CN110252272B - Method and device for continuously preparing olefin epoxidation catalyst on large scale - Google Patents
Method and device for continuously preparing olefin epoxidation catalyst on large scale Download PDFInfo
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Abstract
The invention relates to a method for continuously producing olefin epoxidation catalyst in large scale, which adopts four rotary furnace reactors connected in sequence for continuous reaction preparation, and the preparation steps comprise: (1) respectively heating the four rotary furnaces to reaction temperature, and respectively and continuously introducing reactant steam and/or carrier gas; (2) continuously adding carrier particles into a rotary furnace, and continuously and sequentially carrying out active center vapor deposition, high-temperature treatment, water treatment and silanization treatment; (3) and cooling and collecting outlet materials. The invention also provides a continuous large-scale production device for realizing the preparation method. The method and the device provided by the invention realize large-scale continuous production of the epoxidation catalyst, and the obtained catalyst can be used for industrial production of propylene epoxidation and the like, and has higher activity and yield.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a method and a device for continuously preparing an olefin epoxidation catalyst on a large scale.
Background
The ethylbenzene co-oxidation process (PO/SM) using ethylbenzene hydroperoxide (EBHP) as an oxidant and the CHP process using Cumene Hydroperoxide (CHP) as an oxidant are two important processes for producing Propylene Oxide (PO), the two processes overcome the defects of large corrosion, more sewage and the like of a chlorohydrin method, and have the advantages of low product cost, small environmental pollution and the like. The catalyst used in the two processes is a large-aperture Ti-Si molecular sieve or Ti-SiO2The composite oxide has a reported service life of less than or equal to 1 year, but a set of industries producing 30 ten thousand tons of PO each yearThe annual demand of the catalyst of the device is more than 200 tons, and the using amount of the catalyst is large.
Patents CN1250775A and CN1248579A disclose a process for producing propylene oxide by epoxidation of propylene with ethylbenzene hydroperoxide as an oxidant and a Ti-MCM-41 molecular sieve as a catalyst; U.S. Pat. No. 5,5783167 discloses a hydrothermal synthesis method of titanium-containing mesoporous material Ti-MCM-41, U.S. Pat. No. 5,6323147 discloses a process for preparing propylene oxide by using cumene hydroperoxide as an oxidant and Ti-MCM-41 molecular sieve as a catalyst; japanese Sumitomo also discloses a method for synthesizing a titanium-containing catalyst Ti-MCM-41 with a mesoporous structure; patent CN106582809A discloses a synthesis method of a modified titanium silicalite molecular sieve, the pore diameter of the molecular sieve is more than 10 nm. The method adopts a hydrothermal method to synthesize the catalyst, a template agent with specific molecular weight and structure is used, a reaction kettle is adopted to prepare the catalyst under the high-temperature hydrothermal condition, the hydrothermal kettle is required to be dried, demoulded and roasted after synthesizing the molecular sieve to obtain the molecular sieve raw powder, and the epoxidation catalyst is prepared by molding.
In patents US3829392, US3923843 and US4021454, a SiO with large pores is disclosed2Loading a titanium source on the surface of the carrier by a vapor deposition method or a liquid phase impregnation method, and drying, roasting, silanizing and the like to obtain the titanium-silicon catalyst. However, the vapor deposition method has the following disadvantages: the fixed bed reactor is adopted for intermittent operation, the preparation process is complicated, the operation is complex, frequent switching needs to be carried out among all steps, the process parameters are many and are not easy to control; at the same time, because of the large pores of SiO2The density is low, the heat conductivity coefficient is low, the preparation time of the catalyst is long, and the large-scale production of the catalyst is limited.
In summary, the conventional epoxidation catalyst preparation methods all have the problems of complex operation of the preparation process, low preparation efficiency and difficulty in realizing industrial continuous large-scale production.
Disclosure of Invention
Aiming at the problems, the invention provides a method which is simple to operate and high in preparation efficiency and can be used for industrially and continuously producing epoxidation catalysts on a large scale.
The invention also provides a device for realizing the preparation method of the catalyst.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for continuously preparing olefin epoxidation catalyst in large scale adopts four rotary furnace reactors connected in sequence to prepare the catalyst by continuous reaction, and the preparation steps are as follows:
(1) the raw materials pass through four rotary furnaces which are 1#, 2#, 3# and 4# in sequence, the reaction temperatures are respectively raised to respective reaction temperatures, and respective reactant steam and/or carrier gas are continuously introduced respectively, so that the temperature and gas composition in each furnace are stable;
(2) continuously adding carrier particles into a No. 1 rotary furnace, continuously and sequentially passing through No. 1, No. 2, No. 3 and No. 4 rotary furnaces, and respectively carrying out four reaction steps of active center vapor deposition, high-temperature treatment, water treatment and silanization treatment in each furnace;
(3) and cooling and collecting the outlet material of the 4# rotary furnace to prepare the finished product of the olefin epoxidation catalyst.
