferably, the stirring speed is 1000-5000 rpm / min, such as 1000 rpm / min, 2000 rpm / min, 3000 rpm / min, 4000 rpm / min or 5000 rpm / min, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0035] As a preferred technical solution of the present invention, the degassing in step (1) is carried out using a vacuum pump.

[0036] Preferably, the vacuum degree of degassing in step (1) is 0.08-0.1MPa, such as 0.08MPa, 0.09MPa or 0.1MPa, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0037] Preferably, the degassing time in step (1) is 2-6 hours, such as 2 hours, 3 hours, 4 hours, 5 hours or 6 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0038] Preferably, during the spinning process in step (1), the extrusion rate of the raw solution is 16-40 mL / min, such as 16 mL / min, 20 mL / min, 25 mL / min, 30 mL / min, 35 mL / min or 40 mL / min, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0039] In this invention, water is used as both the inner and outer coagulants during the spinning process. The extrusion speed of the inner coagulant is 23-45 mL / min, such as 23 mL / min, 30 mL / min, 40 mL / min or 45 mL / min, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0040] Preferably, the phase conversion in step (1) is carried out in a phase conversion tank, and the distance between the extrusion port of the spinning and the liquid surface of the phase conversion tank is 1.5-3cm, such as 1.5cm, 1.7cm, 1.9cm, 2.1cm, 2.3cm, 2.5cm, 2.7cm or 3cm, but not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0041] In this invention, a catalyst-alumina hollow fiber carrier green body is obtained after phase transformation, and the green body can be dried and then calcined.

[0042] Preferably, the phase transition time in step (1) is 24-48h, such as 24h, 30h, 36h, 42h or 48h, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0043] Preferably, the calcination in step (1) is carried out under a protective atmosphere, including but not limited to nitrogen.

[0044] Preferably, the calcination temperature in step (1) is 800-1000℃, such as 800℃, 850℃, 900℃, 950℃ or 1000℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0045] Preferably, the calcination time in step (1) is 2-5 hours, such as 2 hours, 3 hours, 4 hours or 5 hours, but it is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0046] As a preferred technical solution of the present invention, the preparation steps of the hafnium-based metal-organic framework powder in step (2) include: mixing a hafnium source, benzoic acid and a second solvent to obtain a first solution; mixing 1,4-2,3,5,6-tetracarboxyphenyl-substituted benzene with the second solvent to obtain a second solution; mixing the first solution, the second solution and benzoic acid, and heating to obtain white hafnium-based metal-organic framework powder.

[0047] Preferably, the hafnium source includes hafnium chloride.

[0048] Preferably, the second solvent comprises a formyl dialkyl substituted product, preferably N,N-dimethylformamide.

[0049] Preferably, the auxiliary regulator in step [1] includes formic acid.

[0050] Preferably, the auxiliary regulator is added at a concentration of 0.05-2500 μL / mg Hf-NU-1000, such as 0.05 μL / mg, 1 μL / mg, 10 μL / mg, 100 μL / mg, 500 μL / mg, 1000 μL / mg, 1500 μL / mg, 2000 μL / mg, or 2500 μL / mg, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0051] Preferably, the reaction temperature in step (2) is 70-120°C, such as 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0052] Preferably, the catalyst-alumina hollow fiber support for the hafnium-based metal-organic framework material film loaded in step (2) is washed.

[0053] Preferably, the solvent used for washing includes any one or at least two of acetone, N,N-dimethylformamide, or N,N-diethylformamide.

[0054] As a preferred technical solution of the present invention, the preparation process of the polymer material of carbon nanofibers encapsulating carbon nanosheets in step (3) includes:

[0055] 2,4,6-trihydroxy-1,3,5-benzyltricarboxaldehyde, triaminoguanidine nitrate, cycloalkanes and water were mixed and then subjected to ultrasonication, condensation and heating reaction in sequence to obtain brown carbon nanosheet material.

[0056] Carbon nanosheets and carbon nanofibers were mixed with water to obtain a first dispersion and a second dispersion. The first dispersion and the second dispersion were mixed and stirred vigorously at 50-70°C to obtain a polymer material in which carbon nanofibers encapsulate carbon nanosheets. Then, the unencapsulated polymer was removed by centrifugation.

[0057] Preferably, during the preparation of the nanosheet material, the heating reaction temperature is 100-130℃, such as 100℃, 110℃, 120℃ or 130℃; the time is not less than 3 days, such as 3 days, 3.2 days, 3.4 days, 3.6 days, 3.8 days or 4 days. The selection of the above values ​​is not limited to the listed values, and other unlisted values ​​within their respective ranges are also applicable.

