CN107602510B - Preparation method and production equipment of propylene oxide - Google Patents
Preparation method and production equipment of propylene oxide Download PDFInfo
- Publication number
- CN107602510B CN107602510B CN201710946598.7A CN201710946598A CN107602510B CN 107602510 B CN107602510 B CN 107602510B CN 201710946598 A CN201710946598 A CN 201710946598A CN 107602510 B CN107602510 B CN 107602510B
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- propylene oxide
- propylene
- microreactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method and production equipment of propylene oxide, which relate to the field of preparation of propylene oxide, and comprise the step of introducing liquid propylene, hydrogen peroxide and a titanium silicalite molecular sieve into a microreactor for oxidation reaction.
Description
Technical Field
The invention relates to the field of preparation of propylene oxide, in particular to a preparation method and production equipment of propylene oxide.
Background
Propylene Oxide (PO) is a colorless, transparent, low-boiling and flammable liquid at normal temperature and pressure, and has an ether-like odor. Freezing point-112.13 deg.C, boiling point 34.24 deg.C, density 0.8309/cm3(20 ℃ C.), a refractive index (nD)1.3664, and a viscosity (25 ℃ C.) of 0.28 mPas. Partially miscible with water, 40.5% by mass of water solubility at 20 ℃; the water has a solubility in propylene oxide of 12.8 mass%, is miscible with ethanol, diethyl ether, and forms binary azeotropes with methylene chloride, pentane, pentene, cyclopentane, cyclopentene, etc.
Currently, industrial production methods of PO mainly include chlorohydrin method and co-oxidation method (Halcon method), and account for more than 90% of the global PO yield. The chlorohydrin process has the problems that the production consumes much chlorine, the equipment is seriously corroded, and the discharged industrial wastewater containing calcium chloride and organic chloride causes serious pollution to the environment. The indirect oxidation method solves the problem of environmental pollution of the chlorohydrin method, but has the defects of large investment, long flow, more co-products and good raw material supply and product sale. With the increasing demand of propylene oxide, the improvement of the existing production process has become an important research topic of attention. Many enterprises have been exploring direct oxidation processes, i.e., processes for producing propylene oxide by direct oxidation of propylene with air or oxygen, over the last decade, but unfortunately the propylene conversion is less than 20% and the propylene oxide selectivity is only 40-60%, which results in a significant reduction in the potential for industrial development of the process.
H2O2The direct oxidation method (HPPO method) is characterized in that a titanium silicalite TS-1 is used as a catalyst, methanol is used as a solvent, propylene and hydrogen peroxide enter a catalyst bed layer in a liquid phase system under proper reaction conditions to carry out oxidation reaction to produce propylene oxide and water, and the method mainly comprises the steps of epoxidation, propylene oxide separation, propylene oxide refining, solvent separation, propylene circulation and the like. The process flow is relatively simple, no by-product is generated, the subsequent treatment equipment and facilities of the product are reduced, the whole production process basically has no pollution, the process belongs to a novel environment-friendly production process, the wastewater discharge can be reduced by 70-80%, and the energy consumption is also reduced by 35%, so the development prospect of the method is generally seen by people. Currently, two techniques are developed for the industrial HPPO method, one developed by BASF and Dow chemical (Dow) and the other developed by the winning group (Degussa) and wood (Uhde). I.e. US6610865B2, discloses a specially made tubular reactor with a series of parallel arranged heat exchange plates between which a fixed bed of catalyst is arranged, after which the heterogeneous mixture is continuously passed through the catalyst layer in a downward flow pattern while the heat of reaction is removed by cooling water. The plate spacing is preferably l0-30mm and the cooling water is preferably passed through the heat exchanger plates in cocurrent flow. The catalyst is preferably coated on the outer surface of the heat exchanger plates, which is advantageous for reducing the plate spacing. On the premise of fixed reactor size, the total heat exchange area can be increased. The temperature distribution in the reactor is uniform, and the phenomena of blockage and structure are not easy to occur, so that the equipment cost can be reduced.
The difference between these two techniques is mainly the reactor type of the epoxidation reaction, which is not too different per se, and both are gradually maturing in the context of the development of catalytic technology, in particular TS-1.
The Chinese patent application No. 201310522487.5 proposes a method for producing propylene oxide by catalytic distillation, which comprises the following steps: feeding propylene, aqueous hydrogen peroxide and an organic solvent into a catalytic rectifying tower, and contacting with an oxidation catalyst under an epoxidation condition, wherein gas-phase materials discharged from the top of the catalytic rectifying tower are condensed and subjected to gas-liquid separation to obtain a gas part mainly containing propylene and a liquid part mainly containing the organic solvent and epoxypropane; separating out the propylene oxide and the organic solvent from the gas part, and returning the separated propylene oxide and the separated organic solvent to the rectifying tower; and (3) carrying out gas stripping on the liquid part, separating out propylene, and refining the obtained material without propylene to obtain the refined propylene oxide.
