CN112279822A - CHPPO device and method for improving yield of propylene oxide - Google Patents

CHPPO device and method for improving yield of propylene oxide Download PDF

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Publication number
CN112279822A
CN112279822A CN202010969093.4A CN202010969093A CN112279822A CN 112279822 A CN112279822 A CN 112279822A CN 202010969093 A CN202010969093 A CN 202010969093A CN 112279822 A CN112279822 A CN 112279822A
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China
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epoxidation
reactor
stage
logic
propylene
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李真泽
吕世军
李勇
张宇剑
杨建平
程微
陈愈安
余超
孙丽丽
何琨
白玫
唐绮颖
王红
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China Petroleum and Chemical Corp
Sinopec Shanghai Engineering Co Ltd
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China Petroleum and Chemical Corp
Sinopec Shanghai Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • 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
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

The invention relates to a CHPPO device and method for improving the yield of propylene oxide, and mainly solves the problems of low yield of PO and unrecovered reaction heat in the prior art. By adopting the device and the method, the epoxidation process flow of the CHPPO device with the production scale of 100 tons/year to 80 ten thousand tons/year is optimized, the activity of the catalyst is gradually improved from a logic 1 position to a logic end position by switching the epoxidation reactor, and the propylene raw material and a reaction product of an outlet with the logic 1 position exchange heat; the conversion rate of CHP is improved to 99.5-99.6%, the PO selectivity is improved to 98.2-98.6%, the PO yield is improved to 97.7-98.2%, and the reaction heat is recovered from 176.2-183.4 kcal/kg PO.

Description

CHPPO device and method for improving yield of propylene oxide
Technical Field
The invention relates to the field of PO production process, in particular to a method for increasing CHP conversion rate and PO selectivity and PO yield by switching reactors in an epoxidation unit of a CHPPO device and carrying out heat exchange on propylene raw materials and reaction products, which can be applied to the production of propylene oxide by a large-scale commercial CHPPO process device.
Background
The propylene oxide is used as an important basic organic chemical raw material, and has large surface tension and high reaction activity. The derivatives are widely applied to the industries of chemical industry, petrifaction, medicine, pesticide, daily chemicals, food, building, household appliances, automobiles, textile and the like. The traditional method for industrially producing propylene oxide PO mainly comprises a chlorohydrin method CHPO, an ethylbenzene co-oxidation method PO/SM, an isobutane co-oxidation method PO/TBA, a hydrogen peroxide oxidation method HPPO and the like. However, the existing propylene oxide production processes such as chlorohydrin CHPO, ethylbenzene co-oxidation PO/SM, isobutane co-oxidation PO/TBA and hydrogen peroxide oxidation HPPO have the defects of heavy pollution, high corrosion, long flow path, more coproducts, high cost, high explosion risk and the like. Therefore, the technology for producing CHPPO propylene oxide by cumene oxidation is actively developed in various countries, which is green, clean, simple in process, economical and safe.
Cumene hydroperoxide CHP and propylene C of cumene oxidation method CHPPO process technology3H6The preparation of propylene oxide PO mainly comprises three reaction processes: (1) oxidizing cumene by air to prepare cumene hydroperoxide CHP; (2) cumene hydroperoxide CHP and propylene C3H6Carrying out epoxidation reaction in the presence of a fixed bed heterogeneous catalyst to produce propylene oxide PO and alpha, alpha-dimethyl benzyl alcohol DMBA; (3) alpha, alpha-dimethylbenzyl alcohol DMBA and H2In the presence of a catalyst, the cumene is generated by hydrogenolysis reaction, and the cumene is circularly returned to the oxidation unit to produce the cumene hydroperoxide CHP.
The invention discloses a method for epoxidizing cumene hydroperoxide and propylene, which belongs to the invention patent application number of 201310236989.1 in the prior art, and discloses a method for epoxidizing cumene hydroperoxide and propylene, which mainly solves the problems that the reaction temperature rise is higher and the molar ratio of propylene to cumene hydroperoxide needs to be higher for keeping higher reaction efficiency in the prior art. The method comprises the steps of enabling raw materials of cumene hydroperoxide and propylene to enter a reaction zone in a liquid phase, and enabling the raw materials to contact a Ti-silicon dioxide catalyst to carry out epoxidation reaction to generate propylene oxide under the conditions that the epoxidation reaction temperature is 15-160 ℃, the pressure is 1.0-12.0 MPa, and the total molar ratio of the propylene to the cumene hydroperoxide is 2-30; wherein, the technical proposal that part of the epoxidation reaction product containing the propylene oxide is circulated to the inlet of the reaction zone better solves the problem, and can be used in the industrial production of preparing the propylene oxide by the epoxidation of the cumene hydroperoxide and the propylene. In the embodiment, the conversion rate of the cumene hydroperoxide CHP is 99.4-99.5%, and the selectivity of the propylene oxide PO is 96.0-96.2%.
The invention has patent application number 201510268975.7A reactor and a method for preparing propylene oxide by using the reactor, the middle part of the reactor is filled with an epoxidation catalyst, the top wall is provided with a gas outlet, the upper side wall is provided with a liquid outlet, the lower side wall is provided with 1 or 2 groups of ejectors, each group of ejectors comprises 2 ejectors, and the two ejectors are distributed on the same plane and are mutually symmetrical; the ejector consists of a spray pipe and a spray nozzle connected with the spray pipe, the spray nozzle is in a truncated cone shape, the diameter of one end of the spray nozzle connected with the spray pipe is larger than that of the other end of the spray nozzle, the spray nozzle extends into the fixed bed reactor, the spray pipe is divided into 2 sections, one section of the spray pipe, far away from the spray nozzle, is in a cylindrical shape, the other section of the spray pipe is in a truncated cone shape, and the diameter of one end of the spray pipe, far; the reactor can realize high-speed clash mixing of reaction materials, strengthen interphase mixing among the reaction materials, enhance the heat and mass transfer effect and improve the conversion rate of cumene hydroperoxide and the selectivity of epoxypropane. In the embodiment, the conversion rate of the cumene hydroperoxide CHP is 90.1-99.5%, and the selectivity of the propylene oxide PO is 91.6-98.2%.
In the process of producing epoxypropane and alpha, alpha-dimethyl benzyl alcohol by carrying out epoxidation reaction on cumene hydroperoxide and propylene, the mole fraction of reaction raw materials is gradually reduced and the mole fraction of reaction products is gradually increased along with the reaction materials gradually passing through an epoxidation reactor. Under the condition that the activity of the fixed bed heterogeneous catalyst is the same, because the epoxidation reaction is an exothermic reaction, the mole fraction of the reaction raw materials of the former-stage reactor is large, the reaction is violent, the temperature is raised, and the selectivity of the propylene oxide is low; the mole fraction of the reaction raw materials of the post reactor is small, the reaction is mild, the temperature rise is low, and the conversion rate of the cumene hydroperoxide is low. The activity of the fixed bed heterogeneous catalyst in the epoxidation reactor gradually decreases as the run time of the epoxidation reactor of a large-scale CHPPO process plant increases. Under the condition that the mole fraction of cumene hydroperoxide and propylene is the same, in a reactor operation period, the catalyst activity is high at the early stage of the reactor operation, the reaction is violent, the temperature is increased, and the selectivity of propylene oxide is low; the catalyst activity is low in the later stage of the operation of the reactor, the reaction is mild, the temperature rise is low, and the conversion rate of the cumene hydroperoxide is low. Therefore, the epoxidation unit of the industrial CHPPO production device needs to comprehensively consider factors such as mole fraction of reaction raw materials, reaction temperature rise, catalyst activity and the like so as to increase CHP conversion rate, improve PO selectivity and PO yield and comprehensively utilize epoxidation reaction heat.