[0058] Preferably, the concentration of carbon nanosheet material in the first dispersion is 0.2-0.4 wt%, such as 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, or 0.4 wt%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0059] Preferably, the concentration of carbon nanofiber material in the second dispersion is 0.03-0.07 wt%, such as 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, or 0.07 wt%, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0060] Thirdly, the present invention provides an application of the membrane catalytic separation reactor described in the first aspect, wherein the membrane catalytic separation reactor is used for the separation of multi-component streams in the production of isocyanates, and simultaneously converts and separates phenyl isocyanate into N,N-diphenylcarbodiimide.

[0061] As a preferred technical solution of the present invention, the application method of the membrane catalysis-separation reactor includes:

[0062] A solution containing phenyl isocyanate, chlorobenzene, and MDI is passed into a reactor containing the membrane catalytic separation reactor. Phenyl isocyanate and chlorobenzene pass through the outer membrane into the catalyst-alumina hollow fiber support, achieving the separation of MDI. Simultaneously, under the action of the catalyst, phenyl isocyanate molecules react to generate N,N-diphenylcarbodiimide. The generated N,N-diphenylcarbodiimide and unreacted chlorobenzene are separated out by the inner membrane.

[0063] Preferably, the separated N,N-diphenylcarbodiimide and unreacted chlorobenzene are separated by distillation.

[0064] In this invention, the membrane catalysis-separation reactor has both separation and catalytic functions. Under the synergistic effect of separation and catalysis, small molecules such as phenyl isocyanate and chlorobenzene continuously enter the interior of the support from the outer membrane, and condense in pairs under the action of the catalyst-alumina hollow fiber support to form N,N-diphenylcarbodiimide. Meanwhile, the strong electrophilic centers provided by the mixed-dimensional COFs membrane on the inner side of the support and the shielding effect provided by the anisotropic one-dimensional carbon nanotubes allow the N,N-diphenylcarbodiimide to be continuously separated out, which not only removes the waste generated in the MDI production process, but also generates an anti-hydrolysis agent widely used in industry, reducing production costs. Furthermore, the chlorobenzene and N,N-diphenylcarbodiimide through the inner COFs membrane can be easily distilled to obtain a widely used anti-hydrolysis stabilizer.

[0065] Preferably, in the solution containing phenyl isocyanate, chlorobenzene and MDI, the content of phenyl isocyanate is 0.1-10 wt%, such as 0.1 wt%, 1 wt%, 2 wt%, 5 wt%, 6 wt%, 8 wt% or 10 wt%, but not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0066] Preferably, the reaction pressure is 0.1-4 MPaG, such as 0.1 MPaG, 1 MPaG, 2 MPaG, 3 MPaG or 4 MPaG, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0067] Preferably, the reaction temperature is 80-250℃, such as 80℃, 100℃, 120℃, 140℃, 160℃, 180℃, 200℃, 220℃ or 250℃, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0068] Preferably, the reaction time is 5-300 min, such as 5 min, 10 min, 60 min, 120 min, 180 min, 240 min or 300 min, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0069] Preferably, the stirring speed of the reaction is 300-2000 rpm / min, such as 300 rpm / min, 500 rpm / min, 1000 rpm / min, 1500 rpm / min, 1800 rpm / min or 2000 rpm / min, but is not limited to the listed values. Other unlisted values ​​within this range are also applicable.

[0070] Compared with the prior art, the present invention has the following beneficial effects:

[0071] (1) The membrane catalysis-separation reactor of the present invention ingeniously integrates the catalyst and the support into a whole, so that the support has both catalytic and supporting functions; at the same time, special selective films are assembled on both the inner and outer sides of the support to prepare a novel membrane catalysis-separation reactor with the structure of (MOF membrane) / (catalyst-alumina hollow fiber support) / (mixed-dimensional COF membrane); the membrane catalysis-separation reactor has both catalytic and separation functions and a large specific surface area, which can provide abundant reaction nests and catalytic active sites, and has long-term stability and a long service life;

[0072] (2) The membrane catalytic separation reactor described in this invention is used to separate multi-component streams in the isocyanate production process, and at the same time converts phenyl isocyanate into N,N-diphenylcarbodiimide and separates it, avoiding further reaction between N,N-diphenylcarbodiimide and phenyl isocyanate; the chlorobenzene and N,N-diphenylcarbodiimide in the inner COFs membrane can be obtained by simple distillation to obtain a widely used anti-hydrolysis stabilizer, realizing the resource utilization and harmless treatment of harmful waste liquid, and eliminating the need for catalyst recovery and regeneration, thus reducing production costs. Attached Figure Description

[0073] Figure 1 This is a scanning electron microscope image of the dimethylcyclopentadienyl samarium-alumina hollow fiber support for the membrane catalytic-separation reactor provided in Example 1 of the present invention.

