CN114478165A - Process for producing styrene - Google Patents
Process for producing styrene Download PDFInfo
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- CN114478165A CN114478165A CN202011165060.0A CN202011165060A CN114478165A CN 114478165 A CN114478165 A CN 114478165A CN 202011165060 A CN202011165060 A CN 202011165060A CN 114478165 A CN114478165 A CN 114478165A
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- producing styrene
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- styrene
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 132
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims description 16
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 14
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 239000010432 diamond Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 14
- 238000006356 dehydrogenation reaction Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical compound [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8872—Alkali or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J35/30—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/889—Manganese, technetium or rhenium
Abstract
The invention provides a method for producing styrene, which comprises the following steps: sequentially passing reaction raw materials through a plurality of reactors connected in series to obtain a product; wherein the reaction feed comprises at least ethylbenzene and water; the last reactor connected in series is filled with catalyst II, the relative porosity of which is not less than 1.01, based on the porosity of the cylindrical catalyst being 1. The method for producing styrene provided by the invention has the advantages that the reaction is carried out by the plurality of reactors connected in series, and the catalyst in the last reactor is designed, so that the raw materials are fully reacted, the specific surface area of the reaction can be effectively improved, the pressure drop of a bed layer is reduced, the conversion rate of the raw materials and the selectivity of the styrene are improved, and the overall reaction effect and the yield of the styrene are improved.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for producing styrene.
Background
Styrene is an important bulk basic organic raw material, is mainly used for producing synthetic resins and rubber, and the industrial production method of more than 85 percent is an ethylbenzene catalytic dehydrogenation method. Based on the wide use of styrene, the production of styrene in various countries in the world develops rapidly. According to the statistics of the global styrene capacity in 2018, the total capacity is 3397.9 ten thousand tons, the total capacity is mainly concentrated in five major areas of northeast Asia, North America, Western Europe, the middle east Asia and southeast Asia, the total capacity is 3226.8 ten thousand tons, the occupation ratio is up to 95%, and the capacity of other areas is less. In 2019, the capacity of China is 925.5 ten thousand tons, and the method is the largest styrene producing country in the world.
For the important petrochemical catalytic process of preparing styrene by ethylbenzene dehydrogenation, the catalyst plays a critical role in the production of styrene, and the quality of the catalyst determines the economy of the dehydrogenation process. The research, development and updating of the ethylbenzene dehydrogenation catalyst are continuously developed from the 30 s in the 20 th century, the basic components of the existing catalyst are Fe/K/Ce/Mo composite/mixed oxides, the performance of the existing commercial styrene catalyst prepared by ethylbenzene dehydrogenation is relatively close to a thermodynamic equilibrium value and reaches a quite high level, and the performance of the catalyst is not easily improved to a great extent by continuously improving the formula of the catalyst.
Chinese patent CN1209194C discloses a catalyst for preparing styrene by ethylbenzene dehydrogenation and a preparation method thereof, vanadium, cobalt, manganese and titanium oxides are added into a Fe/K/Ce/Mo/Mg system for combination, the preparation process is optimized, and the side pressure strength of the catalyst can be enhanced. However, the catalyst contains vanadium, which causes environmental pollution.
Chinese patent CN100443170C discloses a catalyst for preparing styrene by ethylbenzene dehydrogenation and its preparation method, wherein the side pressure strength of the catalyst is not less than 25N/mm, but because the catalyst is added with 1% -9% of cement and silica gel as reinforcing agents, these reinforcing agents are generally acidic substances, which are easy to cause side reactions such as cracking, etc., thereby affecting the selectivity of the catalyst.
On the other hand, styrene devices tend to be large-scale, the original old devices are expanded and modified by adding one reactor and changing two sections into three sections, while the styrene prepared by ethylbenzene dehydrogenation is a reaction for increasing the number of molecules, the higher the vacuum degree of the device is, the more beneficial the styrene is to be generated, the pressure drop of a bed layer is increased along with the increase of the thickness of the catalyst bed layer or the poor compressive strength of the catalyst, the pulverization is easy, the conversion rate is directly influenced, and then most of the styrene devices introduced in the early stage in China have the problems that a compressor is aged, a combined heat exchanger is seriously blocked, the conversion rate and the selectivity level of the catalyst are difficult to give full play, the energy consumption and the material consumption of the device are high, and the like.