Prior art invention patent application No. 201310236989.1 discloses only a partial recycle of propylene oxide containing epoxidation reaction product to the inlet of the reaction zone to reduce the reaction temperature rise and to reduce the molar ratio of propylene to cumene hydroperoxide; the invention patent application No. 201510268975.7 discloses only the technical solution of the combination between the structure inside the reactor equipment for preparing propylene oxide and the equipment; the cumene hydroperoxide conversion rate of the prior art patent is 90.1-99.5%, the propylene oxide selectivity is 91.6-98.2%, the propylene oxide yield is 82.5-97.7%, a technical means for improving the propylene oxide yield by an epoxidation unit is absent, a technical measure for comprehensively utilizing the heat released by the epoxidation reaction is absent, and the problems that the cumene hydroperoxide conversion rate is low, the propylene oxide selectivity is low, the propylene oxide yield is low, and the epoxidation reaction heat cannot be comprehensively utilized exist.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a CHPPO device and a CHPPO method for improving the yield of propylene oxide. In the process of preparing propylene oxide by epoxidation reaction of cumene hydroperoxide and propylene, factors such as mole fraction of reaction raw materials, reaction temperature rise, catalyst activity and the like are comprehensively considered, the process flow of an epoxidation unit is optimized, the activity of the catalyst is gradually improved from a logic 1-bit reactor to a logic last-bit reactor by switching epoxidation reactors connected in series, and the propylene raw materials and the reaction product at the outlet of the logic 1-bit reactor of the epoxidation first-stage reaction are subjected to heat exchange. Under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the epoxidation reaction is gradually deepened, the CHP conversion rate is increased, the PO selectivity and the PO yield are improved, and the heat of the epoxidation reaction can be comprehensively utilized and recovered.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a CHPPO device for improving the yield of propylene oxide, which has the production scale of 100-80 ten thousand tons per year and comprises an oxidation unit, an epoxidation unit, a separation unit, a hydrogenolysis unit and a compression unit;
the epoxidation unit comprises an epoxidation first-stage reaction system, a propylene preheating heat exchange system, an epoxidation first-stage reaction product cooling system, a propylene raw material heating system, an epoxidation second-stage reaction system and an epoxidation second-stage reaction product cooling system;
the epoxidation first-stage reaction system comprises m epoxidation first-stage reactors connected in series, wherein the epoxidation first-stage reactors are respectively epoxidation first-stage reaction logic 1-m reactors;
the epoxidation second-stage reaction system comprises n epoxidation first-stage reactors connected in series, wherein the epoxidation first-stage reactors are respectively epoxidation second-stage reaction logic 1-n reactors;
the m series-connected epoxidation first-stage reactors and the n series-connected epoxidation second-stage reactors are also connected in series;
the propylene preheating heat exchange system comprises m propylene preheating heat exchangers, namely propylene preheating 1-m heat exchangers;
the propylene raw material heating system comprises 1 propylene raw material heater, wherein an inlet pipeline of the propylene raw material heater is connected with an outlet pipeline of the propylene preheating heat exchanger;
the epoxidation first-order reaction product cooling system comprises m epoxidation first-order reaction product coolers which are respectively number 1-m coolers for epoxidation first-order reaction products;
the cooling system for the epoxidation secondary reaction products comprises n epoxidation secondary reaction product coolers, namely coolers from No. 1 to No. n of the epoxidation secondary reaction products;
wherein m is more than or equal to 1, n is more than or equal to 1, and m is equal to n;
when m is 1, the epoxidation first-stage reaction logic 1-bit reactor, the propylene preheating heat exchanger No. 1, the epoxidation first-stage reaction product No. 1 cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through a pipeline;
when m is more than or equal to 2, a connecting pipeline between the epoxidation first-stage reaction logic 1 to (m-1) reactor and the next corresponding epoxidation first-stage reactor is sequentially provided with 1 propylene preheating heat exchanger and 1 epoxidation first-stage reaction product cooler, and the bit numbers of the propylene preheating heat exchanger and the epoxidation first-stage reaction product cooler are respectively 1 to (m-1); the epoxidation first-stage reaction logic m-bit reactor, the propylene preheating m-number heat exchanger, the epoxidation first-stage reaction product m-number cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through pipelines;
when n is 1, the epoxidation second-stage reaction logic 1-bit reactor, the epoxidation second-stage reaction product No. 1 cooler and the separation unit are sequentially connected through pipelines;
when n is more than or equal to 2, 1 epoxidation secondary reaction product cooler is arranged on a connecting pipeline between the epoxidation secondary reaction logic 1 to (n-1) position reactor and the next corresponding epoxidation secondary reactor, and the position number of the epoxidation secondary reaction product cooler is 1 to (n-1); the epoxidation second-stage reaction logic n-bit reactor is connected with an epoxidation second-stage reaction product n cooler through a pipeline;
one pipeline of the separation unit is converged into a first main pipeline through the compression unit and a fresh propylene feeding pipeline, and the first main pipeline is provided with m side pipeline which are respectively connected with fresh propylene inlet pipelines of a propylene preheating No. 1-m heat exchanger; fresh propylene outlets of the propylene preheating No. 1-m heat exchangers are provided with second main pipelines which are converged into a second main pipeline, and the second main pipeline is connected to the top of an epoxidation first-stage reaction logic 1-bit reactor through the propylene raw material heater;
the other pipeline of the separation unit and the hydrogen feeding pipeline form a pipeline respectively through the hydrogenolysis unit, the pipeline is converged with the fresh cumene feeding pipeline and is connected with the oxidation unit, and the air feeding pipeline is also connected with the oxidation unit; an oxidation product outlet pipeline of the oxidation unit is converged with a second main pipeline and is connected with the top of an epoxidation first-stage reaction logic 1-bit reactor;
the outlet of the n-type cooler for the epoxidation secondary reaction product is connected with the inlet of the separation unit through a pipeline, and the separation unit is also provided with a propylene oxide product discharging pipeline.
Further, reactors in the epoxidation first-stage reaction system and the epoxidation second-stage reaction system are switched in series, when a logic 1-bit reactor needs to be replaced due to catalyst deactivation, a logic 2-bit reactor is switched to a logic 1-bit reactor, and so on, and after the original logic 1-bit reactor is replaced with a catalyst, the original logic 1-bit reactor is switched to a logic final-bit reactor. This allows the catalyst activity in the reactors in series to be increased from the logical 1-position reactor to the logical last-position reactor, allowing the epoxidation reaction to proceed further and further until the reaction product leaves the logical last-position reactor. In addition, the epoxidation reaction entering the epoxidation secondary reaction system is mild, the heat release is small, and the recovery energy is limited, so a material heat exchange process flow is not arranged.
A second aspect of the present invention provides a method for increasing the yield of propylene oxide based on the above-mentioned CHPPO device, comprising the steps of:
step one, oxidation: air from the outside enters an oxidation unit, fresh cumene from the outside and circulating cumene from a hydrogenolysis unit are combined and then enter the oxidation unit, and cumene oxidation reaction is carried out in the oxidation unit to generate cumene hydroperoxide.
Step two, epoxidation: fresh propylene from outside and circulating propylene from a compression unit are combined and flow out of a first-stage reaction logic 1-bit reactor through an epoxidation first-stage reaction logic 1-bit reactor, reaction products of the first-stage reaction logic 1-bit reactor exchange heat in a propylene preheating heat exchanger, and are mixed with cumene hydroperoxide after being heated in a propylene raw material No. 1 heater through low-pressure steam. The method comprises the steps of firstly entering the top of an epoxidation first-stage reaction logic 1-bit reactor, starting epoxidation reaction in the epoxidation first-stage reaction logic 1-bit reactor to generate a first-stage reaction logic 1-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), enabling the first-stage reaction logic 1-bit reactor reaction product to flow out from the bottom of the epoxidation first-stage reaction logic 1-bit reactor, preheating a No. 1 heat exchanger by propylene, exchanging heat with fresh propylene, and cooling by circulating cooling water of a No. 1 epoxidation first-stage reaction product cooler. And then entering the top of an epoxidation first-stage reaction logic 2-bit reactor, continuously carrying out epoxidation reaction in the epoxidation first-stage reaction logic 2-bit reactor to generate a first-stage reaction logic 2-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), allowing the first-stage reaction logic 2-bit reactor reaction product to flow out from the bottom of the epoxidation first-stage reaction logic 2-bit reactor, and cooling by circulating cooling water through a reaction product cooler. And repeating the epoxidation reaction until the m-bit reactor of the first-stage reaction logic continues to perform the epoxidation reaction to generate the m-bit reactor reaction products (propylene oxide and alpha, alpha-dimethyl benzyl alcohol) of the first-stage reaction logic. Under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved; and the propylene preheating heat exchanger No. 1 corresponding to the epoxidation first-stage reaction logic 1-bit reactor is used, and the rest propylene preheating heat exchangers are stopped. Cooling the reaction product of the m-bit reactor of the first-stage reaction logic by circulating cooling water through an m-number cooler of the epoxidation first-stage reaction product; and then the reaction product is sent to the top of an epoxidation second-stage reaction logic 1-bit reactor, epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 1-bit reactor to generate a second-stage reaction logic 1-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), the second-stage reaction logic 1-bit reactor reaction product flows out from the bottom of the epoxidation second-stage reaction logic 1-bit reactor, and the epoxidation second-stage reaction product is cooled by circulating cooling water through a No. 1 cooler. And so on until the epoxidation second-stage reaction logic n-bit reactor and the epoxidation second-stage reaction product n-number cooler. Under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved.