The advantages of adopting four rotary furnaces with different temperatures to continuously prepare the catalyst are as follows: SiO carrier2The heat conductivity coefficient is very low, about 7.6W/mK, and if other heating modes are adopted, the heating efficiency is low; meanwhile, the temperature difference of each step of catalyst preparation is large, intermittent operation needs frequent temperature rise and fall, the operation is complex, and the efficiency is low; and four rotary furnaces with different temperatures are adopted, so that reactant steam does not need to be switched, the continuity of catalyst preparation can be realized, and the preparation efficiency of the catalyst is greatly improved.
In the step (1), the reaction temperature of the No. 1 rotary furnace is 150-300 ℃, and introduced gas is titanium compound steam and N2Carrying gas; the concentration of the titanium compound vapor is 5-15% v/v; the titanium compound is selected from one or more of titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate;
in the step (1), the reaction temperature of the 2# rotary furnace is 500-800 ℃, and the introduced gas is N with the purity of more than or equal to 99.5%2；
In the step (1), the reaction temperature of the 3# rotary furnace is 250-400 ℃, and introduced gas is water vapor and N2Carrying gas, wherein the water vapor is obtained by evaporating and gasifying deionized water and does not contain metal ions; the concentration of water vapor in the mixed gas is 5-10% v/v;
in the step (1), the reaction temperature of the 4# rotary furnace is 150-300 ℃, and the introduced gas is organosilane steam and N2A carrier gas, wherein the organosilane is selected from one or more of hexamethyldisilazane, hexamethylchlorosilazane, heptamethylchlorosilazane, trimethylchlorosilane, dimethylchlorosilane, tetramethyldisilazane, dimethyldiethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, and trimethylethoxysilane, preferably hexamethyldisilazane; the concentration of the organosilane vapor in the mixed gas is 10 to 25% v/v.
In the step (1), the mixed gas preheated to the temperature consistent with the reaction temperature of each rotary furnace is respectively introduced into each rotary furnace, and the gas flow is 5-20 m3H; the rotating speed of the rotary furnace is 3-10 r/min. The process conditions are favorable for realizing the uniform distribution of the temperature in each rotary furnace and ensuring the continuity of the preparation process of the catalyst.
In the step (2), the carrier is dried SiO2Materials, preferably silica gel particles; the particle size distribution is 0.2-2 mm, the pore diameter is 5-15 nm, and the specific surface area is 200-500 m2(ii)/g, water content is less than or equal to 2 wt%.
In the step (2), the carrier is added from the inlet of a No. 1 rotary furnace, the feeding speed is constant, and the speed is 100-400 kg/h; the reaction residence time of the carrier in each rotary furnace is 2-6 h.
The carrier particles are conveyed between the rotary furnaces in the step (2) of the invention through a conveying device which is filled with nitrogen atmosphere.
In the step (2) of the invention, in the reaction process, the preheating reactant steam and/or carrier gas of the No. 1-4 rotary furnace respectively needs to be continuously supplemented, so that the temperature and the gas composition in each furnace are stable.
In the step (3) of the invention, the material at the outlet of the 4# rotary furnace is cooled to room temperature and then is screened to obtain the finished catalyst.
An apparatus for preparing the catalyst comprises four rotary furnace reactors connected in sequence, namely a 1# rotary furnace, a 2# rotary furnace, a 3# rotary furnace and a 4# rotary furnace in turn according to the raw material passing sequence; the four rotary furnace reactors are sequentially connected through a spiral feeder, and the inlet of the 1# rotary furnace is provided with the spiral feeder connected with a bin; the inlets of the 1# to 4# rotary furnaces are respectively connected with corresponding evaporation tanks of mixed gas of reactant vapor/carrier gas or directly connected with a carrier gas source; the outlets of the 1# -4# rotary furnaces are respectively connected with a tail gas absorption device; the outlet of the 4# rotary furnace is also connected with a catalyst product bin.