Therefore, it is highly desirable to provide a method for producing styrene, which can design a catalyst, combine the characteristics of various catalysts, and optimize the process, thereby reducing the cost of the production apparatus, reducing the energy consumption, and being suitable for higher reaction pressure.
Disclosure of Invention
The invention aims to solve the technical problems that the device for producing styrene in the prior art has high energy consumption, poor effect and is not suitable for the condition of overhigh reaction pressure, and provides a method for producing styrene, which can ensure higher raw material conversion rate and styrene yield under higher pressure, simultaneously has very high selectivity and can reduce the device cost and energy consumption.
To achieve the object of the present invention, in a first aspect, the present invention provides a process for producing styrene, comprising the steps of: sequentially passing reaction raw materials through a plurality of reactors connected in series to obtain a product; wherein the reaction feed comprises at least ethylbenzene and water; the last reactor connected in series is filled with catalyst II, the relative porosity of which is not less than 1.01, based on the porosity of the cylindrical catalyst being 1.
Preferably, the relative porosity of the catalyst II is not more than 1.25.
The catalyst bed layer with smaller bulk density is obtained by designing the relative porosity of the catalyst II, certain activity can be still kept under larger pressure, and the specific surface area of the reaction can be effectively improved, so that higher raw material conversion rate and styrene yield can be ensured under higher pressure, and meanwhile, the catalyst bed layer has higher selectivity.
The method for producing styrene provided by the invention has the advantages that the reaction is carried out by the plurality of reactors connected in series, and the catalyst in the last reactor is designed, so that the raw materials are fully reacted, the specific surface area of the reaction can be effectively improved, the pressure drop of a bed layer is reduced, the conversion rate of the raw materials and the selectivity of the styrene are improved, and the overall reaction effect and the yield of the styrene are improved.
As a specific embodiment of the invention, the outlet pressure of the last reactor is in the range of 40kPaA to 101kPaA, such as 60kPaA to 101kPaA, 70kPaA to 80kPaA, 40kPaA, 50kPaA, 60kPaA, 70kPaA, 80kPaA, 90kPaA, 101kPaA and any combination thereof. The pressure in the present invention refers to absolute pressure.
The raw materials are subjected to preliminary reaction through a plurality of reactors connected in series, so that the temperature of the material entering the last reactor has a proper reaction temperature when entering the reactors, and the reaction efficiency can be improved.
Preferably, the plurality of reactors is two reactors.
As a specific embodiment of the present invention, the temperature in each reactor can be set to a range between 570 ℃ and 640 ℃, such as 590 ℃ to 620 ℃, 600 ℃ to 610 ℃, 570 ℃ to 590 ℃, 575 ℃, 585 ℃, 595 ℃, 605 ℃, 615 ℃, 625 ℃, 635 ℃ and any combination thereof. The temperature of each reactor may be the same or different and is within the scope of the present invention.
In addition, in order to ensure the temperature of the material at the inlet of the last reactor, a heating system may be provided between the reactors connected in series, specifically, the heating system may be a heating device conventional in the art, such as an interstage heater, and the heating temperature of the heater may be further adjusted, for example, the temperature of the reaction raw material after passing through the heating system is not less than 590 ℃, so that the material at the inlet of the last reactor can be ensured to reach the proper reaction temperature.
The catalyst in the other reactors except the last reactor may be the same catalyst as the catalyst II or an existing conventional catalyst, and the present invention is not particularly limited thereto. Any catalyst suitable for the reaction to produce styrene, which is conventional in the art, is within the scope of the present invention.
In a preferred embodiment of the invention, at least two reactors are packed with catalyst II.
In a preferred embodiment of the invention, each reactor is packed with catalyst II.