Step three, separation: and (3) sending a reaction product containing the components of propylene oxide, alpha-dimethyl benzyl alcohol, circulating propylene and the like which flows out of the n-th cooler of the epoxidation secondary reaction product into a separation unit, and rectifying and separating the reaction product in multiple towers of the separation unit to obtain the products of the circulating propylene, the alpha, alpha-dimethyl benzyl alcohol and the propylene oxide, wherein the propylene oxide product is sent out.
Step four, hydrogenolysis: hydrogen from the outside and alpha, alpha-dimethyl benzyl alcohol from the separation unit enter a hydrogenolysis unit, the hydrogen and the alpha, alpha-dimethyl benzyl alcohol generate hydrogenolysis reaction to generate circulating isopropyl benzene in the presence of a catalyst, and the circulating isopropyl benzene returns to the hydrogenolysis unit and is combined with fresh isopropyl benzene to enter an oxidation unit.
Step five, compression: the circulating propylene flowing out of the separation unit is pressurized by a compression unit-propylene compressor and then returned and combined with fresh propylene to enter an epoxidation unit.
Further, the operating temperature of the epoxidation first-stage reactor is 40-180 ℃, the operating pressure is 0.6-15.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 1-50: 1, the mass concentration of the cumene hydroperoxide feed is 2-95%, and the weight space velocity of the cumene hydroperoxide feed is 0.1-8.0 h-1The number of the epoxidation first-stage reactors connected in series is 1-10, the service life of the epoxidation first-stage reactor filled with the catalyst is 1-24 months, and the operation period of the epoxidation first-stage reactor is 0.5-12 months.
Further preferably, the operating temperature of the epoxidation first-stage reactor is 60-160 ℃, the operating pressure is 2.0-12.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 2-40: 1, the mass concentration of the cumene hydroperoxide feed is 4-90%, and the weight space velocity of the cumene hydroperoxide feed is 0.2-5.0 h-1The number of the epoxidation first-stage reactors connected in series is 2-8, the service life of the epoxidation first-stage reactor filled with a catalyst is 2-12 months, and the preferred range of the operation period of the epoxidation first-stage reactor is 1-9 months
More preferably, the operating temperature of the epoxidation first-stage reactor is 80-140 ℃, the operating pressure is 3.0-9.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 4-20: 1, the mass concentration of the cumene hydroperoxide feed is 8-80%, and the weight space velocity of the cumene hydroperoxide feed is 0.4-2.0 h-1The number of the epoxidation first-stage reactors connected in series is 3-6, the service life of the epoxidation first-stage reactor filled with a catalyst is 3-6 months, and the operation period of the epoxidation first-stage reactor is 3-6 months.
Furthermore, the operating temperature of the epoxidation secondary reactor is 40-180 ℃, the operating pressure is 0.1-12.0 MPaA, the number of the epoxidation secondary reactors connected in series is 1-10, the service life of the catalyst filled in the epoxidation secondary reactor is 1-24 months, and the operating cycle of the secondary epoxidation reactor is 0.5-12 months.
Further preferably, the operating temperature of the epoxidation secondary reactor is 60-160 ℃, the operating pressure is 1.0-10.0 MPaA, the number of the epoxidation secondary reactors connected in series is 2-8, the service life of the catalyst filled in the epoxidation secondary reactor is 2-12 months, and the operating cycle of the epoxidation secondary reactor is 1-9 months.
Preferably, the operating temperature of the epoxidation secondary reactor is 80-140 ℃, the operating pressure is 2.0-7.0 MPaA, the number of the epoxidation secondary reactors connected in series is 3-6, the service life of the catalyst filled in the epoxidation secondary reactor is 3-6 months, and the operating cycle of the epoxidation secondary reactor is 3-6 months.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the invention relates to a CHPPO device and a method for improving the yield of propylene oxide, wherein in the CHPPO device with the production scale of 100 tons/year to 80 ten thousand tons/year, an optimized epoxidation unit process flow is adopted, the activity of a catalyst is gradually improved from a logic 1-position reactor to a logic last-position reactor by switching epoxidation reactors connected in series, and a propylene raw material and a reaction product at the outlet of the logic 1-position reactor of the epoxidation first-stage reaction are subjected to heat exchange. Along with the gradual reduction of the mole fraction of the reaction raw materials, the activity of the catalyst is gradually improved, so that the epoxidation reaction is gradually deepened, the conversion rate of cumene hydroperoxide is improved to 99.5-99.6% from 90.1-99.5% in the prior art, the selectivity of propylene oxide is improved to 98.2-98.6% from 91.6-98.2% in the prior art, and the yield of the propylene oxide is improved to 97.7-98.2% from 82.5-97.7% in the prior art; meanwhile, the epoxidation reaction heat is recovered from 176.2-183.4 kcal/kg PO, the consumption of low-pressure steam and circulating cooling water is reduced, the quantity of process equipment is reduced, the equipment engineering construction investment and the operation cost are saved, and a better technical effect is obtained.
Drawings
FIG. 1 is a schematic diagram of a process flow of a method for increasing the yield of propylene oxide from a CHPPO device; take 3 first-stage epoxidation reactors connected in series and 3 second-stage epoxidation reactors connected in series as an example;
1-an oxidation unit; 2-epoxidation first-stage reaction logic 1-bit reactor; 3-epoxidation first-stage reaction logic 2-bit reactor; a 4-epoxidation first-stage reaction logic 3-bit reactor; 5-propylene preheat heat exchanger No. 1; 6-propylene preheat No. 2 heat exchanger; 7-propylene preheat No. 3 heat exchanger; an 8-propylene feed heater; no. 1 cooler for the first-stage epoxidation reaction product 9; no. 2 cooler for the first-stage epoxidation reaction product; 11-epoxidation first-order reaction product No. 3 cooler; 12-epoxidation second-order reaction logic 1-bit reactor; 13-epoxidation second-order reaction logic 2-bit reactor; 14-epoxidation second-stage reaction logic 3-bit reactor; no. 1 cooler for 15-epoxidation secondary reaction product; no. 2 cooler for 16-epoxidation secondary reaction product; 17-epoxidation second-order reaction product No. 3 cooler; 18-a separation unit; 19-a hydrogenolysis unit; 20-a compression unit; a-air; b1-fresh cumene; b2-recycle cumene; c1-fresh propylene; c2-recycle propylene; d-hydrogen; e-cumene hydroperoxide; f- α, α -dimethylbenzyl alcohol; g1-first order reaction logic 1-position reactor reaction product; g2-first order reaction logic 2-position reactor reaction product; g3-first order reaction logic 3-position reactor reaction product; g4-second order reaction logic 1-position reactor reaction product; g5-second order reaction logic 2-position reactor reaction product; g6-second order reaction logic 3-position reactor reaction product; g7-propylene oxide product.