So far, in many methods developed and developed by a new propylene oxide process, a catalytic oxidation system consisting of a titanium silicalite molecular sieve and dilute hydrogen peroxide has the advantages of excellent catalytic performance, mild reaction conditions, no pollution and the like, and has the greatest industrial prospect. In particular, the process uses H202The byproduct is water after being used as the oxidant, does not pollute the environment, and is a good environment-friendly process. However, since propylene and hydrogen peroxide are not mutually soluble, a mixed solvent which can dissolve propylene and hydrogen peroxide is needed to be found. Currently, a large amount of methanol is industrially used as a mixed solvent of the two. The method can greatly improve the conversion rate of the reactant propylene and the yield of the product propylene oxide, but the use of the mixed solvent methanol makes the purification of the product and the recovery of the solvent methanol difficult, and the cost is increased.
In conclusion, the reactors for preparing propylene oxide by direct oxidation of propylene all adopt fixed bed or slurry bed technology, and have the defects of difficult recovery of solvent methanol, incapability of timely removing reaction heat, large investment on reactor equipment, difficult regeneration of catalyst, explosion possibly caused by high-concentration peroxide oxidation and the like.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a method for preparing propylene oxide, which adopts direct oxidation of propane to prepare propylene oxide, so as to relieve the problems that the prior reactors for preparing propylene oxide by direct oxidation of propylene all adopt fixed bed or slurry bed technology, and the problems of difficult recovery of solvent methanol, untimely removal of reaction heat, large investment on reactor equipment, difficult regeneration of catalyst and possible explosion caused by oxidation of high-concentration peroxide exist.
The second purpose of the invention is to provide a propylene oxide production facility which can continuously carry out the reaction, is safe and effective and does not generate waste in the whole process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of propylene oxide comprises the step of introducing liquid propylene, hydrogen peroxide and a titanium silicalite molecular sieve into a microreactor to carry out oxidation reaction.
Further, firstly, liquid propylene is introduced into the microreactor, and then the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is introduced into the microreactor to carry out oxidation reaction to produce propylene oxide.
Further, the reaction conditions in the microreactor are as follows: the reaction temperature is 30-90 ℃, the reaction pressure is 2.0-4.5MPa, and the mass space velocity of the liquid propylene is 1.0-15h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-6, and the reaction time is 0.1-1.5 h; preferably: the reaction temperature is 40-80 ℃, the reaction pressure is 2.5-4.5MPa, and the mass space velocity of the liquid propylene is 2.0-14h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-4, and the reaction time is 0.2-1.3 h.
Further, the particle size of the titanium silicalite molecular sieve is less than 260 μm; preferably less than 60 μm.
Furthermore, in the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve, the mass fraction of the titanium silicalite molecular sieve is 2-30%, preferably 5-25%.
Further, a step of separating a product after the oxidation reaction is completed;
preferably, the product is separated and then subjected to a catalyst regeneration step;
preferably, the catalyst regeneration comprises a process of supercritical extraction of the catalyst;
preferably, the process conditions of the method for supercritical extraction of the catalyst are as follows: the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-15), extracting for 5-100 min; preferably, the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-4), extracting for 15-40 min;
preferably, the extraction solvent is propylene, acetone or a hydrocarbon compound; propylene is preferred.
An epoxy propane production device comprises a micro-reactor.
Furthermore, a plurality of microreactors are arranged, the microreactors form a microreactor group through series connection, and the microreactor group forms a microreactor array through parallel connection;
preferably, the number of the microreactors in each group of microreactor groups is 1-10;
preferably, the number of sets of microreactor groups in the microreactor array is 1-50 sets.
Further, the microreactor array is connected with a flash tank for product separation, a middle outlet of the flash tank for discharging propylene oxide is connected with a propylene oxide refining system, and a bottom outlet of the flash tank for discharging reactants is connected with an inlet of the microreactor array;
preferably, the micro-reactor array is connected with the flash tank through a buffer tank.
Furthermore, the production equipment also comprises a mixing tank for mixing hydrogen peroxide and a catalyst, and an outlet of the mixing tank is connected with an inlet of the microreactor array;
preferably, the inlet of the mixing tank is connected to the bottom outlet of the flash tank.
Furthermore, a branch pipeline is arranged between the mixing tank and the flash tank, and a supercritical extraction regenerator for regenerating the catalyst is arranged on the branch pipeline;
preferably, the upper outlet of the supercritical extraction regenerator is connected with a fractionating tower, and the fractionating tower is connected with a diesel oil storage tank.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the propylene oxide provided by the invention comprises the steps of putting liquid propylene, hydrogen peroxide and the titanium silicalite molecular sieve into a microreactor together, so that the liquid propylene is directly contacted with the hydrogen peroxide to carry out oxidation reaction under the catalytic action of the titanium silicalite molecular sieve, and the propylene oxide is obtained. Wherein, the hydrogen peroxide reacts with the liquid propylene under the condition of no solvent, thereby reducing the use of the solvent, avoiding the pollution of the solvent to the environment and solving the problem of solvent recovery. In addition, the method for preparing the propylene oxide by directly oxidizing the propylene is a regeneration process for carrying out oxidation reaction by continuous solid catalyst catalysis and liquid phase direct contact, not only can keep the activity and the better selectivity of the catalyst, but also can effectively prolong the service life of the catalyst, does not need hydrogen regeneration, does not need shutdown to regenerate the catalyst, and effectively solves the regeneration problem of the catalyst. The method provided by the invention is carried out in the microreactor, so that the reaction time is short, the heat extraction is rapid, the investment on reaction equipment is small, the method is safe, and the problems of regeneration and safety of the deactivated catalyst can be effectively solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a production apparatus provided in embodiment 14 of the present invention.