In order to make the catalyst suitable for higher pressure range due to the higher pressure of the last reactor, the catalyst II in the present invention is a shaped catalyst, and may be at least one selected from the group consisting of butterfly, hollow cylinder, diamond, honeycomb, clover, tetrafoil, pentafoil, sphere, wheel, gear, star, cross and quincunx.
Preferably, the catalyst II is at least one selected from the group consisting of clover-shaped, quincunx-shaped and five-gear-shaped.
It is well known to those skilled in the art that the heterogeneous catalyst has the disadvantages of low strength, high attrition, etc. The inventors have further defined the side pressure strength and attrition rate of catalyst II in order to reduce attrition of the catalyst while increasing its strength.
Specifically, the side pressure strength of the catalyst II is not less than 120N/5mm, for example, in the range of 130N/5mm, 140N/5mm, 150N/5mm, 160N/5mm, 170N/5mm, 180N/5mm, 190N/5mm, 200N/5mm and any combination thereof.
As a specific embodiment of the present invention, catalyst II has an attrition rate in the range of 0.3% to 2.5%, such as 0.3% to 2.5%, 0.8% to 2%, 1.3% to 1.7%, 0.3%, 0.8%, 1.3%, 1.8%, 2.5%, and any combination thereof.
In addition, the inventor finds in the research process that the physical properties of the catalyst can be properly adjusted by adjusting the content and the form of Ce in the catalyst. For example, providing C in catalyst IIeO2On the premise of ensuring the activity of the catalyst, the strength of the catalyst can be improved, and the abrasion of the catalyst can be reduced.
May be further prepared by adjusting CeO2The particle size of (a) is in the range of 10nm to 60nm, for example 20nm to 50nm, 30nm to 40nm, 15nm, 25nm, 35nm, 45nm, 55nm and any combination thereof, whereby the strength of the catalyst can be further improved and the attrition can be reduced.
As a specific embodiment of the invention, the catalyst II comprises the following components in percentage by mass based on the mass of the catalyst II: fe2O3 60％-85％、K2O 6％-14％、CeO2 6％-16％、MoO30.5-5%, CaO 0.2-5% and MnO2 0.1％-2％。
Preferably, CaO and MnO2In a weight ratio of 1-10:1, for example 2-8:1, 1-5:1, 5-10: 1.
As a specific embodiment of the present invention, when two reactors are arranged in series, the catalyst in the first reactor may comprise the following components in percentage by mass based on the mass of the catalyst: fe2O3 65％-80％、K2O 6％-14％、CeO2 9％-16％、MoO30.5 to 5 percent of CaO, 0.2 to 5 percent of CaO and TiO2 0.01％-1％。
As a specific embodiment of the invention, the catalyst II at least comprises CeO prepared by taking cerium nitrate as a precursor2。
Preferably, in the catalyst II, CeO obtained by preparing the cerium nitrate2Is in the range of 5% to 50%, such as 10% to 40%, 20% to 30%, 5%, 15%, 25%, 35%, 45% and any combination thereof, of the total mass of Ce oxides prepared from all Ce-containing precursors.
As a specific embodiment of the present invention, the volume ratio of the catalyst in the last reactor to the catalyst in the other reactor is independently set to be in the range of 1:1 to 1:1.3, such as 1:1, 1:1.1, 1:1.2, 1:1.3 and any combination thereof, that is, the volume ratio of the catalyst in the last reactor to the catalyst in the other reactor may be the same or different, and is within the protection scope of the present invention.
As a particular embodiment of the invention, the weight ratio of water to ethylbenzene in the feed is in the range of from 0.9 to 2:1, such as from 1.3 to 1.8:1, 0.9:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, and any combination thereof.
Preferably, the ethylbenzene liquid volume space velocity is 0.1h-1-1h-1E.g. 0.3h-1-0.5h-1E.g. 0.1h-1，0.2h-1，0.3h-1，0.4h-1，0.5h-1，0.6h-1，0.7h-1，0.8h-1，0.9h-1，1h-1And any combination thereof.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
The test methods in the following examples and comparative examples are as follows:
1. calculation of void fraction
Void ratio (1-bulk density of catalyst/apparent density of catalyst) × 100%;
relative voidage-the profiled catalyst voidage/cylindrical catalyst voidage.