Still taking 3 first-stage epoxidation reactors connected in series and 3 second-stage epoxidation reactors connected in series as an example, the invention and patent describes a process flow of the method for improving the yield of propylene oxide of the CHPPO device as follows:
a) and (3) oxidation: air a from the outside enters the oxidation unit 1, and fresh cumene B1 from the outside and recycle cumene B2 from the hydrogenolysis unit are combined and then enter the oxidation unit 1, and cumene oxidation reaction occurs in the oxidation unit 1 to produce cumene hydroperoxide E.
b) Epoxidation: fresh propylene C1 from the outside and circulating propylene C2 from a compression unit are combined and pass through a first-stage reaction logic 1-position reactor which flows out of an epoxidation first-stage reaction logic 1-position reactor, and a reaction product G1 of the first-stage reaction logic 1-position reactor exchanges heat in a propylene preheating heat exchanger No. 1, is heated in a propylene raw material heater 8 by low-pressure steam, and is mixed with cumene hydroperoxide E. Firstly, the product enters the top of an epoxidation first-stage reaction logic 1-bit reactor 2, under the condition of a fixed bed heterogeneous catalyst, epoxidation reaction is started to be carried out in the epoxidation first-stage reaction logic 1-bit reactor 2 to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a first-stage reaction logic 1-bit reactor reaction product G1 flows out from the bottom of the epoxidation first-stage reaction logic 1-bit reactor 2, heat exchange is carried out between a propylene preheating heat exchanger No. 1 and propylene, and cooling is carried out through circulating cooling water of an epoxidation first-stage reaction product No. 1 cooler 9. And then the reaction product enters the top of an epoxidation first-stage reaction logic 2-bit reactor 3, epoxidation reaction is continuously carried out in the epoxidation first-stage reaction logic 2-bit reactor 3 in the presence of a fixed bed heterogeneous catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a first-stage reaction logic 2-bit reactor reaction product G2 flows out from the bottom of the epoxidation first-stage reaction logic 2-bit reactor 3, and the epoxidation first-stage reaction product G2 is cooled by circulating cooling water through an epoxidation first-stage reaction product No. 2 cooler 10. And the product enters the top of the epoxidation first-stage reaction logic 3-bit reactor 4 again, the epoxidation reaction is continuously carried out in the epoxidation first-stage reaction logic 3-bit reactor 4 in the presence of a fixed bed heterogeneous catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a first-stage reaction logic 3-bit reactor reaction product G3 flows out from the bottom of the epoxidation first-stage reaction logic 3-bit reactor 4, and the product is cooled by circulating cooling water through an epoxidation first-stage reaction product No. 3 cooler 11. Then the reaction product is sent to the top of an epoxidation second-stage reaction logic 1-bit reactor 12, epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 1-bit reactor 12 in the presence of a fixed bed heterogeneous catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a second-stage reaction logic 1-bit reactor reaction product G4 flows out from the bottom of the epoxidation second-stage reaction logic 1-bit reactor 12, and the epoxidation second-stage reaction product G4 is cooled by circulating cooling water through an epoxidation second-stage reaction product No. 1 cooler 15. Then the reaction product is sent to the top of an epoxidation second-stage reaction logic 2-bit reactor 13, epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 2-bit reactor 13 in the presence of a fixed bed heterogeneous catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a second-stage reaction logic 2-bit reactor reaction product G5 flows out from the bottom of the epoxidation second-stage reaction logic 2-bit reactor 13, and the epoxidation second-stage reaction product G5 is cooled by circulating cooling water through an epoxidation second-stage reaction product No. 2 cooler 16. And finally, the product is sent to the top of an epoxidation second-stage reaction logic 3-bit reactor 14, epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 3-bit reactor 14 in the presence of a fixed bed heterogeneous catalyst to generate propylene oxide and alpha, alpha-dimethyl benzyl alcohol, a second-stage reaction logic 3-bit reactor reaction product G6 flows out from the bottom of the epoxidation second-stage reaction logic 3-bit reactor 14, and the product is cooled by circulating cooling water through an epoxidation second-stage reaction product No. 3 cooler 17. At the moment, the activity of the catalyst in an epoxidation first-stage reaction logic 1-bit reactor 2, an epoxidation first-stage reaction logic 2-bit reactor 3 and an epoxidation first-stage reaction logic 3-bit reactor 4 is gradually improved; propylene preheat No. 1 heat exchanger 5 was on stream while propylene preheat No. 2 heat exchanger 6 and propylene preheat No. 3 heat exchanger 7 were off stream. Similarly, the activity of the catalyst in the epoxidation second-stage reaction logic 1-bit reactor 12, the epoxidation second-stage reaction logic 2-bit reactor 13 and the epoxidation second-stage reaction logic 3-bit reactor 14 is gradually improved.
When the catalyst needs to be replaced due to the deactivation of the catalyst in the epoxidation first-stage reaction logic 1-bit reactor, after the catalyst is replaced, the original epoxidation first-stage reaction logic 2-bit reactor is switched to the epoxidation first-stage reaction logic 1-bit reactor, the original epoxidation first-stage reaction logic 3-bit reactor is switched to the epoxidation first-stage reaction logic 2-bit reactor, and the original epoxidation first-stage reaction logic 1-bit reactor is switched to the epoxidation first-stage reaction logic 3-bit reactor. At the moment, the activity of the catalyst in an epoxidation first-stage reaction logic 1-bit reactor, an epoxidation first-stage reaction logic 2-bit reactor and an epoxidation first-stage reaction logic 3-bit reactor is gradually improved; the propylene preheat No. 2 heat exchanger 6 was on stream while the propylene preheat No. 3 heat exchanger 7 and the propylene preheat No. 1 heat exchanger 5 were off stream. Similarly, the activity of the catalyst in the reactor of the epoxidation secondary reaction system is also gradually increased. And so on, and the process is repeated.
c) Separation: and a second-stage reaction logic 3-bit reactor reaction product G6 containing propylene oxide, alpha-dimethyl benzyl alcohol, circulating propylene and the like flows out of the epoxidation second-stage reaction product No. 3 cooler 17 and is sent into a separation unit 18, and the circulating propylene C2, the alpha, alpha-dimethyl benzyl alcohol F and a propylene oxide product G7 are obtained through multi-tower rectification and separation of the separation unit 18, wherein the propylene oxide product G7 is sent out.
d) And (3) hydrogenolysis: hydrogen D from the outside and alpha, alpha-dimethyl benzyl alcohol F from the separation unit enter a hydrogenolysis unit 19, the hydrogen D and the alpha, alpha-dimethyl benzyl alcohol F generate hydrogenolysis reaction in the presence of a catalyst to generate circulating cumene B2, and the circulating cumene B2 returns to be combined with fresh cumene B1 and enters an oxidation unit.
e) Compression: the recycled propylene C2 leaving the separation unit is pressurized by the compression unit 20 (propylene compressor) and returned and combined with fresh propylene C1 to the epoxidation unit.
Detailed Description
The invention provides a CHPPO device and method for improving the yield of propylene oxide.