Icon: 10-a microreactor array; 11-a microreactor; 20-mixing tank; 30-a buffer tank; 40-a flash tank; a 50-propylene oxide refining system; 60-a catalyst tank; 70-supercritical extraction regenerator; 80-a distillation column; 90-diesel oil storage tank.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
One aspect of the invention provides a preparation method of propylene oxide, which comprises the step of introducing liquid propylene, hydrogen peroxide and a titanium silicalite molecular sieve into a microreactor to perform oxidation reaction.
The preparation method of the propylene oxide provided by the invention comprises the steps of putting liquid propylene, hydrogen peroxide and the titanium silicalite molecular sieve into a microreactor together, so that the liquid propylene is directly contacted with the hydrogen peroxide to carry out oxidation reaction under the catalytic action of the titanium silicalite molecular sieve, and the propylene oxide is obtained. Wherein, the hydrogen peroxide reacts with the liquid propylene under the condition of no solvent, thereby reducing the use of the solvent, avoiding the pollution of the solvent to the environment and solving the problem of solvent recovery. In addition, the method for preparing the propylene oxide by directly oxidizing the propylene is a regeneration process for carrying out oxidation reaction by continuous solid catalyst catalysis and liquid phase direct contact, not only can keep the activity and the better selectivity of the catalyst, but also can effectively prolong the service life of the catalyst, does not need hydrogen regeneration, does not need shutdown to regenerate the catalyst, and effectively solves the regeneration problem of the catalyst. The method provided by the invention is carried out in the microreactor, so that the reaction time is short, the heat extraction is rapid, the investment on reaction equipment is small, the method is safe, and the problems of regeneration and safety of the deactivated catalyst can be effectively solved.
A microreactor refers to a three-dimensional building block made in a solid matrix that can be used to perform chemical reactions by means of special microfabrication techniques. The average size of the width of the internal unit structure is in micron order, and usually contains fluid channels with equivalent diameter of tens to hundreds of microns, while the overall size is in centimeter order. At present, a plurality of novel microreactors can realize heterogeneous catalytic reaction, allow solid catalyst with the particle size less than 350 microns to enter the microreactor for catalytic reaction, avoid the condition of blocking the inside of the microreactor, and have higher requirements on the strength of catalyst particles.
For molecular level reactions, the microreactor is very large in volume, so that the influence on the reaction mechanism and the reaction kinetic characteristics is small, and the main effects are enhancement of mass and heat transfer processes and improvement of fluid flow modes. Thus, good mixing contact is achieved for some substances that are incompatible with each other, without the need for solvents.
The structure characteristics of the micro-reactor are completely different from those of the conventional reactor, so that the micro-reactor has unique advantages in the chemical and chemical practical application, and the advantages are mainly reflected in the following points:
(1) no amplification effect: most of the fine chemical reactions adopt batch reactors, and when the process is enlarged from a small test process to a large reaction kettle, the process conditions generally need to be groped for a period of time due to different mass transfer/heat transfer efficiencies, and the process is enlarged to large production after the pilot plant test. The amplification process of the microreactor is realized by increasing the number of the microchannels instead of the characteristic size of the microchannels.
(2) The reaction time can be accurately controlled: in a conventional one-pot reaction, the reactants are usually added dropwise gradually in order to prevent the reaction from being too vigorous, which results in a part of the reactants added first having a too long residence time. The production of by-products can result from the residence of most of the reactants, products or intermediates of the reaction under reaction conditions for an extended period of time. The micro reactor technology adopts continuous flow reaction in a micro channel, can accurately control the residence time of materials in the micro channel, and immediately transmits the materials to the next reaction or stops the reaction after the reaction reaches the optimal reaction time. This effectively suppresses the formation of by-products due to an excessively long reaction time.
(3) The reaction temperature can be accurately controlled: because the micro-reactor has a larger area/volume ratio, the high-efficiency heat exchange efficiency is determined, and a large amount of heat released in the reaction can be removed to keep the reaction temperature uniform and constant. For strongly exothermic reactions, local overheating often occurs in conventional reactors due to low mixing rate and heat exchange efficiency, and the local overheating often causes by-product formation, thereby reducing yield and selectivity of the reaction. In the fine chemical production, if a large amount of heat generated by violent reaction cannot be timely led out, the material flushing accident or even explosion can be possibly caused.
(4) The materials can be mixed instantaneously in precise proportions: in a conventional reactor, the proportion of some fast reaction materials is strict, and if the stirring is insufficient, the proportion is locally disordered to generate byproducts. This phenomenon can hardly be avoided in conventional reactors, but in microreactor systems, the reaction channels are generally only tens of microns, and the materials can be mixed strictly according to the ratio, so that side reactions are avoided.
The titanium silicalite molecular sieve in the invention comprises a TS-1 molecular sieve and also comprises a TS-1 molecular sieve composition, or a modified TS-1 molecular sieve or a TS-1 molecular sieve composition.
As a preferred embodiment of the invention, liquid propylene is firstly introduced into the microreactor, and then the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is introduced into the microreactor to carry out oxidation reaction to produce propylene oxide. Hydrogen peroxide and the titanium silicalite molecular sieve are simultaneously introduced into the microreactor in the form of mixed slurry to be mixed with liquid propylene and react, so that the reaction can be more effectively controlled, the material ratio can be accurately controlled, and the production of byproducts in the reaction process is reduced.