In the device for preparing the catalyst, a 1# to 4# rotary furnace is horizontally and obliquely arranged, the inlet end is high, the outlet end is low, and the horizontal inclination angle is 5-10 degrees; the 4 rotary furnaces have height difference, the installation height is 1# rotary furnace > 2# rotary furnace > 3# rotary furnace > 4# rotary furnace, and the horizontal inclination angle of the screw feeder can be kept to be 20-40 degrees; 4 have the material pushing scraper blade on the rotary furnace inner wall, guarantee that the carrier granule can realize the continuous ejection of compact.
In the device for preparing the catalyst, a 1# rotary furnace is an active center vapor deposition reactor, a 2# rotary furnace is a high-temperature treatment reactor, a 3# rotary furnace is a water treatment reactor, and a 4# rotary furnace is a silanization treatment reactor.
Use of the catalyst for the epoxidation of olefins, preferably for C3～C10Linear olefin, C3～C10Isoolefin, C6～C16Cycloalkene and C6～C16Epoxidation of one or more of the aromatic olefins.
In the present invention, the oxidizing agent in the epoxidation reaction is an organic peroxide, preferably one or more of tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumyl hydroperoxide.
In the present invention, the epoxidation reaction is a liquid phase epoxidation reaction of an olefin and an oxidant.
In the invention, the process conditions of the prepared catalyst for catalyzing the epoxidation of propylene to prepare propylene oxide are as follows: the reaction temperature is 40-120 ℃, the pressure is 2-4.5 MPa, the mol ratio of propylene to oxidant is (3-10): 1, and the mass space velocity is 1-5 h-1(ii) a Purity of propylene>99.5% of water content of the system<100ppm。
In the invention, when the catalyst prepared by amplification is used in a reaction system for preparing propylene oxide by propylene epoxidation, the conversion rate of an oxidant is more than 99.1 percent (the conversion rate is generally characterized by the oxidant due to the excess olefin), and the average selectivity of the catalyst on the propylene oxide is more than 92.7 percent.
The preparation method of the catalyst solves the problems that the step of preparing the catalyst by a hydrothermal method is complicated, the control difficulty is high due to the mismatching of the hydrolysis speeds of the titanium source and the silicon source, and the preparation cost of the catalyst is high due to the use of an organic titanium source and a macromolecular template agent; meanwhile, the method solves the problems of low heat conductivity coefficient of a carrier and long temperature rise and fall time in the preparation of the catalyst by adopting a vapor deposition method in a tubular furnace reactor, which results in low catalyst preparation efficiency. Thereby realizing continuous large-scale production of the epoxidation catalyst.
The invention has the following positive effects:
(1) the preparation method has the advantages that the operation in the preparation process of the catalyst is simple, the problems that one reactor is frequently lifted and lowered and raw materials are frequently replaced in the preparation process of the existing catalyst batch method are solved, the preparation efficiency of the catalyst is greatly improved, the continuous large-scale preparation of the catalyst is realized, and the production efficiency of the catalyst can reach 100-400 kg/h;
(2) the catalyst device is reasonable in design, so that the solid particle reactant can continuously flow among the reactors, and a plurality of steps for preparing the catalyst can be continuously completed under different reaction conditions in sequence;
(3) when the catalyst prepared by the method in a continuous large scale is used for preparing propylene oxide by propylene epoxidation, the conversion rate of an oxidant is more than 99.1 percent, and the average selectivity of the catalyst to the propylene oxide is more than 92.7 percent.
Drawings
FIG. 1 is a schematic view of a catalyst preparation apparatus in the present invention.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The rotary furnace used in the preparation process of the catalyst is produced by Suiyang blue light thermal technology company Limited.
The carrier is silica gel particles after drying treatment, the particle size distribution of the silica gel particles is 0.2-2 mm, the pore diameter is 5-15 nm, and the specific surface area is 200-500 m2Water content less than or equal to 2 wt%, produced by Qingdao gulf Fine chemical Co.
The main raw material information is shown in the following table:
| raw materials | Manufacturer and purity |
| TiCl4 | Aladdin, analytically pure (greater than or equal to 99%) |
| TiF4 | Xilong chemical industry, analytically pure (more than or equal to 99%) |
| Hexamethyldisilazane | Aladdin, analytically pure (greater than or equal to 98%) |
| EBHP | Self-made, 32% -35% (ethylbenzene and ethylbenzene hydroperoxide mixed solution) |
| CHP | Aladdin is more than or equal to 80 percent |
| Propylene (PA) | Tobacco platform Runlong, high purity (more than or equal to 99.995%) |
| N2 | Hewlett packard in Beijing, high purity (more than or equal to 99.995%) |
The determination of the peroxide conversion in the epoxidation reaction was carried out using the following method:
in the epoxidation reaction using the catalysts prepared in each example and comparative example, the conversion of peroxide was measured by iodometry, and a potentiometric titrator used in the titration step was manufactured by Wantong, Switzerland and was model number 916 Ti-Touch.