[0074] Figure 2This is a scanning electron microscope (SEM) image of the Hf-NU-1000 thin film on the outer membrane of the membrane catalytic-separation reactor provided in Example 1 of the present invention.

[0075] Figure 3 This is a scanning electron microscope (SEM) thickness image of the Hf-NU-1000 thin film on the outer membrane of the membrane catalytic-separation reactor provided in Example 1 of the present invention.

[0076] Figure 4 The membrane TpTG of the membrane catalysis-separation reactor provided in Embodiment 1 of the present invention Cl Scanning electron microscopy thickness image of @CNFs thin film. Detailed Implementation

[0077] To better illustrate the present invention and facilitate understanding of its technical solutions, the present invention is further described in detail below. However, the following embodiments are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.

[0078] The following are typical but non-limiting embodiments of the present invention:

[0079] Example 1:

[0080] This embodiment provides a membrane catalysis-separation reactor, which includes a dimethylcyclopentadienyl samarium-alumina hollow fiber support. The outer surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is coated with a 200 nm Hf-NU-1000 thin film, and the inner surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is provided with a 500 nm TpTG layer. Cl @CNFs film.

[0081] The outer diameter of the dimethylcyclopentadienyl samarium-alumina hollow fiber carrier is 1.7 mm, and the inner diameter is 1 mm.

[0082] The mass ratio of alumina to dimethylcyclopentadienyl samarium is 2:1.

[0083] The loading of Hf-NU-1000 material is 150 mg / cm³. 2 ;TpTG Cl The loading of the CNFs material was 100 mg / cm³. 2 .

[0084] The scanning electron microscope (SEM) image of the dimethylcyclopentadienyl samarium-alumina hollow fiber support for the membrane catalytic-separation reactor described in this embodiment is shown below. Figure 1 As shown; the scanning electron microscope (SEM) surface image of the Hf-NU-1000 thin film on the outer membrane of the membrane catalysis-separation reactor is shown below. Figure 2As shown; the scanning electron microscope (SEM) thickness image of the Hf-NU-1000 thin film on the outer membrane of the membrane catalysis-separation reactor is shown below. Figure 3 As shown; the membrane TpTG inside the membrane catalysis-separation reactor Cl Scanning electron microscopy thickness image of the @CNFs thin film is shown below. Figure 4 As shown.

[0085] Depend on Figure 1 It can be seen that the morphology of the dimethylcyclopentadienyl samarium-alumina hollow fiber support in the membrane catalytic separation reactor is tubular, with an inner diameter of 1.0 mm and an outer diameter of 1.7 mm. Figure 2 It can be seen that the Hf-NU-1000 membrane, the outer membrane of the membrane catalytic separation reactor, has a smooth, dense, and defect-free surface, making it a good separation membrane material. (From...) Figure 3 It can be seen that the thickness of the Hf-NU-1000 thin film on the outer membrane of the membrane catalysis-separation reactor is 200 nm. (From...) Figure 4 It can be seen that the thickness of the COFs film in the membrane mixing dimension of the membrane catalysis-separation reactor is 500 nm.

[0086] Preparation Example 1:

[0087] This preparation example provides a method for preparing the membrane catalytic separation reactor described in Example 1, the preparation method comprising the following steps:

[0088] (1) Take 40g of α-Al2O3 powder, 20g of dimethylcyclopentadienyl samarium, 4g of polyphenylene ether sulfone (PESF) and 120g of N-methyl-2-pyrrolidone (NMP), mix them evenly, and stir at 3000rpm / min for 72h at room temperature to obtain casting solution;

[0089] The above-obtained casting solution was transferred into a mold, inverted on a table, and then connected to a vacuum pump. The mold was degassed at 0.1 MPa for 5 hours to remove the casting solution and the gas in the mold.

[0090] Place the degassed mold on the spinning equipment, take another identical mold with a water outlet pipe, fill it with water as a coagulant, and extrude the coagulant at a speed of 35 mL / min to remove air bubbles from the pipe.