The CHPPO device for improving the yield of the propylene oxide has the production scale of 100 tons/year to 80 ten thousand tons/year and comprises an oxidation unit, an epoxidation unit, a separation unit, a hydrogenolysis unit and a compression unit;
the epoxidation unit comprises an epoxidation first-stage reaction system, a propylene preheating heat exchange system, an epoxidation first-stage reaction product cooling system, a propylene raw material heating system, an epoxidation second-stage reaction system and an epoxidation second-stage reaction product cooling system;
the epoxidation first-stage reaction system comprises m epoxidation first-stage reactors connected in series, wherein the epoxidation first-stage reactors are respectively epoxidation first-stage reaction logic 1-m reactors;
the epoxidation second-stage reaction system comprises n epoxidation first-stage reactors connected in series, wherein the epoxidation first-stage reactors are respectively epoxidation second-stage reaction logic 1-n reactors;
the propylene preheating heat exchange system comprises m propylene preheating heat exchangers, namely propylene preheating 1-m heat exchangers;
the propylene raw material heating system comprises 1 propylene raw material heater, wherein an inlet pipeline of the propylene raw material heater is connected with an outlet pipeline of the propylene preheating heat exchanger;
the epoxidation first-order reaction product cooling system comprises m epoxidation first-order reaction product coolers which are respectively number 1-m coolers for epoxidation first-order reaction products;
the cooling system for the epoxidation secondary reaction products comprises n epoxidation secondary reaction product coolers, namely coolers from No. 1 to No. n of the epoxidation secondary reaction products;
wherein m is more than or equal to 1, n is more than or equal to 1, and m is equal to n;
when m is 1, the epoxidation first-stage reaction logic 1-bit reactor, the propylene preheating heat exchanger No. 1, the epoxidation first-stage reaction product No. 1 cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through a pipeline;
when m is more than or equal to 2, a connecting pipeline between the epoxidation first-stage reaction logic 1 to (m-1) reactor and the next corresponding epoxidation first-stage reactor is sequentially provided with 1 propylene preheating heat exchanger and 1 epoxidation first-stage reaction product cooler, and the bit numbers of the propylene preheating heat exchanger and the epoxidation first-stage reaction product cooler are respectively 1 to (m-1); the epoxidation first-stage reaction logic m-bit reactor, the propylene preheating m-number heat exchanger, the epoxidation first-stage reaction product m-number cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through pipelines;
when n is 1, the epoxidation second-stage reaction logic 1-bit reactor, the epoxidation second-stage reaction product No. 1 cooler and the separation unit are sequentially connected through pipelines;
when n is more than or equal to 2, 1 epoxidation secondary reaction product cooler is arranged on a connecting pipeline between the epoxidation secondary reaction logic 1 to (n-1) position reactor and the next corresponding epoxidation secondary reactor, and the position number of the epoxidation secondary reaction product cooler is 1 to (n-1); the epoxidation second-stage reaction logic n-bit reactor is connected with an epoxidation second-stage reaction product n cooler through a pipeline;
one pipeline of the separation unit is converged into a first main pipeline through the compression unit and a fresh propylene feeding pipeline, and the first main pipeline is provided with m side pipeline which are respectively connected with fresh propylene inlet pipelines of a propylene preheating No. 1-m heat exchanger; fresh propylene outlets of the propylene preheating No. 1-m heat exchangers are provided with second main pipelines which are converged into a second main pipeline, and the second main pipeline is connected to the top of an epoxidation first-stage reaction logic 1-bit reactor through the propylene raw material heater;
the other pipeline of the separation unit and the hydrogen feeding pipeline form a pipeline respectively through the hydrogenolysis unit, the pipeline is converged with the fresh cumene feeding pipeline and is connected with the oxidation unit, and the air feeding pipeline is also connected with the oxidation unit; an oxidation product outlet pipeline of the oxidation unit is converged with a second main pipeline and is connected with the top of an epoxidation first-stage reaction logic 1-bit reactor;
the outlet of the n-type cooler for the epoxidation secondary reaction product is connected with the inlet of the separation unit through a pipeline, and the separation unit is also provided with a propylene oxide product discharging pipeline.
The reactors in the epoxidation first-stage reaction system and the epoxidation second-stage reaction system are switched in series, when the catalyst needs to be replaced due to the deactivation of the catalyst in the logic 1-bit reactor, the logic 2-bit reactor is switched into the logic 1-bit reactor, and so on, and after the catalyst is replaced in the original logic 1-bit reactor, the original logic 1-bit reactor is switched into the logic final-bit reactor. This allows the catalyst activity in the reactors in series to be increased from the logical 1-position reactor to the logical last-position reactor, allowing the epoxidation reaction to proceed further and further until the reaction product leaves the logical last-position reactor. In addition, the epoxidation reaction entering the epoxidation secondary reaction system is mild, the heat release is small, and the recovery energy is limited, so a material heat exchange process flow is not arranged.
A method for improving the yield of propylene oxide based on the CHPPO device comprises the following steps:
step one, oxidation: air from the outside enters an oxidation unit, fresh cumene from the outside and circulating cumene from a hydrogenolysis unit are combined and then enter the oxidation unit, and cumene oxidation reaction is carried out in the oxidation unit to generate cumene hydroperoxide.
Step two, epoxidation: fresh propylene from outside and circulating propylene from a compression unit are combined and pass through a first-stage reaction logic 1-bit reactor which flows out from an epoxidation first-stage reaction logic 1-bit reactor, a reaction product of the first-stage reaction logic 1-bit reactor exchanges heat in a propylene preheating heat exchanger, is heated in a propylene raw material heater by low-pressure steam and is mixed with cumene hydroperoxide. The method comprises the steps of firstly entering the top of an epoxidation first-stage reaction logic 1-bit reactor, starting epoxidation reaction in the epoxidation first-stage reaction logic 1-bit reactor to generate a first-stage reaction logic 1-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), enabling the first-stage reaction logic 1-bit reactor reaction product to flow out from the bottom of the epoxidation first-stage reaction logic 1-bit reactor, preheating a No. 1 heat exchanger by propylene, exchanging heat with fresh propylene, and cooling by circulating cooling water of a No. 1 epoxidation first-stage reaction product cooler. And then entering the top of an epoxidation first-stage reaction logic 2-bit reactor, continuously carrying out epoxidation reaction in the epoxidation first-stage reaction logic 2-bit reactor to generate a first-stage reaction logic 2-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), allowing the first-stage reaction logic 2-bit reactor reaction product to flow out from the bottom of the epoxidation first-stage reaction logic 2-bit reactor, and cooling by circulating cooling water through a reaction product cooler. And repeating the epoxidation reaction until the m-bit reactor of the first-stage reaction logic continues to perform the epoxidation reaction to generate the m-bit reactor reaction products (propylene oxide and alpha, alpha-dimethyl benzyl alcohol) of the first-stage reaction logic. Under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved; and the propylene preheating heat exchanger No. 1 corresponding to the epoxidation first-stage reaction logic 1-bit reactor is used, and the rest propylene preheating heat exchangers are stopped. Cooling the reaction product of the m-bit reactor of the first-stage reaction logic by circulating cooling water through an m-number cooler of the epoxidation first-stage reaction product; and then the reaction product is sent to the top of an epoxidation second-stage reaction logic 1-bit reactor, epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 1-bit reactor to generate a second-stage reaction logic 1-bit reactor reaction product (epoxypropane and alpha, alpha-dimethyl benzyl alcohol), the second-stage reaction logic 1-bit reactor reaction product flows out from the bottom of the epoxidation second-stage reaction logic 1-bit reactor, and the epoxidation second-stage reaction product is cooled by circulating cooling water through a No. 1 cooler. And so on until the epoxidation second-stage reaction logic n-bit reactor and the epoxidation second-stage reaction product n-number cooler. Under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved. The continuous and stable operation of the epoxidation unit of the CHPPO process device is ensured by the series switching operation of the epoxidation reaction system.
Step three, separation: and (3) sending a reaction product containing the components of propylene oxide, alpha-dimethyl benzyl alcohol, circulating propylene and the like which flows out of the n-th cooler of the epoxidation secondary reaction product into a separation unit, and rectifying and separating the reaction product in multiple towers of the separation unit to obtain the products of the circulating propylene, the alpha, alpha-dimethyl benzyl alcohol and the propylene oxide, wherein the propylene oxide product is sent out.
Step four, hydrogenolysis: hydrogen from the outside and alpha, alpha-dimethyl benzyl alcohol from the separation unit enter a hydrogenolysis unit, the hydrogen and the alpha, alpha-dimethyl benzyl alcohol generate hydrogenolysis reaction to generate circulating isopropyl benzene in the presence of a catalyst, and the circulating isopropyl benzene returns to the hydrogenolysis unit and is combined with fresh isopropyl benzene to enter an oxidation unit.
Step five, compression: the circulating propylene flowing out of the separation unit is pressurized by a compression unit-propylene compressor and then returned and combined with fresh propylene to enter an epoxidation unit.
In a preferred embodiment of the present invention, the operating temperature of the epoxidation first-stage reactor is 40 to 180 ℃, the operating pressure is 0.6 to 15.0MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 1 to 50: the mass concentration of the cumene hydroperoxide feeding material is 2-95%, the weight space velocity of the cumene hydroperoxide feeding material is 0.1-8.0 h < -1 >, the number of the epoxidation first-stage reactors connected in series is 1-10, the service life of the epoxidation first-stage reactor filled with a catalyst is 1-24 months, and the operation cycle of the epoxidation first-stage reactor is 0.5-12 months.
Further preferably, the operating temperature of the epoxidation first-stage reactor is 60-160 ℃, the operating pressure is 2.0-12.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 2-40: 1, the mass concentration of the cumene hydroperoxide feed is 4-90%, and the weight space velocity of the cumene hydroperoxide feed is 0.2-5.0 h-1The number of the epoxidation first-stage reactors connected in series is 2-8, the service life of the epoxidation first-stage reactor filled with the catalyst is 2-12 months, and the operation cycle of the epoxidation first-stage reactor is excellentThe selection range is 1-9 months.