1. The specific steps for measuring the EBHP/CHP conversion rate by an iodometry method are as follows:
(1) 20mL of glacial acetic acid was added to the Erlenmeyer flask in N2After emptying, adding about 5g of KI;
(2) adding about 1g of analysis sample into the mixture, and preparing a blank sample as a control;
(3) after water sealing, magnetically stirring in the dark, and reacting for 30 min;
(4) adding 50mL of pure water, and adding Na with prepared concentration2S2O3Titrating the solution;
(5) according to Na2S2O3The total number of moles of organic peroxide was calculated from the amount of the solution used, and the conversion thereof was calculated.
Calculated as follows:
wherein, VNa2S2O3Is Na consumed2S2O3Volume of solution, CNa2S2O3For use of Na2S2O3The molarity of the solution;
2. determination of selectivity of epoxidized product in epoxidation reaction
In the epoxidation reaction using the catalysts prepared in each of the examples and comparative examples, the selectivity test of the epoxidized product was conducted by gas chromatography.
The gas chromatography was performed by GC-2010Plus from Shimadzu under the following analytical conditions:
operating conditions for gas chromatography
The content of the epoxidation product is determined by an internal standard method, and the concentration of the epoxidation product is determined by taking DMF (dimethylformamide) as a solvent and DT (dioxane) as an internal standard substance. And (3) preparing standard solutions with different mass concentrations by using DMF as a solvent for a pure epoxidation product serving as an object to be detected, mixing the standard solutions with fixed mass and an internal standard substance respectively, and then carrying out sample injection analysis. For each standard solution, taking the peak area ratio of the epoxidation product to DT in the chromatogram as x, and the mass concentration (%) of the epoxidation product in each standard solution as y, obtaining an internal standard curve y ═ ax-b). times.100%, ensuring R2The coefficient is more than or equal to 0.999. And then, sampling the mixture in the system after reaction, diluting the sample by adopting an internal standard substance solution, and analyzing by using gas chromatography, wherein the mass of the internal standard substance in the diluted solution to be measured is the same as the mass used when a standard curve is drawn, and the total mass of the diluted solution to be measured is the same as the total mass of the sample injection when the standard curve is drawn. Calculated as follows:
of epoxidation productsMass concentration (a × (a)Epoxidation product/ADT) -b) x dilution factor x 100%
Wherein A is the corresponding peak area of the subscript substance in the chromatogram; the dilution factor is the factor of the volume of the solution to be measured after dilution relative to the volume of the sample before dilution.
Epoxide content in the sample is defined as mass concentration of epoxide product x mass of sample
Selectivity of epoxidation product (total mass of epoxidation product/peroxide actually converted) (EBHP, CHP, etc.)
The theoretical amount of the epoxy compound capable of oxidizing olefin by 100%
Example 1
The continuous rotary furnace reactor shown in figure 1 is adopted for preparing the catalyst, the inclination angles of 1# -4# rotary furnace are all set to be 8 degrees, the installation height is 1# > 2# > 3# > 4#, the inclination angle of the screw feeder is 20 degrees, then the screw feeder connected with the rotary furnace is opened, and according to SiO2The feeding speed is set as the rotating speed of the feeder; and after the rotating speed of the feeder is stable, introducing normal-temperature nitrogen from the inlet of the converter, measuring the nitrogen flow at the outlet of the tail gas, and determining the air tightness of the converter and the gas inlet and outlet pipeline.