As a preferred embodiment of the present invention, the reaction conditions in the microreactor are: the reaction temperature is 30-90 ℃, the reaction pressure is 2.0-4.5MPa, and the mass space velocity of the liquid propylene is 1.0-15h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-6, and the reaction time is 0.1-1.5 h; preferably: the reaction temperature is 40-80 ℃, the reaction pressure is 2.5-4.5MPa, and the mass space velocity of the liquid propylene is 2.0-14h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-4, and the reaction time is 0.2-1.3 h.
In the preferred embodiment, the propylene can be always in a liquid state by keeping high pressure in the microreactor, and the propylene and hydrogen peroxide are always in a liquid-phase reaction, so that the multiphase problem of the reaction is reduced. In addition, the reaction temperature, the mass space velocity of the liquid propylene, the proportion of the raw materials and the reaction time are controlled, so that the reaction effect is further improved, the reaction among the raw materials is more sufficient, the reaction precision is improved, and the generation of byproducts is reduced.
As a preferred embodiment of the present invention, the particle size of the titanium silicalite molecular sieve is less than 260 μm, preferably less than 60 μm. The particle size of the titanium silicalite molecular sieve is limited to ensure the flowability of the catalyst in the microreactor, so that the catalyst can flow in reaction liquid to form gas-liquid-solid slurry flow and has good catalytic activity.
In a preferred embodiment of the present invention, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is 2 to 30%, preferably 5 to 25%. The mass fraction of the titanium silicalite molecular sieve is limited, so that the fluidity of the mixed slurry can be ensured while the catalytic activity of the titanium silicalite molecular sieve is fully ensured.
As a preferred embodiment of the present invention, a step of product separation is performed after the completion of the oxidation reaction; optionally, a step of catalyst regeneration after product separation; optionally, the catalyst regeneration comprises a process of supercritical extraction of the catalyst; optionally, the process conditions of the method for supercritical extraction of the catalyst are: the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-15), extracting for 5-100 min; preferably, the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-4), extracting for 15-40 min; optionally, the extraction solvent is propylene, acetone, or a hydrocarbon compound; propylene is preferred.
The deactivated catalyst can be recycled after regeneration treatment, and the regeneration treatment is carried out by adopting a supercritical solvent extraction mode so as to reduce the using amount of the catalyst.
In another aspect of the present invention, there is provided an apparatus for producing propylene oxide, comprising a microreactor.
The production equipment of the invention is not limited to the specific form of the microreactor, and can be used as long as solid particles can be allowed to flow in the reactor, namely, gas, liquid and solid phases can be allowed to flow.
As a preferred embodiment of the present invention, the microreactor is a plurality of microreactors, the microreactors form a microreactor group by being connected in series, and the microreactor group forms a microreactor array by being connected in parallel; optionally, the number of the microreactors in each group of microreactor groups is 1-10; optionally, the number of sets of microreactor groups in the microreactor array is 1-50 sets.
The processing capacity can be improved and the production scale can be enlarged by increasing the microreactor. In addition, a plurality of microreactors are connected in series to form a microreactor group, hydrogen peroxide and the titanium silicalite molecular sieve can be added in sections, and the accurate control of the reaction is realized.
Liquid propylene is led into a single microreactor in each microreactor group, mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is distributed into the microreactors connected in series according to a certain proportion to react with the liquid propylene in the microreactors, and the selectivity of the reaction process is improved and the occurrence of side reactions is reduced by controlling the reaction conditions.
Each microreactor group can be formed by connecting a plurality of microreactors in series, the number of the microreactors connected in series can be 1, 2, 3, … … n (n is 10), and the number of the microreactor group can be 1, or 2, 4, 3, 4, 5, … …, or 50.
As a preferred embodiment of the present invention, the microreactor array is connected to a flash tank for product separation, a middle outlet of the flash tank for discharging propylene oxide being connected to a propylene oxide refining system, and a bottom outlet of the flash tank for discharging reactants being connected to an inlet of the microreactor array.
The flash tank is used for separating reactants and products; the propylene oxide refining system is used for refining propylene oxide which is a target reaction product. In the production equipment, reaction products in each micro reactor group enter a flash tank through pipelines for separation, and each separated substance is introduced into different equipment through different pipelines. The flash tank separates gas from liquid, the gas is discharged from the top of the flash tank, the target reaction product-epoxypropene enters a epoxypropane refining system as liquid, unreacted reactant propylene, catalyst and hydrogen peroxide are a mixture, the mixture is settled at the bottom of the flash tank and discharged from the bottom outwards, and the unreacted reactant propylene, the catalyst and the hydrogen peroxide enter the microreactor again to react, so that continuous production is realized, the efficiency is high, no waste is discharged in the whole process, and the energy-saving and environment-friendly effects are achieved.
As a preferred embodiment of the present invention, the micro-reactor array is connected with the flash tank through a buffer tank.
And discharging the products after reaction in the micro-reactor array to a buffer tank, and quantitatively flowing the products into the flash tank in batches by the buffer tank according to the requirement of the flash tank so as to better separate the products by the flash tank.