The bulk density of the catalyst was measured in accordance with the regulations of GB/T6286.
The apparent density of the catalyst is measured by a pycnometer method, namely, the mass of a sample is weighed firstly, then distilled water is injected into the pycnometer, the sample is tightly plugged by a plug (ensuring that the volume of the distilled water is equal to that of the pycnometer), and finally the weighed sample is put into the pycnometer filled with the distilled water for weighing, and then the apparent density of the sample is calculated.
2. Lateral pressure strength of catalyst
The assay was performed according to standard HG/T2782-1996 using a DL-II smart particle intensity meter. The test pieces having a length of 5mm were measured in 40 pieces, and the arithmetic mean of the measurement results was taken as the final mechanical strength value in newtons (N).
3. Attrition rate of catalyst
The determination method comprises the following steps: drying the sample at 200 ℃ for 2h, accurately weighing the sample, and sieving the sample through a 20-mesh sieve after 5000 circles of abrasion of an abrasion tester to obtain particles, wherein the difference of the accurate weighing of the particles accounts for the percentage of the original weight.
4. CeO of catalyst2Grain size
According to XRD test results, the X-ray diffraction spectrum is calculated by a Sherrer formula. XRD test is carried out on a D8advance type X-ray powder diffractometer of Bruker company, the tube voltage is 40kV, the tube current is 250mA, the Cu target is scanned in the range of 4-70 degrees at the scanning speed of 6 degrees/min, and the detector is a solid detector.
[ example 1 ]
Example 1 provides a process for producing styrene comprising the steps of: the reaction raw materials sequentially pass through a first reactor and a second reactor which are connected in series to obtain a product.
Wherein the first reactor is charged with 750mL of catalyst I, the second reactor is charged with 750mL of catalyst II, the temperature T in the first reactor1And the temperature T in the second reactor2The outlet pressure P of the second reactor is 615 ℃/620 ℃ respectively2At 60 kPa.
The catalyst II is cloverleaf, the lateral pressure strength is 145N/5mm, the abrasion rate is 1.1 percent, and CeO of the catalyst2The grain size and composition are listed in table 1.
Wherein catalyst II is prepared by mixing 60.44 parts by weight of Fe based on the weight of the oxide2O3Iron oxide red of (1), corresponding to 12.09 parts of Fe2O3Iron oxide yellow of (1), corresponding to 11.45 parts of K2Potassium carbonate of O, corresponding to 9.14 parts of CeO2Cerium oxalate equivalent to 1.07 parts of MoO3Ammonium molybdate of (1), calcium hydroxide equivalent to 2.15 parts of CaO, 0.58 part of MnO20.03 part of TiO2And 5.5 parts of sodium carboxymethylcellulose were stirred in a kneader for 1.5h, which corresponds to 3.05 parts of CeO2Adding the cerium nitrate into deionized water accounting for 23.5 percent of the total weight of the catalyst raw materials for dissolving, then adding the aqueous solution of the cerium nitrate into a kneader, stirring for 0.7h, taking out an extruded strip, and extruding into a strip with the diameter of 3mm and the length of 5mmAnd (3) putting the mm particles into an oven, baking for 6h at 50 ℃, baking for 12h at 120 ℃, then baking for 7h at 350 ℃, and then baking for 4h at 850 ℃ to obtain the catalyst II. The catalyst composition is listed in table 1.