After the preparation work is finished, starting a converter for heating, and respectively heating the 1# to 4# rotary furnaces to 150 ℃, 500 ℃, 250 ℃ and 150 ℃; the rotating speed of the converter is set to be 5 r/min; passing the reactant vapors and/or N through a preheater2Preheating, introducing reactant steam and/or N into the furnace from 1# to 4#2Preheating to 150 deg.C, 500 deg.C, 250 deg.C and 150 deg.C respectively, wherein the gas introduced into the No. 1 furnace contains TiCl with concentration of 5% v/v4Steam, gas flow 10Nm3H; the gas introduced into the 2# furnace is N with the purity of more than or equal to 99.5 percent2Gas flow rate of 20Nm3H; the gas introduced into the 3# furnace contained steam at a concentration of 5% v/v and a flow rate of 15N m3H; the gas introduced into the No. 4 furnace contained hexamethyldisilazane vapor at a concentration of 10% v/v and a flow rate of 5N m3/h；
After the composition of gas at the outlet of the converter is tested to be consistent with that at the inlet, continuously adding silica gel carrier particles into the inlet of the 1# converter by adopting a spiral feeder at the feeding speed of 100kg/h, sequentially passing the silica gel through 1# to 4# rotary furnaces, and keeping the reaction time in each rotary furnace for 4 h. And respectively carrying out four reaction steps of active center vapor deposition, high-temperature treatment, water treatment and silanization treatment on the silica gel carrier in a furnace, cooling the catalyst in a catalyst bin from an outlet of a No. 4 converter, cooling to room temperature, and then screening and collecting to obtain an epoxidation catalyst finished product, wherein the catalyst is numbered A.
Example 2
The continuous rotary furnace reactor shown in figure 1 is adopted for preparing the catalyst, the inclination angles of 1# -4# rotary furnace are all set to be 5 degrees, the installation height is 1# > 2# > 3# > 4#, the inclination angle of the screw feeder is 30 degrees, then the screw feeder connected with the rotary furnace is opened, and according to SiO2The feeding speed is set as the rotating speed of the feeder; and after the rotating speed of the feeder is stable, introducing normal-temperature nitrogen from the inlet of the converter, measuring the nitrogen flow at the outlet of the tail gas, and determining the air tightness of the converter and the gas inlet and outlet pipeline.
After the preparation work is finished, starting a converter for heating, and respectively heating the 1# to 4# rotary furnaces to 200 ℃, 650 ℃, 300 ℃ and 250 ℃; the rotating speed of the converter is set to be 9 r/min; passing the reactant vapors and/or N through a preheater2Preheating, introducing reactant steam and/or N into the furnace from 1# to 4#2Preheating to 200 deg.C, 650 deg.C, 300 deg.C and 250 deg.C respectively, wherein the gas introduced into the No. 1 furnace contains TiCl with concentration of 10% v/v4Steam, gas flow rate 15Nm3H; the gas introduced into the 2# furnace is N with the purity of more than or equal to 99.5 percent2Gas flow rate of 20Nm3H; the gas introduced into the 3# furnace contained water vapor at a concentration of 7.5% v/v and a flow rate of 20N m3H; the gas introduced into the No. 4 furnace contained hexamethyldisilazane vapor at a concentration of 15% v/v and a flow rate of 10N m3/h；
After the composition of gas at the outlet of the converter is tested to be consistent with that at the inlet, continuously adding silica gel carrier particles into the inlet of the 1# converter by adopting a spiral feeder at the feeding speed of 300kg/h, sequentially passing the silica gel through 1# to 4# rotary furnaces, and keeping the reaction time in each rotary furnace for 3 h. And respectively carrying out active center vapor deposition, high-temperature treatment, water treatment and silanization treatment on the silica gel carrier in a furnace, cooling the catalyst in a catalyst bin from an outlet of a No. 4 converter, cooling to room temperature, screening and collecting to obtain an epoxidation catalyst finished product, wherein the catalyst is numbered B.
Example 3
The reactor of a continuous rotary furnace shown in the attached figure 1 (the reaction gas of a 1# rotary furnace is TiF)4) Preparing the catalyst, setting the inclination angles of the 1# -4# rotary furnace to 10 degrees, setting the installation height to be 1# > 2# > 3# > 4#, setting the inclination angle of the screw feeder to 40 degrees, then starting the screw feeder connected with the rotary furnace, and according to SiO2The feeding speed is set as the rotating speed of the feeder; and after the rotating speed of the feeder is stable, introducing normal-temperature nitrogen from the inlet of the converter, measuring the nitrogen flow at the outlet of the tail gas, and determining the air tightness of the converter and the gas inlet and outlet pipeline.