As a preferred embodiment of the present invention, the production equipment further comprises a mixing tank for mixing hydrogen peroxide and a catalyst, and an outlet of the mixing tank is connected with an inlet of the microreactor array. The mixing tank can effectively control the amount of reactants and provide a proper amount of catalyst, so that the reaction materials are fully reacted.
As a preferred embodiment of the invention, the inlet of the mixing tank is connected to the bottom outlet of the flash tank. The unreacted reactants discharged from the flash tank can reenter the mixing tank, are mixed again by the mixing tank and then enter the microreactor.
As a preferred embodiment of the present invention, a branch line is provided between the mixing tank and the flash tank, and a supercritical extraction regenerator for catalyst regeneration is provided on the branch line. Optionally, the upper outlet of the supercritical extraction regenerator is connected with a fractionating tower, and the fractionating tower is connected with a diesel oil storage tank.
In the reaction provided by the invention, the catalyst is slowly deactivated, and generally, the regeneration treatment of all the catalysts is not required each time, so that part of the catalysts can be directly returned to the mixing tank for carrying out catalytic reaction again, and the rest of the catalysts enter a supercritical extraction regenerator for extraction, desorption and regeneration. The ratio of the regeneration of the catalyst and the regeneration amount is adjusted according to the activity, the conversion rate and the selectivity condition of the catalyst. In addition, according to the situation, all the catalysts can be directly returned to the mixing tank, and after a proper amount of hydrogen peroxide is added, the mixture enters a micro-reactor system for catalytic reaction.
All or part of the catalyst separated by the flash tank enters a supercritical extraction regenerator through a pipeline to carry out desorption regeneration on an extracting agent under the driving of power; feeding the regenerated catalyst obtained in the supercritical extraction regenerator into a mixing tank; meanwhile, the catalyst separated by the flash tank can also directly enter a mixing tank; the olefin polymer (coke precursor) extracted and removed from the supercritical extraction regenerator enters a distillation tower through a pipeline to realize the separation of the extracting agent and the olefin polymer, the olefin polymer is a good diesel oil blending component and is sent into a diesel oil storage tank, the olefin polymer can be sent into a diesel oil hydrogenation device after being collected or directly sent out as the diesel oil blending component, and the fractionated extracting agent returns to the supercritical extraction regenerator through the pipeline for extraction.
Example 1
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 20 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 0.5, the residence time of reactants is 0.72 hour, and the particles of the titanium silicalite molecular sieve are less than 60 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 30 ℃, the reaction pressure is 2.0MPa, and the mass space velocity of the liquid propylene is 1.0h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 90 ℃, the pressure is 3.9MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 3, the extraction time is 15 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
In the embodiment, when the reaction is carried out in the microreactor, the rising and falling range of the reaction temperature is controlled to be 0.5-2 ℃, the reaction is stable and rapid, the reaction regeneration can be continuously carried out, and the production efficiency is high. Because the reaction system does not contain solvents such as methanol and the like, the side reaction is less, the separation of the solvents is not needed, and the energy consumption is reduced; meanwhile, as the amount of the hydrogen peroxide is small, the reaction heat taking is quick, so that the explosion danger caused by heat accumulation due to the decomposition of the hydrogen peroxide is avoided, and the safety of equipment is further improved; unreacted reactants and catalyst obtained after the reaction can be recycled, so that the cost is saved; the whole reaction process is continuous in production, no waste is produced, and the method is energy-saving and environment-friendly.
Example 2
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 20 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 0.5, the residence time of reactants is 0.67 hours, and the particles of the titanium silicalite molecular sieve are less than 120 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 45 ℃, the reaction pressure is 3.0MPa, and the mass space velocity of the liquid propylene is 1.5h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 95 ℃, the pressure is 4.0MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 6, the extraction time is 20 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
Example 3
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 20 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 1, the residence time of reactants is 0.5 hour, and the particles of the titanium silicalite molecular sieve are less than 240 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 60 ℃, the reaction pressure is 4.0MPa, and the mass space velocity of the liquid propylene is 2.5h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 93 ℃, the pressure is 4.2MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 9, the extraction time is 30 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
Example 4
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 25 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 5, the residence time of reactants is 0.3 hour, and the particles of the titanium silicalite molecular sieve are less than 160 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 75 ℃, the reaction pressure is 4.5MPa, and the mass space velocity of the liquid propylene is 3.5h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 95 ℃, the pressure is 4.2MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 12, the extraction time is 40 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
Example 5
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 30 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 6, the residence time of reactants is 0.16 hour, and the particles of the titanium silicalite molecular sieve are less than 60 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 75 ℃, the reaction pressure is 4.0MPa, and the mass space velocity of the liquid propylene is 6h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 93 ℃, the pressure is 4.0MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 6, the extraction time is 30 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
Example 6
The embodiment is a method for producing propylene oxide, comprising the following steps:
step a): pumping liquid propylene into the microreactor, and simultaneously adding mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve in the microreactor to carry out oxidation reaction to generate propylene oxide;
wherein, the mass fraction of the titanium silicalite molecular sieve in the mixed slurry is 20 percent, the molar ratio of the liquid propylene to the hydrogen peroxide is 1.5, the residence time of reactants is 0.11 hour, and the particles of the titanium silicalite molecular sieve are less than 20 mu m; controlling the reaction conditions of the microreactor as follows: the reaction temperature is 90 ℃, the reaction pressure is 4.5MPa, and the mass space velocity of the liquid propylene is 9.0h-1；
Step b): carrying out flash separation on the reacted product to respectively obtain a target reaction product, unreacted reactant propylene and a catalyst; returning the unreacted reactant propylene to the microreactor for continuous reaction; after the catalyst titanium silicon molecular sieve is regenerated through supercritical extraction, returning to the mixing tank to be mixed with hydrogen peroxide again, and then entering the microreactor to react;
wherein, the reaction conditions of the supercritical extraction of the titanium-silicon molecular sieve are as follows: the temperature is 95 ℃, the pressure is 4.2MPa, the extraction solvent is propylene, and the mixing ratio of the catalyst to the extraction solvent is 1: 15, the extraction time is 20 minutes;
step c): and (3) fractionating the olefin and the polymer removed by the supercritical extraction, collecting the olefin polymer obtained by fractionation, and returning the extractant propylene obtained by fractionation to a reaction system or recycling.