[0091] Ensure that the air gap height between the liquid level in the phase inversion tank and the extrusion port of the spinning equipment is 1.5 cm. Then adjust the parameters of the spinning equipment to make the extrusion rate of the spinning solution 25 mL / min and the extrusion speed of the coagulant 30 mL / min. The tubular dimethylcyclopentadienyl samarium-alumina hollow fiber carrier is continuously extruded in a spiral manner and gradually settles in the phase inversion tank to undergo solid phase transformation. After 24 hours, the dimethylcyclopentadienyl samarium-alumina hollow fiber carrier green body is obtained.

[0092] The obtained dimethylcyclopentadienyl samarium-alumina hollow fiber carrier green body was segmented and dried at room temperature; then it was glued to the mold in the calcining furnace and heated to 950°C at a heating rate of 5°C / min under a high-purity nitrogen atmosphere, and calcined at high temperature for 3 hours to obtain a dimethylcyclopentadienyl samarium-alumina hollow fiber carrier with an outer diameter of 1.7 mm and an inner diameter of 1 mm.

[0093] (2) Dissolve 58.5 mg hafnium chloride and 24 mg benzoic acid in 1.8 mL N,N-dimethylformamide, heat at 80 °C for 1 h, and cool to room temperature to obtain the first solution; dissolve 36 mg 1,4-2,3,5,6-tetracarboxyphenyl substituted benzene in 1.8 mL N,N-dimethylformamide to obtain the second solution; mix the first solution, the second solution and 288 mg benzoic acid, and heat at 100 °C for 18 h to obtain white Hf-NU-1000 powder;

[0094] 2g of the above Hf-NU-1000 powder was dispersed in 20mL of N,N-dimethylformamide and sonicated for 10min to obtain a homogeneous solution. This solution was then dip-coated onto the outer surface of a dimethylcyclopentadienyl samarium-alumina hollow fiber carrier sealed at both ends. The carrier was placed in a polytetrafluoroethylene liner with a support and reacted at 100℃ for 18h to obtain a dimethylcyclopentadienyl samarium-alumina hollow fiber carrier loaded with Hf-NU-1000 film. During film growth, 250μL of formic acid was used as a regulator. In post-treatment, the Hf-NU-1000 film was washed three times with acetone and N,N-dimethylformamide respectively before use.

[0095] (3) Dissolve 0.2 g of 2,4,6-trihydroxy-1,3,5-benzenetrialdehyde and 0.3 g of triaminoguanidine nitrate in an aqueous solution of cyclohexane. Transfer the solution to a Parker flask, sonicate for 20 min, and then condense under liquid nitrogen vacuum three times. After the reactants have returned to room temperature, react at 120 °C for 3 days to obtain a brown precipitate TpTG. Cl Wash and dry the product sequentially with N,N-dimethylacetamide, water, and acetone, and set aside for later use.

[0096] Take 0.03g TpTG Cl 0.005 g of CNFs were dispersed in 10 g of water to obtain 0.3 wt% TpTG. Cl Dispersion and 0.05wt% CNFs dispersion; 7mL TpTG Cl The dispersion was added to 25 mL of CNF dispersion and stirred vigorously at 60 °C for 12 h to obtain TpTG via self-assembly. Cl @CNFs;

[0097] Take the above TpTG Cl@10 mL of CNFs dispersion was assembled on the inner side of a dimethylcyclopentadienyl samarium-alumina hollow fiber support loaded with Hf-NU-1000 membrane by vacuum filtration coating, resulting in a membrane catalytic-separation reactor with a structure of (MOF membrane) / (dimethylcyclopentadienyl samarium-alumina hollow fiber support) / (mixed-dimensional COF membrane).

[0098] Example 2:

[0099] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 1, except that the dimethylcyclopentadienyl samarium-alumina hollow fiber support is replaced with a 1-phenylphosphonic-alumina hollow fiber support.

[0100] Preparation Example 2:

[0101] This preparation example provides a method for preparing the membrane catalytic separation reactor described in Example 2. The preparation method is the same as that in Preparation Example 1, except that in step (1), dimethylcyclopentadienyl samarium is replaced with 1-phenylphosphonic acid to obtain 1-phenylphosphonic acid-alumina hollow fiber carrier.

[0102] Example 3:

[0103] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 1, except that the dimethylcyclopentadienyl samarium-alumina hollow fiber support is replaced with acetylacetone zirconium-alumina hollow fiber support.