After the preparation work is finished, starting a converter for heating, and respectively heating the 1# to 4# rotary furnaces to 300 ℃, 800 ℃, 400 ℃ and 300 ℃; the rotating speed of the converter is set to be 3 r/min; passing the reactant vapors and/or N through a preheater2Preheating, introducing reactant steam and/or N into the furnace from 1# to 4#2Preheating to 300 deg.C, 800 deg.C, 400 deg.C and 300 deg.C respectively, wherein the gas introduced into the No. 1 furnace contains TiF with concentration of 15% v/v4Steam, gas flow rate 15Nm3H; the gas introduced into the 2# furnace is N with the purity of more than or equal to 99.5 percent2Gas flow rate of 20Nm3H; the gas introduced into the No. 3 furnace contained water vapor with a concentration of 10% v/v and a flow rate of 20N m3H; the gas fed into furnace # 4 contained hexamethyldisilazane vapor at a concentration of 25% v/v and a flow rate of 10N m3/h；
After the composition of gas at the outlet of the converter is tested to be consistent with that at the inlet, continuously adding silica gel carrier particles into the inlet of the 1# converter by adopting a spiral feeder at the feeding speed of 400kg/h, sequentially passing the silica gel through 1# to 4# rotary furnaces, and keeping the reaction time in each rotary furnace for 6 h. And respectively carrying out four reaction steps of active center vapor deposition, high-temperature treatment, water treatment and silanization treatment on the silica gel carrier in a furnace, cooling the catalyst in a catalyst bin from an outlet of a No. 4 converter, cooling to room temperature, and then screening and collecting to obtain an epoxidation catalyst finished product, wherein the catalyst is numbered C.
Comparative example 1
The Ti-MCM-41 epoxidation catalyst is prepared by a hydrothermal synthesis method.
Preparing 25 wt% tetraethylammonium hydroxide (TEAOH) aqueous solution, and dropwise adding 35.0g of tetraethylammonium orthosilicate (TEOS) into 29.7g of tetraethylammonium hydroxide aqueous solution while stirring to form mixed solution A; dropwise adding 1.2g of tetrabutyl titanate (TBOT) into 25.1g of Triethanolamine (TEA) under stirring to form a mixed solution B; dropwise adding the mixed solution B into the mixed solution A under stirring, stirring for 1 hr, and dropwise adding 11.0g deionized water (H)2O) for 0.5H, the ratio of the amounts of the substances formed is 1.0TEOS:0.02TBOT:0.3TEAOH:1TEA:11H2A homogeneous solution of O. Aging at room temperature in dark place for 48 h; drying by air blast for 24h at 100 ℃ in an air blast drying oven to obtain dry white blocky particles; carrying out rotary heat treatment at 180 ℃ for 4h in a homogeneous reactor after grinding; and finally, roasting the mixture in a muffle furnace at the heating rate of 5 ℃/min for 10 hours at the temperature of 600 ℃ to remove the template agent, and obtaining the Ti-MCM-41. And then silanizing the roasted molecular sieve, wherein the silanizing temperature and the dosage of a silanizing reagent are the same as those of a 4# converter in the embodiment 1, preparing Ti-MCM-41 epoxidation catalyst raw powder after the silanizing treatment, adding silica sol for extruding and molding, and recording the molded catalyst as DB-1. The DB-1 catalyst preparation process is intermittent preparation, the total time required by each step is about 100 hours, and the preparation amount of a single-batch catalyst is difficult to amplify because the hydrolysis reaction process needs to be accurately controlled.
Comparative example 2
Adopts a conventional single reactor and a four-step batch method to prepare the epoxidation catalyst.
50kg of SiO2Adding the carrier into a tubular reactor with the inner diameter of 400mm, setting the temperature of a heating furnace to 350 ℃, keeping the temperature for 20 hours, balancing the temperature of a silica gel bed layer, then treating the silica gel bed layer at 350 ℃ for 5 hours, and cooling the treated silica gel bed layer after the treatment is finished; after the treatment is finished, the temperature of the reaction tube is sequentially raised to 200 ℃, 650 ℃, 300 ℃ and 180 ℃, and Ti active centers are respectively carried outDeposition process, roasting process, water treatment process and silanization treatment. Wherein the Ti center deposition process adopts N2With TiCl4Mixing the steam and then entering a reactor for reaction, wherein TiCl4The dosage is 17 kg; the steam treatment process is to mix nitrogen and steam and then enter a reactor, and the total consumption of water is 20 kg; the silanization treatment process is to mix nitrogen and hexamethyldisilazane steam and then enter a reactor, and the dosage of the silanization reagent is 30 kg. The time required to complete a complete preparation of 50kg of catalyst was 120 h. After the reaction was complete, the tubular reactor was cooled to room temperature and disassembled to obtain the epoxidation catalyst, which was designated DB-2.