More preferably, the operating temperature of the epoxidation first-stage reactor is 80-140 ℃, the operating pressure is 3.0-9.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 4-20: 1, the mass concentration of the cumene hydroperoxide feed is 8-80%, and the weight space velocity of the cumene hydroperoxide feed is 0.4-2.0 h-1The number of the epoxidation first-stage reactors connected in series is 3-6, the service life of the epoxidation first-stage reactor filled with a catalyst is 3-6 months, and the operation period of the epoxidation first-stage reactor is 3-6 months.
In a preferred embodiment of the present invention, the operating temperature of the epoxidation secondary reactor is 40 to 180 ℃, the operating pressure is 0.1 to 12.0MPaA, the number of the epoxidation secondary reactors connected in series is 1 to 10, the life of the catalyst filled in the epoxidation secondary reactor is 1 to 24 months, and the operating cycle of the secondary epoxidation reactor is 0.5 to 12 months.
Further preferably, the operating temperature of the epoxidation secondary reactor is 60-160 ℃, the operating pressure is 1.0-10.0 MPaA, the number of the epoxidation secondary reactors connected in series is 2-8, the service life of the catalyst filled in the epoxidation secondary reactor is 2-12 months, and the operating cycle of the epoxidation secondary reactor is 1-9 months.
Preferably, the operating temperature of the epoxidation secondary reactor is 80-140 ℃, the operating pressure is 2.0-7.0 MPaA, the number of the epoxidation secondary reactors connected in series is 3-6, the service life of the catalyst filled in the epoxidation secondary reactor is 3-6 months, and the operating cycle of the epoxidation secondary reactor is 3-6 months.
By adopting the technical method for improving the yield of the propylene oxide of the CHPPO device, the process flow of an epoxidation unit is optimized, and technical means for improving the activity of the catalyst step by step are arranged, so that the epoxidation reaction is gradually deepened, and the problems of low cumene hydroperoxide conversion rate, low propylene oxide selectivity, low propylene oxide yield and difficulty in comprehensive utilization of epoxidation reaction heat in the prior art are better solved.
The present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
Comparative example 1
The epoxidation unit of the CHPPO industrial device adopts the conventional process flow in the prior art to produce the epoxypropane product, an air cooler and a fan are required to be arranged, a propylene raw material is heated to the reaction temperature through low-pressure steam, a large amount of steam is required to be consumed, a reaction product is cooled through circulating cooling water, a large amount of circulating cooling water is required to be consumed, and therefore, the number of process equipment is large, the engineering construction investment is large, the operation and running cost is high, and the epoxidation reaction heat is difficult to comprehensively utilize. The cumene hydroperoxide conversion rate is 90.1-99.5%, the propylene oxide selectivity is 91.6-98.2%, and the propylene oxide yield is 82.5-97.7%.
[ example 1 ]
Taking a CHPPO industrial device with the production scale of 10 ten thousand tons/year as an example, by adopting the method for improving the yield of the propylene oxide of the CHPPO device, the epoxidation unit adopts an optimized process flow, the activity of the catalyst is gradually improved from a logic 1-position reactor to a logic final-position reactor by switching the epoxidation reactors connected in series, and the propylene raw material and the reaction product at the outlet of the logic 1-position reactor of the epoxidation first-stage reaction are subjected to heat exchange. The process operating parameters of the present example are as follows: the epoxidation first stage reactor was operated at 102 ℃, an operating pressure of 6.3mpa, a molar ratio of fresh propylene feed to cumene hydroperoxide feed of 12: 1, the mass concentration of the cumene hydroperoxide feed is 35 percent, and the weight space velocity of the cumene hydroperoxide feed is 3.2h-1The number of the epoxidation first-stage reactors connected in series is m-3, the temperature difference of the epoxidation first-stage reactors is 65.8 ℃, 44.8 ℃ and 23.8 ℃, the service life of the catalyst filled in the epoxidation first-stage reactor is 8 months, and the switching period of the epoxidation first-stage reactor is 4 months. The operation temperature of the epoxidation secondary reactor is 92 ℃, the operation pressure is 5.3MPaA, the number of the epoxidation secondary reactors connected in series is n-3, the temperature difference of the epoxidation secondary reactors is 53.2 ℃, 32.2 ℃ and 11.2 ℃, and the service life of the epoxidation secondary reactor filled with the catalyst is 8 months. The conversion rate of the cumene hydroperoxide is improved to 99.6 percent, and the selectivity of the propylene oxide is improvedThe yield of the propylene oxide is improved to 98.1 percent as high as 98.5 percent; meanwhile, the epoxidation reaction heat is recovered at 2,245,000 kcal/h, and a better technical effect is achieved.
[ example 2 ]
Similarly [ example 1 ], the production scale was changed to 30 million tons/year CHPPO industrial plant only with changes in the production scale and process operating parameters, which were modified as follows: the epoxidation first stage reactor was operated at 147 c, an operating pressure of 10.4MPaA, a molar ratio of fresh propylene feed to cumene hydroperoxide feed of 31: 1, the mass concentration of the cumene hydroperoxide feed is 56 percent, and the weight space velocity of the cumene hydroperoxide feed is 5.3h-1The number of the epoxidation first-stage reactors connected in series is m-4, the temperature difference of the epoxidation first-stage reactors is 68.1 ℃, 52.1 ℃, 36.1 ℃ and 20.1 ℃, the service life of the epoxidation first-stage reactor filled with the catalyst is 14 months, and the switching period of the epoxidation first-stage reactors is 8 months. The operating temperature of the epoxidation secondary reactor was 127 ℃, the operating pressure was 9.4MPaA, the number of epoxidation secondary reactors connected in series was 4, the temperature difference of the epoxidation secondary reactor was 53.4 ℃, 39.4 ℃, 25.4 ℃, 11.4 ℃, and the life of the epoxidation secondary reactor charged with the catalyst was 14 months. Therefore, the conversion rate of the cumene hydroperoxide is improved to 99.6 percent, the selectivity of the propylene oxide is improved to 98.6 percent, and the yield of the propylene oxide is improved to 98.2 percent; meanwhile, the epoxidation reaction heat is recovered at 6,753,750 kcal/h, and a better technical effect is achieved.
[ example 3 ]
Similarly [ example 1 ], the production scale was changed to a 100 ton/year CHPPO pilot plant with only changes in the production scale and in the process operating parameters, which were modified as follows: the number of the epoxidation first-stage reactors in series is m-1, the temperature difference of the epoxidation first-stage reactors is 45.8 ℃, the number of the epoxidation second-stage reactors in series is n-1, and the temperature difference of the epoxidation second-stage reactors is 33.2 ℃; the rest of the process operating parameters are unchanged. Therefore, the conversion rate of the cumene hydroperoxide is improved to 99.5 percent, the selectivity of the propylene oxide is improved to 98.2 percent, and the yield of the propylene oxide is improved to 97.7 percent; meanwhile, the epoxidation reaction heat is recovered at 2,203 kcal/h, and a better technical effect is achieved.
[ example 4 ]
Similarly [ example 1 ], the production scale was changed to 80 million tons/year CHPPO industrial plant only with changes in the production scale and process operating parameters, which were modified as follows: the number of the epoxidation first-stage reactors in series is 10, the temperature difference of the epoxidation first-stage reactors is 67.5 ℃, 62.5 ℃, 57.5 ℃, 52.5 ℃, 47.5 ℃, 42.5 ℃, 37.5 ℃, 32.5 ℃, 27.5 ℃, 22.5 ℃, the number of the epoxidation second-stage reactors in series is 10, and the temperature difference of the epoxidation second-stage reactors is 49.3 ℃, 45.3 ℃, 41.3 ℃, 37.3 ℃, 33.3 ℃, 29.3 ℃, 25.3 ℃, 21.3 ℃, 17.3 ℃ and 13.3 ℃; the rest of the process operating parameters are unchanged. Therefore, the conversion rate of the cumene hydroperoxide is improved to 99.6 percent, the selectivity of the propylene oxide is improved to 98.6 percent, and the yield of the propylene oxide is improved to 98.2 percent; meanwhile, the epoxidation reaction heat is recovered at 18,340,000 kcal/h, and a better technical effect is achieved.