The catalyst I can be Fe used for preparing styrene by ethylbenzene dehydrogenation in the prior art2O3-K2Catalyst I is the same as catalyst II in this example, except that catalyst I is cylindrical in shape. At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 2 ]
Example 2 provides a process for the production of styrene, and example 2 differs from example 1 only in that catalyst II described in example 2 is in the form of a quincunx, the remaining parameters and steps being the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 3 ]
Example 3 provides a process for the production of styrene, example 3 differs from example 1 only in that catalyst II described in example 3 is in the form of a five-gear wheel, the remaining parameters and steps being identical.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 4 ]
Example 4 provides a process for the production of styrene and example 4 differs from example 1 only in that the outlet pressure of the second reactor in example 4 is 70kPaA and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 5 ]
Example 5 provides a process for the production of styrene and example 5 differs from example 1 only in that the outlet pressure of the second reactor in example 5 is 80kPaA and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 6 ]
Example 6 provides a process for the production of styrene and example 6 differs from example 1 only in that the first reactor in example 6 is charged with catalyst II and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 7 ]
Example 7 provides a process for producing styrene, and example 7 differs from example 1 only in that in example 7 the first reactor was charged with 680mL of catalyst I and the second reactor was charged with 820mL of catalyst II, and the remaining parameters and steps were the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
[ example 8 ]
Example 8 provides a process for the production of styrene and example 8 differs from example 1 only in that the composition of the catalyst in example 8 is different and the remaining parameters and steps are the same.
Wherein catalyst II is prepared by mixing 68.91 parts by weight of Fe based on the weight of the oxide2O3Iron oxide red of (1), corresponding to 13.42 parts of K2Potassium carbonate of O, corresponding to 0.97 part of CeO2Corresponding to 2.81 parts of MoO3Ammonium molybdate of (1), calcium carbonate corresponding to 4.78 parts of CaO, 0.50 part of MnO20.01 part of TiO2And 5.8 parts of hydroxyethylcellulose were stirred in a kneader for 1.5h, corresponding to 8.60 parts of CeO2Adding cerium nitrate into the catalyst to make the catalyst be in an amount of 21.5% by weight of the total weight of the catalyst raw materialsDissolving in deionized water, adding the aqueous solution of cerium nitrate into a kneader, stirring for 0.5h, taking out an extruded strip, extruding into particles with the diameter of 3mm and the length of 5mm, putting the particles into an oven, baking for 8h at 45 ℃, baking for 10h at 120 ℃, baking for 7h at 360 ℃, and baking for 5h at 820 ℃ to obtain the catalyst II. The catalyst composition is listed in table 1.
Catalyst I was the same composition as catalyst II except that catalyst I was cylindrical in shape.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
Comparative example 1
Comparative example 1 provides a process for producing styrene, and comparative example 1 differs from example 1 only in that the second reactor in comparative example 1 is filled with a cylindrical catalyst I, and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
Comparative example 2
Comparative example 2 provides a process for producing styrene, and comparative example 2 differs from example 1 only in that the first reactor of comparative example 2 is packed with cloverleaf catalyst II and the second reactor is packed with cylindrical catalyst I, all other parameters and steps being the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
Comparative example 3
Comparative example 3 provides a method for producing styrene, and comparative example 3 differs from example 2 only in that the first reactor in comparative example 3 is filled with catalyst II in the form of a quincunx and the second reactor is filled with catalyst I in the form of a cylinder, and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1Evaluation was made under the condition that the weight ratio (D) of water to ethylbenzene was 1.3:1, and the test results are shown in the followingIn table 2.
Comparative example 4
Comparative example 4 provides a method for producing styrene, and comparative example 4 is different from example 3 only in that the first reactor in comparative example 4 is filled with catalyst II in the form of a five-gear and the second reactor is filled with catalyst I in the form of a cylinder, and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
Comparative example 5
Comparative example 5 provides a process for producing styrene, and comparative example 5 differs from example 4 only in that the first reactor in comparative example 5 is packed with the trilobal catalyst II and the second reactor is packed with the cylindrical catalyst I, and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
Comparative example 6
Comparative example 6 provides a process for producing styrene, and comparative example 6 differs from example 5 only in that the first reactor in comparative example 6 is packed with the trilobal catalyst II and the second reactor is packed with the cylindrical catalyst I, and the remaining parameters and steps are the same.
At the ethylbenzene liquid volume space velocity (V) of 0.5h-1The evaluation was carried out at a weight ratio (D) of water to ethylbenzene of 1.3:1, and the test results are shown in Table 2.
TABLE 2
Note: the first anti-catalyst shape refers to the shape of the catalyst in the first reactor and the second anti-catalyst shape refers to the shape of the catalyst in the second reactor.