Example 4
Respectively filling the catalysts of examples 1-3 and comparative examples 1 and 2 in a fixed bed reactor with the inner diameter of 30mm, wherein the filling amount of the catalyst is 20 g; with propylene (C)3H6) Taking EBHP as an oxidant to perform epoxidation reaction, wherein the molar ratio of propylene to the EBHP raw material is 6:1, and the feeding mass space velocity is 3h-1The reaction pressure was 4.0MPa and the reaction temperature was 60 ℃. The reaction results are shown in Table 1.
As can be seen from Table 1, among the catalysts prepared in the respective examples and comparative examples, the epoxidation catalysts A, B and C prepared in continuous bulk according to the present invention have higher propylene oxide selectivity; meanwhile, the catalysts obtained in the examples of the invention are all significantly higher than the comparative examples in terms of EBHP conversion. The catalyst prepared by the invention can be used for propylene epoxidation reaction with EBHP as an oxidant, and has better reaction performance.
Table 1 results of the reaction of example 4
Example 5
Respectively filling the catalysts of examples 1-3 and comparative examples 1-2 in a fixed bed reactor with an inner diameter of 30mm, wherein the filling amount of the catalyst is 20 g; c3H6The molar ratio to CHP was 8: 1, the space velocity of the feeding mass is 5h-1The reaction pressure is 4MPa, and the reaction temperature is 80 ℃. The reaction results are shown in Table 2.
As can be seen from Table 2: the epoxidation catalyst A, B and C prepared by the method in continuous and large-scale has higher propylene oxide selectivity; meanwhile, the catalysts obtained in the examples of the present invention are all significantly higher than the comparative examples in terms of CHP conversion. The catalyst prepared by the invention can be used for propylene epoxidation reaction with CHP as an oxidant, and has better reaction performance.
Table 2 reaction results of example 5
From the above results, it can be seen that the catalyst preparation method of the present invention can achieve the continuity of different preparation steps of the catalyst by controlling the temperature of the converter reactor, the internal gas composition and the residence time of the carrier, and the prepared catalyst has good activity and selectivity for olefin epoxidation reaction.
Claims (16)
1. A method for continuously preparing olefin epoxidation catalyst in large scale is characterized in that the method adopts four rotary furnace reactors connected in sequence to continuously prepare the catalyst, and the preparation steps are as follows:
(1) the raw materials pass through four rotary furnaces which are 1#, 2#, 3# and 4# in sequence, the reaction temperatures are respectively raised to respective reaction temperatures, and respective reactant steam and/or carrier gas are continuously introduced respectively, so that the temperature and gas composition in each furnace are stable;
(2) continuously adding carrier particles into a No. 1 rotary furnace, continuously and sequentially passing through No. 1, No. 2, No. 3 and No. 4 rotary furnaces, and respectively carrying out four reaction steps of active center vapor deposition, high-temperature treatment, water treatment and silanization treatment in each furnace;
(3) cooling and collecting the outlet material of the 4# rotary furnace to prepare and obtain a finished product of the olefin epoxidation catalyst;
wherein, the reactors of the four rotary furnaces in the step (1) are sequentially connected through screw feeders, and the inlet of the 1# rotary furnace is provided with the screw feeder connected with a bin; the inlets of the 1# -4# rotary furnaces are respectively connected with the evaporation tanks of the corresponding mixed gas of the reactant vapor and the carrier gas, or directly connected with a carrier gas source; the outlets of the 1# -4# rotary furnaces are respectively connected with a tail gas absorption device; the outlet of the No. 4 rotary furnace is also connected with a catalyst product bin;
wherein, the reactant vapor in the step (1) is titanium compound vapor;
wherein, the carrier particles in the step (2) are SiO after drying treatment2A material; the atmosphere of the No. 3 water treatment is water vapor and N2Carrying gas; introducing organosilane vapor and N into the 4# silanization treatment2And (4) a carrier gas.
2. The method for preparing a catalyst according to claim 1,
in the step (1), the reaction temperature of the No. 1 rotary furnace is 150-300 ℃, and introduced gas is titanium compound steam and N2Carrying gas; the concentration of the titanium compound vapor is 5-15% v/v; the titanium compound is selected from one or more of titanium tetrafluoride, titanium tetrachloride, titanium tetrabromide, tetraethyl titanate, tetrapropyl titanate and tetrabutyl titanate;
in the step (1), the reaction temperature of the 2# rotary furnace is 500-800 ℃, and the introduced gas is N with the purity of more than or equal to 99.5%2；
In the step (1), the reaction temperature of the 3# rotary furnace is 250-400 ℃, and the introduced water vapor is deionized water and is obtained through evaporation and gasification, and does not contain metal ions; the concentration of water vapor in the mixed gas is 5-10% v/v;
in the step (1), the reaction temperature of the 4# rotary kiln is 150-300 ℃, and organosilane in the introduced gas is selected from one or more of hexamethyldisilazane, hexamethylchlorosilazane, heptamethylchlorosilazane, trimethylchlorosilane, dimethylchlorosilane, tetramethyldisilazane, dimethyldiethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane and trimethylethoxysilane; the concentration of the organosilane vapor in the mixed gas is 10 to 25% v/v.