[ example 5 ]
As in example 2, the production scale was still 30 million tons/year CHPPO industrial plant with only process operating parameters changed, and the process operating parameters of this example were modified as follows: the epoxidation first stage reactor was operated at 40 ℃ and 0.6MPaA at a molar ratio of propylene feed to cumene hydroperoxide feed of 1: 1, the mass concentration of the cumene hydroperoxide feed is 2 percent, and the weight space velocity of the cumene hydroperoxide feed is 0.1h-1The number of the epoxidation first-stage reactors connected in series is 4, the temperature difference of the epoxidation first-stage reactors is 69.6 ℃, 52.6 ℃, 35.6 ℃ and 18.6 ℃, the service life of the epoxidation first-stage reactor filled with the catalyst is 24 months, and the switching period of the epoxidation first-stage reactors is 0.5 month. The operation temperature of the epoxidation secondary reactor is 40 ℃, the operation pressure is 0.1MPaA, the number of the epoxidation secondary reactors connected in series is 4, the temperature difference of the epoxidation secondary reactors is respectively 55.4 ℃, 40.4 ℃, 25.4 ℃ and 10.4 ℃, and the service life of the epoxidation secondary reactor filled with the catalyst is 24 months. The conversion rate of the cumene hydroperoxide is improved to 99.5 percent, and the propylene oxide is obtainedThe selectivity is improved to 98.4 percent, and the yield of the propylene oxide is improved to 97.9 percent; meanwhile, the epoxidation reaction heat is recovered at 6,648,750 kcal/h, and a better technical effect is achieved.
[ example 6 ]
As in example 2, the production scale was still 30 million tons/year CHPPO industrial plant with only process operating parameters changed, and the process operating parameters of this example were modified as follows: the epoxidation first stage reactor was operated at 180 ℃, an operating pressure of 15.0mpa, and a molar ratio of fresh propylene feed to cumene hydroperoxide feed of 50: 1, the mass concentration of the cumene hydroperoxide feed is 95 percent, and the weight space velocity of the cumene hydroperoxide feed is 8.0h-1The number of the epoxidation first-stage reactors connected in series is m-4, the temperature difference of the epoxidation first-stage reactors is 79.9 ℃, 62.9 ℃, 45.9 ℃ and 28.9 ℃, the service life of the epoxidation first-stage reactor filled with the catalyst is 1 month, and the switching period of the epoxidation first-stage reactors is 12 months. The operation temperature of the epoxidation secondary reactor is 180 ℃, the operation pressure is 12.0MPaA, the number of the epoxidation secondary reactors connected in series is 4, the temperature difference of the epoxidation secondary reactors is 65.0 ℃, 50.0 ℃, 35.0 ℃ and 20.0 ℃, and the service life of the epoxidation secondary reactor filled with the catalyst is 1 month. Therefore, the conversion rate of the cumene hydroperoxide is improved to 99.5 percent, the selectivity of the propylene oxide is improved to 98.3 percent, and the yield of the propylene oxide is improved to 97.8 percent; meanwhile, the epoxidation reaction heat is recovered at 6,690,000 kcal/h, and a better technical effect is achieved.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. It will be appreciated by those skilled in the art that any equivalent modifications and substitutions are within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (8)

1. A CHPPO device for improving the yield of propylene oxide is characterized by comprising an oxidation unit, an epoxidation unit, a separation unit, a hydrogenolysis unit and a compression unit in the CHPPO device with the production scale of 100 tons/year to 80 ten thousand tons/year;
the epoxidation unit comprises an epoxidation first-stage reaction system, a propylene preheating heat exchange system, an epoxidation first-stage reaction product cooling system, a propylene raw material heating system, an epoxidation second-stage reaction system and an epoxidation second-stage reaction product cooling system;
the epoxidation first-stage reaction system comprises m epoxidation first-stage reactors connected in series, wherein the epoxidation first-stage reactors are respectively epoxidation first-stage reaction logic 1-m reactors;
the epoxidation secondary reaction system comprises n epoxidation primary reactors connected in series, wherein the epoxidation primary reactors are respectively epoxidation secondary reaction logic 1-n reactors;
the m series-connected epoxidation first-stage reactors are also connected in series with the n series-connected epoxidation second-stage reactors;
the propylene preheating heat exchange system comprises m propylene preheating heat exchangers which are respectively propylene preheating No. 1-m heat exchangers;
the propylene raw material heating system comprises 1 propylene raw material heater, and an inlet pipeline of the propylene raw material heater is connected with an outlet pipeline of the propylene preheating heat exchanger;
the epoxidation first-stage reaction product cooling system comprises m epoxidation first-stage reaction product coolers which are respectively number 1-m coolers for epoxidation first-stage reaction products;
the epoxidation secondary reaction product cooling system comprises n epoxidation secondary reaction product coolers which are respectively number 1-n coolers for epoxidation secondary reaction products;
wherein m is more than or equal to 1, n is more than or equal to 1, and m is equal to n;
when m is 1, the epoxidation first-stage reaction logic 1-bit reactor, the propylene preheating heat exchanger No. 1, the epoxidation first-stage reaction product No. 1 cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through a pipeline;
when m is more than or equal to 2, a connecting pipeline between the epoxidation first-stage reaction logic 1 to (m-1) reactor and the next corresponding epoxidation first-stage reactor is sequentially provided with 1 propylene preheating heat exchanger and 1 epoxidation first-stage reaction product cooler, and the bit numbers of the propylene preheating heat exchanger and the epoxidation first-stage reaction product cooler are respectively 1 to (m-1); the epoxidation first-stage reaction logic m-bit reactor, the propylene preheating m-number heat exchanger, the epoxidation first-stage reaction product m-number cooler and the epoxidation second-stage reaction logic 1-bit reactor are sequentially connected through pipelines;
when n is 1, the epoxidation second-stage reaction logic 1-bit reactor, the epoxidation second-stage reaction product No. 1 cooler and the separation unit are sequentially connected through pipelines;
when n is more than or equal to 2, 1 epoxidation secondary reaction product cooler is arranged on a connecting pipeline between the epoxidation secondary reaction logic 1 to (n-1) position reactor and the next corresponding epoxidation secondary reactor, and the position number of the epoxidation secondary reaction product cooler is 1 to (n-1); the epoxidation second-stage reaction logic n-bit reactor is connected with an epoxidation second-stage reaction product n cooler through a pipeline;
the reactors in the epoxidation first-stage reaction system and the epoxidation second-stage reaction system are switched in series, when the catalyst needs to be replaced due to the deactivation of the catalyst in the logic 1-bit reactor, the original logic 2-bit reactor is switched into the logic 1-bit reactor, and so on until the logic last-bit reactor; after the catalyst of the original logic 1-bit reactor is replaced, the original logic 1-bit reactor is switched into a logic final-bit reactor; thus, the activity of the catalyst in the reactors connected in series is gradually improved from the logic 1-bit reactor to the logic last-bit reactor, and the epoxidation reaction is gradually deepened until the reaction product leaves the logic last-bit reactor;
one pipeline of the separation unit is converged into a first main pipeline through the compression unit and a fresh propylene feeding pipeline, and the first main pipeline is provided with m side pipeline which are respectively connected with fresh propylene inlet pipelines of a propylene preheating No. 1-m heat exchanger; fresh propylene outlets of the propylene preheating No. 1-m heat exchangers are provided with pipelines which are converged into a second main pipeline, and the second main pipeline is connected to the top of an epoxidation first-stage reaction logic 1-bit reactor through the propylene raw material heater;
the other pipeline of the separation unit and the hydrogen feeding pipeline form a pipeline respectively through the hydrogenolysis unit, the pipeline is converged with the fresh cumene feeding pipeline and is connected with the oxidation unit, and the air feeding pipeline is also connected with the oxidation unit; an oxidation product outlet pipeline of the oxidation unit is converged with a second main pipeline and then is connected with the top of an epoxidation first-stage reaction logic 1-bit reactor;
and the outlet of the n-type cooler for the epoxidation secondary reaction product is connected with the inlet of the separation unit through a pipeline, and the separation unit is also provided with a propylene oxide product discharging pipeline.