[0104] Preparation Example 3:

[0105] This preparation example provides a method for preparing the membrane catalytic separation reactor described in Example 3. The preparation method is the same as that in Preparation Example 1, except that in step (1), dimethylcyclopentadienyl samarium is replaced with zirconium acetylacetonate to obtain zirconium acetylacetonate-alumina hollow fiber carrier.

[0106] Example 4:

[0107] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 1, except that: the dimethylcyclopentadienyl samarium-alumina hollow fiber support is replaced with a zirconium acetylacetonate-alumina hollow fiber support, and the mass ratio of alumina to zirconium acetylacetonate is 1:3, and the loading of TpTGCl@CNFs material is 150 mg / cm³. 2 .

[0108] Preparation Example 4:

[0109] This preparation example provides a method for preparing the membrane catalytic separation reactor described in Example 4. The preparation method is the same as that in Preparation Example 1, except that:

[0110] In step (1), 40g of α-Al2O3 powder was replaced with 15g of α-Al2O3 powder, and 20g of zirconium acetylacetonate was replaced with 45g of zirconium acetylacetonate.

[0111] In step (3), 10 mL of TpTGCl@CNFs dispersion is replaced with 20 mL of TpTGCl@CNFs.

[0112] Example 5:

[0113] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 4, except that the acetylacetone zirconium-alumina hollow fiber support is replaced with an acetylacetone zirconium / 1-phenylphosphonic acid-alumina hollow fiber support, and the mass ratio of alumina to acetylacetone zirconium and / or 1-phenylphosphonic acid is 1:1.5:1.5.

[0114] Preparation Example 5:

[0115] This preparation example provides a method for preparing the membrane catalytic separation reactor described in Example 5. The preparation method is the same as that in Preparation Example 4, except that in step (1), 45g of zirconium acetylacetonate is replaced with 22.5g of zirconium acetylacetonate and 22.5g of 1-phenylphosphonic acid, thereby obtaining zirconium acetylacetonate / 1-phenylphosphonic acid-alumina hollow fiber carrier.

[0116] Example 6:

[0117] This embodiment provides a membrane catalysis-separation reactor, which includes a dimethylcyclopentadienyl samarium-alumina hollow fiber support. The outer surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is coated with a 180 nm Hf-NU-1000 thin film, and the inner surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is provided with a 450 nm TpTG layer. Cl @CNFs film.

[0118] The outer diameter of the dimethylcyclopentadienyl samarium-alumina hollow fiber carrier is 1.6 mm, and the inner diameter is 0.9 mm.

[0119] The loading of Hf-NU-1000 material is 3 mg / cm³. 2 ;TpTG Cl The loading of the CNFs material was 10 mg / cm³. 2 .

[0120] The mass ratio of alumina to dimethylcyclopentadienyl samarium is 2:1.

[0121] Example 7:

[0122] This embodiment provides a membrane catalysis-separation reactor, which includes a dimethylcyclopentadienyl samarium-alumina hollow fiber support. The outer surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is coated with a 230 nm Hf-NU-1000 thin film, and the inner surface of the dimethylcyclopentadienyl samarium-alumina hollow fiber support is provided with a 530 nm TpTG layer. Cl @CNFs film.

[0123] The outer diameter of the dimethylcyclopentadienyl samarium-alumina hollow fiber carrier is 1.5 mm, and the inner diameter is 0.8 mm.

[0124] The loading of Hf-NU-1000 material is 280 mg / cm³. 2 ;TpTG Cl The loading of the CNFs material was 300 mg / cm³. 2 .

[0125] The mass ratio of alumina to dimethylcyclopentadienyl samarium is 2:1.

[0126] Example 8:

[0127] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 7, except that the loading of Hf-NU-1000 material is 300 mg / cm³. 2 This results in the Hf-NU-1000 film having a thickness of 235 nm.

[0128] Example 9:

[0129] This embodiment provides a membrane catalysis-separation reactor, which is the same as the membrane catalysis-separation reactor in Example 7, except that TpTG Cl The loading of the CNFs material was 320 mg / cm³. 2 This leads to TpTG Cl The thickness of the @CNFs film is 537 nm.

[0130] Comparative Example 1:

[0131] This comparative example provides a membrane reactor, which is the same as the membrane reactor in Example 1, except that the dimethylcyclopentadienyl samarium-alumina hollow fiber support is replaced with an alumina hollow fiber support, i.e., no catalyst is loaded.