3. The method for preparing a catalyst according to claim 2, wherein the organosilane introduced into the gas introduced into the # 4 rotary kiln in the step (1) is hexamethyldisilazane.
4. The method for preparing the catalyst according to claim 1, wherein the mixed gas preheated to the temperature consistent with the reaction temperature of each rotary kiln in the step (1) is respectively introduced into each rotary kiln, and the gas flow rate is 5-20 Nm3H; the rotating speed of the rotary furnace is 3-10 r/min.
5. The method for preparing a catalyst according to claim 1, wherein the carrier in the step (2) is silica gel particles; the particle size distribution is 0.2-2 mm, the pore diameter is 5-15 nm, and the specific surface area is 200-500 m2(ii)/g, water content is less than or equal to 2 wt%.
6. The preparation method of the catalyst according to claim 1, wherein the carrier in the step (2) is added from the inlet of a No. 1 rotary kiln at a constant feeding speed of 100-400 kg/h; the reaction residence time of the carrier in each rotary furnace is 2-6 h.
7. The method of claim 1, wherein in the step (2), the preheating reactant vapor and/or the carrier gas of each rotary kiln # 1 to # 4 is continuously supplemented during the reaction to stabilize the temperature and the gas composition in each rotary kiln.
8. The preparation method of the catalyst according to claim 1, wherein the material at the outlet of the 4# rotary kiln in the step (3) is cooled to room temperature and then is screened to obtain the finished catalyst.
9. An apparatus used in the catalyst production method according to any one of claims 1 to 8, characterized in that the apparatus comprises four sequentially connected rotary kiln reactors, which are, in the order of feed passage, a # 1 rotary kiln, a # 2 rotary kiln, a # 3 rotary kiln and a # 4 rotary kiln; the four rotary furnace reactors are sequentially connected through a spiral feeder, and the inlet of the 1# rotary furnace is provided with the spiral feeder connected with a bin; the inlets of the 1# -4# rotary furnaces are respectively connected with the evaporation tanks of the corresponding mixed gas of the reactant vapor and the carrier gas, or directly connected with a carrier gas source; the outlets of the 1# -4# rotary furnaces are respectively connected with a tail gas absorption device; the outlet of the 4# rotary furnace is also connected with a catalyst product bin.
10. The apparatus of claim 9, wherein the # 1- # 4 rotary kiln is horizontally tilted with a high inlet end and a low outlet end, and a horizontal tilt angle of 5-10 °; the 4 rotary furnaces have height difference, the installation height is 1# rotary furnace > 2# rotary furnace > 3# rotary furnace > 4# rotary furnace, and the horizontal inclination angle of the screw feeder can be kept to be 20-40 degrees; the inner walls of the 4 rotary furnaces are provided with pushing scrapers.
11. The apparatus according to claim 9 or 10, wherein the rotary kiln # 1 is an active center vapor deposition reactor, the rotary kiln # 2 is a high temperature treatment reactor, the rotary kiln # 3 is a water treatment reactor, and the rotary kiln # 4 is a silylation treatment reactor.
12. Use of a catalyst prepared by a method of preparing a catalyst according to any one of claims 1 to 8, or a catalyst prepared by an apparatus for preparing a catalyst according to any one of claims 9 to 11, for the epoxidation of an olefin.
13. Use of a catalyst according to claim 12, characterized in that the catalyst is used in C3～C10Linear olefin, C3～C10Isoolefin, C6～C16Cycloalkene and C6～C16Epoxidation of one or more of the aromatic olefins.
14. Use of a catalyst according to claim 12 or 13, characterized in that the oxidant in the epoxidation reaction is an organic peroxide.
15. Use of a catalyst according to claim 14, wherein the oxidant in the epoxidation reaction is one or more of tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumyl hydroperoxide.
16. Use of a catalyst according to claim 12 or 13, wherein the epoxidation reaction is a liquid phase epoxidation of an olefin with an oxidant.
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