The activity of the prepared catalyst is evaluated in a two-stage adiabatic fixed bed, and the process of evaluating the activity of preparing styrene by ethylbenzene dehydrogenation is briefly described as follows:
the reaction raw materials are respectively input into a preheating mixer through a metering pump, the preheating and mixing are carried out to form gas state, then the gas state sequentially enters two reactors, and reactants flowing out of the reactors are analyzed through a gas chromatograph after being condensed by water.
The ethylbenzene conversion, styrene selectivity and styrene yield were calculated according to the following formulas:
styrene yield%
As can be seen from tables 1 and 2, the method for producing styrene according to the example of the present invention can effectively improve the conversion of the raw material and the selectivity of styrene, thereby improving the yield of styrene, compared to the comparative example.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of a component, or a value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88 … …, and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined within the scope of the claims and modifications may be made without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (11)
1. A process for the production of styrene comprising the steps of: sequentially passing reaction raw materials through a plurality of reactors connected in series to obtain a product;
wherein the reaction feed comprises at least ethylbenzene and water; filling a catalyst II in the last reactor connected in series, wherein the relative porosity of the catalyst II is not less than 1.01 in terms of the porosity of the cylindrical catalyst being 1; preferably, the void ratio of the catalyst II is not more than 1.25; preferably, the plurality of reactors is two reactors.
2. The process for producing styrene according to claim 1, wherein the outlet pressure of the last reactor is from 40kPaA to 101 kPaA; preferably, the outlet pressure of the last reactor is between 60kPaA and 101 kPaA.
3. The method for producing styrene according to claim 1 or 2, wherein the temperatures of the plurality of reactors are independently set to 570 ℃ to 640 ℃ respectively; preferably, a heating system is further included before the last reactor; further preferably, the temperature of the reaction feed when entering the last reactor is not less than 590 ℃.
4. A process for producing styrene according to any one of claims 1 to 3, wherein at least two reactors are packed with catalyst II, preferably each reactor is packed with catalyst II.
5. The process for producing styrene according to any one of claims 1 to 4, wherein the catalyst II is a shaped catalyst selected from at least one of a butterfly shape, a hollow cylindrical shape, a diamond shape, a honeycomb shape, a clover shape, a tetrafoil shape, a pentafoil shape, a sphere shape, a wheel shape, a gear shape, a star shape, a cross shape and a quincunx shape; preferably, the catalyst II is at least one selected from the group consisting of clover-shaped, quincunx-shaped and five-gear-shaped.
6. The process for producing styrene according to any one of claims 1 to 5, wherein the side pressure strength of the catalyst II is not less than 120N/5 mm; preferably, the attrition rate of the catalyst II is 0.3% to 2.5%.
7. The process for producing styrene according to any one of claims 1 to 6, wherein the catalyst II comprises at least CeO2(ii) a Preferably, CeO2The particle size of (A) is 10nm-60 nm.
8. The process for producing styrene according to any one of claims 1 to 7, wherein the catalyst II comprises the following components in percentage by mass based on the mass of the catalyst II: fe2O3 60％-85％、K2O 6％-14％、CeO2 6％-16％、MoO30.5-5%, CaO 0.2-5% and MnO20.1% -2%; preferably, CaO and MnO2The weight ratio of (A) to (B) is 1-10: 1.
9. The process for producing styrene according to any one of claims 1 to 8The method is characterized in that the catalyst II at least comprises CeO prepared by taking cerium nitrate as a precursor2(ii) a Preferably, in the catalyst II, CeO obtained by preparing the cerium nitrate2The mass of (b) is 5-50% of the total mass of the oxides of Ce prepared from all Ce-containing precursors.
10. The process for producing styrene according to any one of claims 1 to 9, wherein each reactor is packed with a catalyst, and the volume ratio of the catalyst in the last reactor to the catalyst in each of the other reactors is independently set to 1 to 1.3: 1.
11. The process for producing styrene according to any one of claims 1 to 10, wherein the weight ratio of water to ethylbenzene in the feed is 0.9 to 2:1, and/or the ethylbenzene liquid volume space velocity is 0.1h-1-1h-1。
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