[0132] Comparative preparation example 1:

[0133] This comparative preparation example provides a method for preparing the membrane reactor described in Comparative Example 1. The preparation method is the same as that in Preparation Example 1, except that 20g of dimethylcyclopentadienyl samarium is replaced with 20g of α-Al2O3 powder.

[0134] Effect evaluation:

[0135] The membrane catalytic separation reactors obtained in Examples 1-9 and Comparative Example 1 were used in the treatment of multi-component streams during isocyanate production. The specific application methods are as follows:

[0136] A solution containing phenyl isocyanate, chlorobenzene, and MDI was introduced into a reactor equipped with a membrane catalytic separation reactor. The reactor volume was 1L. The mixture was stirred at 1000rpm / min for 200min at 150℃ and 0.1MPaG. The content of the feed isocyanate was 10wt%. The composition of the product was then analyzed by gas chromatography. The product analysis results are shown in Table 1.

[0137] Table 1

[0138]

[0139] As shown in Table 1, changing the type and ratio of catalysts resulted in good catalytic conversion rates. Comparing Examples 1-3, it was found that zirconium acetylacetonate exhibited the best catalytic effect when the ratio was constant. Comparing Examples 3 and 4, it was found that increasing the proportion of catalyst in the catalyst-alumina hollow fiber support improved the conversion rate of phenyl isocyanate by nearly 5%. Comparing Examples 4 and 5, the composite catalyst significantly improved the conversion rate of phenyl isocyanate compared to the single catalyst, resulting in near-complete conversion when passing through the zirconium acetylacetonate / 1-phenylphosphonic acid-alumina hollow fiber support.

[0140] Comparing Examples 1 and 6, it can be seen that when the loading of Hf-NU-1000 material is relatively small, the thickness of the Hf-NU-1000 film obtained after the solvothermal reaction is relatively small, resulting in a larger transmittance of phenyl isocyanate and TpTG. ClWhen the loading of @CNFs material is low, the selectivity of N,N-diphenylcarbodiimide decreases. Comparative examples 7-9 show that when the loading of Hf-NU-1000 material is too high, the thicker Hf-NU-1000 film reduces the permeability of phenyl isocyanate, thereby reducing the amount of feedstock participating in the catalytic reaction and resulting in a lower catalytic conversion rate; TpTG Cl When the loading of COFs material is too large, the bonding force between it and the carrier decreases, causing some COFs films to detach, which in turn reduces the selectivity of the COFs films.

[0141] In contrast, in Comparative Example 1 without the addition of a catalyst, the conversion rate of phenyl isocyanate was extremely low. The novel catalytic membrane reactor designed in this invention effectively integrates the separation-catalysis-separation process, allowing phenyl isocyanate to continuously generate N,N-diphenylcarbodiimide and be separated out. This not only effectively controls the further reaction of phenyl isocyanate during MDI production but also provides a widely used hydrolysis-resistant stabilizer.

[0142] As can be seen from the above embodiments and comparative examples, the membrane catalytic separation reactor of the present invention, through optimized design of materials and structure, can be used for the separation of multi-component streams in the isocyanate production process, while simultaneously converting and separating phenyl isocyanate into N,N-diphenylcarbodiimide, avoiding further reaction between N,N-diphenylcarbodiimide and phenyl isocyanate. This reactor can achieve a phenyl isocyanate content of 91.4% or higher, preferably 93.4% or higher, through the Hf-NU-1000 membrane; a phenyl isocyanate conversion rate of 88.6% or higher, preferably 90.85% or higher, and up to 99.5%; an N,N-diphenylcarbodiimide selectivity of 87.7% or higher, preferably 90.9% or higher, and up to 99.7%; and an N,N-diphenylcarbodiimide content of 87.3% or higher, preferably 90% or higher, through the mixed-dimensional COFs membrane.