2. A method for increasing the yield of propylene oxide based on the CHPPO device of claim 1, comprising the steps of:
step one, oxidation: air from the outside enters the oxidation unit, fresh cumene from the outside and circulating cumene from the hydrogenolysis unit are combined and then enter the oxidation unit, and cumene oxidation reaction is carried out in the oxidation unit to generate cumene hydroperoxide;
step two, epoxidation: the fresh propylene from the outside and the circulating propylene from the compression unit are combined and flow out through the first-stage reaction logic 1-bit reactor, and the reaction product of the first-stage reaction logic 1-bit reactor flows out from the epoxidation first-stage reaction logic 1-bit reactor, exchanges heat in a propylene preheating No. 1 heat exchanger, is heated in a propylene raw material heater through low-pressure steam, and then is mixed with cumene hydroperoxide; firstly, the propylene enters the top of an epoxidation first-stage reaction logic 1-bit reactor, epoxidation reaction is started in the epoxidation first-stage reaction logic 1-bit reactor to generate a first-stage reaction logic 1-bit reactor reaction product, the first-stage reaction logic 1-bit reactor reaction product flows out from the bottom of the epoxidation first-stage reaction logic 1-bit reactor, heat exchange is carried out between the propylene preheating heat exchanger 1 and fresh propylene, and cooling is carried out through circulating cooling water of the epoxidation first-stage reaction product 1 cooler; secondly, entering the top of the epoxidation first-stage reaction logic 2-bit reactor, continuously carrying out epoxidation reaction in the epoxidation first-stage reaction logic 2-bit reactor to generate a first-stage reaction logic 2-bit reactor reaction product, wherein the first-stage reaction logic 2-bit reactor reaction product flows out of the bottom of the epoxidation first-stage reaction logic 2-bit reactor, and is cooled by circulating cooling water through a reaction product cooler; repeating the epoxidation reaction until the m-bit reactor of the epoxidation first-stage reaction logic continues to perform the epoxidation reaction to generate a reaction product of the m-bit reactor of the epoxidation first-stage reaction logic; under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved; the propylene preheating heat exchanger No. 1 corresponding to the epoxidation first-stage reaction logic 1-bit reactor is used, and the rest propylene preheating heat exchangers are stopped; the reaction product of the m-bit reactor of the first-stage reaction logic is cooled by circulating cooling water through an m-number cooler of the epoxidation first-stage reaction product; then the reaction product is sent to the top of the epoxidation second-stage reaction logic 1-bit reactor, the epoxidation reaction is continuously carried out in the epoxidation second-stage reaction logic 1-bit reactor to generate a second-stage reaction logic 1-bit reactor reaction product, the second-stage reaction logic 1-bit reactor reaction product flows out from the bottom of the epoxidation second-stage reaction logic 1-bit reactor, and the epoxidation second-stage reaction product is cooled by circulating cooling water through a No. 1 cooler; repeating the steps until an epoxidation second-stage reaction logic n-bit reactor and an epoxidation second-stage reaction product n-number cooler are obtained; under the condition that the mole fraction of the reaction raw materials is gradually reduced, the activity of the catalyst is gradually improved, so that the depth of the epoxidation reaction is gradually improved;
step three, separation: a reaction product containing epoxypropane, alpha-dimethyl benzyl alcohol and circulating propylene flows out of the epoxidation secondary reaction product n cooler and is sent into a separation unit, and the reaction product is rectified and separated in multiple towers of the separation unit to obtain circulating propylene, alpha-dimethyl benzyl alcohol and epoxypropane products, wherein the epoxypropane product is sent out;
step four, hydrogenolysis: hydrogen from the outside and alpha, alpha-dimethyl benzyl alcohol from the separation unit enter the hydrogenolysis unit, and the hydrogen and the alpha, alpha-dimethyl benzyl alcohol are subjected to hydrogenolysis reaction in the presence of a catalyst to generate the circulating isopropyl benzene, and the circulating isopropyl benzene returns to the hydrogenolysis unit and is combined with the fresh isopropyl benzene to enter the oxidation unit;
step five, compression: the recycled propylene flowing out of the separation unit is pressurized by the compression unit and then returned and combined with the fresh propylene to the epoxidation unit.
3. The method for improving the yield of propylene oxide according to claim 2, wherein the operating temperature of the epoxidation first-stage reactor is 40-180 ℃, the operating pressure is 0.6-15.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 1-50: 1, the mass concentration of the cumene hydroperoxide feed is 2-95%, and the weight space velocity of the cumene hydroperoxide feed is 0.1-8.0 h-1The number of the epoxidation first-stage reactors connected in series is 1-10, the service life of a catalyst filled in the epoxidation first-stage reactor is 1-24 months, and the operation period of the epoxidation first-stage reactor is 0.5-12 months.
4. The method for improving the yield of propylene oxide according to claim 3, wherein the operating temperature of the epoxidation first-stage reactor is 60-160 ℃, the operating pressure is 2.0-12.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 2-40: 1, the mass concentration of the cumene hydroperoxide feed is 4-90%, and the weight space velocity of the cumene hydroperoxide feed is 0.2-5.0 h-1The number of the epoxidation first-stage reactors connected in series is 2-8, the service life of a catalyst filled in the epoxidation first-stage reactor is 2-12 months, and the preferred range of the operation period of the epoxidation first-stage reactor is 1-9 months.
5. The method for improving the yield of propylene oxide according to claim 4, wherein the operating temperature of the epoxidation first-stage reactor is 80-140 ℃, the operating pressure is 3.0-9.0 MPaA, and the molar ratio of the fresh propylene feed to the cumene hydroperoxide feed is 4-20: 1, the mass concentration of the cumene hydroperoxide feed is 8-80%, and the weight space velocity of the cumene hydroperoxide feed is 0.4-2.0 h-1The number of the epoxidation first-stage reactors connected in series is 3-6, the service life of a catalyst filled in the epoxidation first-stage reactor is 3-6 months, and the epoxidation first-stage reactor is used for epoxidationThe operation period of the reactor is 3-6 months.
6. The method for improving the yield of propylene oxide according to claim 2, wherein the operating temperature of the epoxidation secondary reactor is 40 to 180 ℃, the operating pressure is 0.1 to 12.0MPaA, the number of the epoxidation secondary reactors connected in series is 1 to 10, the service life of the catalyst filled in the epoxidation secondary reactor is 1 to 24 months, and the operating cycle of the secondary epoxidation reactor is 0.5 to 12 months.
7. The method for improving the yield of propylene oxide according to claim 6, wherein the operating temperature of the epoxidation secondary reactor is 60 to 160 ℃, the operating pressure is 1.0 to 10.0MPaA, the number of the epoxidation secondary reactors connected in series is 2 to 8, the service life of the catalyst filled in the epoxidation secondary reactor is 2 to 12 months, and the operating period of the epoxidation secondary reactor is 1 to 9 months.
8. The method for improving the yield of propylene oxide according to claim 7, wherein the operating temperature of the epoxidation secondary reactor is 80 to 140 ℃, the operating pressure is 2.0 to 7.0MPaA, the number of the epoxidation secondary reactors connected in series is 3 to 6, the service life of the catalyst filled in the epoxidation secondary reactor is 3 to 6 months, and the operating period of the epoxidation secondary reactor is 3 to 6 months.
CN202010969093.4A 2020-09-15 2020-09-15 CHPPO device and method for improving yield of propylene oxide Pending CN112279822A (en)

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CN113512013A (en) * 2021-06-30 2021-10-19 中国石油化工股份有限公司 System and method for preparing propylene oxide from large-scale industrial methanol
CN113527228A (en) * 2021-06-30 2021-10-22 中国石油化工股份有限公司 System and method for continuously producing epoxypropane by using methanol in two-step method

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CN112898239A (en) * 2021-01-22 2021-06-04 中国石油化工股份有限公司 Crude separation system and crude separation method for epoxidation product by isopropyl benzene method
CN113121298A (en) * 2019-12-31 2021-07-16 中国石油化工股份有限公司 Method for producing isopropyl benzene

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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
CN113121298A (en) * 2019-12-31 2021-07-16 中国石油化工股份有限公司 Method for producing isopropyl benzene
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Publication number Priority date Publication date Assignee Title
CN113512013A (en) * 2021-06-30 2021-10-19 中国石油化工股份有限公司 System and method for preparing propylene oxide from large-scale industrial methanol
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