The selectivity to propylene oxide and the conversion to hydrogen peroxide were measured in examples 1-6, respectively, and the results are shown in Table 1.
TABLE 1 results of the reactions of examples 1-6
Examples 7 to 13 respectively employed the same processes as in example 1, except that the reaction temperature, the reaction pressure, the oil agent ratio, the molar ratio of liquid propylene to hydrogen peroxide, and the catalyst content were varied, and the specific parameters and the reaction results of each example are shown in tables 2 and 3. Wherein, the molar ratio of the liquid propylene to the hydrogen peroxide in the examples 7 to 10 is 1.0, and the molar ratio of the liquid propylene to the hydrogen peroxide in the examples 11 to 13 is 2.0. In examples 7 to 13, the oil ratio is the mass ratio of liquid propylene to the catalyst.
TABLE 2 results of the reactions of examples 7 to 10
TABLE 3 results of the reactions of examples 11 to 13
Example 14
As shown in fig. 1, the embodiment is a propylene oxide production apparatus, including a microreactor array 10 composed of a plurality of microreactors 11, liquid propylene is pumped into the microreactors 11 through a pipeline, hydrogen peroxide is pumped into a mixing tank 20 through a pipeline, a titanium silicalite molecular sieve is stored in a catalyst tank 60, the catalyst tank 60 is connected with the mixing tank 20, and the titanium silicalite molecular sieve and the hydrogen peroxide are mixed in the mixing tank 20 and then are pumped into the microreactors 11 through a pipeline.
The outlet of the microreactor array 10 is connected with the buffer tank 30 and then connected with the inlet of the flash tank 40, the middle outlet of the flash tank 40 for discharging propylene oxide is connected with the inlet of the propylene oxide refining system 50, and the bottom outlet of the flash tank 40 for discharging reactants is connected with the inlet of the microreactor array 10.
The separated substances in the flash tank 40 are introduced into different devices through different pipelines, wherein the target reaction product, namely propylene oxide, flows into the propylene oxide refining system 50 through the pipeline, and unreacted reactants, namely propylene, hydrogen peroxide and the titanium silicalite, enter the mixing tank 20 or the supercritical extraction regenerator 70 from the bottom outlet of the flash tank 40 through the pipeline. The regenerated catalyst obtained from the supercritical extraction regenerator 70 enters the mixing tank 20, the olefin polymer (coke precursor) removed by extraction in the supercritical extraction regenerator 70 enters the distillation tower 80 through a pipeline to realize the separation of the extractant and the olefin polymer, the olefin polymers are good diesel oil blending components, and are sent to the diesel oil storage tank 90, and can be sent to a diesel oil hydrogenation device after being collected or directly sent out as the diesel oil blending components.
Part (or all) of the reacted catalyst can enter the supercritical extraction regenerator 70 for regeneration, and part of the catalyst directly returns to the mixing tank 20 and then is introduced into the microreactor 11 for reaction again, so that continuous production is realized. The production equipment has high efficiency, no waste is discharged in the whole process, and the production equipment is energy-saving and environment-friendly.
In conclusion, the preparation method provided by the invention is characterized in that propylene is kept in a liquid state under higher pressure, a solid titanium silicalite molecular sieve (TS-1) microspherical particle catalyst is added into hydrogen peroxide to form mixed slurry, and the hydrogen peroxide reacts with the liquid propylene in a microreactor under the condition of catalyst and no solvent. The microreactor can promote the solution of liquid propylene and hydrogen peroxide, and the reaction is carried out under the specific reaction condition through the catalytic action of the catalyst, so that the reaction is fast, the reaction time is greatly shortened, the safety of equipment and the selectivity of the reaction process are improved, and the occurrence of side reactions is avoided; meanwhile, the microreactor can timely emit reaction heat energy, so that the safety of equipment and the selectivity of a reaction process are improved, and side reactions are avoided. The catalyst and the product can be regenerated on line after being separated, so that the catalyst has higher activity level, and unreacted propylene can return to the microreactor for continuous reaction after being separated. In addition, olefin polymers causing catalyst deactivation are separated and used by hydrotreating. The method has the following advantages:
(1) the preparation method provided by the invention has the advantages that the reaction is carried out in the microreactor under specific reaction conditions, the reaction is rapid, the reaction time is greatly shortened, the safety of equipment and the selectivity of the reaction process are improved, and the occurrence of side reactions is avoided; the unreacted reactant and the catalyst obtained after the reaction can be recycled, no waste is generated, the cost is saved, and the pollution is prevented.