[0143] This invention has been illustrated with the above embodiments to demonstrate the product and detailed method of the invention. However, the invention is not limited to the above-described product and detailed method, meaning that the invention does not necessarily depend on the above-described product and detailed method for implementation. Those skilled in the art should understand that any improvements to the invention, equivalent substitutions for the operation of the invention, additions of auxiliary operations, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A membrane catalytic separation reactor, characterized in that, The membrane catalysis-separation reactor includes a catalyst-alumina hollow fiber support, the outer surface of which is coated with a hafnium-based metal-organic framework material film, and the inner surface of which is provided with a polymer film of carbon nanofibers encapsulating carbon nanosheets. The polymer film containing carbon nanofibers encapsulating carbon nanosheets includes a TpTGCl@CNFs film. 2,4,6-trihydroxy-1,3,5-benzyltricarboxaldehyde, triaminoguanidine nitrate, and cycloalkanes are mixed with water, and then subjected to ultrasonication, condensation, and heating reactions sequentially to obtain a brown carbon nanosheet material. The carbon nanosheet material and carbon nanofiber material are then mixed with water to obtain a first dispersion and a second dispersion. The first dispersion and the second dispersion are mixed and stirred to obtain the polymer material containing carbon nanofibers encapsulating carbon nanosheets.

2. The membrane catalysis-separation reactor according to claim 1, characterized in that, In the catalyst-alumina hollow fiber support, the catalyst includes any one or a combination of at least two of the following: dimethylcyclopentadienyl samarium, phosphorene compounds, phosphonic pyridine oxides, phosphate esters, phosphine oxides, and metal oxides of acetylacetone.

3. The membrane catalysis-separation reactor according to claim 1, characterized in that, In the catalyst-alumina hollow fiber support, the mass ratio of alumina to catalyst is 0.2-100:

1.

4. The membrane catalysis-separation reactor according to claim 1, characterized in that, The hafnium-based metal-organic framework material thin film includes the Hf-NU-1000 thin film.

5. The membrane catalysis-separation reactor according to claim 1, characterized in that, The loading of hafnium-based metal-organic framework materials relative to the catalyst-alumina hollow fiber support is 3-280 mg / cm³. 2 .

6. The membrane catalysis-separation reactor according to claim 1, characterized in that, Compared to the catalyst-alumina hollow fiber support, the loading of carbon nanofiber-encapsulated carbon nanosheets is 10-300 mg / cm³. 2 .

7. The membrane catalysis-separation reactor according to claim 1, characterized in that, The outer diameter of the catalyst-alumina hollow fiber carrier is 1.5-1.7 mm, and the inner diameter is 0.8-1 mm.

8. The membrane catalysis-separation reactor according to claim 1, characterized in that, The thickness of the hafnium-based metal-organic framework material film is 180-240 nm.

9. The membrane catalysis-separation reactor according to claim 1, characterized in that, The thickness of the polymer film in which carbon nanofibers encapsulate carbon nanosheets is 450-540 nm.

10. A method for preparing a membrane catalytic separation reactor as described in any one of claims 1-9, characterized in that, The preparation method includes the following steps: (1) After mixing α-Al2O3 powder, catalyst, ether sulfone polymer and first solvent, the mixture is degassed, spun, phase-inverted and calcined in sequence to obtain catalyst-alumina hollow fiber carrier; (2) The hafnium-based metal-organic framework material is mixed with the second solvent and the auxiliary regulator, and then dipped into the outer surface of the catalyst-alumina hollow fiber support. After the reaction, a catalyst-alumina hollow fiber support loaded with hafnium-based metal-organic framework material film is obtained. (3) Carbon nanofibers are used to encapsulate carbon nanosheets on the inner surface of a catalyst-alumina hollow fiber carrier supported by a hafnium-based metal-organic framework material film by vacuum filtration coating to obtain a membrane catalysis-separation reactor. The preparation process of the polymer material with carbon nanofibers encapsulating carbon nanosheets in step (3) includes: 2,4,6-trihydroxy-1,3,5-benzyltricarboxaldehyde, triaminoguanidine nitrate, cycloalkanes and water were mixed and then subjected to ultrasonication, condensation and heating reaction in sequence to obtain brown carbon nanosheet material. Carbon nanosheets and carbon nanofibers were mixed with water to obtain a first dispersion and a second dispersion. The first dispersion and the second dispersion were mixed and stirred to obtain a polymer material in which carbon nanofibers encapsulate carbon nanosheets.

11. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The ether sulfone polymers mentioned in step (1) include polyphenylene ether sulfone.

12. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, Step (1) The first solvent includes a nitrogen heterocyclic compound.

13. The method for preparing the membrane catalytic separation reactor according to claim 12, characterized in that, Step (1) The first solvent is N-methyl-2-pyrrolidone.

14. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The mass ratio of α-Al2O3 powder to catalyst in step (1) is 0.2-100:

1.

15. The method for preparing the membrane catalytic separation reactor according to claim 11, characterized in that, In step (1), the mass ratio of the α-Al2O3 powder to the polyphenylene ether sulfone is 1:0.05-1.

16. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, Stirring is performed during the mixing process described in step (1).

17. The method for preparing the membrane catalytic separation reactor according to claim 16, characterized in that, The stirring time is 24-72 hours.

18. The method for preparing the membrane catalytic separation reactor according to claim 16, characterized in that, The stirring speed is 1000-5000 rpm / min.

19. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The degassing in step (1) is performed using a vacuum pump.

20. The method for preparing the membrane catalytic separation reactor according to claim 19, characterized in that, The vacuum degree of degassing in step (1) is 0.08-0.1 MPa.

21. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The degassing time in step (1) is 2-6 hours.

22. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, In the spinning process described in step (1), the extrusion rate of the raw solution is 16-40 mL / min.

23. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The phase conversion in step (1) is carried out in a phase conversion tank, and the distance between the extrusion port of the spinning and the liquid surface of the phase conversion tank is 1.5-3cm.

24. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The phase transformation time in step (1) is 24-48 hours.

25. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The calcination in step (1) is carried out under a protective atmosphere.

26. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The calcination temperature in step (1) is 800-1000℃.

27. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The calcination time in step (1) is 2-5 hours.

28. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The preparation steps of the hafnium-based metal-organic framework powder in step (2) include: mixing a hafnium source, benzoic acid and a second solvent to obtain a first solution; mixing 1,4-2,3,5,6-tetracarboxyphenyl-substituted benzene with the second solvent to obtain a second solution; mixing the first solution, the second solution and benzoic acid, and heating to obtain hafnium-based metal-organic framework powder.

29. The method for preparing the membrane catalytic separation reactor according to claim 28, characterized in that, The hafnium source includes hafnium chloride.

30. The method for preparing the membrane catalytic separation reactor according to claim 28, characterized in that, The second solvent includes a formyl dialkyl substituted product.

31. The method for preparing the membrane catalytic separation reactor according to claim 30, characterized in that, The second solvent is N,N-dimethylformamide.

32. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The auxiliary regulator includes formic acid.

33. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The auxiliary regulator is added at a rate of 0.05-2500 μL / mg Hf-NU-1000.

34. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The reaction temperature in step (2) is 70-120℃.

35. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, The catalyst-alumina hollow fiber support for the hafnium-based metal-organic framework material film described in step (2) is washed.

36. The method for preparing the membrane catalytic separation reactor according to claim 35, characterized in that, The solvent used for washing includes any one or at least two of acetone, N,N-dimethylformamide, or N,N-diethylformamide.

37. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, In the process of preparing the carbon nanosheet material, the heating reaction temperature is 100-130℃ and the time is not less than 3 days.

38. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, In the first dispersion, the concentration of carbon nanosheet material is 0.2-0.4 wt%.

39. The method for preparing the membrane catalytic separation reactor according to claim 10, characterized in that, In the second dispersion, the concentration of carbon nanofiber material is 0.03-0.07 wt%.

40. An application of the membrane catalytic separation reactor as described in any one of claims 1-9, characterized in that, The membrane catalytic separation reactor is used for the separation of multi-component streams in the isocyanate production process, and simultaneously converts phenyl isocyanate into N,N-diphenylcarbodiimide and separates it.

41. The application of the membrane catalytic separation reactor according to claim 40, characterized in that, The application methods of the membrane catalytic separation reactor include: A solution containing phenyl isocyanate, chlorobenzene, and MDI is passed into a reactor containing the membrane catalytic separation reactor. Phenyl isocyanate and chlorobenzene pass through the outer membrane into the catalyst-alumina hollow fiber support, achieving the separation of MDI. Simultaneously, under the action of the catalyst, phenyl isocyanate reacts to generate N,N-diphenylcarbodiimide. The generated N,N-diphenylcarbodiimide and unreacted chlorobenzene are separated out by the inner membrane.

42. The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The separated N,N-diphenylcarbodiimide and unreacted chlorobenzene were separated by distillation.

43. The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The solution containing phenyl isocyanate, chlorobenzene and MDI has a phenyl isocyanate content of 0.1-10 wt%.

44. The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The reaction is carried out at a pressure of 0.1-4 MPaG.

45. The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The reaction temperature is 80-250℃.

46. ​​The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The reaction time is 5-300 min.

47. The application of the membrane catalytic separation reactor according to claim 41, characterized in that, The stirring speed for the reaction is 300-2000 rpm / min.

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