(2) According to the preparation method provided by the invention, a plurality of microreactors can be connected in series, a microreactor group can be formed by connecting a plurality of microreactor groups in parallel, and the reaction can be carried out simultaneously by controlling conditions, so that the development expenditure of expanding the reactors is saved, and the cost is further saved.
(3) The invention also specifically limits the type and parameters of the catalyst to facilitate the catalyst flow and continuous reaction.
(4) The invention also limits the proportion of the propylene and the hydrogen peroxide and the feeding speed so as to ensure that the hydrogen peroxide and the olefin react more fully and effectively.
(5) The invention also provides the extraction regeneration condition of the catalyst, the catalyst regeneration operation is simple, the catalyst recovery efficiency is high, the recovered catalyst keeps good activity, continuous reaction and regeneration can be realized, and the problem that the catalyst is difficult to regenerate in other reactor forms is solved.
(6) The preparation method provided by the invention belongs to liquid phase reaction, reduces the multiphase problem of the reaction, and improves the catalytic effect of the catalyst by utilizing the characteristic of high-efficiency mixing of a microreactor because liquid propylene, liquid-phase hydrogen peroxide and a solid-phase catalyst are in contact mixing and the propylene is always kept in a liquid-phase state.
(7) The production equipment provided by the invention realizes solvent-free continuous production, has high efficiency, reduces solvent recovery, reduces side reaction, does not discharge waste in the whole process, is energy-saving and environment-friendly, improves the selectivity of a target product, and reduces equipment investment and operation cost.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (14)
1. The preparation method of the epoxypropane is characterized in that liquid propylene is firstly introduced into a microreactor, and then mixed slurry of hydrogen peroxide and a titanium silicalite molecular sieve is introduced into the microreactor to carry out oxidation reaction to produce the epoxypropane.
2. The method for producing propylene oxide according to claim 1, wherein the reaction conditions in the microreactor are: the reaction temperature is 30-90 ℃, the reaction pressure is 2.0-4.5MPa, and the mass space velocity of the liquid propylene is 1.0-15h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-6, and the reaction time is 0.1-1.5 h.
3. The method for producing propylene oxide according to claim 2, wherein the reaction conditions in the microreactor are: the reaction temperature is 40-80 ℃, the reaction pressure is 2.5-4.5MPa, and the mass space velocity of the liquid propylene is 2.0-14h-1The mol ratio of the liquid propylene to the hydrogen peroxide is 0.5-4, and the reaction time is 0.2-1.3 h.
4. The method for preparing propylene oxide according to claim 1, wherein the particle size of the titanium silicalite molecular sieve is less than 260 μm.
5. The method for preparing propylene oxide according to claim 4, wherein the particle size of the titanium silicalite molecular sieve is less than 60 μm.
6. The preparation method of propylene oxide according to claim 4, wherein the mass fraction of the titanium silicalite molecular sieve in the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is 2-30%.
7. The preparation method of propylene oxide according to claim 6, wherein the mass fraction of the titanium silicalite molecular sieve in the mixed slurry of hydrogen peroxide and the titanium silicalite molecular sieve is 5-25%.
8. The method for producing propylene oxide according to claim 1, wherein the step of separating the product is carried out after the completion of the oxidation reaction.
9. The method for producing propylene oxide according to claim 8, wherein the step of regenerating the catalyst is carried out after the product is separated.
10. The method for producing propylene oxide according to claim 9, wherein the catalyst regeneration comprises a method of supercritical extraction of the catalyst.
11. The method for preparing propylene oxide according to claim 10, wherein the process conditions of the method for supercritical extraction of the catalyst are as follows: the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-15) and the extraction time is 5-100 min.
12. The method for preparing propylene oxide according to claim 11, wherein the process conditions of the method for supercritical extraction of the catalyst are as follows: the extraction temperature is 90-95 ℃, the extraction pressure is 3.9-4.2MPa, and the mixing ratio of the catalyst to the extraction solvent is 1: (3-4), and the extraction time is 15-40 min.
13. The method for producing propylene oxide according to claim 11, wherein the extraction solvent is propylene, acetone, or a hydrocarbon compound.
14. The method for producing propylene oxide according to claim 13, wherein the extraction solvent is propylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710946598.7A CN107602510B (en) | 2017-10-12 | 2017-10-12 | Preparation method and production equipment of propylene oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710946598.7A CN107602510B (en) | 2017-10-12 | 2017-10-12 | Preparation method and production equipment of propylene oxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107602510A CN107602510A (en) | 2018-01-19 |
| CN107602510B true CN107602510B (en) | 2020-04-28 |
Family
ID=61068728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710946598.7A Active CN107602510B (en) | 2017-10-12 | 2017-10-12 | Preparation method and production equipment of propylene oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107602510B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217678B (en) * | 2018-04-09 | 2019-12-13 | 浙江巨化技术中心有限公司 | Method for preparing titanium-silicon molecular sieve by using microreactor |
| CN109928943B (en) * | 2019-04-08 | 2020-12-18 | 江苏扬农化工集团有限公司 | Method for synthesizing propylene oxide by using microchannel reactor |
| CN109942513B (en) * | 2019-04-08 | 2020-11-06 | 江苏扬农化工集团有限公司 | Method for synthesizing epoxypropane by filling catalysts with different particle sizes |
| CN111440130A (en) * | 2020-04-26 | 2020-07-24 | 中国石油化工股份有限公司 | Method and equipment for producing epoxypropane |
| CN117466839B (en) * | 2023-10-07 | 2024-07-26 | 中建安装集团有限公司 | Process for preparing propylene oxide by directly oxidizing propylene with hydrogen peroxide by using flat-plate membrane reactor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641800A (en) * | 2013-12-12 | 2014-03-19 | 中石化上海工程有限公司 | Production method of epoxy propane |
| CN104130215A (en) * | 2014-08-11 | 2014-11-05 | 河南骏化发展股份有限公司 | Method for continuously producing propylene oxide by directly oxidizing propylene with hydrogen peroxide |
| CN104907009A (en) * | 2015-05-22 | 2015-09-16 | 南京红宝丽股份有限公司 | Reactor and method for preparing epoxypropane by reactor |
| CN105061129A (en) * | 2015-09-18 | 2015-11-18 | 中石化炼化工程（集团）股份有限公司 | Isoalkane/olefin alkylation method and device |
| CN106632147A (en) * | 2016-12-20 | 2017-05-10 | 红宝丽集团股份有限公司 | Method for preparing propylene oxide by utilizing micro-channel reactor |
| CN106831661A (en) * | 2017-01-24 | 2017-06-13 | 南京工业大学 | Method for preparing epoxypropane by using micro-reaction device |
-
2017
- 2017-10-12 CN CN201710946598.7A patent/CN107602510B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103641800A (en) * | 2013-12-12 | 2014-03-19 | 中石化上海工程有限公司 | Production method of epoxy propane |
| CN104130215A (en) * | 2014-08-11 | 2014-11-05 | 河南骏化发展股份有限公司 | Method for continuously producing propylene oxide by directly oxidizing propylene with hydrogen peroxide |
| CN104907009A (en) * | 2015-05-22 | 2015-09-16 | 南京红宝丽股份有限公司 | Reactor and method for preparing epoxypropane by reactor |
| CN105061129A (en) * | 2015-09-18 | 2015-11-18 | 中石化炼化工程（集团）股份有限公司 | Isoalkane/olefin alkylation method and device |
| CN106632147A (en) * | 2016-12-20 | 2017-05-10 | 红宝丽集团股份有限公司 | Method for preparing propylene oxide by utilizing micro-channel reactor |
| CN106831661A (en) * | 2017-01-24 | 2017-06-13 | 南京工业大学 | Method for preparing epoxypropane by using micro-reaction device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107602510A (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107602510B (en) | Preparation method and production equipment of propylene oxide | |
| CN104130215B (en) | The method of hydrogen peroxide direct oxidation propylene continuous preparation of epoxypropane | |
| CN202460629U (en) | Reaction device for preparing cyclohexene from benzene through selective hydrogenation | |
| CN101337950A (en) | Method for continuously preparing epichlorohydrin by glycerine reaction fractional distillation | |
| CN102548950B (en) | Process for preparing alkanediol and dialkyl carbonate | |
| CN104557784A (en) | Method for producing epoxypropane | |
| CN102367223A (en) | Synthesis method of isophorone | |
| CN102516051B (en) | Method for preparing isophorone by acetone liquid condensation with alkali catalyst | |
| WO2023138074A1 (en) | Method and system for preparing cyclic carbonate by catalyzing carbon dioxide cycloaddition | |
| CN114315767A (en) | Preparation method and preparation device of 5-hydroxymethylfurfural | |
| CN102452934B (en) | Preparation method of sec-butyl acetate | |
| CN103709001B (en) | The method of Synthesis of Ethylene Glycol by Ethylene Oxide Hydration | |
| CN112156731A (en) | Reinforced micro-interface preparation system and method for polyglycolic acid | |
| CN115745918A (en) | Process for producing propylene oxide by using HPPO method of liquid-solid circulating fluidized bed reaction-regeneration system | |
| CN109970511B (en) | Method for synthesizing 1, 3-propylene glycol by resource utilization of HPPO byproduct | |
| CN101570469A (en) | Method for continuously producing isobutyl alcohol through hydrogenation of methylacrolein | |
| CN102190636A (en) | Method for preparing epoxy chloropropane by cyclizing chloropropene | |
| EP2745924B1 (en) | Integrated process for coupling fixed bed and jet floating bed to separator unit | |
| CN109928943B (en) | Method for synthesizing propylene oxide by using microchannel reactor | |
| CN112441883A (en) | Enhanced reaction system and method for preparing ethylene glycol by gas-phase catalytic hydration method | |
| CN102755910A (en) | Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof | |
| CN101423454B (en) | Method for preparing tert-butyl alcohol by reaction extraction of carbon-tetrahydrocarbon containing isobutene | |
| CN111440130A (en) | Method and equipment for producing epoxypropane | |
| CN108640889B (en) | Device and method for preparing low-carbon epoxy hydrocarbon compound by oxidizing low-carbon olefin | |
| CN102757406B (en) | Styrene epoxidation method for preparing styrene oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |